U.S. patent application number 16/588050 was filed with the patent office on 2020-01-23 for electrolyte stabilizing materials, non-aqueous electrolyte, rechargeable batteries using the same, secondary battery-use electro.
The applicant listed for this patent is MURATA MANUFACTURING CO., LTD.. Invention is credited to Dennis CHERCKA, David DANNER, Vitor DEICHMANN, William FORD, Takumi HIASA, Qiaoshu HU, Nadejda KRASTEVA, Gabriele NELLES, Silvia ROSSELLI, Graham SANDFORD, Kazumasa TAKESHI, Clemens WALL, Joshua WALTON.
Application Number | 20200028213 16/588050 |
Document ID | / |
Family ID | 61972181 |
Filed Date | 2020-01-23 |
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United States Patent
Application |
20200028213 |
Kind Code |
A1 |
HU; Qiaoshu ; et
al. |
January 23, 2020 |
ELECTROLYTE STABILIZING MATERIALS, NON-AQUEOUS ELECTROLYTE,
RECHARGEABLE BATTERIES USING THE SAME, SECONDARY BATTERY-USE
ELECTROLYTIC SOLUTION, SECONDARY BATTERY, BATTERY PACK, ELECTRIC
VEHICLE, ELECTRIC POWER STORAGE SYSTEM, ELECTRIC POWER TOOL, AND
ELECTRONIC APPARATUS
Abstract
a secondary battery is provided. The secondary battery includes
a cathode; an anode; and an electrolytic solution including a
carbonyl compound.
Inventors: |
HU; Qiaoshu; (Kyoto, JP)
; HIASA; Takumi; (Kyoto, JP) ; TAKESHI;
Kazumasa; (Kyoto, JP) ; SANDFORD; Graham;
(Durham, GB) ; WALTON; Joshua; (Durham, GB)
; KRASTEVA; Nadejda; (Stuttgart, DE) ; ROSSELLI;
Silvia; (Stuttgart, DE) ; NELLES; Gabriele;
(Stuttgart, DE) ; DANNER; David; (Stuttgart,
DE) ; DEICHMANN; Vitor; (Stuttgart, DE) ;
CHERCKA; Dennis; (Stuttgart, DE) ; FORD; William;
(Stuttgart, DE) ; WALL; Clemens; (Stuttgart,
DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
MURATA MANUFACTURING CO., LTD. |
Kyoto |
|
JP |
|
|
Family ID: |
61972181 |
Appl. No.: |
16/588050 |
Filed: |
September 30, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
PCT/JP2018/013531 |
Mar 30, 2018 |
|
|
|
16588050 |
|
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01M 2300/0037 20130101;
H01M 10/0567 20130101; H01M 10/0525 20130101; H01G 11/64 20130101;
H01M 4/525 20130101; H01M 4/587 20130101; Y02E 60/13 20130101; Y02T
10/70 20130101; Y02E 60/10 20130101; H01M 4/364 20130101; H01M
10/052 20130101; H01G 11/06 20130101; H01M 2300/0025 20130101; H01M
4/386 20130101 |
International
Class: |
H01M 10/0567 20060101
H01M010/0567; H01M 10/0525 20060101 H01M010/0525 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 31, 2017 |
EP |
17164208.5 |
Aug 29, 2017 |
JP |
2017-164109 |
Claims
1. A non-aqueous electrolyte for secondary batteries comprising: a
polar aprotic solvent; an alkali metal salt; and at least one
additive, wherein the at least one additive is at least one
compound selected from compounds represented by chemical formula I:
##STR00062## wherein Z.sub.1, Z.sub.2 represent one of alkyl
(--C.sub.nH.sub.2n+1), cycloalkyl, alkenyl (CnEI2,), aryl (--Ar),
heteroaryl; halogenated alkyl ((--C.sub.nX.sub.2n+1) or
(--CH.sub.2--C.sub.nX.sub.2n+1)), halogenated cycloalkyl
((--C.sub.nX.sub.2n) or (--CH.sub.2--C.sub.nX.sub.2n)), halogenated
alkenyl (C.sub.nX.sub.n), halogenated aryl (--Ar--X), halogenated
heteroaryl with halogen X being F, Cl, Br or I; alkoxy, aryloxy,
heteroaryloxy, halogenated aryloxy; --CN-substituted-alkyl,
-cycloalkyl, -aryl, -heteroaryl; --NO.sub.2-substituted-alkyl,
-cycloalkyl, -aryl, -heteroaryl; halogen or nitrile (--CN); wherein
X.sub.1, X.sub.2 represent one of hydrogen; halogen X ; halogenated
alkyl, -alkenyl, -aryl, -heteroaryl; --CN-substituted-alkyl,
-alkenyl, -heteroaryl; --NO.sub.2-substituted-alkyl, -alkenyl,
-aryl and -heteroaryl; and wherein X.sub.1 and X.sub.2 are not
hydrogen concurrently.
2. The non-aqueous electrolyte for secondary batteries according to
claim 1, wherein the at least one additive is at least one compound
selected from compounds represented by chemical formula I-I:
##STR00063## wherein R.sub.1, R.sub.2 represent alkyl
(--C.sub.nH.sub.2n+1), cycloalkyl, alkenyl (C.sub.nH.sub.2n), aryl
(--Ar), heteroaryl; halogenated alkyl ((--C.sub.nX.sub.2n+1) or
(--CH.sub.2--C.sub.nX.sub.2n+1)), halogenated cycloalkyl
((--C.sub.nX.sub.2n) or (--CH.sub.2--C.sub.nX.sub.2n)), halogenated
alkenyl (C.sub.nX.sub.n), halogenated aryl (--Ar--X) or halogenated
heteroaryl with halogen X being F, Cl, Br or I; and wherein R.sub.1
and R.sub.2 do not form a cyclic compound together; and wherein
X.sub.1, X.sub.2 represent one of hydrogen; halogen X; halogenated
alkyl, -alkenyl, -aryl, -heteroaryl; --CN-substituted-alkyl,
-alkenyl, -aryl, -heteroaryl; --NO.sub.2-substituted-alkyl,
-alkenyl, -aryl and -heteroaryl; wherein X.sub.1 and X.sub.2 are
not hydrogen concurrently.
3. The non-aqueous electrolyte for secondary batteries according to
claim 1, wherein the at least one additive is at least one compound
selected from compounds represented by chemical formula I-II:
##STR00064## wherein R.sub.1, R.sub.2 represent one of alkyl
(--C.sub.nH.sub.2n+1), cycloalkyl, alkenyl (C.sub.nH.sub.2n), aryl
(--Ar), heteroaryl; halogenated alkyl ((--C.sub.nX.sub.2n+1) or
(--CH.sub.2--C.sub.nX.sub.2n+1)), halogenated cycloalkyl
((--C.sub.nX.sub.2n) or (--CH.sub.2--C.sub.nX.sub.2n)), halogenated
alkenyl (C.sub.nX.sub.n), halogenated aryl (--Ar--X), halogena.ted
heteroaryl with halogen X being F, Cl, Br or I;
--CN-substituted-alkyl, -cycloalkyl, -aryl, -heteroaryl;
--NO.sub.2--substituted-alkyl, -cycloalkyl, -aryl, -heteroaryl;
halogen (--F, --Cl, --Br, --I) and nitrile (--CN); and wherein
X.sub.1, X.sub.2 represents one of hydrogen; halogen X; halogenated
alkyl, -alkenyl, -aryl, -heteroaryl; --CN-substituted-alkyl,
-alkenyl, -aryl, -heteroaryl; --NO.sub.2-substituted-alkyl,
-alkenyl, -aryl and -heteroaryl.
4. The non-aqueous electrolyte for secondary batteries according to
claim 1, wherein the at least one additive is at least one compound
selected from compounds represented by chemical formula
##STR00065## wherein R.sub.1 represents one of alkyl
(--C.sub.nH.sub.2n+1), cycloalkyl, alkenyl (C.sub.nH.sub.2n), aryl
(--Ar), heteroaryl; halogenated alkyl ((--C.sub.nX.sub.2n+1) or
(--CH.sub.2--C.sub.nX.sub.2n)) halogenated cycloalkyl
((--C.sub.nX.sub.2n) or (--CH.sub.2--C.sub.nX.sub.2n)), halogenated
alkenyl (C.sub.nX.sub.n) halogenated aryl (--Ar--X), and
halogenated heteroaryl with halogen X being F, Cl, Br or I; wherein
R.sub.2 represents one of alkyl (--C.sub.nH.sub.2n+1), cycloalkyl,
alkenyl (C.sub.nH.sub.2n), aryl (--Ar), heteroaryl; halogenated
alkyl ((--C.sub.nX.sub.2n+1) or (--CH.sub.2--C.sub.nX.sub.2n+1)),
halogenated cycloalkyl ((--C.sub.nX.sub.2n) or
(--CH.sub.2--C.sub.nX.sub.2n)), halogenated alkenyl
(C.sub.nX.sub.n), halogenated aryl (--Ar--X), halogenated
heteroaryl with halogen X being F, Cl, Br or I;
--CN-substituted-alkyl, -cycloalkyl, -aryl, -heteroaryl;
--NO.sub.2--substituted-alkyl, -cycloalkyl, -aryl, -heteroaryl;
halogen (--F, --Cl, --Br, --I) and nitrile (--CN); and wherein
X.sub.1, X.sub.2 represent one of hydrogen; halogen X; halogenated
alkyl, -alkenyl, -aryl, -heteroaryl; --CN-substituted-alkyl,
-alkenyl, -aryl, -heteroaryl; --NO.sub.2-substituted-alkyl,
-alkenyl, -aryl and -heteroaryl.
5. A non-aqueous electrolyte for secondary batteries comprising: a
polar aprotic solvent; an alkali metal salt; and at least one
additive, wherein the at least one additive is at least one
compound selected from compounds represented by chemical formula
I-IV: ##STR00066## wherein R.sub.1 represents one of alkyl
(--C.sub.nH.sub.2n+1), cycloalkyl, alkenyl (C.sub.nH.sub.2n), aryl
(--Ar), heteroaryl; halogenated cycloalkyl ((--C.sub.nX.sub.2n) or
(--CH.sub.2--C.sub.nX.sub.2n)), halogenated alkenyl
(C.sub.nX.sub.n), halogenated aryl (--Ar--X), halogenated
heteroaryl with halogen X being F, Cl, Br or I; halogen and nitrile
(--CN); wherein R.sub.2 represents one of alkyl
(--C.sub.nH.sub.2n+1), cycloalkyl, alkenyl (C.sub.nH.sub.2n), aryl
(--Ar), heteroaryl; halogenated cycloalkyl ((--C.sub.nX.sub.2n) or
(--CH.sub.2--C.sub.nX.sub.2n)), halogenated alkenyl
(C.sub.nX.sub.n), halogenated aryl (--Ar--X), halogenated
heteroaryl with halogen X being F, Cl, Br or I; alkoxy, aryloxy,
heteroaryloxy, halogenated aryloxy, --CN-substituted-alkyl,
-cycloalkyl, -aryl, -heteroaryl; --NO.sub.2-substituted-alkyl,
-cycloalkyl, -aryl, -heteroaryl; halogen and nitrile (--CN);
wherein R.sub.1, R.sub.2 is each not a halogenated alkyl; wherein
X.sub.1, X.sub.2 represents one of hydrogen; halogen X; halogenated
alkyl, -alkenyl, -aryl, -heteroaryl; --CN-substituted-alkyl,
-alkenyl, -aryl, -heteroaryl; --NO.sub.2-substituted-alkyl,
-alkenyl, -aryl and -heteroaryl; wherein X.sub.1 and X.sub.2 are
not hydrogen concurrently.
6. The non-aqueous electrolyte for secondary batteries according to
claim 1, wherein an amount of the at least one additive in the
non-aqueous electrolyte is between 0.001 and 10 wt %.
7. The non-aqueous electrolyte for secondary batteries according
claim 1, wherein an amount of the at least one additive in the
non-aqueous electrolyte is between 0.01 and 2 wt %.
8. The non-aqueous electrolyte for secondary batteries according to
claim 1, wherein the at least one additive in the non-aqueous
electrolyte is a mixture of compounds selected from compounds
represented by chemical formula I-I.
9. The non-aqueous electrolyte for secondary batteries according to
claim 1, further comprising a second additive, wherein the second
additive includes at least one of vinylene carbonate,
fluoroethylene carbonate, trifluoromethyl ethylene carbonate, and
succinonitrile.
10. The non-aqueous electrolyte for secondary batteries according
to claim 1, wherein the non-aqueous electrolyte includes a liquid
or polymer-gel electrolyte.
11. The non-aqueous electrolyte for secondary batteries according
to claim 1, wherein the polar aprotic solvent includes at least one
of cyclic ester carbonate(s), chain ester carbonate(s), lactone(s),
and chain carboxylic ester(s).
12. The non-aqueous electrolyte according to claim 1, wherein the
alkali metal salt includes one or more Li salts.
13. A secondary battery comprising: a cathode, an anode, and an
non-aqueous electrolyte according to claim 1, wherein the secondary
battery includes a secondary Li-ion battery.
14. The secondary battery according to claim 13, wherein the
cathode includes an intercalation type cathode including one or
more kinds of active cathode material configured to reversibly
insert and extract Li ions, wherein the anode includes an
intercalation type anode including one or more kinds of active
anode material configured to reversibly insert and extract Li ions,
and wherein the anode includes at least one of graphitizable
carbon, non-graphitizable carbon, graphite, Li-metal, Si, Si oxide,
Si alloy, Sn, Sn oxide, LiTi.sub.2O.sub.5, and Sn
15. An electric device comprising a secondary battery according to
claim 13, wherein the electric device includes at least one of a
battery pack, an electric vehicle, an electric power storage
system, an electric power tool and an electronic apparatus.
16. A secondary battery, comprising: a cathode; an anode; and an
electrolytic solution including a cyano compound represented by
chemical formula (1), ##STR00067## wherein R1 represents one of a
monovalent hydrocarbon group and a monovalent halogenated.
hydrocarbon group, R2 represents one of a cyano group, a monovalent
chain hydrocarbon cyano group, and a monovalent halogenated chain
hydrocarbon cyano group, X1 represents a halogen group, X2
represents one of a hydrogen group, a halogen group, a monovalent
hydrocarbon group, and a monovalent halogenated hydrocarbon
group.
17. The secondary battery according to claim 16, wherein in the R2,
the monovalent chain hydrocarbon cyano group includes an alkyl
group having one or more cyano groups.
18. The secondary battery according to claim 17, wherein one cyano
group is introduced into an end of the alkyl group.
19. The secondary battery according to claim 18, wherein number of
carbons in the alkyl group is 3 or more.
20. The secondary battery according to claim 16, wherein in the R1
and the X2, the monovalent hydrocarbon group includes one of an
alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl
group, an aryl group, and wherein in the X1 and the X2, the halogen
group includes one of a fluorine group, a chlorine group, a bromine
group, and a iodine group.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This present application is a continuation of PCT
Application No. PCT/JP2018/013531, filed on Mar. 30, 2018, which
claims priority to Japanese Patent Application No. JP 2017-164109
filed on Aug. 29, 2017 and European Patent Application No:
EP17164208.5 filed on Mar. 31, 2017, the entire contents of which
are being incorporated herein by reference.
BACKGROUND
[0002] The field of the DISCLOSURE lies in materials for secondary
batteries.
[0003] The present application relates to non-aqueous electrolytes
for secondary batteries and their uses in electrochemical devices
or electric devices.
[0004] The disclosure relates to a secondary battery that includes
the non-aqueous electrolyte.
[0005] Moreover, the disclosure relates to an electric device that
includes the secondary battery.
[0006] The disclosure relates to an electrolytic solution used for
a secondary battery and a secondary battery that uses the
electrolytic solution, and to a battery pack, an electric vehicle,
an electric power storage system, an electric power tool, and an
electronic apparatus each of which uses the secondary battery.
[0007] Various electronic apparatuses such as mobile phones have
been widely used, and it has been demanded to further reduce size
and weight of the electronic apparatuses and to achieve their
longer lives. Accordingly, small and light-weight secondary
batteries capable of providing high energy density have been
developed as electric power sources for the electronic
apparatuses.
[0008] Applications of the secondary batteries are not limited to
the electronic apparatuses described above, and it has been also
considered to apply the secondary batteries to various other
applications. Examples of such other applications may include: a
battery pack attachably and detachably mounted on, for example, an
electronic apparatus; an electric vehicle such as an electric
automobile; an electric power storage system such as a home
electric power server; and an electric power tool such as an
electric
[0009] The secondary battery includes a cathode, an anode, and
electrolytic solution. The configuration of the electrolytic
solution exerts a large influence on battery characteristics.
Accordingly, various studies have been conducted on the
configuration of the electrolytic solution.
[0010] More specifically, in order to improve electrochemical
characteristics in a wide temperature range, the electrolytic
solution includes carboxylate ester.
SUMMARY
[0011] In association with higher performance and more
multi-functionality of electronic apparatuses and other apparatuses
including the secondary batteries, the electronic apparatuses and
the other apparatuses are more frequently used, and usage
environment thereof expands. For this reason, there is still room
for improvement in battery characteristics of the secondary
batteries.
[0012] It is therefore desirable to provide a secondary battery-use
electrolytic solution, a secondary battery, a battery pack, an
electric vehicle, an electric power storage system, an electric
power tool, and an electronic apparatus each of which makes it
possible to achieve superior battery characteristics.
[0013] According to an embodiment of the present disclosure, a
non-aqueous electrolyte for secondary batteries is provided. The
non-aqueous electrolyte includes:
[0014] a polar aprotic solvent;
[0015] an alkali metal salt; and
[0016] at least one additive in which the at least one additive is
at least one compound selected from compounds represented by
chemical formula I:
##STR00001##
[0017] in which Z.sub.1, Z.sub.2 represent one of alkyl
(--C.sub.nH.sub.2n+1), cycloalkyl, alkenyl (C.sub.nH.sub.2n), aryl
(--Ar), heteroaryl; halogenated alkyl ((--C.sub.nX.sub.2n+1) or
(--CH.sub.2--C.sub.nX.sub.2n+1)), halogenated cycloalkyl
((--C.sub.nX.sub.2n) or (--CH.sub.2--C.sub.nX.sub.2n)), halogenated
alkenyl (C.sub.nX.sub.n), halogenated aryl (--Ar--X), halogenated
heteroaryl with halogen X being F, Cl, Br or I; alkoxy, aryloxy,
heteroaryloxy, halogenated aryloxy; --CN-substituted-alkyl,
-cycloalkyl, -aryl, -heteroaryl; --NO.sub.2-substituted-alkyl,
-cycloalkyl, -aryl, -heteroaryl; halogen; and nitrile (--CN);
[0018] in which X.sub.1, X.sub.2 represent one of hydrogen; halogen
X; halogenated alkyl, alkenyl, aryl, heteroaryl;
--CN-substituted-alkyl, -alkenyl, -aryl, -heteroaryl;
--NO.sub.2-substituted-alkyl, -alkenyl, -aryl and -heteroaryl.
[0019] According to an embodiment of the present disclosure, a
non-aqueous electrolyte for secondary batteries is presented. The
non-aqueous electrolyte includes:
[0020] a polar aprotic solvent;
[0021] an alkali metal salt; and
[0022] at least one additive in which the at least one additive is
at least one compound selected from compounds represented by
chemical
##STR00002##
[0023] in which R.sub.1 represents one of alkyl
(--C.sub.nH.sub.2n+1), cycloalkyl, alkenyl (C.sub.nH.sub.2n), aryl
(--Ar), heteroaryl, halogenated cycloalkyl ((--C.sub.nX.sub.2n) or
(--CH.sub.2-C.sub.nX.sub.2n)), halogenated alkenyl
(C.sub.nX.sub.n), halogenated aryl (--Ar--X), halogenated
heteroaryl with halogen X being F, Cl, Br or I, halogen (--F, --Cl,
--Br, --I) and nitrile (--CN);
[0024] in which R.sub.2 represents one of alkyl
(--C.sub.nH.sub.2n+1), cycloalkyl, alkenyl (C.sub.nH.sub.2n), aryl
(--Ar), heteroaryl; halogenated cycloalkyl ((--C.sub.nX.sub.2n) or
(--CH.sub.2--C.sub.nX.sub.2n)), halogenated alkenyl
(C.sub.nX.sub.n), halogenated aryl (--Ar--X), halogenated
heteroaryl with halogen X being F, Cl, Br or I, alkoxy, aryloxy,
heteroaryloxy, halogenated aryloxy; --CN-substituted-alkyl,
-cycloalkyl, -aryl, -heteroaryl; --NO.sub.2-substituted-alkyl,
-cycloalkyl, -aryl, -heteroaryl; halogen (--F, --Cl, --Br, --I) and
nitrile (--CN);
[0025] in which R.sub.1, R.sub.2 is each not a halogenated
alkyl;
[0026] in which X.sub.1, X.sub.2 represents one of hydrogen,
halogen X, halogenated alkyl, -alkenyl, -aryl, -heteroaryl,
--CN-substituted-alkyl, -alkenyl, -aryl, -heteroaryl,
--NO.sub.2-substituted-alkyl, -alkenyl, -aryl and -heteroaryl;
[0027] in which X.sub.1 and X.sub.2 are not hydrogen
concurrently.
[0028] According to an embodiment of the present disclosure, there
is provided use of the non-aqueous electrolyte according to the
embodiments described herein, in
[0029] an electrochemical device,
[0030] such as, but not limited to, a secondary battery, a super
capacitor,
[0031] an electric device,
[0032] such as, but not limited to, a battery pack, an electric
vehicle, an electric power storage system, an electric power tool,
an electronic apparatus.
[0033] According to an embodiment of the present disclosure, there
is provided a secondary battery including,
[0034] a cathode,
[0035] an anode, and
[0036] a non-aqueous electrolyte according to the embodiments
described herein, in which the secondary battery includes a
secondary Li-ion battery.
[0037] According to an embodiment of the present disclosure, there
is provided an electric device including a secondary battery
according to the embodiments as described herein.
[0038] The foregoing paragraphs have been provided by way of
general introduction, and are not intended to limit the scope of
the following claims. The described embodiments, together with
further advantages, will be best understood by reference to the
following detailed description taken in conjunction with the
accompanying drawings.
[0039] According to an embodiment of the present disclosure, a
electrolytic solution for a secondary battery is provided. The
electrolytic solution includes a cyano compound represented by
chemical formula (1).
##STR00003##
[0040] where R1 represents one of a monovalent hydrocarbon group
and a monovalent halogenated hydrocarbon group, R2 represents one
of a cyano group, a monovalent chain hydrocarbon cyano group, and a
monovalent halogenated chain hydrocarbon cyano group, X1 represents
a halogen group, X2 represents one of a hydrogen group, a halogen
group, a monovalent hydrocarbon group, and a monovalent halogenated
hydrocarbon group.
[0041] According to an embodiment of the present disclosure, a
secondary battery is provided. The secondary battery includes: a
cathode; an anode; and an electrolytic solution, and the
electrolytic solution has a configuration similar to that of the
electrolytic solution according to the embodiments as described
herein.
[0042] According to an embodiment of the present disclosure, there
are provided a battery pack, an electric vehicle, an electric power
storage system, an electric power tool, and an electronic apparatus
each of which includes a secondary battery, and the secondary
battery has a configuration similar to that of the secondary
battery according to the embodiments as described herein.
[0043] Herein, the "monovalent chain hydrocarbon cyano group"
described above is a generic name of a group in which one or more
cyano groups are introduced into a monovalent chain hydrocarbon
group. In other words, the monovalent chain hydrocarbon cyano group
is a group in which one or more hydrogen groups in a monovalent
chain hydrocarbon group are substituted by one or more cyano
groups.
[0044] It is to be noted that a position where the one or more
cyano groups are introduced into the monovalent chain hydrocarbon
group is not particularly limited.
[0045] The "monovalent chain hydrocarbon group" described herein is
a generic name of a monovalent chain group including carbon (C) and
hydrogen (H), and may be a straight-chain group or a branched group
having one or more side chains. The monovalent chain hydrocarbon
group may include one or more carbon-carbon unsaturated bonds, or
may not include the carbon-carbon unsaturated bond. It should be
understood that non-limiting examples of the carbon-carbon
unsaturated bond may include a carbon-carbon double bond
(>C.dbd.C<) and a carbon-carbon triple bond
(--C.ident.C--).
[0046] Moreover, the "monovalent halogenated chain hydrocarbon
cyano group" described above is a group in which one or more
hydrogen groups in the foregoing monovalent chain hydrocarbon cyano
group are substituted by a halogen group. The halogen group may be
of one kind or of two or more kinds.
[0047] According to the electrolytic solution and the secondary
battery of the respective embodiment as described herein, the
electrolytic solution includes the foregoing cyano compound, which
makes it possible to achieve superior battery characteristics.
Moreover, in each of the battery pack, the electric vehicle, the
electric power storage system, the electric power tool, and the
electronic apparatus of the respective embodiments of the
disclosure, similar effects are achievable.
[0048] It should be understood that effects described herein are
non-limiting. Effects achieved by the disclosure may he one or more
of effects described in the disclosure.
[0049] It is to be understood that both the foregoing general
description and the following detailed description are exemplary,
and are provided to provide further explanation of the technology
as claimed.
BRIEF DESCRIPTION OF THE FIGURES
[0050] The accompanying drawings are included to provide a further
understanding of the technology, and are incorporated in and
constitute a part of this specification. The drawings show
illustrative embodiments and, together with the specification,
serve to explain various principles of the technology.
[0051] FIG. 1 is a cross-sectional view illustrating a
configuration of a secondary battery (of a cylindrical type) that
uses the non-aqueous electrolyte according an embodiment of the
present disclosure.
[0052] FIG. 2 is a cross-sectional view illustrating an enlarged
part of a spirally wound electrode body illustrated in FIG. 1.
[0053] FIG. 3 is a perspective view illustrating a configuration of
another secondary battery (of a laminated film type) that uses the
non-aqueous electrolytic solution according to an embodiment of the
present disclosure.
[0054] FIG. 4 is a cross-sectional view of a spirally wound
electrode body taken along a line IV-IV illustrated in FIG. 3.
[0055] FIG. 5 is a block diagram illustrating a configuration of an
application example (a battery pack) of the secondary battery
according to an embodiment of the present disclosure. For example,
the battery pack may include a control section 61, an electric
power source 62, a switch section 63, a current measurement section
64, a temperature detection section 65, a voltage detection section
66, a switch control section 67, a memory 68, a temperature
detection device 69, a current detection resistance 70, a cathode
terminal 71, and an anode terminal 72 in a housing 60. The housing
60 may be made, for example, of a plastic material or the like.
[0056] FIG. 6 is a block diagram illustrating a configuration of an
application example (an electric vehicle) of the secondary battery
according to an embodiment of the present disclosure. For example,
the electric vehicle may include a control section 74, an engine
75, an electric power source 76, a driving motor 77, a differential
78, an electric generator 79, a transmission 80, a clutch 81,
inverters 82 and 83, and various sensors 84 in a housing 73 made of
metal. In addition thereto, the electric vehicle may include, for
example, a front drive shaft 85 and a front tire 86 that are
connected to the differential 78 and the transmission 80, a rear
drive shaft 87, and a rear tire 88.
[0057] FIG. 7 is a block diagram illustrating a configuration of an
application example (an electric power storage system) of the
secondary battery according to an embodiment of the present
disclosure. For example, the electric power storage system may
include a control section 90, an electric power source 91, a smart
meter 92, and a power hub 93 inside a house 89 such as a general
residence and a commercial building.
[0058] FIG. 8 is a block diagram illustrating a configuration of an
application example (an electric power tool) of the secondary
battery according to an embodiment of the present disclosure. For
example, the electric power tool may be an electric drill, and may
include a control section 99 and an electric power source 100 in a
tool body 98 made of a plastic material and/or the like. For
example, a drill section 101 as a movable section may be attached
to the tool body 98 in an operable (rotatable) manner.
[0059] FIG. 9 is a cross-sectional view illustrating a
configuration of a secondary battery (of a cylindrical type)
according to an embodiment of the present disclosure.
[0060] FIG. 10 is a cross-sectional view illustrating an enlarged
part of a spirally wound electrode body illustrated in FIG. 9.
[0061] FIG. 11 is a perspective view illustrating a configuration
of a secondary battery (of a laminated film type) according to an
embodiment of the present disclosure.
[0062] FIG. 12 is a cross-sectional view of a spirally wound
electrode body taken along a line IV-IV illustrated in FIG. 11.
[0063] FIG. 13 is a perspective view of a configuration of an
application example (a battery pack: single battery) of the
secondary battery according to an embodiment of the present
disclosure.
[0064] FIG. 14 is a block diagram illustrating a configuration of
the battery pack illustrated in FIG. 13.
[0065] FIG. 15 is a block diagram illustrating a configuration of
an application example (a battery pack: assembled battery) of the
secondary battery according to an embodiment of the present
disclosure.
[0066] FIG. 16 is a block diagram illustrating a configuration of
an application example (an electric vehicle) of the secondary
battery according to an embodiment of the present disclosure.
[0067] FIG. 17 is a block diagram illustrating a configuration of
an application example (an electric power storage system) of the
secondary battery according to an embodiment of the present
disclosure.
[0068] FIG. 18 is a block diagram illustrating a configuration of
an application example (an electric power tool) of the secondary
battery according to an embodiment of the present disclosure.
DETAILED DESCRIPTION
[0069] As described herein, the present disclosure will be
described based on examples with reference to the drawings, but the
present disclosure is not to be considered limited to the examples,
and various numerical values and materials in the examples are
considered by way of example.
[0070] The non-aqueous electrolyte for secondary batteries
according to the disclosure includes:
[0071] a polar aprotic solvent;
[0072] an alkali metal salt; and
[0073] at least one additive,
[0074] in which the additive is at least one compound selected from
compounds with general formula I
##STR00004##
[0075] in which Z.sub.1, Z.sub.2 is alkyl (--C.sub.nH.sub.2n+1),
cycloalkyl, alkenyl (C.sub.nH.sub.2n), aryl (--Ar), heteroaryl;
halogenated alkyl ((--C.sub.nX.sub.2n+1) or
(--CH.sub.2-C.sub.nX.sub.2n+1)), halogenated cycloalkyl
((--C.sub.nX.sub.2n) or (--CH.sub.2--C.sub.nX.sub.2n)), halogenated
alkenyl (C.sub.nX.sub.n), halogenated aryl (--Ar--X), halogenated
heteroaryl with halogen X being F, Cl, Br or I; alkoxy, aryloxy,
heteroaryloxy, halogenated aryloxy; --CN-substituted-alkyl,
-cycloalkyl, -aryl, -heteroaryl; --NO.sub.2-substituted-alkyl,
-cycloalkyl, -aryl, -heteroaryl; halogen (--F, --Cl, --Br, --I); or
nitrile (--CN);
[0076] in which X.sub.1, X.sub.2 is H; halogen X (X being F, Cl, Br
or I); halogenated alkyl, -alkenyl, -aryl, -heteroaryl;
[0077] --CN-substituted-alkyl, -alkenyl, -aryl, -heteroaryl;
--NO.sub.2-substituted-alkyl, -alkenyl, -aryl or -heteroaryl;
[0078] in which Z.sub.1 and Z.sub.2 can be equal or different;
and
[0079] in which X.sub.1 and X.sub.2 can be equal or different.
[0080] In an embodiment, the non-aqueous electrolyte for secondary
batteries according to the disclosure includes at least one
additive, which is at least one compound selected from compounds
with general formula I,
##STR00005##
[0081] in which Z.sub.1, Z.sub.2 is alkyl (--C.sub.nH.sub.2n+1),
cycloalkyl, alkenyl (C.sub.nH.sub.2n), aryl (--Ar), heteroaryl;
halogenated alkyl ((--C.sub.nX.sub.2n+1) or
(--CH.sub.2--C.sub.nX.sub.2n+1)), halogenated cycloalkyl
((--C.sub.nH.sub.2n) or (--CH.sub.2----C.sub.nX.sub.2n)),
halogenated alkenyl (C.sub.nX.sub.n), halogenated aryl (--Ar--X),
halogenated heteroaryl with halogen X being F, Cl, Br or I;
--CN-substituted-alkyl, -cycloalkyl, -aryl, -heteroaryl;
--NO.sub.2-substituted-alkyl, -cycloalkyl, -aryl, -heteroaryl;
halogen (--F, --Cl, --Br, --I) or nitrile (--CN); in which Z.sub.1,
Z.sub.2 is not alkoxy, aryloxy, heteroaryloxy or halogenated
aryloxy;
[0082] in which X.sub.1, X.sub.2 is H; halogen X (X being F, Cl, Br
or I); halogenated alkyl, -alkenyl, -aryl, -heteroaryl;
--CNsubstituted-alkyl, -alkenyl, -aryl, -heteroaryl;
--NO.sub.2-substituted-alkyl, -alkenyl, -aryl or -heteroaryl;
[0083] in which Z.sub.1 and Z.sub.2 can be equal or different;
and
[0084] in which X.sub.1 and X.sub.2 can be equal or different.
[0085] In an embodiment, the non-aqueous electrolyte for secondary
batteries according to the disclosure includes at least one
additive, which is at least one compound selected from compounds
with general formula I,
##STR00006##
[0086] in which Z.sub.1, Z.sub.2 is alkyl (--C.sub.nH.sub.2n+1),
cycloalkyl, alkenyl (C.sub.nH.sub.2n), aryl (--Ar), heteroaryl;
halogenated alkyl ((--C.sub.nX.sub.2n+1) or
(--CH.sub.2--C.sub.nX.sub.2n+1)), halogenated cycloalkyl
((--C.sub.nX.sub.2n) or (--CH.sub.2--C.sub.nX.sub.2n)), halogenated
alkenyl (C.sub.nX.sub.n), halogenated aryl (--Ar--X), halogenated
heteroaryl with halogen X being F, Cl, Br or I; alkoxy, aryloxy,
heteroaryloxy, halogenated aryloxy; --CN-substituted-alkyl,
-cycloalkyl, -aryl, -heteroaryl; --NO.sub.2-substituted-alkyl,
-cycloalkyl, -aryl, -heteroaryl; halogen (--F, --Cl, --Br, --I) or
nitrile (--CN);
[0087] in which X.sub.1, X.sub.2 is H; halogen X (X being F, Cl, Br
or I); halogenated alkyl, -alkenyl, -aryl, -heteroaryl;
--CN-substituted-alkyl, -alkenyl, -aryl, -heteroaryl;
--NO.sub.2-substituted-alkyl, -alkenyl, -aryl or -heteroaryl;
[0088] but in which X.sub.1 and X.sub.2 are not hydrogen H
concurrently;
[0089] in which Z.sub.1 and Z.sub.2 can be equal or different;
and
[0090] in which X.sub.1 and X.sub.2 can be equal or different.
[0091] In an embodiment, the non-aqueous electrolyte for secondary
batteries according to the disclosure includes at least one
additive, which is at least one compound selected from compounds
with general formula I,
##STR00007##
[0092] in which Z.sub.1, Z.sub.2 is alkyl (--C.sub.nH.sub.2n+1),
cycloalkyl, alkenyl (C.sub.nH.sub.2n), aryl (--Ar), heteroaryl;
halogenated alkyl ((--C.sub.nX.sub.2n+1) or
(--CH.sub.2-C.sub.nX.sub.2n+1)), halogenated cycloalkyl
((--C.sub.nX.sub.2n) or (--CH.sub.2-C.sub.nX.sub.2n)), halogenated
alkenyl (C.sub.nX.sub.n), halogenated aryl (--Ar--X), halogenated
heteroaryl with halogen X being F, Cl, Br or I;
--CN-substituted-alkyl, -cycloalkyl, -aryl, -heteroaryl;
--NO.sub.2-substituted-alkyl, -cycloalkyl, -aryl, -heteroaryl;
halogen (--F, --Cl, --Br, --I) or nitrile (--CN); in which Z.sub.1,
Z.sub.2 is not alkoxy, aryloxy, heteroaryloxy or halogenated
aryloxy; in which X.sub.1, X.sub.2 is H; halogen X (X being F, Cl,
Br or I); halogenated alkyl, -alkenyl, -aryl, -heteroaryl;
--CN-substituted-alkyl, -alkenyl, -heteroaryl;
--NO.sub.2-substituted-alkyl, -alkenyl, -aryl or -heteroaryl;
[0093] but in which X.sub.1 and X.sub.2 are not hydrogen H
concurrently;
[0094] in which Z.sub.1 and Z.sub.2 can be equal or different;
and
[0095] in which X.sub.1 and X.sub.2 can be equal or different.
[0096] In an embodiment, the non-aqueous electrolyte for secondary
batteries according to the disclosure includes at least one
additive, which is at least one compound selected from compounds
with general formula I-I,
##STR00008##
[0097] in which R.sub.1, R.sub.2 is alkyl (--C.sub.nH.sub.2n+1),
cycloalkyl, alkenyl (C.sub.nH.sub.2n), aryl (--Ar), heteroaryl;
halogenated alkyl ((--C.sub.nX.sub.2n+1) or
(--CH.sub.2--C.sub.nX.sub.2n+1)), halogenated cycloalkyl
((--C.sub.nX.sub.2n) or (--CH.sub.2--C.sub.nX.sub.2n)), halogenated
alkenyl (C.sub.nX.sub.n), halogenated aryl (--Ar--X) or halogenated
heteroaryl with halogen X being F, Cl, Br or I; and
[0098] in which X.sub.1, X.sub.2 is H; halogen X (X being F, Cl, Br
or I); halogenated alkyl, -alkenyl, -heteroaryl;
--CN-substituted-alkyl, -alkenyl, -aryl, -heteroaryl;
--NO.sub.2-substituted-alkyl, -alkenyl, -aryl or -heteroaryl;
[0099] in which R.sub.1, R.sub.2 can be equal or different; and
[0100] in which X.sub.1, X.sub.2 can be equal or different.
[0101] In one embodiment, the non-aqueous electrolyte for secondary
batteries according to the disclosure includes at least one
additive, which is at least one compound selected from compounds
with general formula I-I,
##STR00009##
[0102] in which R.sub.1, R.sub.2 is alkyl (--C.sub.nH.sub.2n+1),
cycloalkyl, alkenyl (C.sub.nH.sub.2n), aryl (--Ar), heteroaryl;
halogenated alkyl ((--C.sub.nX.sub.2n+1) or
(--CH.sub.2--C.sub.nX.sub.2n+1)), halogenated cycloalkyl
((--C.sub.nX.sub.2n) or (--CH.sub.2--C.sub.nX.sub.2n)), halogenated
alkenyl (C.sub.nX.sub.n), halogenated aryl (--Ar--X) or halogenated
heteroaryl with halogen X being F, Cl, Br or I;
[0103] in which R.sub.1, R.sub.2 do not contain one or more
Si-containing substituent(s); and
[0104] in which X.sub.1, X.sub.2 is H; halogen X (X being F, Cl, Br
or F); halogenated alkyl, -alkenyl, -aryl, -heteroaryl;
--CN-substituted-alkyl, -alkenyl, -heteroaryl;
--NO.sub.2-substituted-alkyl, -alkenyl, -aryl or -heteroaryl;
[0105] in which R.sub.1, R.sub.2 can be equal or different; and
[0106] in which X.sub.1, X.sub.2 can be equal or different.
[0107] In one embodiment, the non-aqueous electrolyte for secondary
batteries according to the disclosure includes at least one
additive, which is at least one compound selected from compounds
with general formula I-I,
##STR00010##
[0108] in which R.sub.1, R.sub.2 is alkyl (--C.sub.nH.sub.2n+1),
cycloalkyl, alkenyl (C.sub.nH.sub.2n), aryl (--Ar), heteroaryl;
halogenated alkyl ((--C.sub.nX.sub.2n+1) or
(--CH.sub.2--C.sub.nX.sub.2n+1)), halogenated cycloalkyl
((--C.sub.nX.sub.2n) or --CH.sub.2-C.sub.nX.sub.2n)), halogenated
alkenyl (C.sub.nX.sub.n), halogenated aryl (--Ar--X) or halogenated
heteroaryl with halogen X being F, Cl, Br or I;
[0109] in which R.sub.1 and R.sub.2 do not form a cyclic compound
together; and
[0110] in which X.sub.1, X.sub.2 is H; halogen X (X being F, Cl, Br
or I); halogenated alkyl, -alkenyl, -aryl, -heteroaryl;
--CN-substituted-alkyl, -alkenyl, -aryl, -heteroaryl;
--NO.sub.2-substituted-alkyl, -alkenyl, -aryl or -heteroaryl;
[0111] in which R.sub.1, R.sub.2 can he equal or different; and
[0112] in which X.sub.1, X.sub.2 can be equal or different.
[0113] In one embodiment, the non-aqueous electrolyte for secondary
batteries according to the disclosure includes at least one
additive, which is at least one compound selected from compounds
with general formula I-I,
##STR00011##
[0114] in which R.sub.1, R.sub.2 is alkyl (--C.sub.nH.sub.2n+1),
cycloalkyl, alkenyl (C.sub.nH.sub.2n), aryl (--Ar), heteroaryl;
halogenated alkyl ((--C.sub.nX.sub.2n+1) or
(--CH.sub.2--C.sub.nX.sub.2n+1)), halogenated cycloalkyl
((--C.sub.nX.sub.2n) or (--CH.sub.2--C.sub.nX.sub.2n)), halogenated
alkenyl (C.sub.nX.sub.n), halogenated aryl (--Ar--X) or halogenated
heteroaryl with halogen X being F, Cl, Br or I;
[0115] in which R.sub.1, R.sub.2 do not contain one or more
Si-containing substituent(s) and
[0116] in which R.sub.1 and R.sub.2 do not form a cyclic compound
together; and
[0117] in which X.sub.1, X.sub.2 is H; halogen X (X being F, Cl, Br
or F); halogenated alkyl, -alkenyl, -aryl, -heteroaryl;
--CN-substituted-alkyl, -alkenyl, -aryl, -heteroaryl;
--NO.sub.2-substituted-alkyl, -alkenyl, -aryl or -heteroaryl;
[0118] in which R.sub.1, R.sub.2 can be equal or different; and
[0119] in which X.sub.1, X.sub.2 can be equal or different.
[0120] In an embodiment, the non-aqueous electrolyte for secondary
batteries according to the disclosure includes at least one
additive, which is at least one compound selected from compounds
with general formula I-I,
##STR00012##
[0121] in which R.sub.1, R.sub.2 is alkyl (--C.sub.nH.sub.2n+1),
cycloalkyl, alkenyl (C.sub.nH.sub.2n), aryl (--Ar), heteroaryl;
halogenated alkyl ((--C.sub.nX.sub.2n+1) or
(--CH.sub.2--C.sub.nX.sub.2n+1)), halogenated cycloalkyl
((--C.sub.nX.sub.2n) or (--CH.sub.2--C.sub.nX.sub.2n), halogenated
alkenyl (C.sub.nX.sub.n), halogenated aryl (--Ar--X) or halogenated
heteroaryl with halogen X being F, Cl, Br or I; and
[0122] in which X.sub.1, X.sub.2 is H; halogen X (X being F, Cl, Br
or I); halogenated alkyl, -alkenyl, -aryl, -heteroaryl;
--CN-substituted-alkyl, -alkenyl, -aryl, -heteroaryl;
--NO.sub.2-substituted-alkyl, -alkenyl, -aryl or -heteroaryl;
and
[0123] in which X.sub.1 and X.sub.2 are not hydrogen H
concurrently;
[0124] in which R.sub.1, R.sub.2 can be equal or different; and
[0125] in which X.sub.1, X.sub.2 can be equal or different.
[0126] In an embodiment, the non-aqueous electrolyte for secondary
batteries according to the disclosure includes at least one
additive, which is at least one compound selected from compounds
with general formula I-I,
##STR00013##
[0127] in which R.sub.1, R.sub.2 is alkyl (--C.sub.nH.sub.2n+1),
cycloalkyl, alkenyl (C.sub.nH.sub.2n), aryl (--Ar), heteroaryl;
[0128] halogenated alkyl ((--C.sub.nX.sub.2n+1) or
(--CH.sub.2--C.sub.nX.sub.2n+1)), halogenated cycloalkyl
((--C.sub.nX.sub.2n) or --CH.sub.2--C.sub.nX.sub.2n)), halogenated
alkenyl (C.sub.nX.sub.n), halogenated aryl (--Ar--X) or halogenated
heteroaryl with halogen X being F, Cl, Br or I;
[0129] in which R.sub.1, R.sub.2 do not contain one or more
Si-containing substituent(s); and
[0130] in which X.sub.1, X.sub.2 is H; halogen X (X being F, Cl, Br
or F); halogenated alkyl, -alkenyl, -aryl, -heteroaryl;
--CN-substituted-alkyl, -alkenyl, -aryl, -heteroaryl;
--NO.sub.2-substituted-alkyl, -alkenyl, -aryl or -heteroaryl;
and
[0131] but in which X.sub.1 and X.sub.2 are not hydrogen H
concurrently;
[0132] in which R.sub.1, R.sub.2 can be equal or different; and
[0133] in which X.sub.1, X.sub.2 can be equal or different.
[0134] In an embodiment, the non-aqueous electrolyte for secondary
batteries according to the disclosure includes at least one
additive, which is at least one compound selected from compounds
with general formula I-I,
##STR00014##
[0135] in which R.sub.1, R.sub.2 is alkyl (--C.sub.nH.sub.2n+1),
cycloalkyl, alkenyl (C.sub.nH.sub.2n), aryl (--Ar), heteroaryl;
[0136] halogenated alkyl ((--C.sub.nX.sub.2n+1) or
(--CH.sub.2--C.sub.nX.sub.2n+1)), halogenated cycloalkyl
((--C.sub.nX.sub.2n) or --CH.sub.2--C.sub.nX.sub.2n)), halogenated
alkenyl (C.sub.nX.sub.n), halogenated aryl (--Ar--X) or halogenated
heteroaryl with halogen X being F, Cl, Br or I;
[0137] in which R.sub.1 and R.sub.2 do not form a cyclic compound
together;
[0138] in which X.sub.1, X.sub.2 is H; halogen X (X being F, Cl, Br
or I); halogenated alkyl, -alkenyl, -aryl, -heteroaryl;
--CN-substituted-alkyl, -alkenyl, -aryl, -heteroaryl;
--NO.sub.2-substituted-alkyl, -alkenyl, -aryl or -heteroaryl;
[0139] but in which X.sub.1 and X.sub.2 are not hydrogen H
concurrently;
[0140] in which R.sub.1, R.sub.2 can be equal or different; and
[0141] in which X.sub.1, X.sub.2 can be equal or different.
[0142] In an embodiment, the non-aqueous electrolyte for secondary
batteries according to the disclosure includes at least one
additive, which is at least one compound selected from compounds
with general formula I-I,
##STR00015##
[0143] in which R.sub.1, R.sub.2 is alkyl (--C.sub.nH.sub.2n+1),
cycloalkyl, alkenyl (C.sub.nH.sub.2n), aryl (--Ar), heteroaryl;
[0144] halogenated alkyl ((--C.sub.nX.sub.2n+1) or
(--CH.sub.2--C.sub.nX.sub.2n+1)), halogenated cycloalkyl
((--C.sub.nX.sub.2n) or --CH.sub.2--C.sub.nX.sub.2n)), halogenated
alkenyl (C.sub.nX.sub.n), halogenated aryl (--Ar--X) or halogenated
heteroaryl with halogen X being F, Cl, Br or I;
[0145] in which R.sub.1, R.sub.2 do not contain one or more
Si-containing substituent(s) and
[0146] in which R.sub.1and R.sub.2 do not form a cyclic compound
together,
[0147] in which X.sub.1, X.sub.2 is H; halogen X (X being F, Cl, Br
or I); halogenated alkyl, -alkenyl, -aryl, -heteroaryl;
--CN-substituted-alkyl, -alkenyl, -aryl, -heteroaryl;
--NO.sub.2-substituted-alkyl, -alkenyl, -aryl or -heteroaryl;
[0148] but in which X1 and X2 are not hydrogen H concurrently;
[0149] in which R.sub.1, R.sub.2 can be equal or different; and
[0150] in which X.sub.1, X.sub.2 can be equal or different.
[0151] Preferred embodiments of formula I-I:
[0152] In an preferred embodiment, the at least one additive is one
or more compound(s) with general formula selected from:
##STR00016## ##STR00017## ##STR00018##
[0153] In a further preferred embodiment, the at least one additive
is one or more compounds) with general formula I-I selected
from:
##STR00019##
[0154] In one embodiment, the at least one non-aqueous electrolyte
for secondary batteries according to the disclosure includes at
least one additive, which is at least one compound selected from
compounds with general formula I-II,
##STR00020##
[0155] in which R.sub.1, R.sub.2 is alkyl (--C.sub.nH.sub.2n+1),
cycloalkyl, alkenyl (C.sub.nH.sub.2n), aryl (--Ar), heteroaryl;
halogenated alkyl ((--C.sub.nX.sub.2n+1) or
(--CH.sub.2--C.sub.2n+1), halogenated cycloalkyl
((--C.sub.nX.sub.2n) or (--CH.sub.2--C.sub.nX.sub.2n)), halogenated
alkenyl (C.sub.nX.sub.n), halogenated aryl (--Ar--X), halogenated
heteroaryl with halogen X being F, Cl, Br or I;
--CN-substituted-alkyl, -cycloalkyl, -aryl, -heteroaryl;
--NO.sub.2-substituted-alkyl, -cycloalkyl, -aryl, -heteroaryl;
halogen (--F, --Cl, --Br, --I) or nitrile (--CN); and in which
X.sub.1, X.sub.2 is H; halogen X (X being F, Cl, Br or I);
halogenated alkyl, -alkenyl, -aryl, -heteroaryl;
--CN-substituted-alkyl, -alkenyl, -aryl, -heteroaryl;
--NO.sub.2-substituted-alkyl, -alkenyl, -aryl or -heteroaryl;
[0156] in which R.sub.1, R.sub.2 can be equal or different; and
[0157] in which X.sub.1, X.sub.2 can be equal or different.
[0158] In an embodiment, the at least one additive is one or more
compound(s) with general formula I-II selected from:
[0159] 3-methylpentane-2,4-dione
##STR00021## ##STR00022## ##STR00023## ##STR00024##
[0160] In one embodiment, the at least one non-aqueous electrolyte
for secondary batteries according to the disclosure includes at
least one additive, which is at least one compound selected from
compounds with general formula I-III,
##STR00025##
[0161] in which R.sub.1 is alkyl (--C.sub.nH.sub.2n+1), cycloalkyl,
alkenyl (C.sub.nH.sub.2n), aryl (--Ar), heteroaryl; halogenated
alkyl ((--C.sub.nX.sub.2n+1) or (--CH.sub.2--C.sub.2n+1)),
halogenated cycloalkyl ((--C.sub.nX.sub.2n) or
(--CH.sub.2-C.sub.nX.sub.2n)), halogenated alkenyl
(C.sub.nX.sub.n), halogenated aryl (--Ar--X), halogenated
heteroaryl with halogen X being F, Cl, Br or I;
[0162] in which R.sub.2 is alkyl cycloalkyl, alkenyl
(C.sub.nH.sub.2n), aryl (--Ar), heteroaryl; halogenated alkyl
((--C.sub.nX.sub.2n+1) or (--CH.sub.2--C.sub.nX.sub.2n+1)),
halogenated cycloalkyl ((--C.sub.nX.sub.2n) or
(--CH.sub.2--C.sub.nX.sub.2n)), halogenated alkenyl
(C.sub.nX.sub.n), halogenated aryl (--Ar--X), halogenated
heteroaryl with halogen X being F, Cl, Br or I;
--CN-substituted-alkyl, -cycloalkyl, -aryl, -heteroaryl;
--NO.sub.2-substituted-alkyl, -cycloalkyl, -aryl, -heteroaryl;
halogen (--F, --Cl, --Br, --I) or nitrile (--CN); and
[0163] in which X.sub.1, X.sub.2 is H; halogen X (X being F, Cl, Br
or I); halogenated alkyl, -alkenyl, -aryl, -heteroaryl;
--CN-substituted-alkyl, -alkenyl, -aryl, -heteroaryl;
:NO.sub.2-substituted-alkyl, -alkenyl, -aryl or -heteroaryl;
[0164] in which R.sub.1, R.sub.2 can be equal or different; and
[0165] in which X.sub.1, X.sub.2 can be equal or different.
[0166] In an embodiment, the at least one additive is one or more
compound(s) with general formula III selected from:
##STR00026## ##STR00027##
[0167] In one embodiment, the at least one non-aqueous electrolyte
for secondary batteries according to the disclosure includes at
least one additive, which is at least one compound selected from
compounds with general formula I-IV,
##STR00028##
[0168] in which R.sub.1 is alkyl (--C.sub.nH.sub.2n+1), cycloalkyl,
alkenyl (C.sub.nH.sub.2n), aryl (--Ar), heteroaryl; halogenated
alkyl ((--C.sub.nX.sub.2n+1) or (--CH.sub.2--C.sub.nX.sub.2n+1)),
halogenated cycloalkyl ((--C.sub.nX.sub.2n) or
(--CH.sub.2--C.sub.nX.sub.2n)), halogenated alkenyl
(C.sub.nX.sub.n), halogenated aryl (--Ar--X), halogenated
heteroaryl with halogen X being F, Cl, Br or I; halogen (--F, --Cl,
--Br, --I) or nitrile (--CN);
[0169] in which R2 is alkyl (--C.sub.nH.sub.2n+1), cycloalkyl,
alkenyl (C.sub.nH.sub.2n), aryl (--Ar), heteroaryl; halogenated
alkyl ((--C.sub.nX.sub.2n+1) or (--CH.sub.2--C.sub.nX.sub.2n+1)),
halogenated cycloalkyl ((--C.sub.nX.sub.2n) or
(--CH.sub.2--C.sub.nX.sub.2n), halogenated alkenyl
(C.sub.nX.sub.n), halogenated aryl (--Ar--X), halogenated
heteroaryl with halogen X being F, Cl, Br or I; alkoxy, aryloxy,
heteroaryloxy, halogenated aryloxy; --CN-substituted-alkyl,
-cycloalkyl, -aryl, -heteroaryl; --NO.sub.2-substituted-alkyl,
-cycloalkyl, -aryl, -heteroaryl; halogen (--F, --Cl, --Br, --I) or
nitrile (--CN);
[0170] in which X.sub.1, X.sub.2 is H; halogen X (X being F, Cl, Br
or I); halogenated alkyl, -alkenyl, -aryl, -heteroaryl;
--CN-substituted-alkyl, -alkenyl, -aryl, -heteroaryl;
--NO.sub.2-substituted-alkyl, -alkenyl, -aryl or -heteroaryl;
[0171] in which R.sub.1, R.sub.2 can be equal or different; and
[0172] in which X.sub.1, X.sub.2 can be equal or different.
[0173] In one embodiment, the at least one non-aqueous electrolyte
for secondary batteries according to the disclosure includes at
least one additive, which is at least one compound selected from
compounds with general formula I-IV,
##STR00029##
[0174] in which R.sub.1 is alkyl (--C.sub.nH.sub.2n+1), cycloalkyl,
alkenyl (C.sub.nH.sub.2n), aryl (--Ar), heteroaryl; halogenated
alkyl ((--C.sub.nX.sub.2n+1) or (--CH.sub.2--C.sub.nX.sub.2n+1)),
halogenated cycloalkyl ((--C.sub.nX.sub.2n) or
(--CH.sub.2--C.sub.nX.sub.2n)), halogenated alkenyl
(C.sub.nX.sub.n), halogenated aryl (--Ar--X), halogenated
heteroaryl with halogen X being F, Cl, Br or I; halogen (--F, --Cl,
--Br, --I) or nitrile (--CN);
[0175] in which R.sub.2 is alkyl (--C.sub.nH.sub.2n+1), cycloalkyl,
alkenyl (C.sub.nH.sub.2n), aryl (--Ar), heteroary; halogenated
alkyl ((--C.sub.nX.sub.2n+1) or (--CH.sub.2--C.sub.nX.sub.2n+1),
halogenated cycloalkyl ((--C.sub.nX.sub.2n) or
(--CH.sub.2-C.sub.nX.sub.2n)), halogenated alkenyl
(C.sub.nX.sub.n), halogenated aryl (--Ar--X), halogenated
heteroaryl with halogen X being F, Cl, Br or I; alkoxy, aryloxy,
heteroaryloxy, halogenated aryloxy; --CN-substituted-alkyl,
-cycloalkyl, -aryl, -heteroaryl; --NO.sub.2-substituted-alkyl,
-cycloalkyl, -aryl, -heteroaryl; halogen (--F, --Cl, --Br, --I) or
nitrile (--CN);
[0176] in which X.sub.1, X.sub.2 is H; halogen X (X being F, Cl, Br
or I); halogenated alkyl, -alkenyl, -aryl, -heteroaryl;
--CN-substituted-alkyl, -alkenyl, -aryl, -heteroaryl;
--NO.sub.2-substituted-alkyl, -alkenyl, -aryl or -heteroaryl;
[0177] in which X.sub.1 and X.sub.2 are not hydrogen H
concurrently;
[0178] in which R.sub.1, R.sub.2 can be equal or different; and
[0179] in which X.sub.1, X.sub.2 can be equal or different.
[0180] In one embodiment, the at least one non-aqueous electrolyte
for secondary batteries according to the disclosure includes at
least one additive, which is at least one compound selected from
compounds with general formula I-IV,
##STR00030##
[0181] in which R.sub.1 is alkyl (--C.sub.nH.sub.2n+1), cycloalkyl,
alkenyl (C.sub.nH.sub.2n) , aryl (--Ar), heteroaryl; halogenated
cycloalkyl ((--C.sub.nX.sub.2n) or (--CH.sub.2--C.sub.nX.sub.2n),
halogenated alkenyl (C.sub.nX.sub.n), halogenated aryl (--Ar--X),
halogenated heteroaryl with halogen X being F, Cl, Br or I; halogen
(--F, --Cl, --Br, --I) or nitrile (--CN);
[0182] in which R.sub.2 is alkyl (--C.sub.nH.sub.2n+1), cycloalkyl,
alkenyl (C.sub.nH.sub.2n), aryl (--Ar), heteroaryl; halogenated
cycloalkyl ((--C.sub.nX.sub.2n) or (--CH.sub.2--C.sub.nX.sub.2n)),
halogenated alkenyl (CAR), halogenated aryl (--Ar--X), halogenated
heteroaryl with halogen X being F, Cl, Br or I; alkoxy, aryloxy,
heteroaryloxy, halogenated aryloxy; --CN-substituted-alkyl,
-cycloalkyl, -aryl, -heteroaryl; --NO.sub.2-substituted-alkyl,
-cycloalkyl, -aryl, -heteroaryl; halogen (--F, --Cl, --Br, --I) or
nitrile (--CN);
[0183] but in which R.sub.1, R.sub.2, is each not a halogenated
alkyl;
[0184] in which X.sub.1, X.sub.2 is H; halogen X (X being F, Cl, Br
or I); halogenated alkyl, -alkenyl, -aryl, -heteroaryl;
--CN-substituted-alkyl, -alkenyl, -aryl, -heteroaryl;
--NO.sub.2-substituted-alkyl, -alkenyl, -aryl or -heteroaryl;
[0185] in which R.sub.1, R.sub.2 can be equal or different; and
[0186] in which X.sub.1, X.sub.2 can be equal or different.
[0187] In one embodiment, the at least one non-aqueous electrolyte
for secondary batteries according to the disclosure includes at
least one additive, which is at least one compound selected from
compounds with general formula I-IV,
##STR00031##
[0188] in which R.sub.1 is alkyl (--C.sub.nH.sub.2n+1), cycloalkyl,
alkenyl (C.sub.nH.sub.2n), aryl (--Ar), heteroaryl; halogenated
cycloalkyl ((--C.sub.nX.sub.2n) or (--CH.sub.2--C.sub.nX.sub.2n)),
halogenated alkenyl (C.sub.nX.sub.n), halogenated aryl (--Ar--X),
halogenated heteroaryl with halogen X being F, Cl, Br or I; halogen
(--F, --Cl, --Br, --I) or nitrile (--CN);
[0189] in which R2 is alkyl (--C.sub.nH.sub.2n+1), cycloalkyl,
alkenyl (C.sub.nH.sub.2n), aryl (--Ar), heteroaryl; halogenated
cycloalkyl ((--C.sub.nX.sub.2n) or (--CH.sub.2--C.sub.nX.sub.2n),
halogenated alkenyl (C.sub.nX.sub.n), halogenated aryl (--Ar--X),
halogenated heteroaryl with halogen X being F, Cl, Br or I; alkoxy,
aryloxy, heteroaryloxy, halogenated aryloxy;
--CN-substituted-alkyl, -cycloalkyl, -aryl, -heteroaryl;
--NO.sub.2-substituted-alkyl, -cycloalkyl, -aryl, -heteroaryl;
halogen (--F, --Cl, --Br, --I) or nitrile (--CN);
[0190] but in which R.sub.1, R.sub.2 is each not a halogenated
alkyl;
[0191] in which X.sub.1, X.sub.2 is H; halogen X (X being F, Cl, Br
or I); halogenated alkyl, -alkenyl, -aryl, -heteroaryl;
--CN-substituted-alkyl, -alkenyl, -aryl, -heteroaryl;
--NO.sub.2-substituted-alkyl, -alkenyl, -aryl or -heteroaryl;
[0192] but in which X.sub.1 and X.sub.2 are not hydrogen H
concurrently;
[0193] in which R.sub.1, R.sub.2 can be equal or different; and
[0194] in which X.sub.1, X.sub.2 can be equal or different.
[0195] In an embodiment, the at least one additive is one or more
compound(s) with general formula I-IV selected from:
##STR00032##
[0196] The redox stability of the additive can be controlled
through the number of fluorine atomes and through the position of
the fluorine-containing substituent. A preferred redox reaction
site, i.e. oxidation at the cathode or reduction at the anode can
be achieved by tuning of the highest occupied molecular orbital
(HOMO) or the lowest unoccupied molecular orbital (LUMO) energy.
Further, good solubility of the additive in the carbonate
electrolyte can be achieved by introducing polar substituents.
[0197] The additives according to the disclosure need to comply
with several requirements, for example, the oxidative decomposition
at the cathode should be less positive than those of the polar
aprotic solvent in the electrolyte, the reductive composition at
the anode should be higher than those of the polar aprotic solvent
in the electrolyte and a fast and irreversible redox reaction
should take place to form a homogenous, thin and dense SEI already
during the first charging. Further, reactive groups should be
present, either in the molecular core or at the side substituents,
to allow oligomerization or polymerization to a thin film at the
cathode. Further, the additives should have good solubility in the
electrolyte solution.
[0198] In an embodiment, the amount of the at least one additive in
the non-aqueous electrolyte, which is at least one compound
selected from compounds with general formula I, is between 0.001
and 10 wt %, preferably between 0.01 and 5 wt %, more preferably
between 0.1 and 3 wt %. In an embodiment, the amount of the at
least one additive in the non-aqueous electrolyte, which is at
least one compound selected from compounds with general formula
I-I, is between 0.001 and 10 wt %, preferably between 0.01 and 5 wt
%, more preferably between 0.1 and 3 wt %. In an embodiment, the
amount of the at least one additive in the non-aqueous electrolyte,
which is at least one compound selected from compounds with general
formula I-I, is between 0.01 and 2 wt %, preferably between 0.01
and 1.8 wt % and more preferably between 0.1 and 1.6 wt %. In an
embodiment, the amount of the at least one additive in the
non-aqueous electrolyte, which is at least one compound selected
from compounds with general formula I-Il, is between 0.001 and 10
wt %, preferably between 0.01 and 5 wt %, more preferably between
0.1 and 3 wt %. In an embodiment, the amount of the at least one
additive in the non-aqueous electrolyte, which is at least one
compound selected from compounds with general formula is between
0,001 and 10 wt %, preferably between 0.01 and 5 wt %, more
preferably between 0.1 and 3 wt %. In an embodiment, the amount of
the at least one additive in the non-aqueous electrolyte, which is
at least one compound selected from compounds with general formula
MV, is between 0.001 and 10 wt %, preferably between 0.01 and 5 wt
%, more preferably between 0.1 and 3 wt %.
[0199] In an embodiment, the at least one additive in the
non-aqueous electrolyte is a mixture of compounds selected from
compounds with general formulas I-I, I-II, and I-IV as described
above. In an embodiment, the at least one additive in the
non-aqueous electrolyte is a mixture of compounds selected from
compounds with general formulas I-I and I-II. In an embodiment, the
at least one additive in the non-aqueous electrolyte is a mixture
of compounds selected from compounds with general formulas I-I and
I-III. In an embodiment, the at least one additive in the
non-aqueous electrolyte is a mixture of compounds selected from
compounds with general formulas I-I and I-IV. In an embodiment, the
at least one additive in the non-aqueous electrolyte is a mixture
of compounds selected from compounds with general formulas I-II and
I-III. In an embodiment, the at least one additive in the
non-aqueous electrolyte is a mixture of compounds selected from
compounds with general formulas and I-IV. In an embodiment, the at
least one additive in the non-aqueous electrolyte is a mixture of
compounds selected from compounds with general formulas I-III and
I-IV.
[0200] In an embodiment, the least one additive in the non-aqueous
electrolyte is a mixture of compounds selected from compounds with
general formulas I-I, I-II, I-III and I-IV as described above, in
which the total amount of these additives in the non-aqueous
electrolyte is between 0.001 and 10 wt %, preferably between 0.01
and 5 wt %, more preferably between 0.1 and 3 wt %. In an
embodiment, the at least one additive in the non-aqueous
electrolyte is a mixture of compounds selected from compounds with
general formulas I-I and MI, in which the total amount of these
additives in the non-aqueous electrolyte is between 0.001 and 10 wt
%, preferably between 0.01 and 5 wt %, more preferably between 0.1
and 3 wt %, In an embodiment, the at least one additive in the
non-aqueous electrolyte is a mixture of compounds selected from
compounds with general formula I-I and I-II, in which the total
amount of these additives in the non-aqueous electrolyte is between
0.01 and 2 wt %, preferably between 0.01 and 1.8 wt % and more
preferably between 0.1 and 1.6 wt %. In an embodiment, the at least
one additive in the non-aqueous electrolyte is a mixture of
compounds selected from compounds with general formula I-I and
I-III, in which the total amount of these additives in the
non-aqueous electrolyte is between 0.001 and 10 wt %, preferably
between 0.01 and 5 wt %, more preferably between 0.1 and 3 wt %. In
an embodiment, the at least one additive in the non-aqueous
electrolyte is a mixture of compounds selected from compounds with
general formula I-I and I-III, in which the total amount of these
additives in the non-aqueous electrolyte is between 0.01 and 2 wt
%, preferably between 0.01 and 1.8 wt % and more preferably between
0.1 and 1.6 wt %. In an embodiment, the at least one additive in
the non-aqueous electrolyte is a mixture of compounds selected from
compounds with general formula and I-IV, in which the total amount
of these additives in the non-aqueous electrolyte is between 0.001
and 10 wt %, preferably between 0.01 and 5 wt %, more preferably
between 0.1 and 3 wt %. In an embodiment, the at least one additive
in the non-aqueous electrolyte is a mixture of compounds selected
from compounds with general formula I-I and I-IV, in which the
total amount of these additives in the non-aqueous electrolyte is
between 0.01 and 2 wt %, preferably between 0.01 and 1.8 wt % and
more preferably between 0.1 and 1.6 wt %. In an embodiment, the at
least one additive in the non-aqueous electrolyte is a mixture of
compounds selected from compounds with general formula I-II and
I-III in which the total amount of these additives in the
non-aqueous electrolyte is between 0.001 and 10 wt %, preferably
between 0.01 and 5 wt %, more preferably between 0.1 and 3 wt %. In
an embodiment, the at least one additive in the non-aqueous
electrolyte is a mixture of compounds selected from compounds with
general formula and I-IV, in which the total amount of these
additives in the non-aqueous electrolyte is between 0.001 and 10 wt
%, preferably between 0.01 and 5 wt %, more preferably between 0.1
and 3 wt %. In an embodiment, the at least one additive in the
non-aqueous electrolyte is a mixture of compounds selected from
compounds with general formula I-III and I-IV, in which the total
amount of these additives in the non-aqueous electrolyte is between
0.001 and 10 wt %, preferably between 0.01 and 5 wt %, more
preferably between 0.1 and 3 wt %.
[0201] The additives according to the disclosure provide
improvement of charge/discharge capacity and coulomb efficiency of
the batteries in presence of the additives. Further advantages are
enhancement of the electrolyte stability, enhancement of
battery-lifetime, increase of battery power density retention,
increase of battery capacity retention by cycling at high charging
voltage, increase of battery voltage retention in fully charged
state during storage by using at least one additive or a mixture of
additives according to the disclosure. Additionally, the risk of
abuse cases due to reduced swelling of battery during storage
decreases.
[0202] In an embodiment, the polar aprotic solvent is preferably
selected from cyclic ester carbonate(s),
[0203] such as, but not limited to, ethylene carbonate (EC),
propylene carbonate (PC), and butylene carbonate (BC),
[0204] chain ester carbonate(s),
[0205] such as, but not limited to, dimethyl carbonate (DMC),
diethyl carbonate (DEC), ethyl methyl carbonate (EMC), and methyl
propyl carbonate (MPC), lactone(s),
[0206] such as, but not limited to, .gamma.-butyrolactone and
.gamma.-valerolactone, chain carboxylic ester(s),
[0207] such as, but not limited to, methyl acetate, ethyl acetate,
methyl propionate, ethyl propionate, methyl butyrate, methyl
isobutyrate, methyl trimethylacetate, and ethyl trimethylacetate,
nitrile(s),
[0208] such as, but not limited to, acetonitrile, glutaronitrile,
adiponitrile, methoxyacetonitrile, and 3-methoxypropionitrile,
[0209] 1,2-dimethoxyethane, tetrahydrofuran,
2-methyltetrahydrofuran, tetrahydropyran, 1,3-dioxolane,
4-methyl-1,3-dioxolane, 1,3-dioxane, 1,4-dioxane,
N,N-dimethylformamide, N-methylpyrrolidone, N-methyloxazolidinone,
N,N'-dimethylimidazolidinone, nitromethane, nitroethane, sulfolane,
trimethyl phosphate, and dimethylsulfoxide and further polar
aprotic solvents.
[0210] Other than this, the non-aqueous solvent may be one or more
of unsaturated cyclic ester carbonates, because a stable protective
film is thereby formed on the surface of the electrode at the time
of charge and discharge, and the decomposition reaction of the
electrolytic solution is therefore suppressed.
[0211] The alkali metal salt of the non-aqueous-electrolyte may
contain, for example, one or more salts, such as lithium salt.
However, the electrolyte salt may contain, for example, salt other
than the lithium salt. Examples of "salt other than the lithium
salt" may include light metal salt other than lithium salt.
[0212] In an embodiment, the alkali metal salt is one or more
lithium salts (Li salts).
[0213] Examples of the lithium salt may include lithium
hexafluorophosphate (LiPF.sub.6), lithium tetrafluoroborate
(LiBF.sub.4), lithium perchlorate (LiClO.sub.4), lithium
perchlorate (LiClO.sub.4), lithium hexafluoroarsenate
(LiAsF.sub.6), lithium tetraphenylborate
(LiB(C.sub.6H.sub.5).sub.4), lithium methanesulfonate
(LiCH.sub.3SO.sub.3), lithium trifluoromethane sulfonate
(LiCF.sub.3SO.sub.3), lithium tetrachloroaluminate (LiAlCl.sub.4),
di lithiumhexafluorosilicate (Li.sub.2SiF.sub.6), lithium chloride
(LiCl), and lithium bromide (LiBr). However, specific examples of
the lithium salt are not limited to the compounds described
above.
[0214] In an embodiment, the non-aqueous electrolyte includes at
least one further additive or compound, such as, but not limited
to, carbonate(s) and nitrile(s), preferably at least one further
additive or compound, such as, but not limited to, cyclic carbonate
and nitrile,
[0215] more preferably at least one further additive or compound,
such as, but not limited to, ethylene carbonate (EC), propylene
carbonate (PC), butylene carbonate (BC), vinylene carbonate (VC),
fluoroethylene carbonate (FEC), trifluoromethylethylene carbonate,
acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile,
and 3-methoxypropionitrile, adipic acid dinitrile, sebacic acid
dinitrile, malonic dinitrile and succinonitrile.
[0216] In an embodiment, the non-aqueous electrolyte according to
the disclosure is a liquid or polymer-gel electrolyte.
[0217] As discussed above, the disclosure provides the use of the
non-aqueous electrolyte in an electrochemical device,
[0218] such as, but not limited to, a secondary battery (such as a
secondary Li-ion battery), a super capacitor.
[0219] As discussed above, the disclosure provides the use of the
non-aqueous electrolyte in an electric device,
[0220] such as, but not limited to, a battery pack, an electric
vehicle, an electric power storage system, an electric power tool,
an electronic apparatus.
[0221] As discussed above, the disclosure provides a secondary
battery.
[0222] A secondary battery according to the disclosure includes: a
cathode,
[0223] an anode, and
[0224] a non-aqueous electrolyte according to the disclosure.
[0225] In an embodiment, the secondary battery according to the
disclosure is a secondary Li-ion battery.
[0226] In an embodiment, the cathode is an intercalation type
cathode including one or more kinds of active cathode material
which is capable of reversible inserting and extracting Li ions,
preferably including layered, spinet or olivine structure type
transition metal oxide(s), such as, but not limited to, metal(s)
selected from Co, Ni, Mn, V, Fe and combinations thereof.
[0227] The cathode material may be preferably a lithium-containing
compound, because high energy density is obtained thereby. Examples
of the lithium-containing compound may include a
lithium-transition-metal composite oxide and a
lithium-transition-metal-phosphate compound. The
lithium-transition-metal composite oxide is an oxide containing
lithium and one or more transition metal elements as constituent
elements. The lithium-transition-metal-phosphate compound is a
phosphate compound containing lithium and one or more transition
metal elements as constituent elements. In particular, the
transition metal element may be preferably one or more of cobalt
(Co), nickel (Ni), manganese (Mn), iron (Fe), and the like, because
a higher voltage is obtained thereby. The chemical formula thereof
may be expressed, for example, by Li.sub.xM1O.sub.2 or by
Li.sub.yM.sub.2PO.sub.4. In the formulas, M1 and M2 represent one
or more transition metal elements. Values of x and y vary according
to the charge and discharge state, but may be generally in the
range of 0.05.ltoreq.x.ltoreq.1.10 and
0.05.ltoreq.y.ltoreq.1.10.
[0228] Examples of the lithium-transition-metal composite oxide may
include LiCoO.sub.2, LiNiO.sub.2 and a lithium-nickel-based
composite oxide represented by the formula:
LiNi.sub.1-zM.sub.zO.sub.2.
[0229] Specific examples of the lithium-transition-metal-phosphate
compound may include LiFePO.sub.4 and LiFe.sub.1-uMn.sub.uPO.sub.4
(u<1), because a high battery capacity is thereby obtained and
superior cycle characteristics are also obtained.
[0230] (M is one or more of cobalt, manganese, iron, aluminum,
vanadium (V), tin (Sn), magnesium (Mg), titanium (Ti), strontium
(Sr), calcium (Ca), zirconium (Zr), molybdenum (Mo), technetium
(Tc), ruthenium (Ru), tantalum (Ta), tungsten (W), rhenium (Re),
ytterbium (Yb), copper (Cu), zinc (Ln), barium (Ba), boron (B),
chromium (Cr), silicon (Si), gallium (Ga), phosphorus (P), antimony
(Sb), and niobium (Nb). z satisfies 0.005<z<0.5.)
[0231] In an embodiment, the anode is an intercalation type anode
including one or more kinds of active anode material which is
capable of reversible inserting and extracting Li ions, such as,
but not limited to, graphitizable carbon, non-graphitizable carbon,
graphite, Li-metal, Si, Si oxide, Si alloy, Sn, Sn oxide,
LiTi.sub.2O.sub.5, Sn alloy.
[0232] Examples of the carbon material may include graphitizable
carbon, non-graphitizable carbon, and graphite. However, the
spacing of (002) plane in the non-graphitizable carbon may be
preferably equal to or greater than 0.37 nm, and the spacing of
(002) plane in graphite may be preferably equal to or smaller than
0.34 nm. More specifically, examples of the carbon material may
include pyrolytic carbons, cokes, glassy carbon fibers, an organic
polymer compound fired body, activated carbon, and carbon blacks.
Examples of the cokes may include pitch coke, needle coke, and
petroleum coke. The organic polymer compound tired body is obtained
by tiring (carbonizing) a polymer compound such as phenol resin and
furan resin at appropriate temperature. In addition thereto, the
carbon material may be low crystalline carbon heat-treated at a
temperature of about 1000.degree. C. or less, or may be amorphous
carbon. It is to be noted that the shape of the carbon material may
be any of a fibrous shape, a spherical shape, a granular shape, and
a scale-like shape.
[0233] Moreover, the anode material may be, for example, a material
(a metal-based material) containing one or more of metal elements
and metalloid elements as constituent elements, because high energy
density is thereby achieved.
[0234] The metal-based material may be a simple substance, alloy,
or a compound, may be two or more thereof, or may have one or more
phases thereof in part or all thereof "Alloy" includes a material
containing one or more metal elements and one or more metalloid
elements, in addition to a material configured of two or more metal
elements. Further, the "alloy" may contain a non-metallic element.
Examples of the structure thereof may include a solid solution, a
eutectic crystal (eutectic mixture), an intermetallic compound, and
a structure in which two or more thereof coexist.
[0235] Examples of the foregoing metal elements and the foregoing
metalloid elements may include one or more of metal elements and
metalloid elements capable of forming an alloy with lithium.
Specific examples thereof may include magnesium, boron, aluminum,
gallium, indium (In), silicon, germanium (Ge), tin (Sn), lead (Pb),
bismuth (Bi), cadmium (Cd), silver (Ag), zinc, hafnium (Hf),
zirconium, yttrium (Y), palladium (Pd), and platinum (Pt).
[0236] In particular, silicon, tin, or both may be preferable,
because silicon and tin have superior ability of inserting and
extracting lithium, and therefore achieve high energy density.
[0237] A material containing silicon, tin, or both as constituent
elements may be any of a simple substance, alloy, and a compound of
silicon, may be any of a simple substance, alloy, and a compound of
tin, may be two or more thereof, or may have one or more phases
thereof in part or all thereof. It is to be noted that "simple
substance" described herein merely refers to a simple substance in
a general sense (a small amount of impurity may be therein
contained), and does not necessarily refer to a purity 100% simple
substance.
[0238] The alloys of silicon may contain, for example, one or more
of elements such as tin, nickel, copper, iron, cobalt, manganese,
zinc, indium, silver, titanium, germanium, bismuth, antimony, and
chromium, as a constituent element other than silicon. The
compounds of silicon may contain, for example, one or more of
carbon (C), oxygen (O), and the like as constituent elements other
than Si. It is to be noted that the compounds of silicon may
contain, for example, one or more of the series of elements
described for the alloys of silicon, as constituent elements other
than silicon.
[0239] Specific examples of the alloys of silicon and the compounds
of silicon may include SiB.sub.4, SiB.sub.6, Mg.sub.2Si,
Ni.sub.2Si, TiSi.sub.2, MoSi.sub.2, CoSi.sub.2, NiSi.sub.2,
CaSi.sub.2, CrSi.sub.2, Cu.sub.5Si, FeSi.sub.2, MnSi.sub.2,
NbSi.sub.2, TaSi.sub.2, VSi.sub.2, WSi.sub.2, ZnSi.sub.2, SiC,
Si.sub.3N.sub.4, Si.sub.2N.sub.2O, SiO (0<v.ltoreq.2), and
LiSiO. v in SiO.sub.v may be in a range of 0.2<v<1.4.
[0240] The alloys of tin may contain, for example, one or more of
elements such as silicon, nickel, copper, iron, cobalt, manganese,
zinc, indium, silver, titanium, germanium, bismuth, antimony, and
chromium, as constituent elements other than tin. The compounds of
tin may contain, for example, one or more of elements such as
carbon and oxygen as constituent elements other than tin. It is to
be noted that the compounds of tin may contain, for example, one or
more of the series of elements described for the alloys of tin, as
constituent elements other than tin.
[0241] FIG. 1 and FIG. 2 each illustrate a cross-sectional
configuration of a secondary battery of an embodiment of the
present application (in particular a cylindrical type battery).
FIG. 2 illustrates an enlarged part of a spirally wound electrode
body 20 illustrated in FIG. 1.
[0242] The secondary battery described here as an embodiment is a
lithium secondary battery (a lithium ion secondary battery) in
which a capacity of an anode 22 is obtained by insertion and
extraction of lithium as an electrode reactant.
[0243] The secondary battery may be, for example, a secondary
battery of a so-called cylindrical type. The secondary battery may
contain a pair of insulating plates 12 and 13 and a spirally wound
electrode body 20 inside a battery can 11 in the shape of a
substantially-hollow cylinder. In the spirally wound electrode body
20, for example, a cathode 21 and the anode 22 are laminated with a
separator 23 in between and are spirally wound.
[0244] The battery can 11 may have a hollow structure in which one
end of the battery can 11 is closed and the other end of the
battery can 11 is opened. The battery can 11 may be made, for
example, of iron (Fe), aluminum (Al), alloy thereof, or the like.
The surface of the battery can 11 may be plated with nickel (Ni) or
the like. The pair of insulating plates 12 and 13 is arranged to
sandwich the spirally wound electrode body 20 in between, and to
extend perpendicularly to the spirally wound periphery surface of
the spirally wound electrode body 20.
[0245] At the open end of the battery can 11, a battery cover 14, a
safety valve mechanism 15, and a positive temperature coefficient
device (PTC device) 16 are attached by being swaged with a gasket
17. Thereby, the battery can 11 is hermetically sealed. The battery
cover 14 may be made, for example, of a material similar to that of
the battery can 11. The safety valve mechanism 15 and the PTC
device 16 are provided inside the battery cover 14. The safety
valve mechanism 15 is electrically connected to the battery cover
14 via the PTC device 16. In the safety valve mechanism 15, in the
case where the internal pressure becomes a certain level or higher
by internal short circuit, external heating, or the like, a disk
plate 15A inverts to cut electric connection between the battery
cover 14 and the spirally wound electrode body 20. The PTC device
16 prevents abnormal heat generation resulting from a large
current. As temperature rises, resistance of the PTC device 16 is
increased accordingly. The gasket 17 may be made, for example, of
an insulating material. The surface of the gasket 17 may be coated
with asphalt.
[0246] In the center of the spirally wound electrode body 20, for
example, a center pin 24 may be inserted. However, the center pin
24 may not be inserted in the center of the spirally wound
electrode body 20. For example, a cathode lead 25 made of a
conductive material such as aluminum may be connected to the
cathode 21. For example, an anode lead 26 made of a conductive
material such as nickel may be connected to the anode 22. For
example, the cathode lead 25 may be attached to the safety valve
mechanism 15 by welding or the like, and may be electrically
connected to the battery cover 14. For example, the anode lead 26
may be attached to the battery can 11 by welding or the like, and
may be electrically connected to the battery can 11.
[0247] The cathode 21 has a cathode active material layer 21B on a
single surface or both surfaces of a cathode current collector 21A.
The cathode current collector 21A may be made, for example, of a
conductive material such as aluminum, nickel, or stainless steel.
The cathode active material layer 21B contains, as a cathode active
material, one or more of cathode materials capable of inserting and
extracting lithium. It is to be noted that the cathode active
material layer 21B may further contain one or more of other
materials such as a cathode binder and a cathode electric
conductor. The anode 22 has an anode active material layer 22B on a
single surface or both surfaces of an anode current collector
22A.
[0248] FIG. 3 illustrates an exploded perspective configuration of
another secondary battery of an embodiment of the present
application. FIG. 4 illustrates an enlarged cross-section taken
along a line IV-IV of a spirally wound electrode body 30
illustrated in FIG. 3. In the following description, the elements
of the cylindrical-type secondary battery described above will be
used where appropriate.
[0249] The secondary battery described here is a so-called
laminated-film-type lithium ion secondary battery. The secondary
battery contains the spirally wound electrode body 30 in a
film-like outer package member 40. In the spirally wound electrode
body 30, a cathode 33 and an anode 34 are laminated with a
separator 35 and an electrolyte layer 36 in between and are
spirally wound. A cathode lead 31 is attached to the cathode 33,
and an anode lead 32 is attached to the anode 34. The outermost
periphery of the spirally wound electrode body 30 is protected by a
protective tape 37.
[0250] The cathode lead 31 and the anode lead 32 may be, for
example, led out from inside to outside of the outer package member
40 in the same direction. The cathode lead 31 may be made, for
example, of an electrically-conductive material such as aluminum,
and the anode lead 32 may be made, for example, of an
electrically-conducive material such as copper, nickel, and
stainless steel. These electrically-conductive materials may be in
the shape of, for example, a thin plate or mesh.
[0251] The outer package member 40 may be a laminated film in
which, for example, a fusion bonding layer, a metal layer, and a
surface protective layer are laminated in this order. In the
laminated film, outer edges of the two film-shaped fusion bonding
layers are fusion bonded so that the fusion bonding layers are
opposed to the spirally wound electrode body 30. However, the two
films may be bonded to each other by an adhesive, or the like.
Examples of the fusion bonding layer may include a film made of one
or more of polyethylene, polypropylene, and the like. Examples of
the metal layer may include an aluminum foil. Examples of the
surface protective layer may include a film made of one or more of
nylon, polyethylene terephthalate, and the like.
[0252] In particular, the outer package member 40 may be preferably
an aluminum laminated film in which a polyethylene film, an
aluminum foil, and a nylon film are laminated in this order.
However, the outer package member 40 may be a laminated film having
other laminated structure, a polymer film such as polypropylene, or
a metal film.
[0253] For example, a close-attachment film 41 to prevent outside
air intrusion may be inserted between the outer package member 40
and the cathode lead 31 and between the outer package member 40 and
the anode lead 32. The close-attachment film 41 is made of a
material having close-attachment characteristics with respect to
the cathode lead 31 and the anode lead 32. Examples of the material
having close-attachment characteristics may include polyolefin
resin that may include one or more of polyethylene, polypropylene,
modified polyethylene, and modified polypropylene.
[0254] The cathode 33 may have, for example, a cathode active
material layer 33B on one surface or both surfaces of a cathode
current collector 33A. The anode 34 may have, for example, an anode
active material layer 34B on one surface or both surfaces of an
anode current collector 34A. The configurations of the cathode
current collector 33A, the cathode active material layer 33B, the
anode current collector 34A, and the anode active material layer
34B are similar to the configurations of the cathode current
collector 21A, the cathode active material layer 21B, the anode
current collector 22A, and the anode active material layer 22B,
respectively. The configuration of the separator 35 may be, for
example, similar to the configuration of the separator 23.
[0255] The electrolyte layer 36 includes electrolytic solution and
a polymer compound, and the electrolytic solution is held by the
polymer compound. The electrolyte layer 36 is a so-called gel
electrolyte, because thereby, high ion conductivity (for example, 1
mS/cm or more at room temperature) is obtained and liquid leakage
of the electrolytic solution is prevented. The electrolyte layer 36
may further contain other material such as an additive as
necessary.
[0256] The polymer compound may include, for example, one or more
of polyacrylonitrile, polyvinylidene fluoride,
polytetrafluoroethylene, polyhexafluoropropylene, polyethylene
oxide, polypropylene oxide, polyphosphazene, polysiloxane,
polyvinyl fluoride, polyvinyl acetate, polyvinyl alcohol,
polymethacrylic acid methyl, polyacrylic acid, polymethacrylic
acid, styrene-butadiene rubber, nitrile-butadiene rubber,
polystyrene, polycarbonate, a copolymer of vinylidene fluoride and
hexafluoropropyrene, and the like. In particular, polyvinylidene
fluoride or the copolymer of vinylidene fluoride and hexafluoro
propylene may be preferable, and polyvinylidene fluoride may be
more preferable, because such a polymer compound is
electrochemically stable.
[0257] For example, the configuration of the electrolytic solution
may be similar to the configuration of the electrolytic solution of
the cylindrical-type secondary battery. However, in the electrolyte
layer 36 as a gel electrolyte, the solvent of the electrolytic
solution refers to a wide concept including not only a liquid
solvent but also a material having ion conductivity capable of
dissociating the electrolyte salt. Therefore, in the case where a
polymer compound having ion conductivity is used, the polymer
compound is also included in the solvent.
[0258] It should be understood that the electrolytic solution may
be used as it is instead of the gel electrolyte layer 36. In this
case, the spirally wound electrode body 30 is impregnated with the
electrolytic solution.
[0259] As discussed above, the disclosure provides an electric
device including a secondary battery of the disclosure.
[0260] The electric device is a battery pack, an electric vehicle,
an electric power storage system, an electric power tool or an
electronic apparatus.
[0261] FIG. 5 is a block diagram illustrating a battery pack.
[0262] FIG. 6 is a block diagram illustrating an electric
vehicle.
[0263] FIG. 7 is a block diagram illustrating an electric power
storage system.
[0264] FIG. 8 is a block diagram illustrating an electric power
tool.
[0265] In the following, some embodiments of the disclosure are
described in detail with reference to the drawings.
[0266] First, description is given of a secondary battery-use
electrolytic solution (hereinafter simply referred to as
"electrolytic solution") according to an embodiment of the
disclosure.
[0267] The electrolytic solution described herein is mainly used
for a secondary battery. The kind of secondary battery is not
particularly limited, but non-limiting examples of the secondary
battery may include a lithium-ion secondary battery and a lithium
metal secondary battery that use lithium as an electrode reactant.
The "electrode reactant" is a material involving electrode reaction
(charge-discharge reaction). It is to be noted that each of the
lithium-ion secondary battery and the lithium metal secondary
battery is described in detail later.
[0268] First, description is given of a configuration of the
electrolytic solution.
[0269] (Cyano Compound)
[0270] The electrolytic solution includes a cyano compound. The
cyano compound includes one or more of compounds represented by the
following chemical formula (1).
##STR00033##
[0271] where R1 is one of a monovalent hydrocarbon group and a
monovalent halogenated hydrocarbon group, R2 is one of a cyano
group, a monovalent chain hydrocarbon cyano group, and a monovalent
halogenated chain hydrocarbon cyano group, X1 is a halogen group,
X2 is one of a hydrogen group, a halogen group, a monovalent
hydrocarbon group, and a monovalent halogenated hydrocarbon
group.
[0272] As can be seen from the formula (1), the cyano compound
described herein is a compound including an ester bond
(R1-O--C(.dbd.O)--), a halogen group (--X1), and one of a cyano
group and a cyano group-containing group (--R2).
[0273] The electrolytic solution includes the cyano compound, which
improves chemical stability of the electrolytic solution, thereby
suppressing decomposition reaction of the electrolytic solution.
This suppresses generation of gas resulting from the decomposition
reaction of the electrolytic solution and suppresses an increase in
electrical resistance, thereby improving battery characteristics of
the secondary battery using the electrolytic solution. In this
case, even if the secondary battery is used (charged and
discharged) specifically in a hostile environment such as a high
temperature environment and the secondary battery is stored in the
hostile environment, decomposition reaction of the electrolytic
solution is sufficiently suppressed.
[0274] Details of a configuration of the cyano compound are as
described below.
[0275] (R1)
[0276] The R1 is one of a monovalent hydrocarbon group and a
monovalent halogenated hydrocarbon group, as described above.
[0277] (Monovalent Hydrocarbon Group)
[0278] The "monovalent hydrocarbon group" is a generic name of a
monovalent group including carbon and hydrogen, and may be one of a
straight-chain group, a branched group having one or more side
chains, and a cyclic group having one or more rings, or a group
including two or more thereof. The monovalent hydrocarbon group may
include one or more carbon-carbon unsaturated bonds, or may not
include the carbon-carbon unsaturated bond. Non-limiting examples
of the carbon-carbon unsaturated bond may include a carbon-carbon
double bond and a carbon-carbon triple bond.
[0279] Specific but non-limiting examples of the monovalent
hydrocarbon group may include an alkyl group, an alkenyl group, an
alkynyl group, a cycloalkyl group, an aryl group, and a binding
group.
[0280] The "binding group" may be a monovalent group in which two
or more of an alkyl group, an alkenyl group, an alkynyl group, an
cycloalkyl group, and an aryl group are bound to one another.
Non-limiting examples of the binding group may include a monovalent
group in which an alkyl group and an alkenyl group are bound to
each other, a monovalent group in which an alkyl group and an
alkynyl group are bound to each other, a monovalent group in which
an alkenyl group and an alkynyl group are bound to each other, a
monovalent group in which an alkyl group and an cycloalkyl group
are bound to each other, a monovalent group in which an alkyl group
and an aryl group are bound to each other, and a monovalent group
in which a cycloalkyl group and an aryl group are bound to each
other.
[0281] The kind of the alkyl group is not particularly limited;
however, non-limiting examples of the alkyl group may include a
methyl group, an ethyl group, a propyl group, a butyl group, a
pentyl group, a hexyl group, a heptyl group, an octyl group, a
nonyl group, and a decyl group.
[0282] The kind of the alkenyl group is not particularly limited;
however, non-limiting examples of the alkenyl group may include an
ethenyl group, a propenyl group, a butenyl group, a pentynyl group,
a hexenyl group, a heptenyl group, an octenyl group, a nonenyl
group, and a decenyl group.
[0283] The kind of the alkynyl group is not particularly limited;
however, non-limiting examples of the alkynyl group may include an
ethynyl group, a propynyl group, a butynyl group, a pentynyl group,
a hexynyl group, a heptynyl group, an octynyl group, a nonynyl
group, and a decynyl group.
[0284] The kind of the cycloalkyl group is not particularly
limited; however, non-limiting examples of the cycloalkyl group may
include a cyclopropyl group, a cyclobutyl group, a cyclopentyl
group, a cyclohexyl group, and a cyclodecyl group.
[0285] The kind of the aryl group is not particularly limited;
however, non-limiting examples of the aryl group may include a
phenyl group and a naphthyl group.
[0286] The number of carbons in the alkyl group is not particularly
limited, but may be, for example from 1. to 4. The number of
carbons in each of the alkenyl group and the alkynyl group is not
particularly limited, but may be, for example, from 2 to 4. The
number of carbons in each of the cycloalkyl group and the aryl
group is not particularly limited, but may be, for example, from 6
to 10. This improves solubility, compatibility, and other
properties of the cyano compound.
[0287] The kind of the binding group is not particularly limited;
however, non-limiting examples of the binding group may include a
benzyl group
[0288] (Monovalent Halogenated Hydrocarbon Group)
[0289] The "monovalent halogenated hydrocarbon group" is a group in
which one or more hydrogen groups in the foregoing monovalent
hydrocarbon group are substituted by a halogen group. The halogen
group included in the monovalent halogenated hydrocarbon group may
be, for example, one or more of a fluorine group, a chlorine group,
a bromine group, and an iodine group.
[0290] In particular, the halogen group included in the monovalent
halogenated hydrocarbon group may be preferably a fluorine group,
which further improves chemical stability of the electrolytic
solution, thereby further suppressing decomposition reaction of the
electrolytic solution.
[0291] (Preferable R1)
[0292] In particular, R1 may be preferably an alkyl group. The
number of carbons in the alkyl group may be, for example, as
described above, which further improves chemical stability of the
electrolytic solution, thereby further suppressing decomposition
reaction of the electrolytic solution.
[0293] (R2)
[0294] R2 is one of a cyano group, a monovalent chain hydrocarbon
cyano group, and a monovalent halogenated chain hydrocarbon cyano
group, as described above. Each of the monovalent chain hydrocarbon
cyano group and the monovalent halogenated chain hydrocarbon cyano
group described herein is the "cyano group-containing group"
described above.
[0295] (Monovalent Chain Hydrocarbon Cyano Group)
[0296] The "monovalent chain hydrocarbon cyano group" is a generic
name of a group in which one or more cyano groups are introduced
into a monovalent chain hydrocarbon group, as described above. In
other words, the monovalent chain hydrocarbon cyano group is a
group in which one or more hydrogen groups in a monovalent chain
hydrocarbon group are substituted by one or more cyano groups. It
is to be noted that a position where the one or more cyano groups
are introduced into the monovalent chain hydrocarbon group is not
particularly limited, and the one or more cyano groups may be
introduced into one or both of a middle site of the monovalent
chain hydrocarbon group and an end of the monovalent chain
hydrocarbon group.
[0297] The "monovalent chain hydrocarbon group" described herein is
a generic name of a monovalent chain group including carbon and
hydrogen, as described above, and may be a straight-chain group or
a branched group having one or more side chains. The monovalent
chain hydrocarbon group may include one or more carbon-carbon
unsaturated bonds, or may not include the carbon-carbon unsaturated
bond. Details of the carbon-carbon unsaturated bond are as
described above.
[0298] In other words, non-limiting examples of the monovalent
chain hydrocarbon group may include an alkyl group, an alkenyl
group, an alkynyl group, and a chain binding group. Details of each
of the alkyl group, the alkenyl group, and the alkynyl group are as
described above.
[0299] The "chain binding group" is a monovalent group in which two
or more of an alkyl group, an alkenyl group, and alkynyl group are
bound to one another. Non-limiting examples of the chain binding
group may include a monovalent group in which an alkyl group and an
alkenyl group are bound to each other, a monovalent group in which
an alkyl group and an alkynyl group are bound to each other, and a
monovalent group in which an alkyl group, an alkenyl group, and an
alkynyl group are bound to one another.
[0300] Specific but non-limiting examples of the group in which one
or more cyano groups are introduced into an alkyl group may include
a group in which one cyano group is introduced into an end of a
methyl group, a group in which one cyano group is introduced into a
middle site of an methyl group, a group in which one cyano group is
introduced into an end of an ethyl group, a group in which one
cyano group is introduced into a middle site of an ethyl group, a
group in which one cyano group is introduced into an end of a
propyl group, a group in which one cyano group is introduced into a
middle site of a propyl group, a group in which one cyano group is
introduced into an end of a butyl group, and a group in which one
cyano group is introduced into a middle site of a butyl group. A
case where the number of introduced cyano groups is one is
described herein as an example; however, the number of introduced
cyano groups may be two or more.
[0301] Non-limiting examples of the group in which one or more
cyano groups are introduced into an alkenyl group may include a
group in which one cyano group is introduced into an end of an
ethenyl group, a group in which one cyano group is introduced into
a middle site of an ethenyl group, a group in which one cyano group
is introduced into an end of a propenyl group, a group in which one
cyano group is introduced into a middle of a propenyl group, a
group in which one cyano group is introduced into an end of a
butenyl group, and a group in which one cyano group is introduced
into a middle site of a butenyl group. A case where the number of
introduced cyano groups is one is described herein as an example;
however, the number of introduced cyano groups may be two or
more.
[0302] Non-limiting examples of the group in which one or more
cyano groups are introduced into an alkynyl group may include a
group in which one cyano group is introduced into an end of an
ethynyl group, a group in which one cyano group is introduced into
a middle site of an ethynyl group, a group in which one cyano group
is introduced into an end of a propynyl group, a group in which one
cyano group is introduced into a middle site of a propynyl group, a
group in which one cyano group is introduced into an end of a
butynyl group, and a group in which one cyano group is introduced
into a middle site of a butynyl group. A case where the number of
introduced cyano groups is one is described herein as an example;
however, the number of introduced cyano groups may be two or
more.
[0303] Details of the number of carbons in each of the alkyl group,
the alkenyl group, and the alkynyl group may be, for example, as
described above.
[0304] Non-limiting examples of the group in which one or more
cyano groups are introduced into a chain binding group may include
a group in which one cyano group is introduced into an end of a
monovalent group in which an ethenyl group and an ethynyl group are
bound to each other, and a group in which one cyano group is
introduced into a middle of a monovalent group in which an ethenyl
group and an ethynyl group are bound to each other. A case where
the number of introduced cyano groups is one is described herein as
an example; however, the number of introduced cyano groups may be
two or more.
[0305] (Monovalent Halogenated Chain Hydrocarbon Cyano Group)
[0306] The "monovalent halogenated chain hydrocarbon cyano group"
is a group in which one or more hydrogen groups in a monovalent
chain hydrocarbon cyano group is substituted by a halogen group, as
described above. Details of the halogen group included in a
monovalent halogenated hydrocarbon cyano group may be similar to,
for example, details of the halogen group included in the foregoing
monovalent halogenated hydrocarbon group. It goes without saying
that the halogen group included in the monovalent halogenated
hydrocarbon cyano group may be preferably a fluorine group.
[0307] (Preferable R2)
[0308] In particular, R2 may be preferably a group in which one or
more cyano groups are introduced into an alkyl group, and more
preferably a group in which one cyano group is introduced into an
end of an alkyl group, which suppresses induced interaction between
an ester bond and the cyano group. This further improves chemical
stability of the electrolytic solution, thereby further suppressing
decomposition reaction of the electrolytic solution.
[0309] In this case, the number of carbons in the alkyl group into
which one or more cyano groups are introduced is not particularly
limited. In particular, the number of carbons in the alkyl group
may be preferably as large as possible. Specifically, the number of
carbons in the alkyl group may be preferably 3 or more, and more
preferably 4 or more. The larger the number of carbons in the alkyl
group is, the further the induced interaction between the ester
bond and the cyano group is suppressed. This further improves
chemical stability of the electrolytic solution, thereby further
suppressing decomposition reaction of the electrolytic solution.
Note that the number of carbons in the alkyl group may be
preferably 5 or less, which secures solubility, compatibility, and
other properties of the cyano compound.
[0310] (X1)
[0311] X1 is a halogen group, as described above. The halogen group
may be, for example, one of a. fluorine group, a chlorine group, a
bromine group, and an iodine group.
[0312] (Preferable X1)
[0313] In particular, X1 may be preferably a fluorine group, which
further improves chemical stability of the electrolytic solution,
thereby further suppressing decomposition reaction of the
electrolytic solution.
[0314] (X2)
[0315] X2 is one of a hydrogen group, a halogen group, a monovalent
hydrocarbon group, and a monovalent halogenated hydrocarbon group,
as described above. Details of the halogen group are similar to
those described in a case of X1. Moreover, details of each of the
monovalent hydrocarbon group and the monovalent halogenated
hydrocarbon group are as described above.
[0316] (Preferable X2)
[0317] In particular, X2 may be preferably a hydrogen group, which
further improves chemical stability of the electrolytic solution,
thereby further suppressing decomposition reaction of the
electrolytic solution.
[0318] (Specific Examples of Cyano Compound)
[0319] The kind of the cyano compound is not particularly limited;
however, non-limiting examples of the cyano compound may include
respective compounds represented by the following chemical formulas
(1-1) to (1-18).
##STR00034## ##STR00035##
[0320] Herein, as described above, R1, R2, X1, and X2 in the
formula (1) may be preferably an alkyl group, a group in which one
cyano group is introduced into an end of an alkyl group, a fluorine
group, and an hydrogen group, respectively.
[0321] For this reason, in particular, the cyano compound may be
preferably respective compounds represented by the formulas (1-2)
to (1-5), more preferably the respective compounds represented by
the formulas (1-4) and (1-5), and still more preferably the
compound represented by the formula (1-5), which further improves
chemical stability of the electrolytic solution, thereby further
suppressing decomposition reaction of the electrolytic
solution.
[0322] A content of the cyano compound in the electrolytic solution
is not particularly limited; however, the content of the cyano
compound in the electrolytic solution may be specifically
preferably within a range from 0.1 wt % to 5 wt % both inclusive.
In this case, the content of the cyano compound may be more
preferably within a range from 0.5 wt % to 5 wt % both inclusive.
Alternatively, the content of the cyano compound may be more
preferably within a range from 0.1 wt % to 3 wt % both inclusive,
and still more preferably within a range from 0.1 wt % to 1 wt %
both inclusive. On the basis of both appropriate ranges, the
content of the cyano compound may be more preferably within a range
from 0.5 wt % to 3 wt % both inclusive, and still more preferably
within a range from 0.5 wt % to 1 wt % both inclusive, which
further improves chemical stability of the electrolytic solution
while securing solubility, compatibility, and other properties of
the cyano compound.
[0323] It should be understood that in a case where the
electrolytic solution includes two or more cyano compounds, the
"content of the cyano compound" described above is a total sum of
respective contents of the cyano compounds.
[0324] It should be understood that the electrolytic solution may
include one or more other materials together with the foregoing
cyano compound.
[0325] The other materials may include, for example, one or more of
solvents such as non-aqueous solvents (organic solvents). An
electrolytic solution including the non-aqueous solvent is a
so-called non-aqueous electrolytic solution.
[0326] Non-limiting examples of the non-aqueous solvent may include
a carbonate ester, a chain carboxylate ester, a lactone, and a
nitrile (mononitrile) compound, which make it possible to achieve
high battery capacity, superior cycle characteristics, superior
storage characteristics, and other characteristics.
[0327] The carbonate ester may include, for example, one or both of
a cyclic carbonate ester and a chain carbonate ester. Specific but
non-limiting examples of the cyclic carbonate ester may include
ethylene carbonate, propylene carbonate, and butylene carbonate.
Specific but non-limiting examples of the chain carbonate ester may
include dimethyl carbonate, diethyl carbonate, ethyl methyl
carbonate, and methylpropyl carbonate. Specific but non-limiting
examples of the chain carboxylate ester may include methyl acetate,
ethyl acetate, methyl propionate, ethyl propionate, propyl
propionate, methyl butyrate, methyl isobutyrate, methyl
trimethylacetate, and ethyl trimethylacetate. Specific but
non-limiting examples of the lactone may include
.gamma.-butyrolactone and .gamma.-valerolactone. Specific but
non-limiting examples of the nitrile compound may include
acetonitrile, methoxyacetonitrile, and 3-methoxypropionitrile.
[0328] Other than the materials mentioned above, non-limiting
examples of the non-aqueous solvent may include
1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran,
tetrahydropyran, 1,3-dioxolane, 4-methyl-1,3-dioxolane,
1,3-dioxane, 1,4-dioxane, N,N-dimethylformamide,
N-methylpyrrolidinone, N-methyloxazolidinone,
N,N'-dimethylimidazolidinone, nitromethane, nitroethane, sulfolane,
trimethyl phosphate, and dimethylsulfoxide. These solvents make it
possible to achieve similar advantages.
[0329] In particular, the non-aqueous solvent may preferably
include a carbonate ester. Specifically, the non-aqueous solvent
may more preferably include one or more of ethylene carbonate,
propylene carbonate, dimethyl carbonate, diethyl carbonate, and
ethyl methyl carbonate. These materials make it possible to achieve
high battery capacity, superior cycle characteristics, superior
storage characteristics, and other characteristics.
[0330] More specifically, the carbonate ester may preferably
include both the cyclic carbonate ester and the chain carbonate
ester. In this case, a combination of a high-viscosity (high
dielectric constant) solvent (having, for example, specific
dielectric constant .epsilon..gtoreq.30) such as ethylene carbonate
and propylene carbonate and a low-viscosity solvent (having, for
example, viscosity.ltoreq.1 mPas) such as dimethyl carbonate,
ethylmethyl carbonate, and diethyl carbonate may be more
preferable. The combination allows for an improvement in the
dissociation property of the electrolyte salt and ion mobility.
[0331] In particular, the non-aqueous solvent may preferably
include one or more of an unsaturated cyclic carbonate ester, a
halogenated carbonate ester, a sulfonate ester, an acid anhydride,
a multivalent nitrile compound, a diisocyanate compound, and a
phosphate ester, which improves chemical stability of the
electrolytic solution.
[0332] The unsaturated cyclic carbonate ester is a cyclic carbonate
ester having one or more carbon-carbon unsaturated bonds
(carbon-carbon double bonds), and may be, for example, one or more
of respective compounds represented by the following chemical
formulas (2) to (4). A content of the unsaturated cyclic carbonate
ester in the non-aqueous solvent is not particularly limited, but
may be, for example, from 0.01 wt % to 10 wt % both inclusive.
##STR00036##
[0333] where each of R11 and R12 is one of a hydrogen group and an
alkyl group, each of R13 to R16 is one of a hydrogen group, an
alkyl group, a vinyl group, and an allyl group, one or more of R13
to R16 are one of the vinyl group and the allyl group, R17 is a
group represented by .dbd.CR171R172, and each of R171 and R172 is
one of a hydrogen group and an alkyl group.
[0334] The compound represented by the formula (2) is a vinylene
carbonate-based compound. R11 and R12 may be groups of a same kind
or groups of different kinds. Details of the alkyl group are as
described above. Specific but non-limiting examples of the vinylene
carbonate-based compound may include vinylene carbonate
(1,3-dioxol-2-one), methylvinylene carbonate
(4-methyl-1,3-dioxol-2-one), ethylvinylene carbonate
(4-ethyl-1,3-dioxol-2-one), 4,5-dimethyl-1,3-dioxol-2-one, and
4,5-diethyl-1,3-dioxol-2-one. In addition, non-limiting examples of
the vinylene carbonate-based compound may include
4-fluoro-1,3-dioxol-2-one, and
4-trifluoromethyl-1,3-dioxol-2-one.
[0335] The compound represented by the formula (3) is a vinyl
ethylene carbonate-based compound. R13 to R16 may be groups of a
same kind or groups of different kinds. It goes without saying that
some of R13 to R16 may be groups of a same kind. Specific but
non-limiting examples of the vinyl ethylene carbonate-based
compound may include vinyl ethylene carbonate
(4-vinyl-1,3-dioxolane-2-one),
4-methyl-4-vinyl-1,3-dioxolane-2-one,
4-ethyl-4-vinyl-1,3-dioxolane-2-one,
4-n-propyl-4-vinyl-I,3-dioxolane-2-one,
5-methyl-4-vinyl-1,3-dioxolane-2-one,
4,4-divinyl-1,3-dioxolane-2-one, and
4,5-divinyl-1,3-dioxolane-2-one.
[0336] The compound represented by the formula (4) is a methylene
ethylene carbonate-based compound. R171 and R172 may be groups of a
same kind or groups of different kinds. Specific but non-limiting
examples of the methylene ethylene carbonate-based compound may
include methylene ethylene carbonate
(4-methylene-1,3-dioxolane-2-one),
4,4-dimethyl-5-methylene-1,3-dioxolane-2-one, and
4,4-diethyl-5-methylene-1,3-dioxolane-2-one.
[0337] In addition, the unsaturated cyclic carbonate ester may be a
catechol carbonate having a benzene ring.
[0338] The halogenated carbonate ester is a carbonate ester
including one or more halogens as constituent elements, and may be,
for example, one or both of respective compounds represented by the
following chemical formulas (5) and (6). A content of the
halogenated carbonate ester in the non-aqueous solvent is not
particularly limited, but may be, for example, from 0.01 wt % to 10
wt % both inclusive.
##STR00037##
[0339] where each of R18 to R21 is one of a hydrogen group, a
halogen group, an alkyl group, and a halogenated alkyl group, one
or more of R18 to R21 is one of the halogen group and the
halogenated alkyl group, each of R22 to R27 is one of a hydrogen
group, a halogen group, an alkyl group, and a halogenated alkyl
group, and one or more of R22 to R27 is one of the halogen group
and the halogenated alkyl group.
[0340] The compound represented by the formula (5) is a cyclic
halogenated carbonate ester. R18 to R21 may be groups of a same
kind or groups of different kinds. It goes without saying that some
of R18 to R21 may be groups of a same kind.
[0341] The kind of the halogen group is not particularly limited;
however, in particular, the halogen group may be preferably one or
more of a fluorine group, a chlorine group, a bromine group and an
iodine group, and may be more preferably the fluorine group. It is
to be noted that the number of halogen groups may be one or two or
more.
[0342] Details of the alkyl group are as described above. The
halogenated alkyl group is a group in which one or more hydrogen
groups in the alkyl group are substituted (halogenated) by a
halogen group. Details of the halogen group are as described
above.
[0343] Specific but non-limiting examples of the cyclic halogenated
carbonate ester may include respective compounds represented by the
following formulas (5-1) to (5-21), which include geometric
isomers. In particular, for example, 4-fluoro-1,3-dioxolane-2-one
represented by the chemical formula (5-1) and
4,5-difluoro-1,3-dioxolane-2-one represented by the formula (5-3)
may be preferable. It is to be noted that as
4,5-difluoro-1,3-dioxolane-2-one, a trans-isomer may be more
preferable than a cis-isomer, which is easily available and makes
it possible to achieve a higher effect.
##STR00038## ##STR00039## ##STR00040##
[0344] The compound represented by the formula (6) is a halogenated
chain carbonate ester. R22 to R27 may be groups of a same kind or
groups of different kinds. It goes without saying that some of R22.
to R27 may be groups of a same kind.
[0345] Specific but non-limiting examples of the halogenated chain
carbonate ester may include fluoromethyl methyl carbonate,
bis(fluoromethyl) carbonate, and difluoromethyl methyl
carbonate.
[0346] Non-limiting examples of the sulfonate ester may include a
monosulfonate ester and a disulfonate ester. A content of the
sulfonate ester in the non-aqueous solvent is not particularly
limited, but may be, for example, from 0.01 wt % to 10 wt % both
inclusive.
[0347] The monosulfonate ester may be a cyclic monosulfonate ester
or a chain monosulfonate ester. Specific but non-limiting examples
of the cyclic monosulfonate ester may include sultone such as
1,3-propane sultone and 1,3-propene sultone. Specific but
non-limiting examples of the chain monosulfonate ester may include
a compound in which a cyclic monosulfonate ester is cleaved at a
middle site.
[0348] The disulfonate ester may be a cyclic disulfonate ester or a
chain disulfonate ester. Specific but non-limiting examples of the
cyclic disulfonate ester may include respective compounds
represented by chemical formulas (7-1) to (7-3). Specific but
non-limiting examples of the chain disulfonate ester may include a
compound in which a cyclic di sulfonate ester is cleaved at a
middle site.
##STR00041##
[0349] Non-limiting examples of the acid anhydride may include a
carboxylic anhydride, a disulfonic anhydride, and a
carboxylic-sulfonic anhydride. A content of the acid anhydride in
the non-aqueous solvent is not particularly limited, but may be,
for example, from 0.01 wt % to 10 wt % both inclusive.
[0350] Specific but non-limiting examples of the carboxylic
anhydride may include succinic anhydride, glutaric anhydride, and
maleic anhydride. Specific but non-limiting examples of the
disulfonic anhydride may include ethanedisulfonic anhydride and
propanedisulfonic anhydride. Specific but non-limiting examples of
the carboxylic-sulfonic anhydride may include sulfobenzoic
anhydride, sulfopropionic anhydride, and sulfobutyric
anhydride.
[0351] The multivalent nitrile compound is a compound having two or
more nitrile groups (--CN). Specific but non-limiting examples of
the multivalent nitrile compound may include a compound represented
by R28-(CA).sub.n, where R28 is an n-valent hydrocarbon group. A
content of the multivalent nitrile compound in the non-aqueous
solvent is not particularly limited, but may be, for example, from
0.01 wt % to 10 wt % both inclusive, and may be preferably from 0.5
wt % to 5 wt % both inclusive.
[0352] The n-valent hydrocarbon group may be, for example, a group
in which a number n of hydrogen groups are eliminated from one of
alkane, alkene, alkyne, alicyclic hydrocarbon, aromatic
hydrocarbon, and a binding compound. The kind of alkane is not
particularly limited; however, non-limiting examples of alkane may
include methane, ethane, propane, and butane. The kind of alkene is
not particularly limited; however, non-limiting examples of alkene
may include ethylene (ethene), propylene (propene), and butene. The
kind of alkyne is not particularly limited; however, non-limiting
examples of alkyne may include ethyne (acetylene), propyne, and
butyric. The kind of alicyclic hydrocarbon is not particularly
limited; however, non-limiting examples of alicyclic hydrocarbon
may include cyclopropane, cyclobutane, cyclopentane, and
cyclohexane. The kind of aromatic hydrocarbon is not particularly
limited; however, non-limiting examples of aromatic hydrocarbon may
include benzene, naphthalene, anthracene, biphenyl, and
terphenyl.
[0353] Specific but non-limiting examples of the mutivalent nitrile
compound may include succinonitrile (NC--C.sub.2H.sub.4--CN),
glutaronitrile (NC--C.sub.3H.sub.6--CN), adiponitrile
(NC--C.sub.4H.sub.8--CN), sebaconitrile (NC--C.sub.8H.sub.10--CN),
and phthalonitrile (NC--C.sub.6H.sub.4--CN).
[0354] Non-limiting examples of the diisocyanate compound may
include a compound represented by OCN-R29-NCO, where R29 is one of
an alkylene group and an arylene group. A content of the
diisocyanate compound in the non-aqueous solvent is not
particularly limited, but may be, for example, from 0.1 wt % to 10
wt % both inclusive.
[0355] Details of each of the alkylene group and the arylene group
may be, for example, as described above. The number of carbons in
the alkylene group is not particularly limited, but may be, for
example, from 1 to 18. The number of carbons in the arylene group
is not particularly limited, but may be, for example, from 6 to 18.
Specific but non-limiting examples of the diisocyanate compound may
include OCN--C.sub.6H.sub.12--NCO.
[0356] Specific but non-limiting examples of the phosphate ester
may include trimethyl phosphate, triethyl phosphate, and triallyl
phosphate. A content of the phosphate ester in the non-aqueous
solvent is not particularly limited, but may be, for example, from
0.5 wt % to 5 wt % both inclusive.
[0357] In particular, the electrolytic solution may preferably
include, together with the foregoing cyano compound, one or more of
unsaturated cyclic carbonate ester (vinylene carbonate-based
compound) represented by the formula (2). A synergistic effect
between the cyano compound and the unsaturated cyclic carbonate
ester further improves chemical stability of the electrolytic
solution. Specific but non-limiting examples of the vinylene
carbonate-based compound may include vinylene carbonate, as
described above.
[0358] Moreover, the other materials may include, for example, one
or more of electrolyte salts such as lithium salt. However, the
electrolyte salt may include a salt other than the lithium salt.
Non-limiting examples of the salt other than the lithium salt may
include a salt of a light metal other than lithium.
[0359] Specific but non-limiting examples of the lithium salt may
include lithium hexafluorophosphate (LiPF.sub.6), lithium
tetrafluoroborate (LiBF.sub.4), lithium perchlorate (LiClO.sub.4),
lithium hexafluoroarsenate (LiAsF.sub.6), lithium tetraphenylborate
(LiB(C.sub.6H.sub.5).sub.4), lithium methanesulfonate
(LiCH.sub.3SO.sub.3), lithium trifluoromethane sulfonate
(LiCF.sub.3SO.sub.3), lithium tetrachloroaluminate (LiAlCl.sub.4),
dilithium hexafluorosilicate (Li.sub.2SiF.sub.6), lithium chloride
(LiCl), and lithium bromide (LiBr).
[0360] In particular, one or more of lithium hexafluorophosphate,
lithium tetrafluoroborate, lithium perchlorate, and lithium
hexafluoroarsenate may be preferable, and lithium
hexafluorophosphate may be more preferable. These lithium salts
make it possible to decrease internal resistance.
[0361] Moreover, non-limiting examples of the electrolyte salt may
include respective compounds represented by the following chemical
formulas (8) to (10). R41 and R43 may be groups of a same kind or
groups of different kinds. R51 to R53 may be groups of a same kind
or groups of different kinds. It goes without saying that some of
R51 to R53 may be groups of a same kind. R61 and R62 may be groups
of a same kind or groups of different kinds.
##STR00042##
[0362] where X41 is one of Group 1 elements and Group 2 elements in
the long form of the periodic table of the elements and aluminum
(Al), M41 is one of transition metals, and Group 13 elements, Group
14 elements, and Group 15 elements in the long form of the periodic
table of the elements, R41 is a halogen group, Y41 is one of
--C(.dbd.O)--R42-C(.dbd.O)--, --C(.dbd.O)--CR43.sub.2-, and
--C(.dbd.O)--C(.dbd.O)--, R42 is one of an alkylene group, a
halogenated alkylene group, an arylene group, and a halogenated
arylene group, R43 is one of an alkyl group, a halogenated alkyl
group, an aryl group, and a halogenated aryl group, a4 is an
integer of 1 to 4, b4 is an integer of 0, 2, or 4, and each of c4,
d4, m4, and n4 is an integer of 1 to 3.
##STR00043##
[0363] where X51 is one of Group 1 elements and Group 2 elements in
the long form of the periodic table of the elements, M51 is one of
transition metals, and Group 13 elements, Group 14 elements, and
Group 15 elements in the long form of the periodic table of the
elements, Y51 is one of
--C(.dbd.O)--(CR51.sub.2).sub.b5-C(.dbd.O)--,
--R53.sub.2C-(CR52.sub.2).sub.c5-C(.dbd.O)--,
--R53.sub.2C--(CR52.sub.2).sub.c5-CR53.sub.2-,
--R53.sub.2C--(CR52.sub.2).sub.c5-S(.dbd.O).sub.2-,
--S(.dbd.O).sub.2--(CR52.sub.2).sub.d5-S(.dbd.O).sub.2-, and
-C(-0)-(CR522).sub.d5-S(-0)2-, each of R51 and R53 is one of a
hydrogen group, an alkyl group, a halogen group, and a halogenated
alkyl group, one or more of R51's are one of the halogen group and
the halogenated alkyl group, one or more of R53's are one of the
halogen group and the halogenated alkyl group, R52 is one of a
hydrogen group, an alkyl group, a halogen group, and a halogenated
alkyl group, each of a5, e5, and n5 is an integer of 1 or 2, each
of b5 and d5 is an integer of 1 to 4, c5 is an integer of 0 to 4,
and each of f5 and m5 is an integer of 1 to 3.
##STR00044##
[0364] where X61 is one of Group 1 elements and Group 2 elements in
the long form of the periodic table of the elements, M61 is one of
transition metals, and Group 13 elements, Group 14 elements, and
Group 15 elements in the long form of the periodic table of the
elements, Rf is one of a fluorinated alkyl group and a fluorinated
aryl group, the number of carbons in each of the fluorinated alkyl
group and the fluorinated aryl group is from 1 to 10, Y61 is one of
--C(.dbd.O)--(CR61.sub.2).sub.d6-C(.dbd.O)--,
--R62.sub.2C-(CR61.sub.2).sub.d6-C(.dbd.O)--,
--R62.sub.2C--(CR61.sub.2).sub.d6-CR62.sub.2-,
--R62.sub.2C-(CR61.sub.2).sub.d6-S(.dbd.O).sub.2--,
--S(.dbd.O).sub.2--(CR61.sub.2).sub.e6-S(.dbd.O).sub.2--, and
--C(.dbd.O)--(CR61.sub.2).sub.e6-S(.dbd.O).sub.2--, R61 is one of a
hydrogen group, an alkyl group, a halogen group, and a halogenated
alkyl group, R62 is one of a hydrogen group, an alkyl group, a
halogen group, and a halogenated alkyl group, one or more of R62's
are one of the halogen group and the halogenated alkyl group, each
of a6, f6, and n6 is an integer of 1 or 2, each of b6, c6, and e6
is an integer of 1 to 4, d6 is an integer of 0 to 4, and each of g6
and m6 is an integer of 1 to 3.
[0365] It should be understood that the Group 1 elements include
hydrogen (H), lithium (Li), sodium (Na), potassium (K), rubidium
(Rb), cesium (Cs), and francium (Fr). The Group 2 elements include
beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr),
barium (Ba), and radium (Ra), The Group 13 elements include boron
(B), aluminum (Al), gallium (Ga), indium (In), and thallium (Tl).
The Group 14 elements include carbon (C), silicon (Si), germanium
(Ge), tin (Sn), and lead (Pb). The Group 15 elements include
nitrogen (N), phosphorus (P), arsenic (As), antimony (Sb), and
bismuth (Bi).
[0366] Specific but non-limiting examples of the compound
represented by the formula (8) may include respective compounds
represented by the following formulas (8-1) to (8-6). Specific but
non-limiting examples of the compound represented by the formula
(9) may include respective compounds represented by the following
chemical formulas (9-1) to (9-8). Specific but non-limiting
examples of the compound represented by the formula (10) may
include a compound represented by the following formula (10-1).
##STR00045## ##STR00046##
[0367] Moreover, the electrolyte salt may be respective compounds
represented by the following chemical formulas (11) to (13). Values
of m and n may be the same as or different from each other. Values
of p, q, and r may be the same as or different from one another. It
goes without saying that the values of two of p, q, and r may be
the same as each other.
LiN(C.sub.mF.sub.2m+1SO.sub.2)(C.sub.nF.sub.2n+1SO.sub.2) (11)
[0368] where each of m and n is an integer of 1 or more.
##STR00047##
[0369] where R71 is a straight-chain perfluoroalkylene group having
2 to 4 carbons or a branched perfluoroalkylene group having 2 to 4
carbons.
LiC(C.sub.pF.sub.2p+1SO.sub.2)(C.sub.qF.sub.2q+1SO.sub.2)(C.sub.rF.sub.2-
r+1SO.sub.2) (13)
[0370] where each of p, q, and r is an integer of I or more.
[0371] The compound represented by the formula (11) is a chain
amide compound. Specific but non-limiting examples of the chain
amide compound may include lithium bis(fluorosulfonyl)amide
(LiN(SO.sub.2F).sub.2), lithium
(fluorosulfonyl)(trifluoromethanesulfonyl)amide
(LiN(SO.sub.2F)(CF.sub.3SO.sub.2)), lithium
bis(trifluoromethanesulfonyl)amide (LiN(CF.sub.3SO.sub.2).sub.2),
lithium bis(pentafluoroethanesulfonyl)amide
(LIN(C.sub.2F.sub.5SO.sub.2).sub.2), lithium
(trifluoromethanesulfonyl)(pentafluoroethanesulfonyl)amide
(LiN(CF.sub.3SO.sub.2)(C.sub.2F.sub.5SO.sub.2)), lithium
(trifluoromethanesulfonyl)(heptafluoropropanesulfonyl)amide
(LiN(CF.sub.3SO.sub.2)(C.sub.3F.sub.7SO.sub.2)), and lithium
(trifluoromethanesulfonyl)(nonafluorobutanesulfonyl)amide
(LiN(CF.sub.3SO.sub.2)(C.sub.4F.sub.9SO.sub.2)).
[0372] The compound represented by the formula (12) is a cyclic
imide compound. Specific but non-limiting examples of the cyclic
imide compound may include respective compounds represented by the
following chemical formulas (12-1) to (12-4).
##STR00048##
[0373] The compound represented by the formula (13) is a chain
methide compound. Specific but non-limiting examples of the chain
methide compound may include lithium
tris(trifluoromethanesulfonyl)methide (Li
C(CF.sub.3SO.sub.2).sub.3).
[0374] Moreover, the electrolyte salt may be a
phosphorus-fluorine-containing salt such as lithium
difluorophosphate (LiPF.sub.2O.sub.2) and lithium fluorophosphate
(Li.sub.2PFO.sub.3).
[0375] A content of the electrolyte salt is not particularly
limited; however, in particular, the content of the electrolyte
salt may be preferably from 0.3 mol/kg to 3.0 mol/kg both inclusive
with respect to the solvent. This makes it possible to achieve high
ionic conductivity.
[0376] Next, description is given of a method of manufacturing the
electrolytic solution. The electrolytic solution may be
manufactured by the following procedure, for example.
[0377] In a case where the electrolytic solution is manufactured,
the electrolyte salt may be added to the solvent, and thereafter,
the solvent may be stirred to dissolve or disperse the electrolyte
salt in the solvent. Subsequently, the cyano compound may be added
to the solvent in which the electrolyte salt is dissolved or
dispersed, and thereafter, the solvent may be stirred to dissolve
or disperse the cyano compound in the solvent. Thus, the
electrolytic solution including the cyano compound may be
prepared,
[0378] <1-3. Action and Effects>
[0379] The electrolytic solution includes the foregoing cyano
compound. In this case, as compared with a case where the
electrolytic solution does not include the cyano compound and a
case where the electrolytic solution includes any other compound in
place of the cyano compound, chemical stability of the electrolytic
solution is improved, as described above. Non-limiting examples of
the "other compound" may include respective compounds represented
by the following chemical formulas (14-1) and (14-2). Accordingly,
decomposition reaction of the electrolytic solution is suppressed,
which makes it possible to improve battery characteristics of a
secondary battery using the electrolytic solution.
##STR00049##
[0380] In particular, in a case where, with regard to R2 in the
formula (1), the monovalent chain hydrocarbon cyano group is a
group in which one or more cyano groups are introduced into an
alkyl group, decomposition reaction of the electrolytic solution is
further suppressed. This makes it possible to achieve a higher
effect.
[0381] In this case, in a case where the monovalent chain
hydrocarbon cyano group is a group in which one cyano group is
introduced into an end of the alkyl group, induced interaction
between the ester bond and the cyano group is suppressed, thereby
further suppressing decomposition reaction of the electrolytic
solution. This makes it possible to achieve a higher effect.
Moreover, in a case where the number of carbons in the alkyl group
is 3 or more, induced interaction between the ester bond and the
cyano group is suppressed, thereby further suppressing
decomposition reaction of the electrolytic solution. This makes it
possible to achieve an extremely high effect.
[0382] Further, in a case where, with regard to R1 and X2 in the
formula (1), the monovalent hydrocarbon group is a group such as an
alkyl group, and with regard to X1 and X2 in the formula (1), the
halogen group is a group such as a fluorine group, decomposition
reaction of the electrolytic solution is further suppressed. This
makes it possible to achieve a higher effect.
[0383] Furthermore, in a case where R1 is an alkyl group, R2 is a
group in which one cyano group is introduced into an end of an
alkyl group, X1 is a fluorine group, and X2 is a hydrogen group,
decomposition reaction of the electrolytic solution is further
suppressed. This makes it possible to achieve a higher effect.
[0384] In addition, in a case where the content of the cyano
compound in the electrolytic solution is from 0.1 wt % to 5 wt %
both inclusive, decomposition reaction of the electrolytic solution
is further suppressed. This makes it possible to achieve a higher
effect.
[0385] Next, description is given of a secondary battery according
to an embodiment of the disclosure using the foregoing electrolytic
solution.
[0386] FIG. 9 illustrates a cross-sectional configuration of the
secondary battery. FIG. 10 is an enlarged view of a part of a
cross-sectional configuration of a spirally wound electrode body 20
illustrated in FIG. 9.
[0387] The secondary battery described herein may be, for example,
a lithium-ion secondary battery in which battery capacity (capacity
of an anode 22) is obtained with use of a lithium insertion
phenomenon and a lithium extraction phenomenon.
[0388] The secondary battery may be, for example, a secondary
battery of a cylindrical type in which the spirally wound electrode
body 20 as a battery element is contained inside a battery can 11
in the shape of a substantially-hollow cylinder, as illustrated in
FIG. 9.
[0389] Specifically, the secondary battery may contain, for
example, a pair of insulating plates 12 and 13 and the spirally
wound electrode body 20 inside the battery can 11. The spirally
wound electrode body 20 may be formed as follows. For example, a
cathode 21 and the anode 22 may be laminated with a separator 23 in
between, and the cathode 21, the anode 22, and the separator 23 may
be spirally wound to form the spirally wound electrode body 20. The
spirally wound. electrode body 20 may be impregnated with, for
example, an electrolytic solution that is a liquid electrolyte.
[0390] The battery can 11 may have, for example, a hollow structure
in which one end of the battery can 11 is closed and the other end
of the battery can 11 is opened. The battery can 11 may include,
for example, one or more of iron, aluminum, and an alloy thereof. A
surface of the battery can 11 may be plated with, for example, a
metal material such as nickel. Note that the pair of insulating
plates 12 and 13 may be so disposed as to sandwich the spirally
wound electrode body 20 in between and extend perpendicularly to a
spirally wound periphery surface of the spirally wound electrode
body 20.
[0391] At the open end of the battery can 11, a battery cover 14, a
safety valve mechanism 15, and a positive temperature coefficient
device (PTC device) 16 may be swaged with a gasket 17, by which the
battery can 11 is hermetically sealed. A formation material of the
battery cover 14 may be similar to, for example, a formation
material of the battery can 11. Each of the safety valve mechanism
15 and the PTC device 16 may be provided on the inner side of the
battery cover 14, and the safety valve mechanism 15 may be
electrically coupled to the battery cover 14 via the PTC device 16.
In the safety valve mechanism 15, when an internal pressure of the
battery can 11 reaches a certain level or higher as a result of for
example, internal short circuit or heating from outside, a disk
plate 15 A inverts. This cuts electric connection between the
battery cover 14 and the spirally wound electrode body 20. In order
to prevent abnormal heat generation resulting from a large current,
resistance of the PTC device 16 increases as a temperature rises.
The gasket 17 may include, for example, an insulating material. A
surface of the gasket 17 may be coated with, for example,
asphalt.
[0392] For example, a center pin 24 may be inserted in a space
provided at a center of the spirally wound electrode body 20.
However, the center pin 24 may be omitted. A cathode lead 25 may be
attached to the cathode 21, and an anode lead 26 may be attached to
the anode 22. The cathode lead 25 may include, for example, a
conductive material such as aluminum. For example, the cathode lead
25 may be attached to the safety valve mechanism 15, which may be
thereby electrically coupled to the battery cover 14. The anode
lead 26 may include, for example, a conductive material such as
nickel. For example, the anode lead 26 may be attached to the
battery can 11, which may be thereby electrically coupled to the
battery can 11.
[0393] The cathode 21 may include, for example, a cathode current
collector 21A and two cathode active material layers 21B provided
on both surfaces of the cathode current collector 21A, as
illustrated in FIG. 10. Alternatively, only one cathode active
material layer 21B may be provided on a single surface of the
cathode current collector 21A.
[0394] The cathode current collector 21A may include, for example,
one or more of conductive materials. The kind of the conductive
materials is not particularly limited; however, non-limiting
examples of the conductive materials may include metal materials
such as aluminum, nickel, and stainless steel. The cathode current
collector 21A may be configured of a single layer or may be
configured of multiple layers.
[0395] The cathode active material layer 21B may include, as a
cathode active material, one or more of cathode materials capable
of inserting and extracting lithium. It is to be noted that the
cathode active material layer 21B may further include one or more
of other materials such as a cathode binder and a cathode
conductor.
[0396] The cathode material may be preferably a lithium-containing
compound, which makes it possible to achieve high energy density.
The kind of the lithium-containing compound is not particularly
limited; however, non-limiting examples of the lithium-containing
compounds may include a lithium-containing composite oxide and a
lithium-containing phosphate compound.
[0397] The lithium-containing composite oxide is an oxide that
includes lithium and one or more other elements as constituent
elements. The lithium-containing composite oxide may have, for
example, one of crystal structures such as a layered rock-salt
crystal structure and a spinel crystal structure. The
lithium-containing phosphate compound is a phosphate compound that
includes lithium and one or more other elements as constituent
elements. The lithium-containing phosphate compound may have, for
example, a crystal structure such as an olivine crystal
structure.
[0398] It should be understood that the "other elements" mentioned
above are elements other than lithium. The kind of the other
elements is not particularly limited as long as the other elements
are one or more of optional elements; however, non-limiting
examples of the other elements may include elements that belong to
Groups 2 to 15 in the long form of the periodic table of the
elements. More specifically, the other elements may be preferably
nickel (Ni), cobalt (Co), manganese (Mn), iron (Fe), etc., which
make it possible to obtain a high voltage.
[0399] Non-limiting examples of the lithium-containing composite
oxide having the layered rock-salt crystal structure may include
respective compounds represented by the following formulas (21) to
(23).
Li.sub.aMn.sub.(1-b-c)Ni.sub.bM11.sub.cO.sub.(2-d)F.sub.e (21)
[0400] where M11 is one or more of cobalt (Co), magnesium (Mg),
aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium
(Cr), iron (Fe), copper (Cu), zinc (Zn), zirconium (Zr), molybdenum
(Mo), tin (Sn), calcium (Ca), strontium (Sr), and tungsten (W), "a"
to "e" satisfy 0.8.ltoreq.a.ltoreq.1.2, 0<b<0.5,
0.ltoreq.c.ltoreq.0.5, and (b+c)<1, -0.1.ltoreq.d.ltoreq.0.2,
and 0.ltoreq.e.ltoreq.0.1, it is to be noted that the composition
of lithium varies depending on charge and discharge states, and "a"
is a value in a completely-discharged state.
Li.sub.aNi.sub.(1-b)M12.sub.bO.sub.(2-c)F.sub.d (22)
[0401] where M12 is one or more of cobalt (Co), manganese (Mn),
magnesium (Mg), aluminum boron (B), titanium (Ti), vanadium (V),
chromium (Cr), iron (Fe), copper (Cu), zinc (Zn), molybdenum (Mo),
tin (Sn), calcium (Ca), strontium (Sr), and tungsten (W), "a" to
"d" satisfy 0.8.ltoreq.a.ltoreq.1.2, 0.005.ltoreq.b.ltoreq.0.5,
-0.1.ltoreq.c.ltoreq.0.2, and 0.ltoreq.d.ltoreq.0.1, it is to be
noted that the composition of lithium varies depending on charge
and discharge states, and "a" is a value in a completely-discharged
state.
Li.sub.aCo.sub.(1-b)M13.sub.bO.sub.(2-c)F.sub.d (23)
[0402] where M13 is one or more of nickel (Ni), manganese (Mn),
magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium
(V), chromium (Cr), iron (Fe), copper (Cu), zinc (Zn), molybdenum
(Mo), tin (Sn), calcium (Ca), strontium (Sr), and tungsten (NV),
"a" to "d" satisfy 0.8.ltoreq.a.ltoreq.1.2, 0.ltoreq.b<0.5,
-0.1.ltoreq.c.ltoreq.0.2, and 0.ltoreq.d.ltoreq.0.1, it is to be
noted that the composition of lithium varies depending on charge
and discharge states, and "a" is a value in a completely-discharged
state.
[0403] Specific but non-limiting examples of the lithium-containing
composite oxide having the layered rock-salt crystal structure may
include LiNiO.sub.2, LiCoO.sub.2,
LiCo.sub.0.98Al.sub.0.01Mg.sub.0.01O.sub.2,
LiNi.sub.0.5Co.sub.0.2Mn.sub.0.3O.sub.2,
LiNi.sub.0.8Co.sub.0.15Al.sub.0.05O.sub.2,
LiNi.sub.0.33Co.sub.0.33Mn.sub.0.33O.sub.2,
Li.sub.1.2Mn.sub.0.52Co.sub.0.175Ni.sub.0.1O.sub.2, and
Li.sub.1.15(Mn.sub.0.65Ni.sub.0.22Co.sub.0.13)O.sub.2.
[0404] It should be understood that in a case where the
lithium-containing composite oxide having the layered rock-salt
crystal structure includes nickel, cobalt, manganese, and aluminum
as constituent elements, an atomic ratio of nickel may be
preferably 50 at % or more, which makes it possible to achieve high
energy density.
[0405] Non-limiting examples of the lithium-containing composite
oxide having the spinel crystal structure may include a compound
represented by the following formula (24).
Li.sub.aMn.sub.(2-b)M14.sub.bO.sub.cF.sub.d (24)
[0406] where M14 is one or more of cobalt (Co), nickel (Ni),
magnesium (Mg), aluminum (Al) boron (B), titanium (Ti), vanadium
(V), chromium (Cr), iron (Fe), copper (Cu), zinc (Zn), molybdenum
(Mo), tin (Sn), calcium (Ca), strontium (Sr), and tungsten (W), "a"
to "d" satisfy 0.9.ltoreq.a.ltoreq.1.1, 0.ltoreq.b.ltoreq.0.6,
3.7.ltoreq.c.ltoreq.4.1, and 0.ltoreq.d.ltoreq.0.1, it is to be
noted that the composition of lithium varies depending on charge
and discharge states, and "a" is a value in a completely-discharged
state.
[0407] Specific but non-limiting examples of the lithium-containing
composite oxide having the spinel crystal structure may include
LiMn.sub.2O.sub.4.
[0408] Non-limiting examples of the lithium-containing phosphate
compound having the olivine crystal structure may include a
compound represented by the following formula (25).
Li.sub.aM15PO.sub.4 (25)
[0409] where M15 is one or more of cobalt (Co), manganese (Mn),
iron (Fe), nickel (Ni), magnesium (Mg), aluminum (Al), boron (B),
titanium (Ti), vanadium (V), niobium (Nb), copper (Cu), zinc (Zn),
molybdenum (Mo), calcium (Ca), strontium (Sr), tungsten (W), and
zirconium (Zr), "a" satisfies 0.9.ltoreq.a.ltoreq.1.1, it is to be
noted that the composition of lithium varies depending on charge
and discharge states, and "a" is a value in a completely-discharged
state.
[0410] Specific but non-limiting examples of the lithium-containing
phosphate compound having the olivine crystal structure may include
LiFePO.sub.4, LiMnPO.sub.4, LiFe.sub.0.5Mn.sub.0.5PO.sub.4, and
LiFe.sub.0.3Mn.sub.0.7PO.sub.4.
[0411] It should be understood that the lithium-containing
composite oxide may be, for example, a compound represented by the
following formula (26).
(Li.sub.2MnO.sub.3),(LiMnO.sub.2).sub.1-x (26)
[0412] where "x" satisfies 0.ltoreq.x.ltoreq.1, it is to be noted
that the composition of lithium varies depending on charge and
discharge states, and "x" is a value in a completely-discharged
state.
[0413] Moreover, non-limiting examples of the cathode materials may
include an oxide, a disulfide, a chalcogenide, and a conductive
polymer. Non-limiting examples of the oxide may include titanium
oxide, vanadium oxide, and manganese dioxide. Non-limiting examples
of the disulfide may include titanium disulfide and molybdenum
sulfide. Non-limiting examples of the chalcogenide may include
niobium selenide. Non-limiting examples of the conductive polymer
may include sulfur, polyaniline, and polythiophene.
[0414] The cathode binder may include, for example, one or more of
synthetic rubbers and polymer compounds. Non-limiting examples of
the synthetic rubbers may include a styrene-butadiene-based rubber,
a fluorine-based rubber, and ethylene propylene diene. Non-limiting
examples of the polymer compounds may include polyvinylidene
fluoride and polyimide.
[0415] The cathode conductor may include, for example, one or more
of conductive materials such as carbon materials. Non-limiting
examples of the carbon materials may include graphite, carbon
black, acetylene black, and Ketjen black. Alternatively, the
cathode conductor may be any other material such as a metal
material and a conductive polymer, as long as the cathode conductor
is a material having conductivity.
[0416] The anode 22 may include, for example, an anode current
collector 22A and two anode active material layers 22B provided on
both surfaces of the anode current collector 22A. Alternatively,
only one anode active material layer 22B may be provided on a
single surface of the anode current collector 22A.
[0417] The anode current collector 22A may include, for example,
one or more of conductive materials. The kind of the conductive
materials is not particularly limited; however, non-limiting
examples of the conductive materials may include metal materials
such as copper, aluminum, nickel, and stainless steel. The anode
current collector 22A may be configured of a single layer or may be
configured of multiple layers.
[0418] A surface of the anode current collector 22A may be
preferably roughened. This makes it possible to improve
adhesibility of the anode active material layers 22B with respect
to the anode current collector 22A by a so-called anchor effect. In
this case, it may be only necessary to roughen the surface of the
anode current collector 22A at least in a region facing each of the
anode active material layers 22B. Non-limiting examples of a
roughening method may include a method of forming fine particles
with use of electrolytic treatment. Through the electrolytic
treatment, fine particles are formed on the surface of the anode
current collector 22A in an electrolytic bath by an electrolytic
method to make the surface of the anode current collector 22A
rough. A copper foil fabricated by the electrolytic method is
generally called "electrolytic copper foil".
[0419] The anode active material layers 22B may include, as an
anode active material, one or more of anode materials capable of
inserting and extracting lithium. It is to be noted that the anode
active material layers 22B may further include one or more of other
materials such as an anode binder and an anode conductor.
[0420] In order to prevent lithium from being unintentionally
precipitated on the anode 22 in the middle of charge, chargeable
capacity of the anode material may be preferably larger than
discharge capacity of the cathode 21. In other words,
electrochemical equivalent of the anode material capable of
inserting and extracting lithium may be preferably larger than
electrochemical equivalent of the cathode 21.
[0421] The kind of the anode material is not particularly limited;
however, non-liming examples of the anode material may include a
carbon material and a metal-based material.
[0422] The carbon material is a generic name of a material
including carbon as a constituent element. The carbon material
causes an extremely-small change in a crystal structure thereof
during insertion and extraction of lithium, which stably achieves
high energy density. Further, the carbon material also serves as
the anode conductor, which improves conductivity of the anode
active material layer 22B.
[0423] Non-limiting examples of the carbon material may include
graphitizable carbon, nongraphitizable carbon, and graphite. The
spacing of (002) plane in nongraphitizable carbon may be preferably
equal to or greater than 0.37 nm, and the spacing of (002) plane in
graphite may be preferably equal to or smaller than 0.34 nm. More
specific examples of the carbon material may include pyrolytic
carbons, cokes, glassy carbon fibers, an organic polymer compound
fired body, activated carbon, and carbon blacks. Non-limiting
examples of the cokes may include pitch coke, needle coke, and
petroleum coke. The organic polymer compound fired body is a
polymer compound fired (carbonized) at an appropriate temperature.
Non-limiting examples of the polymer compound may include phenol
resin and furan resin. Other than the materials mentioned above,
the carbon material may be low crystalline carbon heat-treated at a
temperature of about 1000.degree. C. or less, or may be amorphous
carbon. It is to be noted that the shape of the carbon material may
be one or more of a fibrous shape, a spherical shape, a granular
shape, and a scale-like shape.
[0424] The metal-based material is a generic name of a material
including one or more of metal elements and metalloid elements as
constituent elements, and the metal-based material achieves high
energy density.
[0425] The metal-based material may be one of a simple substance,
an alloy, and a compound, may be two or more thereof, or may have
one or more phases thereof. It is to be noted that the "alloy" also
encompasses a material that includes one or more metal elements and
one or more metalloid elements, in addition to a material includes
two or more metal elements. Further, the alloy may include a
non-metallic element. Non-limiting examples of the structure of the
metal-based material may include a solid solution, a eutectic
crystal (a eutectic mixture), an intermetallic compound, and a
structure in which two or more thereof coexist.
[0426] The metal elements and the metalloid elements may be, for
example, one or more of metal elements and metalloid elements that
are capable of forming an alloy with lithium. Specific but
non-limiting examples of the metal elements and the metalloid
elements may include magnesium (Mg), boron (B), aluminum (Al),
gallium (Ga), indium (In), silicon (Si), germanium (Ge), tin (Sn),
lead (Pb), bismuth (Bi), cadmium (Cd), silver Ag), zinc, hafnium
(Hf), zirconium, yttrium (Y), palladium (Pd), and platinum
(Pt).
[0427] In particular, silicon, tin, or both may be preferable, and
silicon may be more preferable. Silicon and tin have superior
ability of inserting and extracting lithium, and achieve remarkably
high energy density accordingly.
[0428] A material containing silicon, tin, or both as constituent
elements may be any of a simple substance, an alloy, and a compound
of silicon, may be any of a simple substance, an alloy, and a
compound of tin, may be two or more thereof, or may be a material
that has one or more phases thereof The "simple substance"
described herein merely refers to a simple substance in a general
sense (a small amount of impurity may be therein contained), and
does not necessarily refer to a purity 100% simple substance.
[0429] The alloy of silicon may contain, for example, one or more
of elements such as tin, nickel, copper, iron, cobalt, manganese,
zinc, indium, silver, titanium, germanium, bismuth, antimony, and
chromium, as constituent elements other than silicon. The compound
of silicon may contain, for example, one or more of elements such
as carbon and oxygen, as constituent elements other than silicon.
It is to be noted that the compound of silicon may contain, for
example, one or more of the elements described for the alloy of
silicon, as constituent elements other than silicon.
[0430] Specific but non-limiting examples of the alloy of silicon
and the compound of silicon may include SiB.sub.4, SiB.sub.6,
Mg.sub.2Si, Ni.sub.2Si, TiSi.sub.2, MoSi.sub.2, CoSi.sub.2,
NiSi.sub.2, CaSi.sub.2, CrSi.sub.2, Cu.sub.5Si, FeSi.sub.2,
MnSi.sub.2, NbSi.sub.2, TaSi.sub.2, VSi.sub.2, WSi.sub.2,
ZnSi.sub.2, SiC, Si.sub.3N.sub.4, Si.sub.2N.sub.2O, SiO.sub.v
(0<v.ltoreq.2), and LiSiO. It is to be noted that "v" in
SiO.sub.v may be, for example, within a range of
0.2<v<1.4.
[0431] The alloy of tin may contain, for example, one or more of
elements such as silicon, nickel, copper, iron, cobalt, manganese,
zinc, indium, silver, titanium, germanium, bismuth, antimony, and
chromium, as constituent elements other than tin. The compound of
tin may contain, for example, one or more of elements such as
carbon and oxygen, as constituent elements other than tin. It is to
be noted that the compound of tin may contain, for example, one or
more of the elements described for the alloy of tin, as constituent
elements other than tin.
[0432] Specific but non-limiting examples of the alloy of tin and
the compound of tin may include SnO.sub.w (0<w.ltoreq.2),
SnSiO.sub.3, LiSnO, and Mg.sub.2Sn.
[0433] In particular, the material containing tin as a constituent
element may be preferably, for example, a material (tin-containing
material) that contains, together with tin as a first constituent
element, a second constituent element and a third constituent
element. The second constituent element may include, for example,
one or more of elements such as cobalt, iron, magnesium, titanium,
vanadium, chromium, manganese, nickel, copper, zinc, gallium,
zirconium, niobium, molybdenum, silver, indium, cesium (Ce),
hafnium (Hf), tantalum, tungsten, bismuth, and silicon. The third
constituent element may include, for example, one or more of
elements such as boron, carbon, aluminum, and phosphorus. The
tin-containing material containing the second constituent element
and the third constituent element makes it possible to achieve high
battery capacity, superior cycle characteristics, and other
characteristics.
[0434] In particular, the tin-containing material may be preferably
a material that contains tin, cobalt, and carbon as constituent
elements (a tin-cobalt-carbon-containing material). In the
tin-cobalt-carbon-containing material, for example, a content of
carbon may be from 9.9 mass % to 29.7 mass % both inclusive, and a
ratio of contents of tin and cobalt (Co/(Sn+Co)) may be from 20
mass % to 70 mass % both inclusive. This makes it possible to
achieve high energy density.
[0435] The tin-cobalt-carbon-containing material may have a phase
that contains tin, cobalt, and carbon. Such a phase may be
preferably low crystalline or amorphous. This phase is a reaction
phase that is able to react with lithium. Hence, existence of the
reaction phase results in achievement of superior characteristics.
A half width (a diffraction angle 2.theta.) of a diffraction peak
obtained by X-ray diffraction of this reaction phase may be
preferably 1.degree. or larger in a case where a CuK.alpha. ray is
used as a specific X-ray, and an insertion rate is 1.degree./min.
This makes it possible to insert and extract lithium more smoothly,
and to decrease reactivity of the tin-cobalt-carbon-containing
material with the electrolytic solution. It is to be noted that, in
some cases, the tin-cobalt-carbon-containing material may include a
phase that contains simple substances of the respective constituent
elements or part thereof in addition to the low-crystalline phase
or the amorphous phase.
[0436] Comparison between X-ray diffraction charts before and after
an electrochemical reaction with lithium makes it possible to
easily determine whether the diffraction peak obtained by the X-ray
diffraction corresponds to the reaction phase that is able to react
with lithium. For example, if a position of the diffraction peak
after the electrochemical reaction with lithium is changed from the
position of the diffraction peak before the electrochemical
reaction with lithium, the obtained diffraction peak corresponds to
the reaction phase that is able to react with lithium. In this
case, for example, the diffraction peak of the low-crystalline
reaction phase or the amorphous reaction phase may be seen within a
range of 20 that is from 20.degree. to 50.degree. both inclusive.
Such a reaction phase may include, for example, the respective
constituent elements mentioned above, and it may be considered that
such a reaction phase has become low crystalline or amorphous
mainly because of existence of carbon.
[0437] In the tin-cobalt-carbon-containing material, part or all of
carbon that is the constituent element thereof may be preferably
bound to one of a metal element and a metalloid element that are
other constituent elements thereof. Binding part or all of carbon
suppresses cohesion or crystallization of tin, etc. It is possible
to confirm a binding state of the elements, for example, by X-ray
photoelectron spectroscopy (XPS). In a commercially-available
apparatus, for example, an Al-K.alpha. ray or a Mg-K.alpha. ray may
be used as a soft X-ray. In a case where part or all of carbon is
bound to one of the metal element, the metalloid element, and any
other element, a peak of a synthetic wave of is orbit of carbon
(Cls) appears in an energy region lower than 284.5 eV. It is to be
noted that energy calibration is so made that a peak of 4f orbit of
a gold atom (Au4f) is obtained at 84.0 eV. In this case, in
general, surface contamination carbon exists on the material
surface. Hence, a peak of Cls of the surface contamination carbon
is regarded to be at 284.8 eV, and this peak is used as energy
standard. In XPS measurement, a waveform of the peak of Cls is
obtained as a form that includes the peak of the surface
contamination carbon and the peak of the carbon in the
tin-cobalt-carbon-containing material. The two peaks may be
therefore separated from each other, for example, by analysis with
use of commercially-available software. In the analysis of the
waveform, a position of the main peak that exists on the lowest
bound energy side is regarded as the energy standard (284.8
eV).
[0438] The tin-cobalt-carbon-containing material is not limited to
a material that contains only tin, cobalt, and carbon as
constituent elements. The tin-cobalt-carbon-containing material may
further contain one or more of elements such as silicon, iron,
nickel, chromium, indium, niobium, germanium, titanium, molybdenum,
aluminum, phosphorus, gallium, and bismuth, as constituent
elements, in addition to tin, cobalt, and carbon.
[0439] Other than the tin-cobalt-carbon-containing material, a
material that contains tin, cobalt, iron, and carbon as constituent
elements (a tin-cobalt-iron-carbon-containing material) may be also
preferable. Any composition of the
tin-cobalt-iron-carbon-containing material may be adopted. To give
an example, in a case where a content of iron is set smaller, a
content of carbon may be from 9.9 mass % to 29.7 mass % both
inclusive, a content of iron may be from 0.3 mass % to 5.9 mass %
both inclusive, and a ratio of contents of tin and cobalt
(Co/(Sn+Co)) may be from 30 mass % to 70 mass % both inclusive.
Alternatively, in a case where the content of iron is set larger,
the content of carbon may be from 11.9 mass % to 29.7 mass % both
inclusive, the ratio of contents of tin, cobalt, and iron
((Co+Fe)/(Sn+Co+Fe)) may be from 26.4 mass % to 48.5 mass % both
inclusive, and the ratio of contents of cobalt and iron
(Co/(Co+Fe)) may be from 9.9 mass % to 79.5 mass % both inclusive.
Such composition ranges allow for achievement of high energy
density. It is to be noted that physical properties (such as a half
width) of the tin-cobalt-iron-carbon-containing material are
similar to physical properties of the foregoing
tin-cobalt-carbon-containing material.
[0440] Other than the materials mentioned above, non-limiting
examples of the anode material include a metal oxide and a polymer
compound. Non-limiting examples of the metal oxide may include iron
oxide, ruthenium oxide, and molybdenum oxide. Non-limiting examples
of the polymer compound may include polyacetylene, polyaniline, and
polypyrrole.
[0441] In particular, the anode material may preferably include
both the carbon material and the metal-based material for a reason
to be described below.
[0442] The metal-based material, in particular, the material
containing one or both of silicon and tin as constituent elements
has a concern that such a material is easily and radically expanded
or contracted during charge and discharge, whereas such a material
has an advantage of high theoretical capacity. In contrast, the
carbon material has an advantage that the carbon material is less
prone to be expanded or contracted during charge and discharge,
whereas the carbon material has a concern of low theoretical
capacity. Hence, using both of the carbon material and the
metal-based material makes it possible to suppress expansion and
contraction during charge and discharge while achieving high
theoretical capacity (in other words, high battery capacity).
[0443] Details of the anode binder may be similar to, for example,
details of the foregoing cathode binder. Moreover, details of the
anode conductor may be similar to, for example, details of the
foregoing cathode conductor.
[0444] In the secondary battery, as described above, in order to
prevent lithium metal from being unintentionally precipitated on a
surface of the anode 22 in the middle of charge, the
electrochemical equivalent of the anode material capable of
inserting and extracting lithium may be preferably larger than the
electrochemical equivalent of the cathode. In a case where an open
circuit voltage (that is, a battery voltage) in a
completely-charged state is equal to or higher than 4.25 V, an
extraction amount of lithium per unit mass is larger than that in a
case where the open circuit voltage is 4.20 V, even if the same
cathode active material is used. Hence, amounts of the cathode
active material and the anode active material are adjusted in
accordance therewith. As a result, high energy density is
achieved.
[0445] The separator 23 may be provided, for example, between the
cathode 21 and the anode 22, as illustrated in FIG. 10. The
separator 23 passes lithium ions therethrough while preventing
current short circuit that results from contact between the cathode
21 and the anode 22.
[0446] More specifically, the separator 23 may include, for
example, one or more of porous films such as porous films of a
synthetic resin and ceramics. The separator 23 may be a laminated
film in which two or more porous films are laminated. Non-limiting
examples of the synthetic resin may include
polytetrafluoroethylene, polypropylene, and polyethylene.
[0447] In particular, the separator 23 may include, for example,
the foregoing porous film (a base layer) and a polymer compound
layer provided on a single surface or both surfaces of the base
layer. This makes it possible to improve adhesibility of the
separator 23 with respect to each of the cathode 21 and the anode
22, thereby suppressing deformation of the spirally wound electrode
body 20. This makes it possible to suppress decomposition reaction
of the electrolytic solution and to suppress liquid leakage of the
electrolytic solution with which the base layer is impregnated.
Accordingly, even if charge and discharge are repeated, resistance
is less prone to increase, and the secondary battery is less prone
to swell.
[0448] The polymer compound layer may include, for example, one or
more of polymer compounds such as polyvinylidene fluoride, which
has high physical strength and is electrochemically stable. In
order to form the polymer compound layer, for example, the base
layer may be coated with a solution prepared by dissolving the
polymer compound in a solvent such as an organic solvent, and
thereafter, the base layer may be dried. Alternatively, the base
layer may be immersed in the solution, and thereafter the base
layer may be dried.
[0449] The polymer compound layer may include, for example, one or
more of insulating particles such as inorganic particles. This
makes it possible to improve safety. The kind of the inorganic
particles may be, for example, aluminum oxide and aluminum
nitride.
[0450] The spirally wound electrode body 20 may be impregnated with
the electrolytic solution, as described above. Since the
electrolytic solution has a configuration similar to that of the
foregoing electrolytic solution according to the embodiment of the
disclosure, the electrolytic solution includes a cyano
compound.
[0451] The secondary battery may operate as follows, for
example.
[0452] When the secondary battery is charged, lithium ions are
extracted from the cathode 21, and the extracted lithium ions are
inserted in the anode 22 through the electrolytic solution. In
contrast, when the secondary battery is discharged, lithium ions
are extracted from the anode 22, and the extracted lithium ions are
inserted in the cathode 21 through the electrolytic solution,
[0453] (Manufacturing Method)
[0454] The secondary battery may be manufactured by the following
procedure, for example.
[0455] In a case where the cathode 21 is fabricated, first, the
cathode active material, and, on as-necessary basis, any other
material such as the cathode binder and the cathode conductor may
be mixed to obtain a cathode mixture. Subsequently, the cathode
mixture may be dispersed in a solvent such as an organic solvent to
obtain paste cathode mixture slurry. Lastly, both surfaces of the
cathode current collector 21A may be coated with the cathode
mixture slurry, and thereafter, the coated cathode mixture slurry
may be dried to form the cathode active material layers 21B.
Thereafter, the cathode active material layers 21B may be
compression-molded with use of, for example, a roll pressing
machine on as-necessary basis. In this case, the cathode active
material layers 21B may be heated, or may be compression-molded a
plurality of times.
[0456] In a case where the anode 22 is fabricated, the anode active
material layers 22B may be formed on both surfaces of the anode
current collector 22A by a procedure similar to the foregoing
procedure of fabricating the cathode 21. More specifically, the
anode active material, and any other material such as the anode
binder and the anode conductor may be mixed to obtain an anode
mixture. Subsequently, the anode mixture may be dispersed in a
solvent such as an organic solvent to obtain paste anode mixture
slurry. Next, both surfaces of the anode current collector 22A may
be coated with the anode mixture slurry, and thereafter, the coated
anode mixture slurry may be dried to form the anode active material
layers 22B. Thereafter, the anode active material layers 22B may be
compression-molded with use of, for example, a roll pressing
machine on as-necessary basis.
[0457] A method of forming the anode active material layer 22B is
not particularly limited; however, the anode active material layer
22B may be formed by, for example, one or more of a coating method,
a vapor-phase method, a liquid-phase method, a spraying method, and
a firing method (sintering method). The coating method may be, for
example, a method in which, after, for example, a particulate
(powder) anode active material are mixed with, for example, an
anode binder to form a mixture, the mixture is dissolved or
dispersed in a solvent such as an organic solvent to prepare a
solution, and the solution is applied onto the anode current
collector 22A. Non-limiting examples of the vapor-phase method may
include a physical deposition method and a chemical deposition
method. More specifically, non-limiting examples thereof may
include a vacuum evaporation method, a sputtering method, an ion
plating method, a laser ablation method, a thermal chemical vapor
deposition method, a chemical vapor deposition (CVD) method, and a
plasma chemical vapor deposition method. Non-limiting examples of
the liquid-phase method may include an electrolytic plating method
and an electroless plating method. The spraying method is a method
in which an anode active material in a fused state or a semi-fused
state is sprayed to the anode current collector 22A. The firing
method may be, for example, a method in which, after the solution
is applied onto the anode current collector 22A by the coating
method, the solution is heat-treated at a temperature higher than a
melting point of the anode binder, etc. Non-limiting examples of
the firing method may include an atmosphere firing method, a
reactive firing method, and a hot press firing method.
[0458] In a case where the secondary battery is assembled, the
cathode lead 25 may be attached to the cathode current collector
21A by a method such as a welding method, and the anode lead 26 may
be attached to the anode current collector 22A by a method such as
a welding method. Subsequently, the cathode 21 and the anode 22 may
be laminated with the separator 23 in between, and the cathode 21,
the anode 22, and the separator 23 may be spirally wound to form a
spirally wound body. Thereafter, the center pin 24 may be inserted
in a space provided at the center of the spirally wound body.
[0459] Subsequently, the spirally wound body may be sandwiched
between the pair of insulating plates 12 and 13, and may be
contained inside the battery can 11. In this case, an end of the
cathode lead 25 may be attached to the safety valve mechanism 15 by
a method such as a welding method, and an end of the anode lead 26
may be attached to the battery can 11 by a method such as a welding
method. Subsequently, the electrolytic solution may be injected
inside the battery can 11, and the spirally wound body may be
impregnated with the injected electrolytic solution, thereby
forming the spirally wound electrode body 20. Lastly, the battery
cover 14, the safety valve mechanism 15, and the PTC device 16 may
be swaged with the gasket 17 at the open end of the battery can 11,
thereby enclosing the spirally wound electrode body 20 in the
battery can 11. Thus, the cylindrical type secondary battery is
completed.
[0460] According to the cylindrical type secondary battery, the
electrolytic solution has a configuration similar to that of the
foregoing electrolytic solution according to the embodiment of the
disclosure. Accordingly, chemical stability of the electrolytic
solution is improved as described above, thereby suppressing
decomposition reaction of the electrolytic solution. This makes it
possible to improve battery characteristics.
[0461] Action and effects related to the cylindrical type secondary
battery other than those described above are similar to action and
effects related to the electrolytic solution according to the
embodiment of the disclosure.
[0462] FIG. 11 illustrates a perspective configuration of another
secondary battery. FIG. 12 illustrates a cross-sectional
configuration taken along a line IV-IV of a spirally wound
electrode body 30 illustrated in FIG. 11. It is to be noted that
FIG. 11 illustrates a state in which the spirally wound electrode
body 30 and an outer package member 40 are separated from each
other.
[0463] In the following description, the elements of the
cylindrical type secondary battery that have been already described
will be used where appropriate.
[0464] As can be seen from FIG. 11, the secondary battery may be,
for example, a laminated film type secondary battery (lithium-ion
secondary battery) in which the spirally wound electrode body 30 as
a battery element is contained inside the film-like outer package
member 40.
[0465] More specifically, for example, the secondary battery may
include the spirally wound electrode body 30 inside the film-like
outer package member 40. The spirally wound electrode body 30 may
be formed as follows, for example. A cathode 33 and an anode 34 may
be laminated with a separator 35 and an electrolyte layer 36 in
between, and the cathode 33, the anode 34, the separator 35, and
the electrolyte layer 36 may be spirally wound to form the spirally
wound electrode body 30. The electrolyte layer 36 may be
interposed, for example, between the cathode 33 and the separator
35 and may be interposed, for example, between the anode 34 and the
separator 35. A cathode lead 31 may be attached to the cathode 33,
and an anode lead 32 may be attached to the anode 34. An outermost
periphery of the spirally wound electrode body 30 may be protected
by a protective tape 37.
[0466] The cathode lead 31 may be led out from inside to outside of
the outer package member 40, for example. The cathode lead 31 may
include, for example, one or more of conductive materials such as
aluminum (Al), and the cathode lead 31 may be in the shape of, for
example, a thin plate or mesh.
[0467] The anode lead 32 may be led out from inside to outside of
the outer package member 40 in a direction similar to that in the
cathode lead 31, for example. The anode lead 32 may include, for
example, one or more of conductive materials such as copper (Cu),
nickel (Ni), and stainless steel, and the anode lead 32 may be in
the shape of, for example, a thin plate or mesh.
[0468] The outer package member 40 may be, for example, one film
that is foldable in a direction of an arrow R illustrated in FIG.
11, and the outer package member 40 may have a depression for
containing of the spirally wound electrode body 30.
[0469] The outer package member 40 may be a laminated film in which
a fusion bonding layer, a metal layer, and a surface protective
layer are laminated in this order, for example. In a process of
manufacturing the secondary battery, the outer package member 40
may be folded so that portions of the fusion-bonding layer face
each other with the spirally wound electrode body 30 in between,
and thereafter outer edges of the portions of the fusion bonding
layer may be fusion-bonded. The fusion bonding layer may include
one or more of films of polyethylene, polypropylene, and other
materials. The metal layer may include, for example, one or more of
an aluminum foil and other metal materials. The surface protective
layer may include, for example, one or more of films of nylon,
polyethylene terephthalate, and other materials. Alternatively, two
laminated films bonded to each other by, for example, an adhesive
may form the outer package member 40.
[0470] In particular, the outer package member 40 may be preferably
an aluminum laminated film in which a nylon film, an aluminum foil,
and a polyethylene film are laminated in this order. Alternatively,
the outer package member 40 may be a laminated film having any
other laminated structure, a polymer film such as polypropylene, or
a metal film.
[0471] For example, an close-attachment film 41 to prevent outside
air intrusion may be inserted between the outer package member 40
and the cathode lead 31. Moreover, for example, the foregoing
close-attachment film 41 may be inserted between the outer package
member 40 and the anode lead 32. The close-attachment film 41 may
include a polymer material having adhesibility with respect to both
the cathode lead 31 and the anode lead 32. Non-limiting examples of
the polymer material may include a polyolefin resin. More
specifically, the polymer material may include one or more of
polyethylene, polypropylene, modified polyethylene, and modified
polypropylene.
[0472] The cathode 33 may include, for example, a cathode current
collector 33A and a cathode active material layer 33B. The anode 34
may include, for example, an anode current collector 34A and an
anode active material layer 34B. The configurations of the cathode
current collector 33A, the cathode active material layer 33B, the
anode current collector 34A, and the anode active material layer
34B may be similar to, for example, the configurations of the
cathode current collector 21A, the cathode active material layer
21B, the anode current collector 22A, and the anode active material
layer 22B, respectively. Moreover, the configuration of the
separator 35 may be similar to, for example, the configuration of
the separator 23.
[0473] The electrolyte layer 36 may include an electrolytic
solution and a polymer compound. The configuration of the
electrolytic solution may be similar to, for example, the
configuration of the electrolytic solution in the foregoing
cylindrical type secondary battery. In other words, the
electrolytic solution may include the cyano compound. The
electrolyte layer 36 described herein may be a so-called gel
electrolyte, and the electrolytic solution may be held by the
polymer compound. The gel electrolyte achieves high ionic
conductivity (for example, 1 mS/cm or more at room temperature),
and prevents liquid leakage of the electrolytic solution. It is to
be noted that the electrolyte layer 36 may further include one or
more of other materials such as an additive.
[0474] The polymer material may include, for example, one or more
of polyacrylonitrile, polyvinylidene fluoride,
polytetrafluoroethylene, polyhexafluoropropylene, polyethylene
oxide, polypropylene oxide, polyphosphazene, polysiloxane,
polyvinyl fluoride, polyvinyl acetate, polyvinyl alcohol,
poly(methyl methacrylate), polyacrylic acid, polymethacrylic acid,
styrene-butadiene rubber, nitrile-butadiene rubber, polystyrene,
and polycarbonate. In addition thereto, the polymer material may be
a copolymer. The copolymer may be, for example, a copolymer of
vinylidene fluoride and hexafluoropylene. In particular,
polyvinylidene fluoride may be preferable as a homopolymer, and a
copolymer of vinylidene fluoride and hexafluoropylene may be
preferable as a copolymer. Such polymer compounds are
electrochemically stable.
[0475] In the electrolyte layer 36 that is a gel electrolyte, the
solvent included in the electrolytic solution refers to a wide
concept including not only a liquid material but also a material
having ionic conductivity capable of dissociating the electrolyte
salt. Hence, in a case where a polymer compound having ionic
conductivity is used, the polymer compound is also included in the
solvent.
[0476] It is to be noted that the electrolytic solution may be used
as it is instead of the electrolyte layer 36. In this case, the
spirally wound electrode body 30 (the cathode 33, the anode 34, and
the separator 35) is impregnated with the electrolytic
solution.
[0477] The secondary battery may operate as follows, for
example.
[0478] When the secondary battery is charged, lithium ions are
extracted from the cathode 33, and the extracted lithium ions are
inserted in the anode 34 through the electrolyte layer 36. In
contrast, when the secondary battery is discharged, lithium ions
are extracted from the anode 34, and the extracted lithium ions are
inserted in the cathode 33 through the electrolyte layer 36.
[0479] The secondary battery including the gel electrolyte layer 36
may be manufactured, for example, by one of the following three
procedures.
[0480] In a first procedure, first, the cathode 33 and the anode 34
may be fabricated by a fabrication procedure similar to that of the
cathode 21 and the anode 22. More specifically, the cathode 33 may
be fabricated by forming the cathode active material layers 33B on
both surfaces of the cathode current collector 33A, and the anode
34 may be fabricated by forming the anode active material layers
34B on both surfaces of the anode current collector 34A.
Subsequently, the electrolytic solution, the polymer compound, an
organic solvent, etc. may be mixed to prepare a precursor solution.
Subsequently, the cathode 33 may be coated with the precursor
solution, and the coated precursor solution may be dried to form
the gel electrolyte layer 36. Further, the anode 34 may be coated
with the precursor solution, and the coated precursor solution may
be dried to form the gel electrolyte layer 36. Subsequently, the
cathode lead 31 may be attached to the cathode current collector
33A by a method such as a welding method, and the anode lead 32 may
be attached to the anode current collector 34A by a method such as
a welding method. Subsequently, the cathode 33 and the anode 34 may
be laminated with the separator 35 in between, and thereafter, the
cathode 33, the anode 34, and the separator 35 may be spirally
wound to fabricate the spirally wound electrode body 30.
Thereafter, the protective tape 37 may be attached onto the
outermost periphery of the spirally wound electrode body 30.
Lastly, the outer package member 40 may be folded to interpose the
spirally wound electrode body 30, and thereafter, the outer edges
of the outer package member 40 may be bonded by a method such as a
thermal fusion bonding method to enclose the spirally wound
electrode body 30 in the outer package member 40. In this case, the
close-attachment film 41 may be inserted between the cathode lead
31 and the outer package member 40, and the close-attachment film
41 may be inserted between the anode lead 32 and the outer package
member 40.
[0481] In a second procedure, first, the cathode 33 and the anode
34 may be fabricated, and thereafter the cathode lead 31 may be
attached to the cathode 33, and the anode lead 32 may be attached
to the anode 34. Subsequently, the cathode 33 and the anode 34 may
be laminated with the separator 35 in between, and thereafter may
be spirally wound to fabricate a spirally wound body. Thereafter,
the protective tape 37 may be adhered to the outermost periphery of
the spirally, wound body. Subsequently, the outer package member 40
may be folded to interpose the spirally wound body, and thereafter,
the outer edges other than one side of the outer package member 40
may be bonded by a method such as a thermal fusion bonding method
to contain the spirally wound body inside a pouch formed of the
outer package member 40. Subsequently, the electrolytic solution,
monomers that are raw materials of the polymer compound, a
polymerization initiator, and, on as-necessary basis, other
materials such as a polymerization inhibitor may be mixed to
prepare a composition for electrolyte. Subsequently, the
composition for electrolyte may be injected inside the pouch formed
of the outer package member 40. Thereafter, the pouch formed of the
outer package member 40 may be hermetically sealed by a method such
as a thermal fusion bonding method. Lastly, the monomers may be
thermally polymerized to form the polymer compound. Accordingly,
the electrolytic solution may be held by the polymer compound to
form the gel electrolyte layer 36.
[0482] In a third procedure, first, the spirally wound body may be
fabricated, and then contained inside the pouch formed of the outer
package member 40 by a procedure similar to the second procedure,
except that the separator 35 in which the polymer compound layer is
provided on the base layer is used. Subsequently, the electrolytic
solution may be injected inside the pouch formed of the outer
package member 40. Thereafter, an opening of the pouch formed of
the outer package member 40 may be hermetically sealed by a method
such as a thermal fusion bonding method. Lastly, the outer package
member 40 may be heated while a weight is applied to the outer
package member 40 to cause the separator 35 to be closely attached
to the cathode 33 with the polymer compound layer in between and to
be closely attached to the anode 34 with the polymer compound layer
in between. Through this heating treatment, each of the polymer
compound layers may be impregnated with the electrolytic solution,
and each of the polymer compound layers may be gelated.
Accordingly, the electrolyte layer 36 may be formed.
[0483] In the third procedure, swollenness of the secondary battery
is suppressed more than in the first procedure. Further, in the
third procedure, for example, the non-aqueous solvent and the
monomers (the raw materials of the polymer compound) are hardly
left in the electrolyte layer 36, as compared with the second
procedure. Accordingly, the formation process of the polymer
compound is favorably controlled. As a result, each of the cathode
33, the anode 34, and the separator 35 is sufficiently and closely
attached to the electrolyte layer 36.
[0484] According to the laminated film type secondary battery, the
electrolyte layer 36 includes the electrolytic solution, and the
electrolytic solution has a configuration similar to that of the
foregoing electrolytic solution according to the embodiment of the
disclosure. This makes it possible to achieve superior battery
characteristics for a reason similar to the reason in the
cylindrical type secondary battery. Action and effects related to
the laminated film type secondary battery other than those
described above are similar to action and effects related to the
electrolytic solution according to the embodiment of the
disclosure.
[0485] Next, description is given of a secondary battery according
to another embodiment, that uses the electrolytic solution
according to the embodiment of the disclosure. The secondary
battery described herein is a cylindrical type lithium metal
secondary battery in which battery capacity (capacity of the anode
22) is obtained with use of a lithium precipitation phenomenon and
a lithium dissolution phenomenon.
[0486] The secondary battery may have a configuration similar to
that of the foregoing cylindrical type lithium-ion secondary
battery, and may be manufactured by a procedure similar to the
procedure of manufacturing the cylindrical type lithium-ion
secondary battery, except that the anode active material layer 22B
includes the lithium metal.
[0487] In the secondary battery, the lithium metal may be used as
an anode active material, which makes it possible to achieve high
energy density. The anode active material layer 22B may exist at
the time of assembling, or the anode active material layer 22B may
not necessarily exist at the time of assembling and may include the
lithium metal precipitated during charge. Further, the anode active
material layer 22B may be used as a current collector, and the
anode current collector 22A may be omitted.
[0488] The secondary battery may operate, for example, as follows.
When the secondary battery is charged, lithium ions may be
extracted from the cathode 21, and the extracted lithium ions may
be precipitated as the lithium metal on the surface of the anode
current collector 22A through the electrolytic solution. In
contrast, when the secondary battery is discharged, the lithium
metal may be eluded as lithium ions from the anode active material
layer 22B into the electrolytic solution, and may be inserted in
the cathode 21 through the electrolytic solution.
[0489] According to the cylindrical type lithium metal secondary
battery, the electrolytic solution has a configuration similar to
that of the electrolytic solution according to the embodiment of
the disclosure. This makes it possible to achieve superior battery
characteristics for a reason similar to the reason in the foregoing
cylindrical type secondary battery. Action and effects related to
the cylindrical type lithium metal secondary battery other than
those described above are similar to the action and the effects
related to the electrolytic solution according to the embodiment of
the disclosure.
[0490] It is to be noted that the lithium metal secondary battery
described herein is not limited to the cylindrical type secondary
battery, and may be a laminated film type secondary battery. Even
in this case, similar effects are achievable.
[0491] Next, description is given of application examples of any of
the secondary batteries mentioned above.
[0492] Applications of the secondary battery are not particularly
limited as long as the secondary battery is applied to, for
example, a machine, a device, an instrument, an apparatus, and a
system (a collective entity of, for example, a plurality of
devices) that are able to use the secondary battery as a driving
power source, an electric power storage source for electric power
accumulation, or any other source. The secondary battery used as
the electric power source may be a main electric power source or an
auxiliary electric power source. The main electric power source is
an electric power source used preferentially irrespective of
presence or absence of any other electric power source. The
auxiliary electric power source may be an electric power source
used instead of the main electric power source or used being
switched from the main electric power source on as-necessary basis.
In a case where the secondary battery is used as the auxiliary
power source, the kind of the main power source is not limited to
the secondary battery.
[0493] Non-limiting examples of the applications of the secondary
battery may include electronic apparatuses (including portable
electronic apparatuses) such as a video camcorder, a digital still
camera, a mobile phone, a notebook personal computer, a cordless
phone, a headphone stereo, a portable radio, a portable television,
and a portable information terminal. Further non-limiting examples
thereof may include: a mobile lifestyle appliance such as an
electric shaver; a storage device such as a backup electric power
source and a memory card; an electric power tool such as an
electric drill and an electric saw; a battery pack used as an
attachable and detachable electric power source of, for example, a
notebook personal computer; a medical electronic apparatus such as
a pacemaker and a hearing aid; an electric vehicle such as an
electric automobile (including a hybrid automobile); and an
electric power storage system such as a home battery system for
accumulation of electric power for, for example, emergency. It goes
without saying that the secondary battery may be employed for an
application other than the applications mentioned above.
[0494] In particular, the secondary battery may be effectively
applicable to, for example, the battery pack, the electric vehicle,
the electric power storage system, the electric power tool, and the
electronic apparatus. In these applications, superior battery
characteristics are demanded, and using the secondary battery of
any of the embodiments of the disclosure makes it possible to
effectively improve performance. It is to be noted that the battery
pack is an electric power source that uses the secondary battery,
and may use, for example, a single battery and an assembled
battery, as described later. The electric vehicle is a vehicle that
operates (runs) using the secondary battery as a driving electric
power source, and may be an automobile (such as a hybrid
automobile) that includes together a drive source other than the
secondary battery, as described above. The electric power storage
system is a system that uses the secondary battery as an electric
power storage source. For example, in a home electric power storage
system, electric power is accumulated in the secondary battery that
is the electric power storage source, which makes it possible to
use, for example, home electric products with use of the
accumulated electric power. The electric power tool is a tool in
which a movable section (such as a drill) is allowed to be moved
with use of the secondary battery as a driving electric power
source. The electronic apparatus is an apparatus that executes
various functions with use of the secondary battery as a driving
electric power source (an electric power supply source).
[0495] Hereinafter, specific description is given of some
application examples of the secondary battery. It is to be noted
that configurations of the respective application examples
described below are mere examples, and may be changed as
appropriate.
[0496] FIG. 13 illustrates a perspective configuration of a battery
pack using a single battery. FIG. 14 illustrates a block
configuration of the battery pack illustrated in FIG. 13. It is to
be noted that FIG. 13 illustrates the battery pack in an exploded
state.
[0497] The battery pack described herein is a simple battery pack
using one secondary battery (a so-called soft pack), and may be
mounted in, for example, an electronic apparatus typified by a
smartphone. For example, the battery pack may include an electric
power source 111 that is the laminated film type secondary battery,
and a circuit board 116 coupled to the electric power source 111,
as illustrated in FIG. 13. A cathode lead 112 and an anode lead 113
may be attached to the electric power source 111.
[0498] A pair of adhesive tapes 118 and 119 may be adhered to both
side surfaces of the electric power source 111. A protection
circuit module (PCM) may be provided in the circuit board 116. The
circuit board 116 may be coupled to the cathode lead 112 through a
tab 114, and be coupled to the anode lead 113 through a tab 115.
Moreover, the circuit board 116 may be coupled to a lead 117
provided with a connector for external connection. It is to be
noted that while the circuit board 116 is coupled to the electric
power source 111, the circuit board 116 may be protected by a label
120 and an insulating sheet 121. The label 120 may be used to fix
the circuit board 116, the insulating sheet 121, etc.
[0499] Moreover, for example, the battery pack may include the
electric power source 111 and the circuit board 116 as illustrated
in FIG. 14. The circuit board 116 may include, for example, a
control section 121, a switch section 122, a PTC device 123, and a
temperature detection section 124. The electric power source 111
may be connectable to outside through a cathode terminal 125 and an
anode terminal 127, and may be thereby charged and discharged
through the cathode terminal 125 and the anode terminal 127. The
temperature detection section 124 may detect a temperature with use
of a temperature detection terminal (a so-called T terminal)
126.
[0500] The control section 121 may control an operation of the
entire battery pack (including a used state of the electric power
source 111), and may include, for example, a central processing
unit (CPU) and a memory.
[0501] For example, in a case where a battery voltage reaches an
overcharge detection voltage, the control section 121 may so cause
the switch section 122 to be disconnected that a charge current
does not flow into a current path of the electric power source 111.
Moreover, for example, in a case where a large current flows during
charge, the control section 121 may cause the switch section 122 to
be disconnected, thereby blocking the charge current.
[0502] In contrast, for example, in a case where the battery
voltage reaches an overdischarge detection voltage, the control
section 121 may so cause the switch section 122 to be disconnected
that a discharge current does not flow into the current path of the
electric power source 111. Moreover, for example, in a case where a
large current flows during discharge, the control section 121 may
cause the switch section 122 to be disconnected, thereby blocking
the discharge current.
[0503] It is to be noted that the overcharge detection voltage is
not particularly limited, but may be, for example, 4.2 V+0.05 V,
and the overdischarge detection voltage is not particularly
limited, but may be, for example, 2.4 V.+-.0.1 V.
[0504] The switch section 122 may switch the used state of the
electric power source 111, that is, presence or absence of
connection of the electric power source 111 to an external device
in accordance with an instruction from the control section 121. The
switch section 122 may include, for example, a charge control
switch and a discharge control switch. The charge control switch
and the discharge control switch each may be, for example, a
semiconductor switch such as a field-effect transistor using a
metal oxide semiconductor (MOSFET). It is to be noted that the
charge current and the discharge current may be detected on the
basis of on-resistance of the switch section 122.
[0505] The temperature detection section 124 may measure a
temperature of the electric power source 11, and output a result of
the measurement to the control section 121. The temperature
detection section 124 may include, for example, a temperature
detecting element such as a thermistor. It is to be noted that the
result of the measurement by the temperature detection section 124
may be used, for example, in a case where the control section 121
performs charge and discharge control at the time of abnormal heat
generation and in a case where the control section 121 performs a
correction process at the time of calculating remaining
capacity.
[0506] It is to be noted that the circuit board 116 may not include
the PTC device 123. In this case, a PTC device may be separately
attached to the circuit board 116.
[0507] FIG. 15 illustrates a block configuration of a battery pack
using an assembled battery.
[0508] For example, the battery pack may include a control section
61, an electric power source 62, a switch section 63, a current
measurement section 64, a temperature detection section 65, a
voltage detection section 66, a switch control section 67, a memory
68, a temperature detection device 69, a current detection
resistance 70, a cathode terminal 71, and an anode terminal 72 in a
housing 60. The housing 60 may include, for example, a plastic
material.
[0509] The control section 61 may control an operation of the
entire battery pack (including a used state of the electric power
source 62). The control section 61 may include, for example, a CPU.
The electric power source 62 may be, for example, an assembled
battery that includes two or more secondary batteries. The
secondary batteries may be connected in series, in parallel, or in
series-parallel combination. To give an example, the electric power
source 62 may include six secondary batteries in which two sets of
series-connected three batteries are connected in parallel to each
other.
[0510] The switch section 63 may switch the used state of the
electric power source 62, that is, presence or absence of
connection of the electric power source 62 to an external device in
accordance with an instruction from the control section 61. The
switch section 63 may include, for example, a charge control
switch, a discharge control switch, a charging diode, and a
discharging diode. The charge control switch and the discharge
control switch each may be, for example, a semiconductor switch
such as a field-effect transistor that uses a metal oxide
semiconductor (a MOSFET).
[0511] The current measurement section 64 may measure a current
with use of the current detection resistance 70, and output a
result of the measurement to the control section 61. The
temperature detection section 65 may measure a temperature with use
of the temperature detection device 69, and output a result of the
measurement to the control section 61. The result of the
temperature measurement may be used, for example, in a case where
the control section 61 performs charge and discharge control at the
time of abnormal heat generation and in a case where the control
section 61 performs a correction process at the time of calculating
remaining capacity. The voltage detection section 66 may measure a
voltage of the electric power source 62 (the secondary batteries),
and supply, to the control section 61, a result of the measurement
of the voltage having subjected to analog-to-digital
conversion.
[0512] The switch control section 67 may control an operation of
the switch section 63 in accordance with signals inputted from the
current measurement section 64 and the voltage detection section
66.
[0513] For example, in a case where a battery voltage reaches an
overcharge detection voltage, the switch control section 67 may so
cause the switch section 63 (the charge control switch) to be
disconnected that a charge current does not flow into a current
path of the electric power source 62. This makes it possible to
perform only discharge through the discharging diode in the
electric power source 62. It is to be noted that, for example, in a
case where a large current flows during charge, the switch control
section 67 may block the charge current.
[0514] Further, for example, in a case where the battery voltage
reaches an overdischarge detection voltage, the switch control
section 67 may so cause the switch section 63 (the discharge
control switch) to be disconnected that a discharge current does
not flow into the current path of the electric power source 62.
This makes it possible to perform only charge through the charging
diode in the electric power source 62. It is to be noted that, for
example, in a case where a large current flows during discharge,
the switch control section 67 may block the discharge current.
[0515] It is to be noted that the overcharge detection voltage is
not particularly limited, but may be, for example, 4.2 V.+-.0.05 V,
and the overdischarge detection voltage is not particularly
limited, but may be, for example, 2.4 V.+-.0.1 V.
[0516] The memory 68 may include, for example, an EEPROM that is a
non-volatile memory. The memory 68 may hold, for example, numerical
values calculated by the control section 61 and information of the
secondary battery measured in a manufacturing process (such as
internal resistance in an initial state). It is to be noted that,
in a case where the memory 68 holds full charge capacity of the
secondary battery, the control section 61 is allowed to comprehend
information such as remaining capacity.
[0517] The temperature detection device 69 may measure a
temperature of the electric power source 62, and output a result of
the measurement to the control section 61. The temperature
detection device 69 may include, for example, a thermistor.
[0518] The cathode terminal 71 and the anode terminal 72 are
terminals that may be coupled to, for example, an external device
(such as a notebook personal computer) driven with use of the
battery pack or an external device (such as a battery charger) used
for charge of the battery pack. The electric power source 62 may be
charged and discharged via the cathode terminal 71 and the anode
terminal 72.
[0519] FIG. 16 illustrates a block configuration of a hybrid
automobile that is an example of an electric vehicle.
[0520] The electric vehicle may include, for example, a control
section 74, an engine 75, an electric power source 76, a driving
motor 77, a differential 78, an electric generator 79, a
transmission 80, a clutch 81, inverters 82 and 83, and various
sensors 84 in a housing 73 made of metal. In addition thereto, the
electric vehicle may include, for example, a front drive shaft 85
and a front tire 86 that are coupled to the differential 78 and the
transmission 80, and a rear drive shaft 87, and a rear tire 88.
[0521] The electric vehicle may be runnable with use of one of the
engine 75 and the motor 77 as a drive source, for example. The
engine 75 is a main power source, and may be, for example, a petrol
engine. In a case where the engine 75 is used as the power source,
drive power (torque) of the engine 75 may be transferred to the
front tire 86 or the rear tire 88 via the differential 78, the
transmission 80, and the clutch 81 that are drive sections, for
example. It is to be noted that the torque of the engine 75 may be
also transferred to the electric generator 79. With use of the
torque, the electric generator 79 may generate alternating-current
electric power. The generated alternating-current electric power
may be converted into direct-current electric power via the
inverter 83, and the direct-current electric power is accumulated
in the electric power source 76. In a case where the motor 77 that
is a conversion section is used as the power source, electric power
(direct-current electric power) supplied from the electric power
source 76 is converted into alternating-current electric power via
the inverter 82, and the motor 77 is driven with use of the
alternating-current electric power. Drive power (torque) obtained
by converting the electric power by the motor 77 may be transferred
to the front tire 86 or the rear tire 8 via the differential 78,
the transmission 80, and the clutch 81 that are the drive sections,
for example.
[0522] It is to be noted that in a case where speed of the electric
vehicle is reduced by a brake mechanism, resistance at the time of
speed reduction may be transferred to the motor 77 as torque, and
the motor 77 may generate alternating-current electric power by
utilizing the torque. It may be preferable that this
alternating-current electric power be converted into direct-current
electric power via the inverter 82, and the direct-current
regenerative electric power be accumulated in the electric power
source 76.
[0523] The control section 74 may control an operation of the
entire electric vehicle, and may include, for example, a CPU. The
electric power source 76 includes one or more secondary batteries.
The electric power source 76 may be coupled to an external electric
power source. In this case, the electric power source 76 may be
allowed to accumulate electric power by receiving electric power
supply from the external power source. The various sensors 84 may
be used, for example, for control of the number of revolutions of
the engine 75 and for control of an opening level (a throttle
opening level) of a throttle valve. The various sensors 84 may
include, for example, a speed sensor, an acceleration sensor, and
an engine frequency sensor.
[0524] It is to be noted that, although the description has been
given with reference to an example in which the electric vehicle is
the hybrid automobile, the electric vehicle may be a vehicle (an
electric automobile) that operates with use of only the electric
power source 76 and the motor 77 and without using the engine
75.
[0525] FIG. 17 illustrates a block configuration of an electric
power storage system.
[0526] The electric power storage system may include, for example,
a control section 90, an electric power source 91, a smart meter
92, and a power hub 93 inside a house 89 such as a general
residence or a commercial building.
[0527] In this example, the electric power source 91 may be coupled
to an electric device 94 provided inside the house 89 and may be
allowed to be coupled to an electric vehicle 96 parked outside the
house 89, for example. Further, for example, the electric power
source 91 may be connectable to a private power generator 95
provided in the house 89 via the power hub 93, and may be
connectable to an outside concentrating electric power system 97
via the smart meter 92 and the power hub 93.
[0528] It is to be noted that the electric device 94 may include,
for example, one or more home electric products. Non-limiting
examples of the home electric products may include a refrigerator,
an air conditioner, a television, and a water heater. The private
power generator 95 may include, for example, one or more of a solar
power generator, a wind power generator, and other power
generators. The electric vehicle 96 may include, for example, one
or more of an electric automobile, an electric motorcycle, a hybrid
automobile, and other electric vehicles. The concentrating electric
power system 97 may include, for example, one or more of a thermal
power plant, an atomic power plant, a hydraulic power plant, a wind
power plant, and other power plants.
[0529] The control section 90 may control an operation of the
entire electric power storage system (including a used state of the
electric power source 91), and may include, for example, a CPU. The
electric power source 91 includes one or more secondary batteries.
The smart meter 92 may be an electric power meter that is
compatible with a network and is provided in the house 89 demanding
electric power, and may be communicable with an electric power
supplier, for example. Accordingly, for example, while the smart
meter 92 communicates with outside, the smart meter 92 may control
balance between supply and demand in the house 89, which allows for
effective and stable energy supply.
[0530] In the electric power storage system, for example, electric
power may be accumulated in the electric power source 91 from the
concentrating electric power system 97, that is an external
electric power source, via the smart meter 92 and the power hub 93,
and electric power may be accumulated in the electric power source
91 from the private power generator 95, that is an independent
electric power source, via the power hub 93. The electric power
accumulated in the electric power source 91 may be supplied to the
electric device 94 and the electric vehicle 96 in accordance with
an instruction from the control section 90. This allows the
electric device 94 to be operable, and allows the electric vehicle
96 to be chargeable. In other words, the electric power storage
system is a system that makes it possible to accumulate and supply
electric power in the house 89 with use of the electric power
source 91.
[0531] The electric power accumulated in the electric power source
91 is allowed to be utilized optionally. Hence, for example,
electric power may be accumulated in the electric power source 91
from the concentrating electric power system 97 in the middle of
night when an electric rate is inexpensive, and the electric power
accumulated in the electric power source 91 may be used during
daytime hours when the electric rate is expensive.
[0532] It should be understood that the foregoing electric power
storage system may be provided for each household (each family
unit), or may be provided for a plurality of households (a
plurality of family units).
[0533] FIG. 18 illustrates a block configuration of an electric
power tool.
[0534] The electric power tool described herein may be, for
example, an electric drill. The electric power tool may include a
control section 99 and an electric power source 100 inside a tool
body 98, for example. A drill section 101 that is a movable section
may be attached to the tool body 98 in an operable (rotatable)
manner, for example.
[0535] The tool body 98 may include, for example, a plastic
material. The control section 99 may control an operation of the
entire electric power tool (including a used state of the electric
power source 100), and may include, for example, a CPU. The
electric power source 100 includes one or more secondary batteries.
The control section 99 may allow electric power to be supplied from
the electric power source 100 to the drill section 101 in
accordance with an operation by an operation switch.
EXAMPLES
[0536] Function of malonate-based, diketone-based, ketoester-based
or ester-based electrolyte additives and the systhesis procedure
thereof are demonstrated by the following examples. Following cells
were prepared and characterized in order to examine the influence
of the additives on the battery characteristics.
Example 1: Malonate-Based Additives Cell type:
[0537] Anode active material: Si(Gr)-composite [0538] Cathode
active material: LiCoO.sub.2 [0539] Electrolyte: 1 M LiPF.sub.6 in
EC/EMC (30/70 w)
[0540] Table 1 summarizes the influence of malonate-based additives
on the initial Coulomb efficiency of Si/LCO-cells after the first
charge/discharge cycle
TABLE-US-00001 TABLE 1 Initial coulomb efficiency: First cycle
Coulomb efficiency, relative to first Content of cycle Coulomb
efficiency Compound name additive with blank electrolyte of
additive Formula (% wt) (with no additive) Blank electrolyte n.a. 0
1 (no additive) Dimethylfluoro- malonate ##STR00050## 1 1.04
Diethylfluoro- malonate ##STR00051## 1 1.03 Dimethyl-2-(2-
cyanoethyl)-2- fluoromalonate ##STR00052## 1 1.02 Bis[2,2,2-
trifluoroethyl] 2-fluoromalonate ##STR00053## 1 1.01
Bis[4,4,4,3,3,- pentafluorobutyl] 2-fluoromalonate ##STR00054## 1
1.01
[0541] Improvement of the first cycle Coulomb efficiency, relative
to first cycle Coulomb efficiency with blank electrolyte, was
observed in the presence of 1 wt % of the selected additives
dimethylfluoromalonate, diethylfluoromalonate,
dimethyl-2-(2-cyanoethyl)-2-fluoromalonate,
bis[2,2,2-trifluoroethyl] 2-fluoromalonate and
bis[4,4,4,3,3,-pentafluorobutyl]2-fluoromalonate.
Example 2: Synthesis Procedure
[0542] Experimental procedure--Synthesis of dimethyl fluoromalonate
(in accordance with A. Harsanyi, G. Sandford, "fluorine gas for
life science syntheses: green metrics to assess selective direct
fluorination for the synthesis of 2-fluoromalonate esters", Green
Chem., 2015, 17, 3000-3009.):
[0543] Dimethyl malonate (22.85 mL, 200 mmol) and copper nitrate
hydrate (Cu(NO.sub.3).sub.2.2.5 H.sub.2O, 4.65 g, 20 mmol) were
dissolved in acetonitrile (100 mL) and placed in a 250 mL
fluorination vessel.
[0544] The reaction mixture was cooled to approx. 2.degree. C.,
stirred at 650 rpm using an overhead stirrer and, after purging the
system with N2 for 5 minutes, fluorine gas (20% v/v in N2, 80 mL
min-1, 235 mmol) was introduced into the solution for 5 hours and
30 minutes.
[0545] The reactor was purged with N2 for 10 minutes, the solvent
removed in vacuo, the residue portioned between water (50 mL) and
ethyl acetate (50 mL) and the aqueous layer was extracted with
ethyl acetate (50 mL).
[0546] The combined organic layers were washed with saturated
iNaHCO3 (3.times.20 mL) and brine 3.times.20 mL) and then dried
over MgSO.sub.4. The solvent was removed in vacuo leaving crude
product. The crude product was purified via vacuum distillation to
give di methyl 2-fluoromalonate (17.28 g, 58% yield, 99% purity) as
clear, transparent oil.
[0547] Spectroscopic measurements gave the following peaks:
.delta.H NMR (CDCl.sub.3, 400 MHz): 5.32 (1H, d, .sup.2J=48.1 Hz,
CFH), 3.88 (6H, s, CH.sub.3); .delta..sub.F, (CDCl.sub.3, 376 MHz):
-195.21 (d, .sup.2J.sub.HF 48.1, CHF); .delta.c (CDCl.sub.3, 101
MHz): 164.42 (d, .sup.3J.sub.CF24.1, C.dbd.O), 85.27 (d,
.sup.2J.sub.CF 197.3, CF), 53.54 (CH.sub.3); m/z (GC-EI.sup.+), 151
(9%, [M+H].sup.+), 119 (36%, [M-CH.sub.3O].sup.+), 91 (51%),
[M-CO.sub.2CH.sub.3].sup.+), 59 (100%,
[M-CHFCO.sub.2CH.sub.3].sup.+).
[0548] In the following, description is given of examples of the
disclosure.
Experimental Examples 1 to 11
[0549] The laminated film type secondary batteries as illustrated
in FIGS. 11 and 12 were fabricated by the following procedure.
[0550] The cathode 33 was fabricated as follows. First, 91 parts by
mass of a cathode active material (lithium cobalt oxide
(LiCoO.sub.2)), 3 parts by mass of a cathode binder (polyvinylidene
fluoride), and 6 parts by mass of a cathode conductor (graphite)
were mixed to obtain a cathode mixture. Subsequently, the cathode
mixture was put into an organic solvent (N-methyl-2-pyrrolidone),
and thereafter, the organic solvent was stirred to prepare paste
cathode mixture slurry. Subsequently, both surfaces of the cathode
current collector 33A (a strip-shaped aluminum foil having a
thickness of 12 .mu.m) were coated with the cathode mixture slurry
with use of a coating apparatus, and thereafter, the cathode
mixture slurry was dried to form the cathode active material layers
33B. Lastly, the cathode active material layers 33B were
compression-molded with use of a roll pressing machine.
[0551] The anode 34 was fabricated as follows. First, 95 parts by
mass of an anode active material (graphite having a median diameter
D50 of 20 .mu.m) and 5 parts by mass of an anode binder
(polyvinylidene fluoride) were mixed to obtain an anode mixture.
Subsequently, the anode mixture was put into an organic solvent
(N-methyl-2-pyrrolidone), and thereafter, the organic solvent was
stirred to obtain paste anode mixture slurry. Subsequently, both
surfaces of the anode current collector 34A (a strip-shaped copper
foil having a thickness of 15 .mu.m) were coated with the anode
mixture slurry with use of a coating apparatus, and thereafter, the
anode mixture slurry was dried to form the anode active material
layers 34B. Lastly, the anode active material layers 34B were
compression-molded with use of a roll pressing machine.
[0552] An electrolytic solution was prepared as follows. An
electrolyte salt (lithium hexafluorophosphate (LiPF.sub.6)) was
added to a solvent (ethylene carbonate and propylene carbonate),
and the solvent was stirred. Thereafter, another solvent (vinylene
carbonate (VC) that was unsaturated cyclic carbonate ester) and a
cyano compound (each of the compounds represented by the formulas
(1-3) to (1-5)) were further added to the solvent, and the solvent
was stirred. In this case, a mixture ratio (weight ratio) of the
solvent was ethylene carbonate:propylene carbonate=50:50, and a
content of the electrolyte salt was 1 mol/kg with respect to the
solvent. A content (wt %) of the unsaturated cyclic carbonate ester
in the electrolytic solution and a content (wt %) of the cyano
compound in the electrolytic solution are as illustrated in Table
1.
[0553] In this case, for comparison, an electrolytic solution was
prepared by a similar procedure, except that the cyano compound was
not used. Moreover, for comparison, an electrolytic solution was
prepared by a similar procedure, except that another compound (each
of the compounds represented by the formulas (14-1) and (14-2)) was
used in place of the cyano compound. The kind of the other compound
and the content of the other compound in the electrolytic solution
are as illustrated in Table 1.
[0554] Herein, as the compound represented by the formula (14-1), a
compound available from Astatech, Inc. was used. In contrast, a
procedure of synthesizing the compounds represented by the formulas
(1-3) to (1-5) and (14-2) are as follows.
[0555] The compound represented by the formula (1-3) was
synthesized as follows. First, a solution in which 0.01 g of sodium
methoxide was dissolved in 20 ml (=20 dm.sup.3) of methanol was
prepared, and thereafter, 0.3 g of dimethyl fluoromalonate was
added to the solution. Subsequently, 0.52 g of acrylonitrile was
added to the solution, and thereafter, the solution (at a
temperature of 60.degree. C.) was stirred (for a stirring time of 1
hour). Next, a solvent was removed from the solution in a vacuum
atmosphere to obtain a residue. Subsequently, 30 ml of water was
added to the residue three times to disperse the residue. Next, the
residue was extracted with use of 30 ml of ethyl acetate three
times, and thereafter, the residue was washed with use of 30 ml of
salt water three times. Subsequently, the residue was dried with
use of magnesium sulfate (MgSO.sub.4), and thereafter, the dried
residue was concentrated in a vacuum atmosphere to obtain a yellow
oily component. Next, the oily component was distilled with use of
a kugelrohr to obtain a compound A (dimethyl
2-(2-cyanoethyl)-2-fluoromalonate) (a synthesization amount of 0.24
g and 59% yield). Subsequently, 5 g of the compound A, 2.09 g of
lithium chloride, and 0.58 g of water was added to 100 ml of
dimethylsulfoxide to obtain a reaction mixture. Next, the reaction
mixture was heated to a temperature of 110.degree. C., and
thereafter, the reaction mixture was kept at the temperature (for a
keeping time of 1.5 hours). Subsequently, 300 ml of water was added
to the reaction mixture, and thereafter, extraction was performed
with use of 50 ml of diethyl ether six times to sort an organic
layer. Next, the organic layer was washed with use of 30 ml of
water three times, and thereafter, the organic layer was washed
with use of 30 ml of salt water three times. Subsequently, the
organic layer was dried with use of magnesium sulfate, and
thereafter, the solvent was removed from the organic layer in a
vacuum atmosphere to obtain a crude product. Lastly, the crude
product was distilled with use of a kugelrohr (at 110.degree. C.
and 15 mbar) to obtain the compound represented by the formula
(1-3) (a synthesization amount of 1.64 g and 46% yield).
[0556] Analysis of the compound represented by the formula (1-3)
synthesized by the procedure described above with use of a nuclear
magnetic resonance (NMR) apparatus gave the following result
(1N.sup.-MR spectrum).
[0557] .delta.H (CDCl.sub.3, 400 MHz) 5.04 (1H, ddd, 2JHF=48.3 Hz,
3JHH=7.9 Hz, 3JHH=4.0 Hz, CFH), 3.84 (3H, s, CH.sub.3), 2.64-2.49
(2H, m, CFHCH.sub.2), 2.42-2.18 (2H, m, CH.sub.2CN); .delta.F
(CDCl.sub.3, 376 MHz)-194.70 (ddd, 2JHF=48.4 Hz, 3JHF=26.1 Hz,
3JHF=20.5 Hz); .delta.C (CDCl.sub.3, 101 MHz) 168.66 (d, 2JCF=23.3
Hz, C.dbd.O), 118.02 (s, CN), 86.56 (d, 1JCF=187.0 Hz, CT), 52.79
(s, CH.sub.3), 28.32 (d, 2JCF=21.3 Hz, CHF--CH.sub.2), 12.74 (d,
3JCF=4.7 Hz, CH.sub.2--CN)
[0558] Moreover, a result (GCEI+) of analysis of the compound
represented by the formula (1-3) with use of a gas chromatograph
mass spectrometer (GCMS) was m/z=146.1 (1%, [M+H]+), 114.1 (5%,
[M-OCH.sub.3]+), 86.1 (21%, [M-O.sub.2CH.sub.3]+).
[0559] In a case where the compound represented by the formula
(1-4) was synthesized, a procedure similar to that in the case
where the compound represented by the formula (1-3) was synthesized
was performed (33% yield), except that bromobutyronitrile was used
in place of acrylonitrile, and 3 g of a compound B (dimethyl
2-(3-cyanopropyl)-2-fluoromalonate) was obtained in place of 5 g of
the compound A (dimethyl 2-(2-cyanoethyl)-2-fluoromalonate).
[0560] In a case where the compound represented by the formula
(1-5) was synthesized, a procedure similar to that in the case
where the compound represented by the formula (1-3) was synthesized
was performed (33% yield), except that bromopentylonitrile was used
in place of acrylonitrile, and 3 g of a compound C (dimethyl
2-(3-cyanobutyl)-2-fluoromalonate) was obtained in place of 5 g of
(dimethyl 2-(2-cyanoethyl)-2-fluoromalonate).
[0561] The compound represented by the formula (14-2) was
synthesized as follows. First, a solution in which 22.85 ml of
dimethyl malonate and 4.65 g of copper (II) nitrate hydrate was
dissolved in 100 ml of acetonitrile was put into a 250 ml
fluorination vessel to obtain a reaction mixture. Subsequently, the
reaction mixture was cooled to a temperature of about 2.degree. C.,
and thereafter, the reaction mixture was stirred (a rotation speed
of 650 rpm) with use of an overhead stirrer. Next, purging from the
fluorination vessel was performed with use of nitrogen gas (for 5
minutes), and thereafter, fluorine gas (20 vol % in nitrogen, 235
mmol) was introduced into the fluorination vessel (at a flow
velocity of 80 mi/min for an introduction time of 5.5 hours).
Subsequently, the solvent was removed from the reaction mixture in
a vacuum atmosphere to obtain residue. Next, the residue was
separated and extracted with use of 50 ml of water and 50 ml of
ethyl acetate, and thereafter, an aqueous layer was extracted with
use of 50 ml of ethyl acetate. Subsequently, an organic layer was
washed with use of 20 ml of a saturated sodium hydrogen carbonate
(NaHCO.sub.3) water solution three times, and thereafter, the
organic layer was washed with use of 20 ml of salt water three
times. Next, the organic layer was dried with use of magnesium
sulfate, and thereafter, the solvent was removed from the organic
layer in a vacuum atmosphere to obtain a crude product. Lastly, the
crude product was distilled with use of a kugelrohr (at 110.degree.
C. and 15 mbar) to obtain the compound represented by the formula
(14-2) (a synthesization amount of 17.28 g and 58% yield).
[0562] Analysis of the compound represented by the formula (14-2)
synthesized by the procedure described above with use of a nuclear
magnetic resonance (NMR) apparatus gave the following result (NMR
spectrum).
[0563] .delta.H (CDCl.sub.3, 400 MHz) 5.32 (1H, d, 2JHF 48.1 Hz,
CFH), 3.88 (6H, s, CH.sub.3); .delta.F (CDCl3, 376 MHz)-195.21 (d,
2JHF 48.1, CHF); .delta.C (CDCl3, 101 MHz) 164.42 (d, 3JCF 24.1,
C.dbd.O), 85.27 (d, 2JCF 197.3, CF), 53.54 (CH.sub.3)
[0564] Moreover, a result (GCEI+) of analysis of the compound
represented by the formula (14-2) with use of a gas chromatograph
mass spectrometer (GCMS) was mlz=151 (9%, [M+H]+), 119 (36%,
[M-CH.sub.3O]+), 91 (51%, [M-CO.sub.2CH.sub.3]+), 59 (100%,
[M-CHFCO.sub.2CH.sub.3]+).
[0565] The secondary battery was assembled as follows. First, the
cathode lead 31 made of aluminum was attached to the cathode
current collector 33A by welding, and the anode lead 32 made of
copper was attached to the anode current collector 34A by welding.
Subsequently, the cathode 33 and the anode 34 were laminated with
the separator 35 (a microporous polyethylene film having a
thickness of 15 .mu.m) in between to obtain a laminated body. Next,
the laminated body was spirally wound in a longitudinal direction,
and the protective tape 37 was attached onto the outermost
periphery of the spirally wound laminated body to fabricate a
spirally wound body. Lastly, the outer package member 40 (outside:
a nylon film having a thickness of 25 .mu.m/an aluminum foil having
a thickness of 40 .mu.m/a polypropylene film having a thickness of
30 .mu.m: inside) was folded to interpose the spirally wound body,
and thereafter, the outer edges on three sides of the outer package
member 40 were thermally fusion-bonded to form a pouch. In this
case, the close-attachment film 41 was inserted between the cathode
lead 31 and the outer package member 40, and the close-attachment
film 41 was inserted between the anode lead 32 and the outer
package member 40. Lastly, the electrolytic solution was injected
inside the pouch formed of the outer package member 40 to
impregnate the spirally wound body with the electrolytic solution,
and thereafter, outer edges on the remaining one side of the outer
package member 40 were thermally fusion-bonded in a
reduced-pressure environment.
[0566] Thus, the spirally wound electrode body 30 was formed, and
the spirally wound electrode body 30 was sealed inside the outer
package member 40 to complete the laminated film type secondary
battery. In a case where the secondary battery was fabricated, the
amount of the cathode active material and the amount of the anode
active material were adjusted to cause a voltage (so-called battery
voltage) at a fully charged state to be 4.45 V,
[0567] Swollenness characteristics after storage and electrical
resistance characteristics after storage were examined to evaluate
battery characteristics of the secondary batteries, and results
illustrated in Table 1 were thereby obtained.
[0568] The swollenness characteristics were examined as follows.
First, each of the secondary batteries were charged and discharged
in an ordinary temperature environment (at a temperature of
23.degree. C.) to stabilize the state of each of the secondary
batteries. Subsequently, each of the secondary batteries was
charged in the same environment, and thereafter, a thickness (a
thickness before storage) of each of the secondary batteries was
measured. Next, each of the secondary batteries in a charged state
was stored for 200 h in a high temperature environment (at a
temperature of 60.degree. C.), and thereafter, the thickness
(thickness after storage) of each of the secondary batteries was
measured. Subsequently, a swollenness rate (%) after storage=[(the
thickness after storage-the thickness before storage)/the thickness
before storage].times.100 was calculated. Lastly, the swollenness
rate after storage was evaluated. In this case, a case where the
swollenness rate after storage is equal to or smaller than 30% is
"A", a case where the swollenness rate after storage is greater
than 30% and equal to or smaller than 35% is "B", a case where the
swollenness rate after storage is greater than 35% and equal to or
smaller than 40% is "C", and a case where swollenness rate after
storage is greater than 40% is "D".
[0569] It should be understood that when each of the secondary
batteries was charged, each of the secondary batteries was charged
at a current density of 1 mA/cm.sup.2 and a constant current until
the voltage reached 4.45 V, and thereafter, each of the secondary
batteries was charged at a constant voltage of 4.45 V until the
current density reached 0.02 mA/cm.sup.2. When each of the
secondary batteries was discharged, each of the secondary batteries
was discharged at a current density of 1 mA/cm.sup.2 until the
voltage reached 3 V.
[0570] The electrical resistance characteristics after storage were
examined as follows. First, the state of each of the secondary
batteries was stabilized by the procedure described above.
Subsequently, one cycle of charge and discharge was performed on
each of the secondary batteries in an ordinary temperature
environment (at a temperature of 23.degree. C.), and thereafter,
electrical resistance (electrical resistance before storage) of
each of the secondary batteries was measured. Next, each of the
secondary batteries were stored in a high temperature environment
(at a temperature of 60.degree. C.), and thereafter, electrical
resistance (electrical resistance after storage) of each of the
secondary batteries was measured. Subsequently, an electrical
resistance ratio after storage=the electrical resistance after
storage/electrical resistance before storage was calculated. It is
to be noted that charge and discharge conditions were similar to
the charge and discharge conditions in a case where the swollenness
characteristics after storage were examined.
[0571] Table 1 shows, together with values of the swollenness rates
after storage, determination results based on the values of the
swollenness rates after storage. Moreover, a value of the
electrical resistance ratio after storage was normalized with a
value of the electrical resistance ratio after storage in an
experimental example 9 taken as 1.00.
TABLE-US-00002 TABLE 1 Electrical Resistance Swollenness
Characteristics Characteristics Cyano Compound Unsaturated Cyclic
After Storage After Storage Other Compound Carbonate Ester
Swollenness Rate Electrical Resistance Experimental Content Content
Determination After Storage Ratio After Storage Example Kind (wt %)
Kind (wt %) Result (%) (Normalized) 1 Formula 0.1 VC 1 B 35 0.99 2
(1-3) 0.5 1 A 30 0.99 3 1 1 A 29 0.99 4 3 1 A 26 1.07 5 5 1 A 22
1.50 6 Formula 1 1 A 20 0.95 7 (1-4) 1 0 A 20 1.00 8 Formula 1 1 A
12 0.94 (1-5) 9 -- -- VC 1 D 105 1.00 10 Formula 1 1 C 38 1.08
(14-1) 11 Formula 1 1 D 101 1.10 (14-2)
[0572] As can be seen from Table 1, the battery characteristics
were largely varied depending on the kind of an additive included
in the electrolytic solution. In the following, an evaluation
result (the swollenness rate after storage) and the electrical
resistance ratio after storage of the experimental example 9 in
which the electrolytic solution included neither the cyano compound
nor the other compound are regarded as comparison criteria.
[0573] More specifically, in a case where the electrolytic solution
included the other compound (experimental examples 10 and 11), the
swollenness rate after storage was slightly improved in some cases,
and the electrical resistance ratio after storage was
increased.
[0574] In contrast, in a case where the electrolytic solution
included the cyano compound (experimental examples 1 to 8),
independent of the kind of the cyano compound, the swollenness rate
after storage was largely improved, while suppressing an excessive
increase in the electrical resistance ratio after storage.
[0575] In this case, in a case where the content of the cyano
compound in the electrolytic solution was from 0.1 wt % to 5 wt %
both inclusive, the swollenness rate after storage was sufficiently
improved. In particular, in a case where the content was from 0.5
wt % to 5 wt % both inclusive, the swollenness rate after storage
was further improved. Alternatively, in a case where the content
was from 0.1 wt % to 3 wt % both inclusive, the electrical
resistance ratio after storage was further decreased while
maintaining a favorable swollenness rate after storage, and in a
case where the content was from 0.1 wt % to 1 wt % both inclusive,
the electrical resistance ratio after storage was still further
decreased while maintaining a favorable swollenness rate after
storage.
[0576] Accordingly, in a case where the content was from 0.5 wt %
to 3 wt % both inclusive, the electrical resistance ratio after
storage was thrther decreased while largely improving the
swollenness rate after storage, and in a case where the content was
from 0.5 wt % to 1 wt % both inclusive, the electrical resistance
ratio after storage was still further decreased while largely
improving the swollenness rate after storage.
[0577] Moreover, in the case where the electrolytic solution
included the unsaturated cyclic carbonate ester together with the
cyano compound, the electrical resistance ratio after storage was
further decreased while maintaining the swollenness rate after
storage.
[0578] As can be seen from the results in Table 1, in a case where
the electrolytic solution included the cyano compound, the
swollenness characteristics after storage and the electrical
resistance characteristics after storage were both improved.
Accordingly, superior battery characteristics were achieved in the
secondary battery.
[0579] Although the disclosure has been described above with
reference to some embodiments and examples, the disclosure is not
limited thereto, and may be modified in a variety of ways.
[0580] More specifically, description has been given with reference
to the cylindrical type secondary battery and the laminated film
type secondary battery; however, the secondary battery is not
limited thereto, and may be, for example, any other secondary
battery such as a square type secondary battery and a coin type
secondary battery.
[0581] Moreover, description has been given with reference to an
example in which the battery element has the spirally wound
structure. However, the structure of the battery element is not
limited thereto. For example, the battery element may have any
other structure such as a laminated structure.
[0582] Further, description has been given with reference to the
lithium-ion secondary battery and the lithium metal secondary
battery; however, the secondary battery is not limited thereto. The
secondary battery may be, for example, a secondary battery in which
capacity of an anode active material capable of inserting and
extracting lithium is set smaller than capacity of a cathode to
obtain capacity of an anode by the sum of capacity derived from a
lithium insertion phenomenon and a lithium extraction phenomenon
and capacity derived from a lithium precipitation phenomenon and a
lithium dissolution phenomenon.
[0583] Furthermore, description has been given with reference to
the secondary battery using lithium as the electrode reactant;
however, the electrode reactant is not limited to lithium. The
electrode reactant may be, for example, any of other Group 1
elements such as sodium and potassium in the long form of the
periodic table of the elements, Group 2 elements such as magnesium
and calcium in the long form of the periodic table of the elements,
and other light-metals such as aluminum.
[0584] It should be understood that the effects described in the
present specification are illustrative and non-limiting. The
disclosure may have effects other than those described in the
present specification.
[0585] In addition, the present technology can also take the
following constituent features.
[0586] (1)
[0587] A non-aqueous electrolyte for secondary batteries
including:
[0588] a polar aprotic solvent;
[0589] an alkali metal salt; and
[0590] at least one additive in which the additive is at least one
compound selected from compounds with general formula I
##STR00055##
[0591] in which Z.sub.1, Z.sub.2 is alkyl (--C.sub.nH.sub.2n+1),
cycloalkyl, alkenyl (C.sub.nH.sub.2n), aryl (--Ar), heteroaryl;
halogenated alkyl ((--C.sub.nX.sub.2n+1) or
(--CH.sub.2--C.sub.nX.sub.2n+1)), halogenated cycloalkyl
((--C.sub.nX.sub.2n) or (--CH.sub.2-C.sub.nX.sub.2n)), halogenated
alkenyl (C.sub.nX.sub.n), halogenated aryl (--Ar--X), halogenated
heteroaryl with halogen X being F, Cl, Br or I; alkoxy, aryloxy,
heteroaryloxy, halogenated aryloxy; --CN-substituted-alkyl,
-cycloalkyl, -aryl, -heteroaryl; --NO.sub.2-substituted-alkyl,
-cycloalkyl, -aryl, -heteroaryl; halogen (--F, --Cl, --Br, --I) or
nitrile (--CN);
[0592] in which X1, X2 is H; halogen X (X being F, Cl, Br, I);
halogenated alkyl, -alkenyl, -aryl, -heteroaryl;
--CN-substituted-alkyl, -alkenyl, -heteroaryl;
--NO.sub.2-substituted-alkyl, -alkenyl, -aryl or -heteroaryl;
[0593] but in which X.sub.1 and X.sub.2 are not hydrogen H
concurrently;
[0594] in which Z.sub.1 and Z.sub.2 can be equal or different;
and
[0595] in which X.sub.1 and X.sub.2 can be equal or different.
[0596] (2)
[0597] The non-aqueous electrolyte for secondary batteries
according to (1), in which the at least one additive is at least
one compound selected from compounds with general formula I-I
##STR00056##
[0598] in which R.sub.1, R.sub.2 is alkyl cycloalkyl, alkenyl
(C.sub.nH.sub.2n), aryl (--Ar), heteroaryl; halogenated alkyl
((--C.sub.nX.sub.2n+1) or (--CH.sub.2--C.sub.nX.sub.2n+1)),
halogenated cycloalkyl ((--C.sub.nX.sub.2n) or
--CH.sub.2--C.sub.nX.sub.2n)), halogenated alkenyl
(C.sub.nX.sub.n), halogenated aryl (--Ar--X) or halogenated
heteroaryl with halogen X being F, Cl, Br or I; and
[0599] in which R.sub.1 and R.sub.2 do not form a cyclic compound
together; and
[0600] in which X.sub.1, X.sub.2 is H; halogen X (X being F, Cl, Br
or I); halogenated alkyl, -alkenyl, -heteroaryl;
--CN-substituted-alkyl, -alkenyl, -aryl, -heteroaryl;
--NO.sub.2-substituted-alkyl, -alkenyl, -aryl or -heteroaryl;
[0601] in which X.sub.1 and X.sub.2 are not hydrogen H
concurrently;
[0602] in which R.sub.1, R.sub.2 can be equal or different; and
[0603] in which X.sub.1, X.sub.2 can be equal or different.
[0604] (3)
[0605] The non-aqueous electrolyte for secondary batteries
according to (1), in which the at least one additive is at least
one compound selected from compounds with general formula
##STR00057##
[0606] in which R.sub.1, R.sub.2 is alkyl (--C.sub.nH.sub.2n+1),
cycloalkyl, alkenyl (C.sub.nH.sub.2n), aryl (--Ar), heteroaryl;
halogenated alkyl ((--C.sub.nX.sub.2n+1) or
(--CH.sub.2--C.sub.nX.sub.2n+1)), halogenated cycloalkyl
((--C.sub.nX.sub.2n) or (--CH.sub.2--C.sub.nX.sub.2n)), halogenated
alkenyl (C.sub.nX.sub.n), halogenated aryl (--Ar--X), halogenated
heteroaryl with halogen X being F, Cl, Br or I;
--CN-substituted-alkyl, -cycloalkyl, -aryl, -heteroaryl;
--NO.sub.2-substituted-alkyl, -cycloalkyl, -aryl, -heteroaryl;
halogen (--F, --C1, --Br, --I) or nitrile (--CN); and in which
X.sub.1, X.sub.2 is H; halogen X (X being F, Cl, Br or I);
halogenated alkyl, -alkenyl, -aryl, -heteroaryl;
--CN-substituted-alkyl, -alkenyl, -aryl, -heteroaryl;
--NO.sub.2-substituted-alkyl, -alkenyl, -aryl or -heteroaryl;
[0607] in which R.sub.1, R.sub.2 can be equal or different; and
[0608] in which X.sub.1, X.sub.2 can be equal or different.
[0609] (4)
[0610] The non-aqueous electrolyte for secondary batteries
according to (1), in which the at least one additive is at least
one compound selected from compounds with general formula I-III
##STR00058##
[0611] in which R.sub.1 is alkyl (--C.sub.nH.sub.2n+1), cycloalkyl,
alkenyl (C.sub.nH.sub.2n), aryl (--Ar), heteroaryl; halogenated
alkyl ((--C.sub.nX.sub.2n+1) or (--CH.sub.2--C.sub.2n+1)),
halogenated cycloalkyl ((--C.sub.nX.sub.2n) or
(--CH2--C.sub.nX.sub.2n)), halogenated alkenyl (C.sub.nX.sub.n),
halogenated aryl (--Ar--X), halogenated heteroaryl with halogen X
being F, Cl, Br or I;
[0612] in which R.sub.2 is alkyl (--C.sub.nH.sub.2n+1), cycloalkyl,
alkenyl (C.sub.nH.sub.2n), aryl (--Ar), heteroaryl; halogenated
alkyl ((--C.sub.nX.sub.2n+1) or (--CH.sub.2--C.sub.nX.sub.2n+1)),
halogenated cycloalkyl ((--C.sub.nX.sub.2n) or
(--CH.sub.2--C.sub.nX.sub.2n), halogenated alkenyl
(C.sub.nX.sub.n), halogenated aryl (--Ar--X), halogenated
heteroaryl with halogen X being F, Cl, Br or I;
--CN-substituted-alkyl, -cycloalkyl, -aryl, -heteroaryl;
--NO.sub.2-substituted-alkyl, -cycloalkyl, -aryl, -heteroaryl;
halogen (--F, --Cl, --Br, --I) or nitrile (--CN); and in which
X.sub.1, X.sub.2 is H; halogen X (X being F, Cl, Br or I);
halogenated alkyl, -alkenyl, -aryl, -heteroaryl;
--CN-substituted-alkyl, -alkenyl, -aryl, -heteroaryl;
--NO.sub.2-substituted-alkyl, -alkenyl, -aryl or -heteroaryl;
[0613] in which R.sub.1, R.sub.2, can be equal or different;
and
[0614] in which X.sub.1, X.sub.2 can be equal or different.
[0615] (5)
[0616] A non-aqueous electrolyte for secondary batteries
including:
[0617] a polar aprotic solvent;
[0618] an alkali metal salt; and
[0619] at least one additive in which the additive is at least one
compound selected from compounds with general formula I-IV
##STR00059##
[0620] in which R.sub.1 is alkyl (--C.sub.nH.sub.2n+1), cycloalkyl,
alkenyl (C.sub.nH.sub.2n), aryl (--Ar), heteroaryl; halogenated
cycloalkyl ((--C.sub.nX.sub.2n) or (--CH.sub.2--C.sub.nX.sub.2n)),
halogenated alkenyl (C.sub.nX.sub.n), halogenated aryl (--Ar--X),
halogenated heteroaryl with halogen X being F, Cl, Br or I; halogen
(--F, --Cl, --Br, --I) or nitrile (--CN);
[0621] in which R.sub.2 is alkyl (--C.sub.nH.sub.2n+1), cycloalkyl,
alkenyl (C.sub.nH.sub.2n), aryl (--Ar), heteroaryl; halogenated
cycloalkyl ((--C.sub.nX.sub.2n) or (--CH.sub.2--C.sub.nX.sub.2n)),
halogenated alkenyl (C.sub.nX.sub.n), halogenated aryl (--Ar--X),
halogenated heteroaryl with halogen X being F, Cl, Br or I; alkoxy,
aryloxy, heteroaryloxy, halogenated aryloxy;
--CN-substituted-alkyl, -cycloalkyl, -aryl, -heteroaryl;
--NO.sub.2-substituted-alkyl, -cycloalkyl, -aryl, -heteroaryl;
halogen (--F, --Cl, --Br, --I) or nitrile (--CN); but in which
R.sub.1, R.sub.2 is each not a halogenated alkyl;
[0622] in which X.sub.1, X.sub.2 is H; halogen X (X being F, Cl, Br
or I); halogenated alkyl, -alkenyl, -aryl, -heteroaryl;
--CN-substituted-alkyl, -alkenyl, -aryl, -heteroaryl;
--NO.sub.2-substituted-alkyl, -alkenyl, -aryl or -heteroaryl;
[0623] but in which X.sub.1 and X2 are not hydrogen H
concurrently;
[0624] in which R.sub.1, R.sub.2 can be equal or different; and
[0625] in which X.sub.1, X.sub.2 can be equal or different.
[0626] (6)
[0627] The non-aqueous electrolyte for secondary batteries
according to any one of the preceding claims, in which the amount
of the at least one additive in the non-aqueous electrolyte is
between 0.001 and 10 wt %, preferably between 0.01 and 5 wt %, more
preferably between 0.1 and 3 wt %.
[0628] (7)
[0629] The non-aqueous electrolyte for secondary batteries
according to any one of the preceding claims, in which the amount
of the at least one additive in the non-aqueous electrolyte is
between 0.01 and 2 wt %, preferably between 0.01 and 1.8 wt %, more
preferably between 0.1 and 1.6 wt %.
[0630] (8)
[0631] The non-aqueous electrolyte for secondary batteries
according to any one of the preceding claims, in which the at least
one additive in the non-aqueous electrolyte is a mixture of
compounds selected from compounds with general formulas I-I, I-II,
or I-III.
[0632] (9)
[0633] The non-aqueous electrolyte for secondary batteries
according to any one of the preceding claims, including at least
one further additive or compound, such as, but not limited to,
vinylene carbonate, fluoroethylene carbonate,
trifluoromethylethylene carbonate, succinonitrile.
[0634] (10)
[0635] The non-aqueous electrolyte for secondary batteries
according to any one of the preceding claims, which is a liquid or
polymer-gel electrolyte.
[0636] (11)
[0637] The non-aqueous electrolyte for secondary batteries
according to any one of the preceding claims, in which the polar
aprotic solvent is particularly selected from cyclic ester
carbonate(s), chain ester carbonate(s), lactone(s), chain
carboxylic ester(s), and further polar aprotic solvents.
[0638] (12)
[0639] The non-aqueous electrolyte for secondary batteries
according to any one of the preceding claims, in which the alkali
metal salt is one or more Li salts.
[0640] (13)
[0641] A secondary battery including:
[0642] a cathode,
[0643] an anode, and
[0644] an non-aqueous electrolyte according to any one of (1) to
(12),
[0645] in which the secondary battery is particularly a secondary
Li-ion battery.
[0646] (14)
[0647] The secondary battery according to (13),
[0648] in which the cathode is an intercalation type cathode
including one or more kinds of active cathode material which is
capable of reversible inserting and extracting Li ions,
particularly including layered, spinel or olivine structure type
transition metal oxide(s), such as, but not limited to, metal(s)
selected from Co, Ni, Mn, V, Fe and combinations thereof; and/or in
which the anode is an intercalation type anode including one or
more kinds of active anode material which is capable of reversible
inserting and extracting Li ions, such as, but not limited to,
graphitizable carbon, non-graphitizable carbon, graphite, Li-metal,
Si, Si oxide, Si alloy, Sn, Sn oxide, LiTi.sub.2O.sub.5, Sn
alloy.
[0649] (15)
[0650] An electric device including a secondary battery according
to (13) or (14), in which the electric device is a battery pack, an
electric vehicle, an electric power storage system, an electric
power tool or an electronic apparatus.
[0651] (16)
[0652] Use of the non-aqueous electrolyte according to any one of
claims 1 to 12, in an electrochemical device,
[0653] such as, but not limited to, a secondary battery, a super
capacitor, an electric device,
[0654] such as, but not limited to, a battery pack, an electric
vehicle, an electric power storage system, an electric power tool,
an electronic apparatus.
[0655] (17)
[0656] A secondary battery, including:
[0657] a cathode;
[0658] an anode; and
[0659] an electrolytic solution including a cyano compound
represented by the following formula (1), [Chem, 18]
##STR00060##
[0660] where R1 is one of a monovalent hydrocarbon group and a
monovalent halogenated hydrocarbon group, R2 is one of a cyano
group, a monovalent chain hydrocarbon cyano group, and a monovalent
halogenated chain hydrocarbon cyano group, X1 is a halogen group,
X2 is one of a hydrogen group, a halogen group, a monovalent
hydrocarbon group, and a monovalent halogenated hydrocarbon
group.
[0661] (18)
[0662] The secondary battery according to (17), in which in the R2,
the monovalent chain hydrocarbon cyano group is a group in which
one or more cyano groups are introduced into an alkyl group.
[0663] (19)
[0664] The secondary battery according to (18), in which the
monovalent chain hydrocarbon cyano group is a group in which one
cyano group is introduced into an end of the alkyl group.
[0665] (20)
[0666] The secondary battery according to (19), in which number of
carbons in the alkyl group is 3 or more.
[0667] (21)
[0668] The secondary battery according to any one of (17) to (20),
in which in the R1 and the X2, the monovalent hydrocarbon group is
one of an alkyl group, an alkenyl group, an alkynyl group, a
cycloalkyl group, an aryl group, and a monovalent group in which
two or more of these groups are bound to one another, and
[0669] in the X1 and the X2, the halogen group is one of a fluorine
group, a chlorine group, a bromine group, and a iodine group.
[0670] (22)
[0671] The secondary battery according to any one of (17) to (21),
in which
[0672] the R1 is an alkyl group,
[0673] the R2 is a group in which one cyano group is introduced
into an end of an alkyl group,
[0674] the X1 is a fluorine group, and
[0675] the X2 is a hydrogen group.
[0676] (23)
[0677] The secondary battery according to any one of (17) to (22),
in which a content of the cyano compound in the electrolytic
solution is within a range from 0.1 wt % to 5 wt % both
inclusive.
[0678] (24)
[0679] The secondary battery according to any one of (17) to (23),
in which the secondary battery is a lithium-ion secondary
battery.
[0680] (25)
[0681] A secondary battery-use electrolytic solution, including a
cyano compound represented by the following formula (1),
[0682] [Chem. 19]
##STR00061##
[0683] where R1 is one of a monovalent hydrocarbon group and a
monovalent halogenated hydrocarbon group, R2 is one of a cyano
group, a monovalent chain hydrocarbon cyano group, and a monovalent
halogenated chain hydrocarbon cyano group, X1 is a halogen group,
X2 is one of a hydrogen group, a halogen group, a monovalent
hydrocarbon group, and a monovalent halogenated hydrocarbon
group.
[0684] (26)
[0685] A battery pack, including:
[0686] the secondary battery according to any one of (17) to
(24);
[0687] a control section that controls an operation of the
secondary battery; and
[0688] a switch section that switches the operation of the
secondary battery in accordance with an instruction from the
control section.
[0689] (27)
[0690] An electric vehicle, including:
[0691] the secondary battery according to any one of (17) to
(24);
[0692] a conversion section that converts electric power supplied
from the secondary battery into drive power;
[0693] a drive section that operates in accordance with the drive
power; and
[0694] a control section that controls an operation of the
secondary battery.
[0695] (28)
[0696] An electric power storage system, including:
[0697] the secondary battery according to any one of (17) to
(24);
[0698] one or more electric devices that are supplied with electric
power from the secondary battery; and
[0699] a control section that controls the supplying of the
electric power from the secondary battery to the one or more
electric devices,
[0700] (29)
[0701] An electric power tool, including:
[0702] the secondary battery according to any one of (17) to (24);
and
[0703] a movable section that is supplied with electric power from
the secondary battery.
[0704] (30)
[0705] An electronic apparatus including the secondary battery
according to any one of (17) to (24) as an electric power supply
source.
[0706] It should be understood that various changes and
modifications to the presently preferred embodiments described
herein will be apparent to those skilled in the art. Such changes
and modifications can be made without departing from the spirit and
scope of the present subject matter and without diminishing its
intended advantages. It is therefore intended that such changes and
modifications be covered by the appended claims.
* * * * *