U.S. patent application number 09/850191 was filed with the patent office on 2002-02-21 for electrolyte for electrochemical device.
Invention is credited to Sugimoto, Hiromi, Takahashi, Mikihiro, Takase, Hironari, Tsujioka, Shoichi.
Application Number | 20020022181 09/850191 |
Document ID | / |
Family ID | 27531522 |
Filed Date | 2002-02-21 |
United States Patent
Application |
20020022181 |
Kind Code |
A1 |
Tsujioka, Shoichi ; et
al. |
February 21, 2002 |
Electrolyte for electrochemical device
Abstract
The invention relates to an electrolyte for an electrochemical
device. This electrolyte includes a first compound that is an ionic
metal complex represented by the general formula (1); and at least
one compound selected from special second to fourth compounds,
fifth to ninth compounds respectively represented by the general
formulas A.sup.a+(PF.sub.6.sup.-).sub.a,
A.sup.a+(ClO.sub.4.sup.-).sub.a, A.sup.a+(BF.sub.4.sup.-).sub.a,
A.sup.a+(AsF.sub.6.sup.-).sub.a, and
A.sup.a+(SbF.sub.6.sup.-).sub.a, and special tenth to twelfth
compounds, 1 The electrolyte is superior in cycle characteristics
and shelf life as compared with conventional electrolytes.
Inventors: |
Tsujioka, Shoichi; (Saitama,
JP) ; Takase, Hironari; (Saitama, JP) ;
Takahashi, Mikihiro; (Saitama, JP) ; Sugimoto,
Hiromi; (Saitama, JP) |
Correspondence
Address: |
CROWELL & MORING LLP
INTELLECTUAL PROPERTY GROUP
P.O. BOX 14300
WASHINGTON
DC
20044-4300
US
|
Family ID: |
27531522 |
Appl. No.: |
09/850191 |
Filed: |
May 8, 2001 |
Current U.S.
Class: |
429/188 ;
252/62.2; 361/502; 361/504; 361/527; 429/307; 429/324 |
Current CPC
Class: |
Y02E 60/10 20130101;
H01M 10/0525 20130101; H01M 10/052 20130101; Y02E 60/13 20130101;
H01G 11/56 20130101; H01G 9/038 20130101; H01G 11/62 20130101; H01M
10/0568 20130101 |
Class at
Publication: |
429/188 ;
429/307; 429/324; 361/502; 361/504; 361/527; 252/62.2 |
International
Class: |
H01M 010/40; H01G
009/02; H01G 009/038 |
Foreign Application Data
Date |
Code |
Application Number |
May 8, 2000 |
JP |
2000-134926 |
Jun 9, 2000 |
JP |
2000-173094 |
Jan 30, 2001 |
JP |
2001-020898 |
Jan 30, 2001 |
JP |
2001-020899 |
Apr 16, 2001 |
JP |
2001-117170 |
Claims
What is claimed is:
1. An electrolyte for an electrochemical device, said electrolyte
comprising: a first compound that is an ionic metal complex
represented by the general formula (1); and at least one compound
selected from the group consisting of second to fourth compounds
respectively represented by the general formulas (2) to (4), fifth
to ninth compounds respectively represented by the general formulas
A.sup.a+(PF.sub.6.sup.-).sub.a, A.sup.a+(ClO.sub.4).sub.a,
A.sup.a+(BF.sub.4.sup.-).sub.a, A.sup.a+(AsF.sub.6.sup.-).sub.a,
and A.sup.a+(SbF.sub.6.sup.-).sub.a, and tenth to twelfth compounds
respectively represented by the general formulas (5) to (7),
8wherein M is a transition metal selected from the group consisting
of elements of groups 3-11 of the periodic table, or an element
selected from the group consisting of elements of groups 12-15 of
the periodic table; A.sup.3+ represents a metal ion, onium ion or
hydrogen ion; a represents a number from 0 to 8; q is 0 or 1; from
1 to 3; p is b/a; m represents a number from 1 to 4; n represents a
number from 0 to 8; q is 0 or 1; X.sup.1 represents O, S, NR.sup.5
or NR.sup.5R.sup.6; each of R.sup.1 and R.sup.2 independently
represents H, a halogen, a C.sub.1-C.sub.10 alkyl group or
C.sub.1-C.sub.10 halogenated alkyl group; R.sup.3 represents a
C.sub.1-C.sub.10 alkylene group, C.sub.1-C.sub.10 halogenated
alkylene group, C.sub.4-C.sub.20 arylene group or C.sub.4-C.sub.20
halogenated arylene group, these alkylene and arylene groups of
said R.sup.3 optionally having substituents and hetero atoms, one
of said R.sup.3 being optionally bonded with another of said
R.sup.3; R.sup.4 represents a halogen, C.sub.1-C.sub.10 alkyl
group, C.sub.1-C.sub.10 halogenated alkyl group, C.sub.4-C.sub.20
aryl group, C.sub.4-C.sub.20 halogenated aryl group or
X.sup.2R.sup.7, these alkyl and aryl groups of said R.sup.4
optionally having substituents and hetero atoms, one of said
R.sup.4 being optionally bonded with another of said R.sup.4;
X.sup.2 represents O, S, NR.sup.5 or NR.sup.5R.sup.6; each of
R.sup.5 and R.sup.6 represents H or a C.sub.1-C.sub.10 alkyl group;
R.sup.7 represents a C.sub.1-C.sub.10 alkyl group, C.sub.1-C.sub.10
halogenated alkyl group, C.sub.4-C.sub.20 aryl group or
C.sub.4-C.sub.20 halogenated aryl group; each of x, y and z
independently represents a number from 1 to 8 each of Y.sup.1,
Y.sup.2 and Y.sup.3 independently represents a SO.sub.2 group or CO
group; and each of R.sup.8, R.sup.9 and R.sup.10 independently
represents an electron-attractive organic substituent optionally
having a substituent or a hetero atom, at least two of said
R.sup.8, R.sup.9 and R.sup.10 being optionally bonded together to
form a ring, at least one of said R.sup.8, R.sup.9 and R.sup.10
being optionally bonded with an adjacent molecule to form a
polymer.
2. An electrolyte according to claim 1, wherein said at least
compound is selected from the group consisting of said second to
fourth compounds, said m represents a number from 1 to 3, said n
represents a number from 0 to 4, said R.sup.3 represents a
C.sub.1-C.sub.10 alkylene group, C.sub.1-C.sub.10 halogenated
alkylene group, C.sub.4-C.sub.20 arylene group or C.sub.4-C.sub.20
halogenated arylene group, and said R.sup.4 represents a halogen,
C.sub.1-C.sub.10 alkyl group, C.sub.1-C.sub.10 halogenated alkyl
group, C.sub.4-C.sub.20 aryl group, C.sub.4-C.sub.20 halogenated
aryl group or said X.sup.2R.sup.7.
3. An electrolyte according to claim 1, wherein said at least one
compound is selected from the group consisting of said fifth to
ninth compounds, said m represents a number from 1 to 3, said n
represents a number from 0 to 4, said R.sup.3 represents a
C.sub.1-C.sub.10 alkylene group, C.sub.1-C.sub.10 halogenated
alkylene group, C.sub.4-C.sub.20 arylene group or C.sub.4-C.sub.20
halogenated arylene group, and said R.sup.4 represents a halogen,
C.sub.1-C.sub.10 alkyl group, C.sub.1-C.sub.10 halogenated alkyl
group, C.sub.4-C.sub.20 aryl group, C.sub.4-C.sub.20 halogenated
aryl group or said X.sup.2R.sup.7.
4. An electrolyte according to claim 1, wherein said M is an
element selected from the group consisting of Al, B, V, Ti, Si, Zr,
Ge, Sn, Cu, Y, Zn, Ga, Nb, Ta, Bi, P, As, Sc, Hf, and Sb.
5. An electrolyte according to claim 4, wherein said M is an
element selected from the group consisting of Al, B and P.
6. An electrolyte according to claim 1, wherein said A.sup.a+ is a
lithium ion, quaternary ammonium ion or hydrogen ion.
7. An electrolyte according to claim 1, wherein at least one of
said R.sup.1 and said R.sup.2 is a fluorinated alkyl group.
8. An electrolyte according to claim 7, wherein said fluorinated
alkyl group is trifluoromethyl group.
9. An electrolyte according to claim 1, wherein said R3 is such
that a chelate ring containing said M in the general formula (1) is
a closed loop of bonded atoms of 5-10 in number.
10. An electrolyte according to claim 1, wherein said R.sup.7 is a
C.sub.1-C.sub.10 fluorinated alkyl group.
11. An electrolyte according to claim 1, wherein a molar ratio of
said first compound to said at least one compound is 1:99 to
99:1.
12. An ion conductor for an electrochemical device, said ion
conductor comprising: an electrolyte according to claim 1; and a
member selected from the group consisting of a nonaqueous solvent,
a polymer and a mixture thereof, said member dissolving therein
said electrolyte.
13. An ion conductor according to claim 12, wherein said nonaqueous
solvent is an aprotic solvent, and thereby said ion conductor is an
electrolytic solution.
14. An ion conductor according to claim 13, wherein said nonaqueous
solvent is a mixture of a first aprotic solvent having a dielectric
constant of 20 or greater and a second aprotic solvent having a
dielectric constant of 10 or less.
15. An ion conductor according to claim 12, wherein said A.sup.a+
is a lithium ion.
16. An ion conductor according to claim 12, wherein said polymer is
an aprotic polymer, and thereby said ion conductor is a solid
electrolyte.
17. An ion conductor according to claim 12, which has a
concentration of said electrolyte within a range of from 0.1
mol/dm.sup.3 to a saturated concentration.
18. An ion conductor according to claim 17, wherein said
concentration is within a range of from 0.5 mol/dm.sup.3 to 1.5
mol/dm.sup.3.
19. An electrochemical device comprising: (a) first and second
electrodes; and (b) an ion conductor receiving therein said first
and second electrodes, said ion conductor comprising: (1) an
electrolyte according to claim 1; and (2) a member selected from
the group consisting of a nonaqueous solvent, a polymer and a
mixture thereof, said member dissolving therein said
electrolyte.
20. An electrochemical device according to claim 19, which is a
cell or an electrical double-layer capacitor.
21. An electrochemical device according to claim 20, wherein said
cell is a lithium cell or a lithium ion cell.
Description
BACKGROUND OF THE INVENTION
[0001] The present invention relates to an electrolyte, an ion
conductor including the electrolyte, and electrochemical devices
including the electrolyte, such as lithium cells, lithium ion
cells, electrical double-layer capacitors.
[0002] Accompanying the evolution of portable equipment in recent
years, there has been active development of electrochemical devices
utilizing electrochemical phenomena, such as cells for use as their
power supplies and capacitors. In addition, electrochromic devices
(ECD), in which a color change occurs due to an electrochemical
reaction, are examples of electrochemical devices for uses other
than power supplies.
[0003] These electrochemical devices are typically composed of a
pair of electrodes and an ion conductor filled between them. The
ion conductor contains a salt (AB) as an electrolyte, which is
dissolved in a solvent, polymer or mixture thereof such that the
salt is dissociated into cations (A.sup.+) and anions (B.sup.-),
resulting in ionic conduction. In order to obtain the required
level of ion conductivity for the device, it is necessary to
dissolve a sufficient amount of this electrolyte in solvent or
polymer. In actuality, there are many cases in which a solvent
other than water is used, such as organic solvents and polymers.
Electrolytes having sufficient solubility in such organic solvents
and polymers are presently limited to only a few types. For
example, electrolytes having sufficient solubility for use in
lithium cells are only LiClO.sub.4, LiPF.sub.6, LiBF.sub.4,
LiAsF.sub.6, LiN(SO.sub.2CF.sub.3).sub.2,
LiN(SO.sub.2C.sub.2F.sub.5).sub.2,
LiN(SO.sub.2CF.sub.3)(SO.sub.2C.sub.4F- .sub.9) and
LiCF.sub.3SO.sub.3. Although the cation type of the electrolyte is
frequently limited by the device as is the case with the lithium
ion of lithium cells, any anion can be used for the electrolyte
provided it satisfies the condition of having high solubility.
[0004] Amidst the considerable diversity of the application range
of these devices, efforts are made to seek out the optimum
electrolyte for each application. Under the present circumstances,
however, optimization efforts have reached their limit due to the
limited types of available anions. In addition, existing
electrolytes have various problems, thereby creating the need for
an electrolyte having a novel anion portion. More specifically,
since ClO.sub.4 ion of LiClO.sub.4 is explosive and AsF.sub.6 ion
of LiAsF.sub.6 is toxic, they cannot be used for reasons of safety.
Even the only practical electrolyte of LiPF.sub.6 has problems
including heat resistance and hydrolysis resistance. Although
electrolytes of LiN(CF.sub.3SO.sub.2).sub.2,
LiN(SO.sub.2C.sub.2F.sub.5).- sub.2,
LiN(SO.sub.2CF.sub.3)(SO.sub.2C.sub.4F.sub.9) and
LiCF.sub.3SO.sub.3 are stable and high in ionic conductivity, they
corrode the aluminum collector inside the cell when a potential is
applied. Therefore, their use presents difficulties.
SUMMARY OF THE INVENTION
[0005] It is therefore an object of the present invention to
provide a useful novel electrolyte, a novel ion conductor
containing the electrolyte, and a novel electrochemical device
containing the ion conductor.
[0006] According to the present invention, there is provided an
electrolyte for an electrochemical device. This electrolyte
comprises:
[0007] a first compound that is an ionic metal complex represented
by the general formula (1); and
[0008] at least one compound selected from the group consisting of
second to fourth compounds respectively represented by the general
formulas (2) to (4), fifth to ninth compounds respectively
represented by the general formulas A.sup.a+(PF.sub.6-).sub.a,
A.sup.a+(ClO.sub.4.sup.-).sub.a, A.sup.a+(BF.sub.4.sup.-).sub.a,
A.sup.a+(AsF.sub.6.sup.-).sub.a, and
A.sup.a+(SbF.sub.6.sup.-).sub.a, and tenth to twelfth compounds
respectively represented by the general formulas (5) to (7), 2
[0009] wherein M is a transition metal selected from the group
consisting of elements of groups 3-11 of the periodic table, or an
element selected from the group consisting of elements of groups
12-15 of the periodic table;
[0010] A.sup.a+ represents a metal ion, onium ion or hydrogen
ion;
[0011] a represents a number from 1 to 3; b represents a number
from 1 to 3; p is b/a; m represents a number from 1 to 4; n
represents a number from 0 to 8; q is 0 or 1;
[0012] X.sup.1 represents O, S, NR.sup.5 or NR.sup.5R.sup.6;
[0013] each of R.sup.1 and R.sup.2 independently represents H, a
halogen, a C.sub.1-C.sub.10 alkyl group or C.sub.1-C.sub.10
halogenated alkyl group;
[0014] R.sup.3 represents a C.sub.1-C.sub.10 alkylene group,
C.sub.1-C.sub.10 halogenated alkylene group, C.sub.4-C.sub.20
arylene group or C.sub.4-C.sub.20 halogenated arylene group, these
alkylene and arylene groups of said R.sup.3 optionally having
substituents and hetero atoms, one of said R.sup.3 being optionally
bonded with another of said R.sup.3;
[0015] R.sup.4 represents a halogen, C.sub.1-C.sub.10 alkyl group,
C.sub.1-C.sub.10 halogenated alkyl group, C.sub.4-C.sub.20 aryl
group, C.sub.4-C.sub.20 halogenated aryl group or X.sup.2R.sup.7,
these alkyl and aryl groups of said R.sup.4 optionally having
substituents and hetero atoms, one of said R.sup.4 being optionally
bonded with another of said R.sup.4;
[0016] X.sup.2 represents O, S, NR.sup.5 or NR.sup.5R.sup.6;
[0017] each of R.sup.5 and R.sup.6 represents H or a
C.sub.1-C.sub.10 alkyl group;
[0018] R.sup.7 represents a C.sub.1-C.sub.10 alkyl group,
C.sub.1-C.sub.10 halogenated alkyl group, C.sub.4-C.sub.20 aryl
group or C.sub.4-C.sub.20 halogenated aryl group;
[0019] each of x, y and z independently represents a number from 1
to 8
[0020] each of Y.sup.1, Y.sup.2 and Y.sup.3 independently
represents a SO.sub.2 group or CO group; and
[0021] each of R.sup.8, R.sup.9 and R.sup.10 independently
represents an electron-attractive organic substituent optionally
having a substituent or a hetero atom, at least two of said
R.sup.8, R.sup.9 and R.sup.10 being optionally bonded together to
form a ring, at least one of said R.sup.8, R.sup.9 and R.sup.10
being optionally bonded with an adjacent molecule to form a
polymer.
[0022] According to the present invention, there is provided an ion
conductor for an electrochemical device. This ion conductor
comprises the electrolyte; and a member selected from the group
consisting of a nonaqueous solvent, a polymer and a mixture
thereof, said member dissolving therein said electrolyte.
[0023] According to the present invention, there is provided an
electrochemical device comprising (a) first and second electrodes;
and (b) the ion conductor receiving therein said first and second
electrodes.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0024] An electrolyte according to the present invention is
superior in cycle characteristics and shelf life as compared with
conventional electrolytes. Thus, the electrolyte can advantageously
be used for electrochemical devices such as lithium cell, lithium
ion cell and electrical double-layer capacitor.
[0025] According to the invention, the alkyl groups, halogenated
alkyl groups, aryl groups and halogenated aryl groups, which are
contained in the ionic metal complex and the raw materials for
synthesizing the same, may be branched and/or may have other
functional groups such as hydroxyl groups and ether bonds.
[0026] The followings are specific nine examples of the ionic metal
complex represented by the general formula (1) of the present
invention. 3
[0027] Here, although lithium ion is indicated as an example of
A.sup.a+ of the general formula (1), examples of other cations that
can be used other than lithium ion include sodium ion, potassium
ion, magnesium ion, calcium ion, barium ion, cesium ion, silver
ion, zinc ion, copper ion, cobalt ion, iron ion, nickel ion,
manganese ion, titanium ion, lead ion, chromium ion, vanadium ion,
ruthenium ion, yttrium ion, lanthanoid ion, actinoid ion,
tetrabutylammonium ion, tetraethylammonium ion, tetramethylammonium
ion, triethylmethylammonium ion, triethylammonium ion, pyridinium
ion, imidazolium ion, hydrogen ion, tetraethylphosphonium ion,
tetramethylphosphonium ion, tetraphenylphosphonium ion,
triphenylsulfonium ion, and triethylsulfonium ion. In the case of
considering the application of the ionic metal complex for
electrochemical devices and the like, lithium ion,
tetraalkylammonium ion and hydrogen ion are preferable. As shown in
the general formula (1), the valency (valence) of the A.sup.a+
cation is preferably from 1 to 3. If the valency is larger than 3,
the problem occurs in which it becomes difficult to dissolve the
ionic metal complex in solvent due to the increase in crystal
lattice energy. Consequently, in the case of requiring solubility
of the ionic metal complex, a valency of 1 is preferable. As shown
in the general formula (1), the valency (b.sup.-) of the anion is
similarly preferably from 1 to 3, and a valency of 1 is
particularly preferable. The constant p expresses the ratio of the
valency of the anion to the valency of the cation, namely b/a.
[0028] In the general formula (1), M at the center of the ionic
metal complex of the present invention is selected from elements of
groups 3-15 of the periodic table. It is preferably Al, B, V, Ti,
Si, Zr, Ge, Sn, Cu, Y, Zn, Ga, Nb, Ta, Bi, P, As, Sc, Hf or Sb, and
more preferably Al, B or P. Although it is possible to use various
elements for the M other than these preferable examples, synthesis
is relatively easy in the case of using Al, B, V, Ti, Si, Zr, Ge,
Sn, Cu, Y, Zn, Ga, Nb, Ta, Bi, P, As, Sc, Hf or Sb. In addition to
ease of synthesis, the ionic metal complex has excellent properties
in terms of low toxicity, stability and production cost in the case
of using Al, B or P.
[0029] In the general formula (1), the organic or inorganic portion
bonded to M is referred to as the ligand. As mentioned above,
X.sup.1 in the general formula (1) represents O, S, NR.sup.5 or
NR.sup.5R.sup.6, and is bonded to M through its hetero atom (O, S
or N). Although the bonding of an atom other than O, S or N is not
impossible, the synthesis becomes extremely bothersome. The ionic
metal complex represented by the general formula (1) is
characterized by these ligands forming a chelate structure with M
since there is bonding with M by a carboxyl group (--COO.sup.-)
other than X.sup.1 within the same ligand. As a result of this
chlelation, the heat resistance, chemical stability and hydrolysis
resistance of the ionic metal complex are improved. Although
constant q in this ligand is either 0 or 1, in the case of 0 in
particular, since the chelate ring becomes a five-member ring,
chelating effects are demonstrated most prominently, making this
preferable due to the resulting increase in stability. In addition,
since the negative charge of the central M is dissipated by
electron attracting effects of the carboxyl group(s) resulting in
an increase in electrical stability of the anion, ion dissociation
becomes extremely easy resulting in corresponding increases of the
ionic metal complex in solvent solubility, ion conductivity,
catalyst activity and so forth. In addition, the other properties
of heat resistance, chemical stability and hydrolysis resistance
are also improved.
[0030] In the general formula (1), each of R.sup.1 and R.sup.2 is
independently selected from H, halogen, C.sub.1-C.sub.10 alkyl
groups and C.sub.1-C.sub.10 halogenated alkyl groups. At least one
of either R.sup.1 and R.sup.2 is preferably a fluorinated alkyl
group, and more preferably, at least one of R.sup.1 and R.sup.2 is
a trifluoromethyl group. Due to the presence of an
electron-attracting halogen and/or a halogenated alkyl group for
R.sup.1 and R.sup.2, the negative charge of the central M is
dissipated. This results in an increase of the anion of the general
formula (1) in electrical stability. With this, the ion
dissociation becomes extremely easy resulting in an increase of the
ionic metal complex in solvent solubility, ion conductivity,
catalyst activity and so forth. In addition, other properties of
heat resistance, chemical stability and hydrolysis resistance are
also improved. The case in which the halogen is fluorine in
particular has significant advantageous effects, while the case of
a trifluoromethyl group has the greatest advantageous effect.
[0031] In the general formula (1), R.sup.3 is selected from
C.sup.1-C.sub.10 alkylene groups, C.sub.1-C.sub.10 halogenated
alkylene groups, C.sub.4-C.sub.20 arylene groups and
C.sub.4-C.sub.20 halogenated arylene groups. R.sup.3 is preferably
one which forms a 5 to 10-membered ring when a chelate ring is
formed with the central M. The case of a ring having more than 10
members is not preferable, since chelating advantageous effects are
reduced. In addition, in the case R.sup.3 has a portion of hydroxyl
group or carboxyl group, it is possible to form a bond between the
central M and this portion.
[0032] In the general formula (1), R.sup.4 is selected from
halogens, C.sub.1-C.sub.10 alkyl groups, C.sub.1-C.sub.10
halogenated alkyl groups, C.sub.4-C.sub.20 aryl groups,
C.sub.4-C.sub.20 halogenated aryl groups and X.sup.2R.sup.7. Of
these, fluorine is preferable. X.sup.2 represents O, S, NR.sup.5 or
NR.sup.5R.sup.6 and bonds to M through one of these heteroatoms (O,
S and N). Although the bonding of an atom other than O, S or N is
not impossible, the synthesis becomes extremely bothersome. Each of
R.sup.5 and R.sup.6 is selected from H and C.sub.1-C.sub.10 alkyl
groups. Each of R.sup.5 and R.sup.6 differs from other groups
(e.g., R.sup.1 and R.sup.2) in that the former is not required to
be an electron attracting group. In the case of introducing an
electron attracting group as R.sup.5 or R.sup.6, the electron
density on N of NR.sup.5R.sup.6 decreases, thereby preventing
coordination on the central M. R.sup.7 is selected from
C.sub.1-C.sub.10 alkyl groups, C.sub.1-C.sub.10 halogenated alkyl
groups, C.sub.4-C.sub.20 aryl groups and C.sub.4-C.sub.20
halogenated aryl groups. Of these, a C.sub.1-C.sub.10 fluorinated
alkyl groups is preferable. Due to the presence of an
electron-attracting halogenated alkyl group as R.sup.7, the
negative charge of the central M is dissipated. Since this
increases the electrical stability of the anion of the general
formula (1), ion dissociation becomes extremely easy resulting in
an increase of the ionic metal complex in solvent solubility, ion
conductivity and catalyst activity. In addition, other properties
of heat resistance, chemical stability and hydrolysis resistance
are also improved. The case in which the halogenated alkyl group as
R.sup.7 is a fluorinated alkyl group in particular results in even
greater advantageous effects.
[0033] In the general formula (1), the values of the constants m
and n relating to the number of the above-mentioned ligands depend
on the type of the central M. In fact, m is preferably from 1 to 4,
while n is preferably from 0 to 8. Furthermore, m may be from 1 to
3, while n may be from 0 to 4.
[0034] According to a first preferred embodiment of the invention,
the electrolyte contains the ionic metal complex represented by the
general formula (1) and another component that is at least one
compound selected from the above-mentioned second to fourth
compounds represented by the general formulas (2), (3) and (4).
Examples of these compounds are LiCF.sub.3SO.sub.3,
LiN(CF.sub.3SO.sub.2).sub.2, LiN(SO.sub.2C.sub.2F.sub- .5).sub.2,
LiN(SO.sub.2CF.sub.3)(SO.sub.2C.sub.4F.sub.9) and
LiC(CF.sub.3SO.sub.2).sub.3. If the ionic metal complex is omitted
in the first preferred embodiment, the following problem occurs.
That is, the another component corrodes the aluminum collector
inside the cell when a potential is applied. With this, the
capacity is lowered by repeating the charge and discharge cycle. In
contrast, according to the first preferred embodiment, the aluminum
collector corrosion can unexpectedly be prevented by using a
mixture of the ionic metal complex and the another component. The
reason of this is not clear. It is, however, assumed that the ionic
metal complex is slightly decomposed on the electrode surface and
that a film of the ionic metal complex's ligand is formed on the
aluminum surface, thereby preventing the aluminum collector
corrosion.
[0035] According to a second preferred embodiment of the invention,
the electrolyte contains the ionic metal complex represented by the
general formula (1) and another component that is at least one
compound selected from the above-mentioned fifth to ninth compounds
respectively represented by the general formulas
A.sup.a+(PF.sub.6.sup.-).sub.a, A.sup.a+(ClO.sub.4.sup.-).sub.a,
A.sup.a+(BF.sub.4.sup.-).sub.a, A.sup.a+(AsF.sub.6.sup.-).sub.a,
and A.sup.a+(SbF.sub.6.sup.-).sub.a where A.sup.a+ is preferably
the same ion as that in the general formula (1). If the ionic metal
complex is omitted in the second preferred embodiment, the
following problem occurs. That is, the anion(s) tends to be
pyrolyzed at a high temperature of 60.degree. C. or higher, thereby
generating a Lewis acid(s). This Lewis acid decomposes the solvent
and makes the electrochemical device inferior in performance and
lifetime. Furthermore, the omission of the ionic metal complex
causes hydrolysis of the anion(s) when the electrolyte is
contaminated with a very small amount of water. This hydrolysis
generates an acid(s) that makes the electrochemical device inferior
in performance and lifetime. In contrast, according to the second
preferred embodiment, the above-mentioned pyrolysis and hydrolysis
can unexpectedly be prevented by using a mixture of the ionic metal
complex and the another component. The reason of this is not clear.
It is, however, assumed that the properties of the solution as a
whole change somehow to achieve this prevention by a certain
interaction between the ionic metal complex and the another
component.
[0036] According to a third preferred embodiment of the invention,
the electrolyte contains the ionic metal complex represented by the
general formula (1) and another component that is at least one
compound selected from the above-mentioned tenth to twelfth
compounds represented by the general formulas (5), (6) and (7).
Examples of these compounds are CF.sub.3CH.sub.2OSO.sub.3Li,
(CF.sub.3).sub.2CHOSO.sub.3Li,
(CF.sub.3CH.sub.2OSO.sub.2).sub.2NLi,
((CF.sub.3).sub.2CHOSO.sub.2).sub.2- NLi,
(CF.sub.3CH.sub.2OSO.sub.2)((CF.sub.3).sub.2CHOSO.sub.2)NLi,
((CF.sub.3).sub.2COSO.sub.2).sub.2NLi, and
((CF.sub.3).sub.2CHOSO.sub.2).- sub.3CLi. Further examples are
polymers and oligomers such as
[N(Li)SO.sub.2OCH.sub.2(CF.sub.2).sub.4CH.sub.2OSO.sub.2].sub.n
where n is a number of 2-1,000. If the ionic metal complex is
omitted in the third preferred embodiment, the following problem
occurs. That is, the another component corrodes the aluminum
collector inside the cell when a potential is applied. With this,
the capacity is lowered by repeating the charge and discharge
cycle. In contrast, according to the third preferred embodiment,
the aluminum collector corrosion can unexpectedly be prevented by
using a mixture of the ionic metal complex and the another
component. The reason of this is not clear. It is, however, assumed
that the ionic metal complex is slightly decomposed on the
electrode surface and that a film of the ionic metal complex's
ligand is formed on the aluminum surface, thereby preventing the
aluminum collector corrosion.
[0037] In the invention, the molar ratio of the ionic metal complex
to the at least one compound is preferably 1:99 to 99:1 (or a range
from 5:95 to 95:5), more preferably 20:80 to 80:20 (or a range from
30:70 to 70:30), in view of improving the electrochemical device in
cycle characteristics and shelf life. If this ratio is less than
1:99 (or 5:95), it may become insufficient to prevent the
above-mentioned aluminum corrosion and/or the above-mentioned
pyrolysis and hydrolysis, thereby making the electrolyte inferior
in cycle characteristics and shelf life. If the ratio is greater
than 99:1 (or 95:5), advantages of adding the at least one compound
to increase ionic conductivity and electrochemical stability may
become insufficient.
[0038] There are no particular restrictions on the process for
synthesizing the ionic metal complex. An exemplary process for
producing the ionic metal complex is disclosed in European Patent
Application EP 1075036 A2.
[0039] In the case of preparing an electrochemical device of the
present invention, its basic structural elements are ion conductor,
negative electrode, positive electrode, collector, separator,
container and the like.
[0040] A mixture of electrolyte and non-aqueous solvent or polymer
is used as the ion conductor. If a non-aqueous solvent is used, the
resulting ion conductor is typically referred to as an electrolytic
solution, while if a polymer is used, it is typically referred to
as a polymer solid electrolyte. Non-aqueous solvent may also be
contained as plasticizer in polymer solid electrolytes.
[0041] There are no particular restrictions on the non-aqueous
solvent provided it is an aprotic solvent that is able to dissolve
an electrolyte of the present invention, and examples of this
non-aqueous solvent that can be used include carbonates, esters,
ethers, lactones, nitrites, amides and sulfones. In addition, the
solvent can either be used alone or in the form of a mixture of two
or more types of solvent. Specific examples of the solvent include
propylene carbonate, ethylene carbonate, diethyl carbonate,
dimethyl carbonate, methylethyl carbonate, dimethoxyethane,
acetonitrile, propionitrile, tetrahydrofuran,
2-methyltetrahydrofuran, dioxane, nitromethane, N,
N-dimethylformamide, dimethylsulfoxide, sulfolane and
.gamma.-butyrolactone.
[0042] In case that A.sup.a+ of the general formula (1) is lithium
ion, the non-aqueous solvent of an electrolytic solution is
preferably a mixture of a first aprotic solvent having a dielectric
constant of 20 or greater and a second aprotic solvent having a
dielectric constant of 10 or less. In fact, lithium salt has a low
solubility in the second aprotic solvent (e.g., diethyl ether and
dimethyl carbonate). Therefore, it may be difficult to obtain a
sufficient ionic conductivity by using only the second aprotic
solvent. In contrast, lithium salt has a high solubility in the
first aprotic solvent. The resulting solution is, however, high in
viscosity. Thus, it may be difficult to obtain a sufficient ionic
conductivity by using only the first aprotic solvent, too. In
contrast, it becomes possible to gain a suitable solubility and a
suitable ionic mobility by using a mixture of the first and second
aprotic solvents, thereby making it possible to obtain a sufficient
ionic conductivity.
[0043] There are no particular restrictions on the polymer to be
mixed with the electrolytes of the invention provided it is an
aprotic polymer. Examples of such polymer include polymers having
polyethylene oxide on their main chain or side chain, homopolymers
or copolymers of polyvinylidene fluoride, methacrylate polymers and
polyacrylonitrile. In the case of adding plasticizer to these
polymers, the above-mentioned aprotic non-aqueous solvent can be
used. The total concentration of the electrolytes of the present
invention in these ion conductors is preferably 0.1 mol/dm.sup.3 or
more up to the saturated concentration, and more preferably from
0.5 mol/dm.sup.3 to 1.5 mol/dm.sup.3. If the concentration is lower
than 0.1 mol/dm.sup.3, ion conductivity may become too low.
[0044] There are no particular restrictions on the negative
electrode material for preparing an electrochemical device. In the
case of lithium cell, lithium metal (metallic lithium) or an alloy
of lithium and another metal can be used. In the case of a lithium
ion cell, it is possible to use an intercalation compound
containing lithium atoms in a matrix of another material, such as
carbon, natural graphite or metal oxide. This carbon can be
obtained by baking polymer, organic substance, pitch or the like.
In the case of electrical double-layer capacitor, it is possible to
use activated carbon, porous metal oxide, porous metal, conductive
polymer and so forth.
[0045] There are no particular restrictions on the positive
electrode material. In the case of lithium cell or lithium ion
cell, lithium-containing oxides such as LiCoO.sub.2, LiNiO.sub.2,
LiMnO.sub.2 and LiMn.sub.2O.sub.4; oxides such as TiO.sub.2,
V.sub.2O.sub.5 and MoO.sub.3; sulfides such as TiS.sub.2 and FeS;
and electrically conductive polymers such as polyacetylene,
polyparaphenylene, polyaniline or polypyrrole can be used. In the
case of electrical double-layer capacitor, activated carbon, porous
metal oxide, porous metal, electrically conductive polymer and so
forth can be used.
[0046] The following nonlimitative examples are illustrative of the
present invention. In fact, Examples 1-1 to 1-5 are illustrative of
the above-mentioned first preferred embodiment of the invention,
and Examples 2-1 to 2-4 are illustrative of the above-mentioned
second preferred embodiment of the invention, and Examples 3-1 to
3-4 are illustrative of the above-mentioned third preferred
embodiment of the invention.
EXAMPLE 1-1
[0047] A lithium borate derivative, represented by the following
formula, and LiN(SO.sub.2C.sub.2F.sub.5).sub.2 were dissolved in a
mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC)
(EC:DMC =1:1 by volume) to prepare an electrolytic solution having
a lithium borate derivative concentration of 0.05 mol/liter and a
LiN(SO.sub.2C.sub.2F.sub- .5).sub.2 concentration of 0.95
mol/liter. 4
[0048] Then, ion conductivity of the electrolytic solution was
measured with an alternating current bipolar-type cell. As a
result, the ion conductivity was 7.6 mS/cm at 25.degree. C.
[0049] A corrosion test of an aluminum collector was performed
using the above-mentioned electrolytic solution. A beaker type cell
was used for the test cell, using aluminum for the working
electrode, and lithium metal (metallic lithium) for the counter
electrode and reference electrode. When the working electrode was
held at 5 V (Li/Li.sup.+), there was no flow of current whatsoever.
Following testing, although the surface of the working electrode
was observed by SEM, there were no changes observed in comparison
with that before testing.
[0050] A charging and discharging test of an actual cell was
conducted using the above-mentioned electrolytic solution. The test
cell (half cell) was prepared in the manner described below. The
positive electrode was prepared by mixing 5 parts by weight of
polyvinylidene fluoride (PVDF) as a binder and 5 parts by weight of
acetylene black as a conductor with 90 parts by weight of a
LiCoO.sub.2 powder followed by the addition of
N,N-dimethylformamide to form a paste. This paste was applied to an
aluminum foil and allowed to dry to obtain the test positive
electrode. Lithium metal was used for the negative electrode. A
glass fiber filter as a separator was impregnated with the
electrolytic solution, thereby assembling the cell.
[0051] Next, a constant current charging and discharging test was
conducted as described below. The current density was 0.35
mA/cm.sup.2 for both charging and discharging, while charging was
performed until 4.2 V and discharging until 3.0 V (vs.
Li/Li.sup.+). As a result, the initial discharge capacity was 118
mAh/g (the positive electrode capacity). Although charging and
discharging were repeated 100 times, results were obtained in which
the capacity of the 100.sup.th cycle was 91% of the initial
capacity.
EXAMPLE 1-2
[0052] A lithium borate derivative, represented by the following
formula, and LiN(SO.sub.2CF.sub.3).sub.2 were dissolved in a
mixture of propylene carbonate (PC) and diethyl carbonate (DEC)
(PC:DEC=1:1 by volume) to prepare an electrolytic solution having a
lithium borate derivative concentration of 0.10 mol/liter and a
LiN(SO.sub.2CF.sub.3).sub.2 concentration of 0.90 mol/liter. 5
[0053] Then, ion conductivity of the electrolytic solution was
measured with an alternating current bipolar-type cell. As a
result, the ion conductivity was 8.6 mS/cm at 25.degree. C.
[0054] A corrosion test of an aluminum collector was performed in
the same manner as that of Example 1-1. When the working electrode
was held at 5 V (Li/Li.sup.+), there was no flow of current
whatsoever. Following testing, although the surface of the working
electrode was observed by SEM, there were no changes observed in
comparison with that before testing.
[0055] The test cell (half cell) was prepared in the same manner as
that of Example 1-1, and a constant current charging and
discharging test was conducted in the same manner as that of
Example 1-1. As a result, the initial discharge capacity was 115
mAh/g (the positive electrode capacity). Although charging and
discharging were repeated 100 times, results were obtained in which
the capacity of the 100.sup.th cycle was 86% of the initial
capacity.
EXAMPLE 1-3
[0056] A lithium borate derivative, represented by the following
formula, and LiN(SO.sub.2CF.sub.3)(SO.sub.2C.sub.4F.sub.9) were
dissolved in a mixture of ethylene carbonate (EC) and dimethyl
carbonate (DMC) (EC:DMC=1:1 by volume) to prepare an electrolytic
solution having a lithium borate derivative concentration of 0.05
mol/liter and a LiN(SO.sub.2CF.sub.3)(SO.sub.2C.sub.4F.sub.9)
concentration of 0.95 mol/liter. 6
[0057] Then, ion conductivity of the electrolytic solution was
measured with an alternating current bipolar-type cell. As a
result, the ion conductivity was 6.7 mS/cm at 25.degree. C.
[0058] A corrosion test of an aluminum collector was performed in
the same manner as that of Example 1-1. When the working electrode
was held at 5 V (Li/Li.sup.+), there was no flow of current
whatsoever. Following testing, although the surface of the working
electrode was observed by SEM, there were no changes observed in
comparison with that before testing.
[0059] The test cell (half cell) was prepared in the same manner as
that of Example 1-1, and a constant current charging and
discharging test was conducted in the same manner as that of
Example 1-1. As a result, the initial discharge capacity was 120
mAh/g (the positive electrode capacity). Although charging and
discharging were repeated 100 times, results were obtained in which
the capacity of the 100.sup.th cycle was 92% of the initial
capacity.
EXAMPLE 1-4
[0060] A lithium borate derivative, represented by the following
formula, and LiN(SO.sub.2CF.sub.3)(SO.sub.2C.sub.4F.sub.9) were
dissolved in a mixture of ethylene carbonate (EC) and dimethyl
carbonate (DMC) (EC:DMC=1:1 by volume) to prepare an electrolytic
solution having a lithium borate derivative concentration of 0.30
mol/liter and a LiN(SO.sub.2CF.sub.3)(SO.sub.2C.sub.4F.sub.9)
concentration of 0.70 mol/liter. 7
[0061] Then, ion conductivity of the electrolytic solution was
measured with an alternating current bipolar-type cell. As a
result, the ion conductivity was 5.8 mS/cm at 25.degree. C.
[0062] A corrosion test of an aluminum collector was performed in
the same manner as that of Example 1-1. When the working electrode
was held at 5 V (Li/Li.sup.+), there was no flow of current
whatsoever. Following testing, although the surface of the working
electrode was observed by SEM, there were no changes observed in
comparison with that before testing.
[0063] The test cell (half cell) was prepared in the same manner as
that of Example 1-1, and a constant current charging and
discharging test was conducted in the same manner as that of
Example 1-1. As a result, the initial discharge capacity was 120
mAh/g (the positive electrode capacity). Although charging and
discharging were repeated 100 times, results were obtained in which
the capacity of the 100.sup.th cycle was 94% of the initial
capacity.
EXAMPLE 1-5
[0064] A solution was prepared by adding acetonitrile to 70 parts
by weight of a polyethylene oxide (average molecular weight:
10,000). Then, 20 parts by weight of a lithium borate derivative,
which is the same as that of Example 1-1, and 10 parts by weight of
LiN(SO.sub.2C.sub.2F.sub.5- ).sub.2 were added to the solution. The
resulting mixture was cast on a glass, followed by drying to remove
the acetonitrile. With this, a polymer solid electrolyte film was
prepared.
[0065] The test cell was prepared in the same manner as that of
Example 1-1 except in that the polymer solid electrolyte film was
used in place of the electrolytic solution and the separator. In
fact, LiCoO.sub.2 was used as a positive electrode material, and
lithium metal was used as a negative electrode material. A constant
current charging and discharging test was conducted at 70.degree.
C. under the following conditions. The current density was 0.1
mA/cm.sup.2 for both charging and discharging, while charging was
performed until 4.2 V and discharging until 3.0 V (vs.
Li/Li.sup.+). As a result, the initial discharge capacity was 120
mAh/g (the positive electrode capacity). Although charging and
discharging were repeated 100 times, results were obtained in which
the capacity of the 100.sup.th cycle was 87% of the initial
capacity.
COMPARATIVE EXAMPLE 1-1
[0066] At first, LiN(SO.sub.2C.sub.2F.sub.5).sub.2 was dissolved in
a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC)
(EC:DMC =1:1 by volume) to prepare an electrolytic solution having
a LiN(SO.sub.2C.sub.2F.sub.5).sub.2 concentration of 1.0
mol/liter.
[0067] A corrosion test of an aluminum collector was performed in
the same manner as that of Example 1-1. When the working electrode
was held at 5 V (Li/Li.sup.+), corrosion current was observed.
Following testing, the surface of the working electrode was
observed by SEM. With this, many pits were observed on its surface.
It is assumed that these pits were caused by corrosion.
[0068] The test cell (half cell) was prepared in the same manner as
that of Example 1-1, and a constant current charging and
discharging test was conducted in the same manner as that of
Example 1-1. As a result, the initial discharge capacity was 117
mAh/g (the positive electrode capacity). Although charging and
discharging were repeated 100 times, results were obtained in which
the capacity of the 100.sup.th cycle was 69% of the initial
capacity.
COMPARATIVE EXAMPLE 1-2
[0069] At first, LiN(SO.sub.2CF.sub.3).sub.2 was dissolved in a
mixture of propylene carbonate (PC) and diethyl carbonate (DEC)
(PC:DEC=1:1 by volume) to prepare an electrolytic solution having a
LiN(SO.sub.2CF.sub.3).sub.2 concentration of 1.0 mol/liter.
[0070] A corrosion test of an aluminum collector was performed in
the same manner as that of Example 1-1. When the working electrode
was held at 5 V (Li/Li.sup.+), corrosion current was observed.
Following testing, the surface of the working electrode was
observed by SEM. With this, many pits were observed on its surface.
It is assumed that these pits were caused by corrosion.
[0071] The test cell (half cell) was prepared in the same manner as
that of Example 1-1, and a constant current charging and
discharging test was conducted in the same manner as that of
Example 1-1. As a result, the initial discharge capacity was 112
mAh/g (the positive electrode capacity). Although charging and
discharging were repeated 100 times, results were obtained in which
the capacity of the 100.sup.th cycle was 67% of the initial
capacity.
COMPARATIVE EXAMPLE 1-3
[0072] At first, LiN(SO.sub.2CF.sub.3)(SO.sub.2C.sub.4F.sub.9) was
dissolved in a mixture of ethylene carbonate (EC) and dimethyl
carbonate (DMC) (EC:DMC =1:1 by volume) to prepare an electrolytic
solution having a LiN(SO.sub.2CF.sub.3)(SO.sub.2C.sub.4F.sub.9)
concentration of 1.0 mol/liter.
[0073] A corrosion test of an aluminum collector was performed in
the same manner as that of Example 1-1. When the working electrode
was held at 5 V (Li/Li.sup.+), corrosion current was observed.
Following testing, the surface of the working electrode was
observed by SEM. With this, many pits were observed on its surface.
It is assumed that these pits were caused by corrosion.
[0074] The test cell (half cell) was prepared in the same manner as
that of Example 1-1, and a constant current charging and
discharging test was conducted in the same manner as that of
Example 1-1. As a result, the initial discharge capacity was 118
mAh/g (the positive electrode capacity). Although charging and
discharging were repeated 100 times, results were obtained in which
the capacity of the 100.sup.th cycle was 74% of the initial
capacity.
EXAMPLE 2-1
[0075] An electrolytic solution was prepared by the same manner as
that of Example 1-1, except that LiN(SO.sub.2C.sub.2F.sub.5).sub.2
was replaced with LiPF.sub.6. This electrolytic solution had a
lithium borate derivative concentration of 0.05 mol/liter and a
LiPF.sub.6 concentration of 0.95 mol/liter.
[0076] A charging and discharging test of an actual cell was
conducted using the above-mentioned electrolytic solution. The test
cell was prepared in the manner described below. The positive
electrode of LiCoO.sub.2 was prepared by the same manner as that of
Example 1-1. The negative electrode of natural graphite was
prepared by mixing 10 parts by weight of polyvinylidene fluoride
(PVDF) as a binder with 90 parts by weight of a LiCoO.sub.2 powder
followed by the addition of N,N-dimethylformamide to form a slurry.
This slurry was applied to an copper foil and allowed to dry at
150.degree. C. for 12 hr to obtain the test negative electrode. A
polyethylene separator was impregnated with the electrolytic
solution, thereby assembling the cell.
[0077] Next, a constant current charging and discharging test was
conducted at 70.degree. C. under the following conditions. The
current density was 0.35 mA/cm.sup.2 for both charging and
discharging, while charging was performed until 4.2 V and
discharging until 3.0 V (vs. Li/Li.sup.+). Although charging and
discharging were repeated 500 times, results were obtained in which
the capacity of the 500.sup.th cycle was 81% of the initial
capacity.
EXAMPLE 2-2
[0078] An electrolytic solution was prepared by substantially the
same manner as that of Example 1-2, in which
LiN(SO.sub.2CF.sub.3).sub.2 was replaced with LiPF.sub.6. The
resulting electrolytic solution had a lithium borate derivative
concentration of 0.30 mol/liter and a LiPF.sub.6 concentration of
0.70 mol/liter.
[0079] The test cell was prepared in the same manner as that of
Example 2-1, and a constant current charging and discharging test
was conducted in the same manner as that of Example 2-1. The
capacity of the 500.sup.th cycle was 86% of the initial
capacity.
EXAMPLE 2-3
[0080] An electrolytic solution was prepared by substantially the
same manner as that of Example 1-3, in which
LiN(SO.sub.2CF.sub.3)(SO.sub.2C.s- ub.4F.sub.9) was replaced with
LiBF.sub.4. The resulting electrolytic solution had a lithium
borate derivative concentration of 0.30 mol/liter and a LiBF.sub.4
concentration of 0.70 mol/liter.
[0081] The test cell was prepared in the same manner as that of
Example 2-1, and a constant current charging and discharging test
was conducted in the same manner as that of Example 2-1. The
capacity of the 500.sup.th cycle was 78% of the initial
capacity.
EXAMPLE 2-4
[0082] A solution was prepared by adding acetonitrile to 80 parts
by weight of a polyethylene oxide-(average molecular weight:
10,000). Then, 10 parts by weight of a lithium borate derivative,
which is the same as that of Example 1-1, and 10 parts by weight of
LiPF.sub.6 were added to the solution. The resulting mixture was
cast on a glass, followed by drying to remove the acetonitrile.
With this, a polymer solid electrolyte film was prepared.
[0083] The test cell was prepared in the same manner as that of
Example 2-1 except in that the polymer solid electrolyte film was
used in place of the electrolytic solution and the separator. In
fact, LiCoO.sub.2 was used as a positive electrode material, and
natural graphite was used as a negative electrode material. A
constant current charging and discharging test was conducted at
70.degree. C. under the following conditions. The current density
was 0.1 mA/cm.sup.2 for both charging and discharging, while
charging was performed until 4.2 V and discharging until 3.0 V (vs.
Li/Li.sup.+). As a result, the initial discharge capacity was 120
mAh/g (the positive electrode capacity). Although charging and
discharging were repeated 500 times, results were obtained in which
the capacity of the 500.sup.th cycle was 91% of the initial
capacity.
COMPARATIVE EXAMPLE 2-1
[0084] At first, LiPF.sub.6 was dissolved in a mixture of ethylene
carbonate (EC) and dimethyl carbonate (DMC) (EC:DMC=1:1 by volume)
to prepare an electrolytic solution having a LiPF.sub.6
concentration of 1.0 mol/liter.
[0085] The test cell was prepared in the same manner as that of
Example 2-1, and a constant current charging and discharging test
was conducted in the same manner as that of Example 2-1. The
capacity of the 500.sup.th cycle was 64% of the initial
capacity.
COMPARATIVE EXAMPLE 2-2
[0086] At first, LiBF.sub.4 was dissolved in a mixture of ethylene
carbonate (EC) and dimethyl carbonate (DMC) (EC:DMC=1:1 by volume)
to prepare an electrolytic solution having a LiBF.sub.4
concentration of 1.0 mol/lliter.
[0087] The test cell was prepared in the same manner as that of
Example 2-1, and a constant current charging and discharging test
was conducted in the same manner as that of Example 2-1. The
capacity of the 500.sup.th cycle was 46% of the initial
capacity.
EXAMPLE 3-1
[0088] A lithium borate derivative, which was the same as that of
Example 1-1, and ((CF.sub.3).sub.2CHOSO.sub.2).sub.2NLi were
dissolved in a mixture of ethylene carbonate (EC) and dimethyl
carbonate (DMC) (EC:DMC=1:1 by volume) to prepare an electrolytic
solution having a lithium borate derivative concentration of 0.01
mol/liter and a ((CF.sub.3).sub.2CHOSO.sub.2).sub.2NLi
concentration of 0.99 mol/liter.
[0089] A corrosion test of an aluminum collector was performed in
the same manner as that of Example 1-1. When the working electrode
was held at 5 V (Li/Li.sup.+), there was no flow of current
whatsoever. Following testing, although the surface of the working
electrode was observed by SEM, there were no changes observed in
comparison with that before testing.
[0090] The test cell was prepared by the same manner as that of
Example 2-1. A constant current charging and discharging test was
conducted by the same manner as that of Example 2-1, except that
the test was conducted at an environmental temperature of
25.degree. C. The capacity of the 500.sup.th cycle was 91% of the
initial capacity.
EXAMPLE 3-2
[0091] A lithium borate derivative, which was the same as that of
Example 1-1, and (CF.sub.3CH20SO.sub.2).sub.2NLi were dissolved in
a mixture of ethylene carbonate (EC) and diethyl carbonate (DEC)
(EC:DEC =1:1 by volume) to prepare an electrolytic solution having
a lithium borate derivative concentration of 0.90 mol/liter and a
(CF.sub.3CH.sub.2OSO.sub- .2).sub.2NLi concentration of 0.10
mol/liter.
[0092] A corrosion test of an aluminum collector was performed in
the same manner as that of Example 1-1. When the working electrode
was held at 5 V (Li/Li.sup.+), there was no flow of current
whatsoever. Following testing, although the surface of the working
electrode was observed by SEM, there were no changes observed in
comparison with that before testing.
[0093] The test cell was prepared by the same manner as that of
Example 2-1. A constant current charging and discharging test was
conducted by the same manner as that of Example 2-1, except that
the test was conducted at an environmental temperature of
60.degree. C. The capacity of the 500.sup.th cycle was 85% of the
initial capacity.
EXAMPLE 3-3
[0094] A lithium borate derivative, which was the same as that of
Example 1-2, and ((CF.sub.3).sub.2CHOSO.sub.2).sub.2NLi were
dissolved in a mixture of ethylene carbonate (EC) and ethylmethyl
carbonate (EMC) (EC:EMC=1:1 by volume) to prepare an electrolytic
solution having a lithium borate derivative concentration of 0.70
mol/liter and a ((CF.sub.3).sub.2CHOSO.sub.2).sub.2NLi
concentration of 0.30 mol/liter.
[0095] A corrosion test of an aluminum collector was performed in
the same manner as that of Example 1-1. When the working electrode
was held at 5 V (Li/Li.sup.+), there was no flow of current
whatsoever. Following testing, although the surface of the working
electrode was observed by SEM, there were no changes observed in
comparison with that before testing.
[0096] The test cell was prepared by the same manner as that of
Example 2-1. A constant current charging and discharging test was
conducted by the same manner as that of Example 2-1, except that
the test was conducted at an environmental temperature of
60.degree. C. The capacity of the 500.sup.th cycle was 88% of the
initial capacity.
EXAMPLE 3-4
[0097] A solution was prepared by adding acetonitrile to 70 parts
by weight of a polyethylene oxide (average molecular weight:
10,000). Then, 5 parts by weight of a lithium borate derivative,
which was the same as that of Example 1-1, and 25 parts by weight
of ((CF.sub.3).sub.2CHOSO.sub- .2).sub.2NLi were added to the
solution. The resulting mixture was cast on a glass, followed by
drying to remove the acetonitrile. With this, a polymer solid
electrolyte film was prepared.
[0098] A corrosion test of an aluminum collector was performed
using a laminate including the solid electrolyte film interposed
between an aluminum electrode (working electrode) and a lithium
electrode. This laminate was prepared by press welding. When the
working electrode was held at 5 V (Li/Li.sup.+), there was no flow
of current whatsoever. Following testing, although the surface of
the working electrode was observed by SEM, there were no changes
observed in comparison with that before testing.
[0099] The test cell was prepared in the same manner as that of
Example 2-4, and a constant current charging and discharging test
was conducted in the same manner as that of Example 2-4 except that
charging and discharging were repeated 100 times. As a result, the
initial discharge capacity was 120 mAh/g (the positive electrode
capacity). The capacity of the 100.sup.th cycle was 94% of the
initial capacity.
COMPARATIVE EXAMPLE 3-1
[0100] At first, ((CF.sub.3).sub.2CHOSO.sub.2).sub.2NLi was
dissolved in a mixture of ethylene carbonate (EC) and dimethyl
carbonate (DMC) (EC:DMC =1:1 by volume) to prepare an electrolytic
solution having a ((CF.sub.3).sub.2CHOSO.sub.2).sub.2NLi
concentration of 1.0 mol/liter.
[0101] A corrosion test of an aluminum collector was performed in
the same manner as that of Example 1-1. When the working electrode
was held at 5 V (Li/Li.sup.+), corrosion current was observed.
Following testing, the surface of the working electrode was
observed by SEM. With this, many pits were observed on its surface.
It is assumed that these pits were caused by corrosion.
[0102] The test cell was prepared in the same manner as that of
Example 2-1, and a constant current charging and discharging test
was conducted in the same manner as that of Example 2-1, except
that the test was conducted at an environmental temperature of
25.degree. C. The capacity of the 500.sup.th cycle was 62% of the
initial capacity.
COMPARATIVE EXAMPLE 3-2
[0103] At first, (CF.sub.3CH.sub.2OSO.sub.2).sub.2NLi was dissolved
in a mixture of ethylene carbonate (EC) and diethyl carbonate (DEC)
(EC:DEC=1:1 by volume) to prepare an electrolytic solution having a
(CF.sub.3CH.sub.2OSO.sub.2).sub.2NLi concentration of 1.0
mol/liter.
[0104] A corrosion test of an aluminum collector was performed in
the same manner as that of Example 1-1. When the working electrode
was held at 5 V (Li/Li.sup.+), corrosion current was observed.
Following testing, the surface of the working electrode was
observed by SEM. With this, many pits were observed on its surface.
It is assumed that these pits were caused by corrosion.
[0105] The test cell was prepared in the same manner as that of
Example 2-1, and a constant current charging and discharging test
was conducted in the same manner as that of Example 2-1, except
that the test was conducted at an environmental temperature of
60.degree. C. The capacity of the 500.sup.th cycle was 58% of the
initial capacity.
COMPARATIVE EXAMPLE 3-3
[0106] At first, a lithium borate derivative, which was the same as
that of Example 1-1, was dissolved in a mixture of ethylene
carbonate (EC) and ethylmethyl carbonate (EMC) (EC:EMC=1:1 by
volume) to prepare an electrolytic solution having a lithium borate
derivative concentration of 1.0 mol/liter.
[0107] The test cell was prepared in the same manner as that of
Example 2-1, and a constant current charging and discharging test
was conducted in the same manner as that of Example 2-1, except
that the test was conducted at an environmental temperature of
60.degree. C. The capacity of the 500.sup.th cycle was 25% of the
initial capacity.
[0108] The entire disclosure of Japanese Patent Applications No.
2000-134926 filed on May 8, 2000, No. 2000-173094 filed on Jun. 9,
2000, and No. 2001-020898 and No. 2001-020899 each filed on Jan.
30, 2001, including specification, claims and summary, is
incorporated herein by reference in its entirety.
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