U.S. patent application number 15/947280 was filed with the patent office on 2018-08-09 for negative material for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery using the negative material.
This patent application is currently assigned to Murata Manufacturing Co., Ltd.. The applicant listed for this patent is Murata Manufacturing Co., Ltd.. Invention is credited to Atsuo Omaru, Hiroaki Tanizaki.
Application Number | 20180226638 15/947280 |
Document ID | / |
Family ID | 26613330 |
Filed Date | 2018-08-09 |
United States Patent
Application |
20180226638 |
Kind Code |
A1 |
Omaru; Atsuo ; et
al. |
August 9, 2018 |
NEGATIVE MATERIAL FOR NONAQUEOUS ELECTROLYTE SECONDARY BATTERY AND
NONAQUEOUS ELECTROLYTE SECONDARY BATTERY USING THE NEGATIVE
MATERIAL
Abstract
A nonaqueous electrolyte secondary battery comprising an anode
(3), a cathode (2) and a nonaqueous electrolyte. The anode includes
composite particles having a carbon material included in a metallic
material. As the metallic material, a metal capable of
electrochemically reacting with lithium in a nonaqueous electrolyte
is included.
Inventors: |
Omaru; Atsuo; (Fukushima,
JP) ; Tanizaki; Hiroaki; (Miyagi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Murata Manufacturing Co., Ltd. |
Kyoto |
|
JP |
|
|
Assignee: |
Murata Manufacturing Co.,
Ltd.
Kyoto
JP
|
Family ID: |
26613330 |
Appl. No.: |
15/947280 |
Filed: |
April 6, 2018 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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15233331 |
Aug 10, 2016 |
9972831 |
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15947280 |
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10297650 |
Dec 5, 2002 |
9450245 |
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PCT/IB02/01115 |
Apr 9, 2002 |
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15233331 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01M 4/405 20130101;
Y02E 60/10 20130101; H01M 10/0569 20130101; H01M 4/136 20130101;
H01M 4/1395 20130101; H01M 4/58 20130101; H01M 4/364 20130101; H01M
4/13 20130101; H01M 4/40 20130101; H01M 4/131 20130101; H01M 4/583
20130101; H01M 4/133 20130101; H01M 4/386 20130101; H01M 4/1393
20130101; H01M 4/625 20130101; H01M 10/0525 20130101; H01M 4/362
20130101; H01M 2004/027 20130101; H01M 4/134 20130101; H01M 4/485
20130101; H01M 10/0568 20130101 |
International
Class: |
H01M 4/36 20060101
H01M004/36; H01M 4/40 20060101 H01M004/40; H01M 4/131 20100101
H01M004/131; H01M 4/133 20100101 H01M004/133; H01M 4/134 20100101
H01M004/134; H01M 10/0569 20100101 H01M010/0569; H01M 10/0568
20100101 H01M010/0568; H01M 10/0525 20100101 H01M010/0525; H01M
4/583 20100101 H01M004/583; H01M 4/58 20100101 H01M004/58; H01M
4/485 20100101 H01M004/485; H01M 4/13 20100101 H01M004/13; H01M
4/1395 20100101 H01M004/1395; H01M 4/1393 20100101 H01M004/1393;
H01M 4/136 20100101 H01M004/136 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 9, 2001 |
JP |
2001-110548 |
Sep 26, 2001 |
JP |
2001-294504 |
Claims
1. A nonaqueous electrolyte secondary battery comprising: an anode;
a cathode; and a nonaqueous electrolyte, wherein, the anode
comprises a negative electrode active material including composite
particles having a metallic material containing a carbon material,
the metallic material including a metal capable of
electrochemically reacting with lithium, and the carbon material is
stuck in a surface of the composite particles.
2. A nonaqueous electrolyte secondary battery according to claim 1,
wherein the composite particles are atomized powder.
3. The nonaqueous electrolyte secondary battery according to claim
1, wherein the carbon material is selected from the group
consisting of non-graphitizable carbon, graphitizable carbon,
graphite, carbon black, and mixtures thereof.
4. The nonaqueous electrolyte secondary battery according to claim
1, wherein the carbon material has a spherical form, a granular
form, a scale form, or a combination of them.
5. The nonaqueous electrolyte secondary battery according to claim
1, wherein the carbon material is at least partially embedded
within the composite particles.
6. The nonaqueous electrolyte secondary battery according to claim
1, wherein the carbon material has fiberous form.
7. The nonaqueous electrolyte secondary battery according to claim
1, wherein the carbon material is present in an amount of 0.3 wt %
to 90 wt %, both inclusive, relative to the metallic material.
8. The nonaqueous electrolyte secondary battery according to claim
1, wherein the carbon material is present in an amount that is
within the range of 1.0 wt % to 70 wt %, both inclusive, relative
to the metallic material.
9. The nonaqueous electrolyte secondary battery according to claim
1, wherein wherein the negative electrode active material comprises
a second carbon material that is different in composition from the
carbon material of the composite particles.
10. The nonaqueous electrolyte secondary battery according to claim
1, wherein the cathode comprises a lithium composite oxide
represented by a general formula Li.sub.xMO.sub.2, where M is one
or more transition metals, and x is different depending on charging
and discharging states of a battery and is within a range of from
about 0.05.ltoreq.x.ltoreq.1.10, both inclusive.
11. The nonaqueous electrolyte secondary battery according to claim
1, wherein the nonaqueous electrolyte comprises ethylene carbonate
and dimethyl carbonate.
12. The nonaqueous electrolyte secondary battery according to claim
11, wherein the nonaqueous electrolyte further comprises LiPF.sub.6
and LiBF.sub.4.
13. An anode active material comprising a composite particle
including a mixture of: (a) a metallic material; (b) a carbon
material; and (c) at least one metallic carbide compound selected
from the group consisting of SiC, WC, W.sub.2C, TiC, ZrC, HfC, VC,
NbC, TaC, MoC, V2C, Ta.sub.2C, Mo.sub.2C, Mn.sub.3C, Fe.sub.3C,
Co.sub.3C, and Ni.sub.3C, wherein, the carbon material is different
from each metallic carbide compound, the metallic material is not a
metallic carbide compound and includes a metal capable of
electrochemically reacting with lithium, the metallic material
includes silicon, tin or both, and the carbon material is at least
partially embedded within the metallic material.
14. The anode active material according to claim 13, wherein the
metallic material comprises a mixture of the metal capable of
electrochemically reacting with lithium and a metal which does not
electrochemically react with lithium.
15. The anode active material according to claim 13, wherein the
carbon material is selected from the group consisting of
non-graphitizable carbon, graphitizable carbon, graphite, carbon
black, and mixtures thereof.
16. The anode active material according to claim 13, wherein the
carbon material has a form selected from the group consisting of
spherical forms, granular forms, scale forms, and mixtures
thereof.
17. The anode active material according to claim 13, wherein the
carbon material and the metallic carbide compound are at least
partially embedded within the composite particles.
18. The anode active material according to claim 13, wherein the
carbon material has a fiber form.
19. The anode active material according to claim 13, wherein the
carbon material is present in an amount that is within the range of
0.3 wt % to 90 wt %, both inclusive, relative to the metallic
material.
20. The anode active material according to claim 13, wherein the
carbon material of the second material is present in an amount that
is within the range of 1 wt % to 70 wt %, both inclusive, relative
to the metallic material.
21. An anode active material comprising: (a) a carbon powder
comprising a first carbon material; and (b) composite particles
wherein, the composite particles include a metal material and a
second carbon material, the metallic material is not a metallic
carbide compound and includes a metal capable of electrochemically
reacting with lithium, the second carbon material comprises (i)
non-graphitizable carbon, graphitizable carbon, graphite, carbon
black, or mixtures of them, and (ii) at least one metallic carbide
compound selected from the group consisting of SiC, WC, W.sub.2C,
TiC, ZrC, HfC, VC, NbC, TaC, MoC, V.sub.2C, Ta.sub.2C, Mo.sub.2C,
Mn.sub.3C, Fe.sub.3C, Co.sub.3C, and Ni.sub.3C, for each composite
particle, the second carbon material is embedded in the metallic
material such that at least a portion of the second carbon material
is exposed from the composite particle and another portion of the
second carbon material is buried in the composite particle, the
non-graphitizable carbon, graphitizable carbon, graphite, carbon
black, or a mixture of them of the second carbon material is
present in an amount of 0.3 wt % to 90 wt %, both in inclusive, of
the metallic material, the metallic carbide compound is present in
an amount of 1.0 wt % to 85 wt %, both inclusive, of the metallic
material, and the carbon powder is present in an amount of 1.0 wt %
to 90 wt %, both inclusive, of the composite particles.
22. The anode active material of claim 21, wherein the first carbon
material consists of non-graphitizable carbon, graphitizable
carbon, graphite, carbon black, or a mixture of them.
23. The anode active material of claim 21, wherein the
non-graphitizable carbon, graphitizable carbon, graphite, carbon
black, or a mixture of them have a fibrous form, a spherical form,
granular form, scale form, or mixtures thereof.
Description
RELATED APPLICATION DATA
[0001] This application is a continuation of U.S. patent
application Ser. No. 15/233,331 filed Aug. 10, 2016, which is a
continuation of U.S. patent application Ser. No. 10/297,650 filed
Dec. 5, 2002, now U.S. Pat. No. 9,450,245 issued Sep. 20, 2016.
U.S. patent application Ser. No. 10/297,650 is the Section 371
National Stage of PCT/IB02/01115 filed Apr. 9, 2002. The entireties
of which are incorporated herein by reference to the extent
permitted by law. The present application claims the benefit of
priority to Japanese Patent Application Nos. JP 2001-110548 filed
on Apr. 9, 2001 and JP 2001-294504 filed on Sep. 26, 2001 in the
Japan Patent Office, the entireties of which are incorporated by
reference herein to the extent permitted by law.
TECHNICAL FIELD
[0002] The present invention relates to a negative material
including metal capable of electrochemically reacting with lithium
in a nonaqueous electrolyte and a nonaqueous electrolyte secondary
battery using the negative material.
BACKGROUND ART
[0003] In recent years, many portable electronic devices such as
video cameras with video tape recorders, portable telephones,
laptop computers, etc. have been produced and they have been made
compact and light. A study and development for improving the energy
density of batteries, especially, secondary batteries as the
portable power sources of these electronic devices have been
actively advanced. Particularly, since nonaqueous electrolyte
secondary batteries such as lithium-ion secondary batteries can
obtain energy density higher than those of lead-acid batteries and
nickel-cadmium batteries as conventional aqueous electrolyte
secondary batteries, the nonaqueous electrolyte secondary batteries
are useful as the power sources of the electronic devices.
[0004] As a negative material used for such a lithium-ion secondary
battery, carbonaceous materials such as non-graphitizable carbon or
graphite have been widely employed, because they have a relatively
high capacity and show good cyclic characteristics.
[0005] As the high capacity of the lithium-ion secondary batteries
is realized, the carbonaceous materials to act as an anode further
need to have higher capacity. For example, Japanese Patent
Application Laid-Open No. HEI 8-315825 proposes that carbonizing
materials and manufacturing conditions are selected to achieve a
high capacity by the carbonaceous materials. In the above-described
carbonaceous materials to act as an anode, since an anode
discharging potential is 0.8 V to 1.0 V relative to lithium,
battery discharging voltage when a battery is formed becomes low,
so that a great improvement of the energy density of the battery is
not anticipated. Further, the carbonaceous anode materials are
disadvantageously large in its hysteresis in the form of a charging
and discharging curve and low in its energy efficiency in each
charging and discharging cycle.
[0006] As an anode having a high capacity, there have been proposed
materials produced by applying a process that a certain kind of
metal is electrochemically alloyed with lithium and the alloy is
reversibly combined/decombined. As such materials, there may be
exemplified, for instance, Li--Al alloy, etc. Further, Si alloys
such as Li--Si alloy are disclosed in the specification of U.S.
Pat. No. 4,950,566. A battery using the Li--Al alloy and the Li--Si
alloy as negative materials exhibits disadvantages that the
expansion and contraction of an anode upon charging and discharging
operations are terrible, the negative material is caused to be
minute every time charging and discharging cycles are repeated and
cyclic characteristics are seriously bad. As one of main factors
that the cyclic characteristics are deteriorated, it may be guessed
that the negative materials are caused to be minute so that the
electronic connection between the negative materials or the
negative materials and a current collector is prevented to hardly
advance charging and discharging reactions.
DISCLOSURE OF THE INVENTION
[0007] The present invention is proposed by taking the problems of
the related art as described above into consideration and it is an
object of the present invention to provide an anode having a high
capacity and capable of realizing excellent cyclic characteristics,
a nonaqueous electrolyte secondary battery using this negative
material and a method for manufacturing a negative material.
[0008] In order to achieve the above-described object, an anode
according to the present invention includes composite particles
having a metallic material containing a carbon material, and metal
capable of electrochemically reacting with lithium in a nonaqueous
electrolyte as the metallic material.
[0009] Since the composite particles of the negative material
include the metal capable of electrochemically reacting with
lithium in the nonaqueous electrolyte as the metallic material, the
anode is used for a nonaqueous electrolyte secondary battery so
that the high capacity of the battery can be realized.
[0010] Since the metal capable of electrochemically reacting with
lithium which forms the anode expands and contracts in accordance
with electrochemical reactions, the composite particles are caused
to be minute when charging and discharging operations are repeated.
In the anode according to the present invention, since the carbon
materials are included in the composite particles, even when the
composite particles are caused to be minute, the carbon materials
are provided between the particles to ensure an electronic
conductivity in the composite particles.
[0011] The present invention concerns a nonaqueous electrolyte
secondary battery comprising an anode, a cathode and a nonaqueous
electrolyte. The anode used in the battery includes composite
particles as negative active material having a metallic material
containing a carbon material and metal capable of electrochemically
reacting with lithium in a nonaqueous electrolyte as the metallic
material.
[0012] In the nonaqueous electrolyte secondary battery according to
the present invention, the anode includes the composite particles
as negative active material having the metallic material containing
the carbon material. Since the composite particles include the
metal capable of electrochemically reacting with lithium in the
nonaqueous electrolyte as the metallic material, the nonaqueous
electrolyte secondary battery with a high capacity can be
realized.
[0013] Since the metal capable of electrochemically reacting with
lithium which forms the anode expands and contracts in accordance
with electrochemical reactions, the composite particles are caused
to be minute when charging and discharging operations are repeated.
In the anode used in the battery according to the present
invention, since the carbon materials are included in the composite
particles, even when the composite particles are caused to be
minute, the carbon materials are provided between the minute
particles so that an electronic conductivity in the composite
particles can be ensured. As a result, in the nonaqueous
electrolyte secondary battery according to the present invention,
even when the charging and discharging operations are repeated, the
increase of internal resistance of the battery due to the
deterioration of electrodes can be suppressed.
[0014] A method for manufacturing an anode according to the present
invention which includes composite particles having a metallic
material containing a carbon material and metal capable of
electrochemically reacting with lithium in a nonaqueous electrolyte
as the metallic material, comprises a step of mixing the metallic
material with the carbon material and pelletizing the mixture, and
at least a part of the step is carried out in a non-oxidizing
atmosphere.
[0015] In the method for manufacturing an anode according to the
present invention, since at least a part of the step of mixing the
metallic material with the carbon material and pelletizing the
mixture is carried out in the non-oxidizing atmosphere, the
oxidation or combustion of the carbon material is prevented.
[0016] In the present invention, a state that the carbon material
is included in the metallic material indicates a state that the
carbon material is stuck to the metallic material. At this time, a
part of the carbon material may be exposed from the surfaces of the
composite particles or the carbon material may be completely buried
in the composite particles.
[0017] Still other objects of the present invention and specific
advantages obtained by the present invention will be more apparent
from the description of an embodiment by referring to the
accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1 is a cross sectional view showing a nonaqueous
electrolyte secondary battery to which the present invention is
applied.
[0019] FIG. 2 is a characteristic view showing the relation between
the content of a carbon material included in composite particles,
the cyclic maintaining/retention ratio and the initial capacity
ratio of the nonaqueous electrolyte secondary battery.
BEST MODE FOR CARRYING OUT THE INVENTION
[0020] A negative material, a nonaqueous electrolyte battery and a
method for manufacturing an anode according to the present
invention will be described below in detail by referring to the
drawings.
[0021] A negative material according to the present invention
includes composite particles having a carbon material contained in
a metallic material. The metallic material includes metal capable
of electrochemically reacting with lithium in a nonaqueous
electrolyte. In the anode, since the composite particles include
the metal capable of electrochemically reacting with lithium in a
nonaqueous electrolyte (simply refer it to as "metal capable of
electrochemically reacting with lithium", hereinafter), when the
anode is used for a battery, it can achieve a higher capacity than
that of an anode using a conventional carbonaceous material.
[0022] Since the metal capable of electrochemically reacting with
lithium expands and contracts due to electrochemical reactions, the
metal is caused to be minute causing a structural destruction by
repeating charging and discharging operations. As a result, the
electronic conductivity between the minute metals capable of
electrochemically reacting with lithium is deteriorated.
[0023] According to the present invention, since the carbon
materials are included in the composite particles, even when the
composite particles are caused to be minute, the contained carbon
materials are interposed between the minute particles. Even when
the composite particles are caused to be minute by repeating the
charging and discharging reactions, the anode to which the present
invention is applied can maintain the electronic conductivity in
the composite particles.
[0024] In the present invention, a state that the carbon materials
are contained in the metallic material means a state that the
carbon materials stick to the metallic material. At this time, the
carbon materials may be partly exposed from the surfaces of the
composite particles or completely buried in the composite
particles. Where the carbon materials are merely stuck on the
surfaces of the composite particles, this case is not included in
the scope of the present invention. Whether or not the carbon
materials are included in the metallic material is decided
depending on whether the carbon materials are mixed in the
composite particles or not, for instance by cutting the composite
particles and observing the cut section by an analytical electron
microscope.
[0025] The metal capable of reacting with lithium in the nonaqueous
electrolyte indicates such metals capable of reacting with lithium
in the nonaqueous electrolyte as described below.
[0026] As the specific metals capable of electrochemically reacting
with lithium in the nonaqueous electrolyte, there may be
exemplified metals capable of electrochemically forming alloys with
lithium and alloy compounds thereof. The alloy compound herein
designates a compound represented by a chemical formula
M.sub.xM'.sub.yLi.sub.z (here, M' in the formula indicates one or
more metal elements except Li and M. x is a numeric value larger
than 0 and y and z are numeric values not smaller than 0.), when
assuming that a certain metal element capable of forming alloy with
lithium is M. In the present invention, there are also included
elements such as B, Si, As, etc. as semiconductor elements. There
may be specifically exemplified metals such as Mg, Al, Ga, In, Si,
Ge, Sn, Pb, Sb, Bi, Cd, Ag, Zn, Hf, Zr, Y, etc. and alloy compounds
thereof, Li--Al, Li--Al-M (here, M in the formula designates one or
more kinds of elements selected from the 2A group, 3B group, 4B
group, and transition metals.), AlSb, CuMgSb, etc.
[0027] As the metals capable of electrochemically forming alloys
with lithium, the 4B group main group elements are preferably
employed and Si or Sn are more preferably used. There are
exemplified compounds represented by a chemical formula
N.sub.xN'.sub.ySi (here, N and N' in the formula respectively
designate one or more metal elements except Si or Sn. Further, x
and y are numeric values larger than 0.), such as SiB.sub.4,
SiB.sub.6, Mg.sub.2Si, Mg.sub.2Sn, 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, etc. As the metallic materials used in
the present invention, a plurality of kinds of metals may be
combined together. There are used mixtures of metals capable of
electrochemically reacting with lithium in the nonaqueous
electrolyte and metals which do not electrochemically react with
lithium in the nonaqueous electrolyte and specifically mixtures of
metals capable of electrochemically forming alloys with lithium and
metals which do not electrochemically form alloys with lithium.
[0028] As the carbon materials included in the composite particles,
various kinds of carbon materials which can ensure an electronic
conductivity even in the minute composite particles can be suitably
selected. For instance, as the carbon materials, there may be used
non-graphitizable carbon, graphitizable carbon, graphite, carbon
black, etc. As the forms of the carbon materials, a fibrous
material, a spherical material, a granular material, a scale
material, etc. can be employed. As the carbon materials, a
plurality of carbon materials may be mixed and the mixture may be
use.
[0029] For instance, in order to obtain a higher electronic
conductivity, a high crystalline graphite is preferably used as the
carbon material includes in the composite particles. Further, when
it is desired to suppress the expansion and contraction of the
composite particles due to an electrochemical reaction, the
non-graphitizable carbon is preferably employed as the carbon
material included in the composite particles. When it is desired to
suppress the structural destruction of the composite particles,
that is, to suppress the minute particle, the fibrous carbon
material is preferably used as the carbon material included in the
composite particles. Further, when it is desired to improve a
dispersibility in the anode, the carbon black is preferably
employed as the carbon material included in the composite
particles. When the filling characteristics of the carbon material
in the composite particles are desirably improved, the granular
carbon material or the spherical carbon material is preferably
employed as the carbon material included in the composite
particles. Further, in order to obtain the effects of the
above-described combinations, two or more kinds of carbon materials
may be mixed as the carbon materials included in the composite
particles and the mixture may be preferably employed.
[0030] When the non-graphitizable carbon, the graphitizable carbon,
the graphite, the carbon black, etc. are used as the carbon
materials, the content of the carbon materials included in the
composite particles is preferably located within a range showing a
higher capacity than that of an anode using a usual carbonaceous
material in view of achieving a high capacity. The specific content
of the non-graphitizable carbon, the graphitizable carbon, the
graphite, the carbon black, etc. is preferably located within a
range to 0.3 wt % to 90 wt % relative to the metallic material
including the metal capable of electrochemically reacting with
lithium, more preferably located within a range of 0.5 wt % to 80
wt %, and especially preferably located within a range of 1 wt % to
70 wt %. When the content of the carbon materials is lower than the
above-described range, there is a fear that the electronic
conductivity may not be possibly maintained in the minute composite
particles. Further, when the content of the carbon materials
exceeds the above-described range, there exists a fear that an
effect of improving a capacity may be more insufficient than that
of the anode using the usual carbonaceous anode material.
[0031] As the carbon materials included in the composite particles,
metallic carbide compounds can be used. The metallic carbide
compounds are included in the composite particles, so that various
of kinds of effects can be obtained as well as the improvement
effect of the electronic conductivity like the above-described
non-graphitizable carbon, graphitizable carbon, graphite, carbon
black, etc. Specifically, when the compatibility of the metallic
carbide compound and the metal capable of electrochemically
reacting with lithium is high, the metallic carbide compound can
stabilize the composition of the metal capable of electrochemically
reacting with lithium. Further, the metallic carbide compound shows
a thermal shock buffer effect in a pelletizing step of the
composite particles to contribute to the stabilization of the
structures of the composite particles.
[0032] As the specific metallic carbide compounds, there are
enumerated SiC, B.sub.4C, WC, W.sub.2C, TiC, ZrC, HfC, VC, NbC,
TaC, MoC, V.sub.2C, Ta.sub.2C, Mo.sub.2C, Mn.sub.3C, Fe.sub.3C,
Co.sub.3C, Ni.sub.3C, etc. These metallic carbide compounds may be
independently used, or two or more kinds of them may be mixed and
the mixture may be used depending on purposes. The metallic carbide
compounds may be mixed with the above-described non-graphitizable
carbon, graphitizable carbon, graphite, carbon black, etc. and the
mixture may be used. Especially, the mixture of the metallic
carbide compounds and the non-graphitizable carbon, the
graphitizable carbon, the graphite, the carbon black, etc. as the
carbon materials is included in the composite particles, so that
the composite particles having more excellent characteristics are
obtained by the synergistic effect thereof.
[0033] The metallic carbide compound hardly has a charging and
discharging capacity by itself. Therefore, the composite particles
containing the metallic carbide compound shows a capacity in a
total of the anode materials lower than that when the
above-described non-graphitizable carbon, graphitizable carbon,
graphite, carbon black, etc. are included in the composite
particles. Accordingly, the content of the metallic carbide
compound included in the composite particles is preferably suitably
adjusted. The specific content of the metallic carbide compound is
preferably located within a range of 1 w % to 85 wt % relative to
the metallic material including the metal capable of
electrochemically reacting with lithium, more preferably located
within a range of 5 wt % to 60 wt %, and especially preferably
located within a range of 10 wt % to 50 wt %. When the content of
the metallic carbide compound is lower than the above-described
range, there exists a fear that the electronic conductivity may not
be possibly ensured in the minute composite particles. Further,
when the content of the carbon material exceeds the above-described
range, there exists a fear that the improvement effect of a
capacity may be possibly more insufficient than that of an anode
using a usual carbonaceous anode material.
[0034] The anode according to the present invention preferably
includes carbon powder as well as the composite particles having
the carbon material contained in the above-described metallic
material. In this case, the carbon powder is different from the
carbon material included in the composite particles, provided
between a plurality of composite particles and serves as a
conductive agent or an anode material. The anode includes the
carbon powder as well as the composite particles, so that the
electronic conductivity between the composite particles or the
composite particles and, for instance, a current collector can be
more improved.
[0035] The amount of mixing of the carbon powder relative to the
composite particles in the anode is preferably located within a
range showing a higher capacity than that of an anode using a usual
carbonaceous anode materials in view of achieving a high capacity.
The specific amount of mixing of the carbon powder is preferably
located within a range of 1 wt % to 95 wt % relative to the
composite particles. When the amount of mixing of the carbon powder
is lower than 1 wt %, there exists a fear that the electronic
conductivity of the composite particles or the composite particles
and, for instance, the current collector may be possibly
deteriorated. Further, when the amount of mixing of the carbon
powder exceeds 95 wt %, the content of the composite particles in
the anode is relatively decreased, and accordingly, an effect of
improving a capacity may be insufficient.
[0036] As the carbon powder to be mixed with the composite
particles, the carbon powder may be the same as or different from
the carbon material included in the composite particles as
described above. As the specific types of the carbon powder, there
may be exemplified, non-graphitizable carbon, graphitizable carbon,
graphite, carbon black, etc. In order to obtain desired battery
characteristics, a plurality of kinds of carbon powder may be mixed
and the mixture may be used.
[0037] As the forms of the carbon powder, there may be used the
powder of fibrous, spherical, granular, scale forms, etc. Further,
a plurality of kinds of forms of powder may be mixed and the
mixture may be used.
[0038] In the anode, a well-known binding agent and a current
collector, etc. can be used as well as the above-described
materials.
[0039] Since the above-described anode includes the composite
particles having the metal capable of electrochemically reacting
with lithium, the anode can realize a nonaqueous electrolyte
secondary battery having a high capacity.
[0040] Since the carbon material is contained in the composite
particles in the anode, even when the composite particles are
caused to be minute, the carbon material is interposed between the
minute composite particles to ensure the electronic conductivity in
the composite particles. Consequently, even when charging and
discharging operations are repeated, the rise of internal
resistance in the battery due to the deterioration of electrodes
can be suppressed. Accordingly, when this anode is used for the
nonaqueous electrolyte battery, the anode suppresses the rise of
the internal resistance in the battery due to the deterioration of
electrodes and realizes excellent cyclic characteristics.
[0041] Now, a method for manufacturing the above-described anode
will be described below.
[0042] When the composite particles included in the anode are
produced, there is provided a step of including the carbon material
in the metallic material, that is, a step of mixing the metallic
material with the carbon material and pelletizing the mixture. At
least a part of the step is carried out in a non-oxidizing
atmosphere. Thus, in the production step of the composite
particles, the oxidation or combustion of the carbon materials is
prevented. In other words, the carbon material included in the
composite particles is prevented from deteriorating its electronic
conductivity in the production step. Accordingly, can be produced
the composite particles which can ensure the electronic
conductivity, because the carbon material is interposed between the
minute composite particles even when the composite particles are
caused to be minute by an electrochemical reaction.
[0043] When all the steps of mixing the metallic material with the
carbon material and pelletizing the mixture is carried out in an
oxidizing atmosphere such as air, the carbon material is oxidized
or burnt. As a result, the manufactured composite particles
insufficiently effectively ensure the electronic conductivity when
the composite particles are caused to be minute.
[0044] As the above-described non-oxidizing atmosphere, there may
be exemplified a vacuum atmosphere, a reducing atmosphere, an inert
atmosphere, etc. More specifically, there may be exemplified a gas
atmosphere such as N.sub.2, Ar, He, H.sub.2, Co, etc. and a
plurality of kinds of them may be mixed and the mixture may be
used.
[0045] As a method for obtaining the composite particles by mixing
the metallic material with the carbon material and pelletizing the
mixture, for instance, such a method as described below is
preferably employed from an industrial point of view.
[0046] Initially, the metallic material including the metal capable
of electrochemically reacting with lithium is heated to be molten.
Then, the carbon material is mixed with the molten metallic
material and dispersed. Then, the mixture of the molten metallic
material and the carbon material is atomized to obtain atomized
powder. After that, the atomized powder is classified by using a
desired mesh, so that the composite particles having the carbon
material included in the metallic material can be obtained.
[0047] In this method, a process for mixing the carbon material
with the molten metallic material and dispersing the mixture is
preferably carried out in a non-oxidizing atmosphere. Since the
temperature of the molten metallic material is high, the metallic
material can be mixed with the carbon material to prevent the
carbon material from being oxidized or burnt. Further, an
atmosphere in which the mixture of the metallic material and the
carbon material is atomized is preferably a non-oxidizing
atmosphere.
[0048] As a method for mixing the carbon material with the molten
metallic material and dispersing the mixture, any of a method for
mechanically agitating the mixture, a method using a self-agitating
action such as an induction heating, etc. may be employed.
[0049] As described above, not only the method for mixing the
carbon material with the molten metallic material, but also the
metallic material may be mixed with the carbon material under a dry
state before the metallic material is molten. In this case, before
a heating process, the ambient atmosphere of the mixture of the
metallic material and the carbon material may be replaced by a
vacuum atmosphere or a non-oxidizing atmosphere.
[0050] As another method for obtaining the composite particles by
mixing the carbon material with the metallic material and
pelletizing the mixture, there may be exemplified a ball mill
method, a mechanical alloying method, etc. In any case, a step in
which the carbon material may be possibly oxidized or burnt is
carried out in a non-oxidizing atmosphere.
[0051] As a time and a method for adding the metallic carbide
compound when the metallic carbide compound is used as the carbon
material, there may be exemplified, for instance, there is
exemplified a method for adding the metallic carbide compound when
the metal capable of electrochemically reacting with lithium is
molten. There may be employed a method or the like that carbon and
metal as component materials of the metallic carbide compound are
respectively added to the molten metal capable of electrochemically
reacting with lithium and the molten metal capable of
electrochemically reacting with lithium is heated up to temperature
at which the molten metal and the added carbon and metal form the
metallic carbide compound.
[0052] According to the method for manufacturing the anode as
mentioned above, the step of mixing the metallic material including
the metal capable of electrochemically reacting with lithium with
the carbon material and forming pellets from the mixture is carried
out in the non-oxidizing atmosphere. Thus, there is no fear that
the carbon material is oxidized or burnt. Therefore, even when the
composite particles are caused to be minute, the carbon material is
interposed between the minute composite particles so that the
composite particles capable of ensuring the electronic conductivity
can be obtained. Accordingly, according to the present invention,
the anode which realizes a nonaqueous electrolyte secondary battery
having a high capacity and excellent cyclic characteristics can be
manufactured.
[0053] Now, a nonaqueous electrolyte secondary battery as one
example of the nonaqueous electrolyte secondary battery using the
above-described anode will be described below.
[0054] A nonaqueous electrolyte secondary battery to which the
present invention is applied is shown in FIG. 1. This nonaqueous
electrolyte secondary battery is, what is called, a cylindrical
type. As shown in FIG. 1, in a substantially hollow cylindrical
battery can 1, is provided a spirally coiled electrode element
formed by laminating an elongated cathode 2 having a cathode
material and an elongated anode 3 having an anode material through
a separator 4, and coiling the laminated body many times and fixing
the final end part of the separator 4 as an outermost periphery by
an adhesive tape 5. The separator 4 is impregnated with, for
instance, nonaqueous electrolyte solution as a nonaqueous
electrolyte.
[0055] To the opened end part of the battery can 1, a battery cover
6 and a safety valve device 7 provided inside the battery cover 6
are attached by caulking through a gasket 8 to seal the battery can
1. The battery cover 6 is made of the same material as that of, for
instance, the battery can 1. Further, in the battery can 1, a pair
of insulating plates 9 and 10 are respectively provided
perpendicularly to the peripheral surface so as to sandwich the
spirally coiled electrode element in there between. The safety
valve device 7 is provided with, what is called a current
cutting-off mechanism which is electrically connected to the
battery cover 6 and cuts off the electrical connection between the
battery cover 6 and the spirally coiled electrode element when the
internal pressure of the battery becomes a prescribed value or
higher due to an internal short circuit or an external heating.
[0056] To the cathode 2, a cathode lead 11 made of aluminum or the
like is connected. The cathode lead 11 is welded to the safety
valve device 7 to be electrically connected to the battery cover 6.
To the anode 3, an anode lead 12 made of nickel or the like is
connected. The anode lead 12 is welded to the battery can 1 to be
electrically connected thereto.
[0057] As the positive material used for the cathode 2, metallic
oxides, metallic sulfides, specific polymers, etc. can be used
depending on kinds of desired batteries. As the specific cathode
materials, there may be exemplified, metallic sulfides or metallic
oxides including no lithium such as TiS.sub.2, MoS.sub.2,
NbSe.sub.2, V.sub.2O.sub.5, etc., lithium composite oxides
including a main component represented by a general formula
Li.sub.xMo.sub.2 (here, M designates one or more kinds of
transition metals, x is different depending on the charging and
discharging states of a battery and ordinarily located within a
range expressed by 0.05.ltoreq.x.ltoreq.1.10).
[0058] The transition metals M forming the lithium composite oxide
preferably include Co, Ni, Mn, etc. As the specific lithium
composite oxides, there may be exemplified LiCoO.sub.2,
LiNiO.sub.2, Li.sub.xNi.sub.yCo.sub.1-yO2 (here, x and y are
different depending on the charging and discharging states of a
battery and ordinarily located within ranges expressed by
0<x<1 and 0.7<y<1.02.), lithium manganese oxides having
spinel type structures, etc. Such lithium composite oxides can
generate high voltage and are excellent in energy density.
[0059] For the cathode 2, a plurality of kinds of the
above-described positive materials may be mixed together and the
mixture may be used. When the cathode 2 is formed by using the
above-described positive materials, a well-known conductive agent
or a binding agent may be added thereto.
[0060] The anode 3 includes the above-described composite particles
having the carbon material contained in the metallic material and
metal capable of electrochemically reacting with lithium in a
nonaqueous electrolyte as the metallic material. Since the anode 3
has the above-described composite particles, a nonaqueous
electrolyte secondary battery having a higher capacity than that
using a usual carbonaceous anode material can be realized.
[0061] Since the carbon material is included in the composite
particles, even when the composite particles are caused to be
minute, the carbon material included in the composite particles is
interposed between the minute composite particles to ensure the
electronic conductivity in the composite particles. Accordingly,
there can be realized a nonaqueous electrolyte secondary battery in
which even when charging and discharging reactions are repeated,
the rise of internal resistance in the battery due to the
deterioration of electrodes can be suppressed and excellent cyclic
characteristics can be achieved.
[0062] The anode 3 may be electrochemically doped with lithium in
the battery after the battery is manufactured, or lithium may be
electrochemically supplied to the anode from the cathode 2 or a
lithium source except the cathode 2 after or before the battery is
manufactured. The anode may be doped with lithium by synthesizing a
material including lithium upon synthesizing the material or
including lithium in the anode 3 upon manufacturing the
battery.
[0063] As the nonaqueous electrolyte, there may be used, for
instance, nonaqueous electrolyte solution formed by dissolving
electrolyte salt in a nonaqueous electrolyte solvent.
[0064] As the nonaqueous electrolyte solvent used for preparing the
nonaqueous electrolyte solution, any of solvents used in such
nonaqueous electrolyte secondary batteries may be employed. There
are exemplified, for instance, propionic carbonate, ethylene
carbonate, diethyl carbonate, dimethyl carbonate,
1,2-dimethoxyethane, 1,2-diethoxyethane, .gamma.-butyrolactone,
tetrahydrofuran, 2-methylhydrofuran, 1-3-dioxolane,
4-methyl-1,3-dioxolane, diethyl ether, sulfolane, methyl sulfolane,
acetonitrile, propiononitrile, anisole, acetic ester, butyric
ester, propionic ester, etc.
[0065] As the electrolyte salts, any of salts used for such
nonaqueous electrolyte secondary batteries may be employed. There
are exemplified, for instance, LiClO.sub.4, LiAsF.sub.6,
LiPF.sub.6, LiBF.sub.4, LiB(C.sub.6H.sub.5).sub.4,
CH.sub.3SO.sub.3Li, CF.sub.3SO.sub.3Li, LiCl, LiBr, etc.
[0066] In the above-described nonaqueous electrolyte secondary
battery, the anode 3 includes the composite particles which have
the carbon material contained in the metallic material including
metal capable of electrochemically reacting with lithium.
Therefore, in the nonaqueous electrolyte secondary battery to which
the present invention is applied, a high capacity is achieved as
compared with a battery using a conventional carbonaceous anode
material. When the composite particles included in the anode 3 are
caused to be minute due to expansion and contraction upon charging
and discharging the battery, the carbon material is interposed
between the minute particles so that the electronic conductivity in
the composite particles can be ensured. Accordingly, in the
nonaqueous electrolyte secondary battery to which the present
invention is applied, the rise of internal resistance in the
battery due to the deterioration of electrodes is suppressed and
excellent cyclic characteristics are achieved.
[0067] As described above, the nonaqueous electrolyte secondary
battery to which the present invention is applied can realize the
high capacity and the excellent cyclic characteristics.
[0068] In the above description, although the nonaqueous
electrolyte secondary battery using the nonaqueous electrolyte
solution obtained by dissolving the electrolyte salt in the
nonaqueous solvent as the nonaqueous electrolyte is mentioned as an
example, the present invention is not limited thereto. The present
invention may be applied to examples using, as the nonaqueous
electrolyte, for instance, a solid electrolyte including
electrolyte salt and a gel electrolyte obtained by impregnating an
organic polymer with a nonaqueous solvent and electrolyte salt,
etc.
[0069] As the specific examples of the solid electrolyte, either an
inorganic solid electrolyte or a solid polymer electrolyte, which
is a material having a lithium ion conductivity, can be employed.
As the specific inorganic solid electrolytes, there may be
exemplified, lithium nitride, lithium iodide, etc. The solid
polymer electrolyte comprises electrolyte salt and a polymer
compound for dissolving it. As the specific polymer compounds,
ether polymers such as poly(ethylene oxide) or bridged materials
thereof, poly(methacrylate) esters, acrylate, etc. are
independently used or copolymerized or mixed in molecules and the
copolymerized or mixed materials can be used.
[0070] As the organic polymers used for the gel electrolyte,
various kinds of polymers absorbing a nonaqueous solvent to gel can
be used. As the specific organic polymers, there can be used
fluorinated polymers such as poly(vinylidene fluoride) or
poly(vinylidene fluoride-co-hexafluoro propylene), ether polymers
such as poly(ethylene oxide) or bridged materials thereof,
poly(acrylonitrile), etc. Especially, fluorinated polymers are
preferably used from the viewpoint of oxidation-reduction
stability. The electrolyte salt is included in these organic
polymers to obtain an ionic conductivity.
[0071] In the above explanation, although what is called a
cylindrical nonaqueous electrolyte secondary battery is described
as an example, the nonaqueous electrolyte secondary battery
according to the present invention is not limited thereto and may
have various kinds of forms. The nonaqueous electrolyte secondary
battery according to the present invention may be formed in any of
shapes of a prismatic type, a coin type, a button type, etc.
[0072] Lithium existing in the battery system of the nonaqueous
electrolyte secondary battery according to the present invention
does not need to be always supplied from the cathode 2 or the anode
3. The cathode 2 or the anode 3 may be electrochemically doped with
lithium during the manufacturing step of electrodes or the
battery.
EXAMPLES
[0073] Specific Examples to which the present invention is applied
will be described on the basis of experimental results. The present
invention is not limited to the following description.
Experiment 1
Sample 1
[0074] Firstly, an anode and negative material were manufactured as
described below.
[0075] Initially, Si powder as metal capable of electrochemically
reacting with lithium in a nonaqueous electrolyte was heated at
1500.degree. C. and molten in an atmosphere of Ar.
[0076] Then, a carbon material of 0.1 wt % was added to Si in a
molten state without changing the atmosphere and they were mixed
for some time. As the carbon material, spherical graphite (trade
name: MCMB 6-28 produced by Osaka Gas Chemicals Co., Ltd.) was
used.
[0077] Then, the mixture was atomized to the atmosphere of Ar to
obtain atomized powder.
[0078] Subsequently, the atomized powder was classified by 200
meshes and the classified product thus obtained was used as
composite particles having the carbon material contained in a
metallic material.
[0079] As a negative material, the composite particles and scale
shaped graphite (trade name: KS-44 produced by Timcal Co., Ltd)
were mixed in the weight ratio 50:50. Polyvinylidene fluoride of 8
parts by weight was added to this mixture of 100 parts by weight
and n-methylpyrrolidone as a solvent was further added to the
mixture to obtain anode composite mixture slurry. The anode
composite mixture slurry was uniformly applied to both the surfaces
of an elongated copper foil having the thickness of 15 m as an
anode current collector and dried, and then, the anode current
collector having the slurry applied and dried was
compression-molded by a roll press machine to obtain an elongated
anode.
[0080] Subsequently, a cathode was manufactured.
[0081] In order to obtain LiCoO.sub.2 as a positive active
material, lithium carbonate and cobalt carbonate were mixed in the
ratio 0.5 mole:1 mole and the mixture was sintered in air at
900.degree. C. for 5 hours.
[0082] Then, obtained LiCoO.sub.2 of 91 parts by weight, graphite
of 6 parts by weight as a conductive agent and polyvinylidene
fluoride of 3 parts by weight as a binding agent were mixed
together to obtain cathode composite mixture slurry. The cathode
composite mixture slurry was applied to both the surfaces of an
elongated aluminum foil having the thickness of 20 m as a cathode
current collector and dried, and the then, the dried cathode
current collector was compression-molded by a roll press machine to
obtain an elongated cathode.
[0083] The anode and the cathode manufacture as described above
were laminated through a separator made of a microporous
polypropylene film having the thickness of 25 m, then stacked the
anode, the separator, the cathode and the separator, respectively.
The laminated body thus obtained was spirally coiled many times and
the final end part of the separator as an outermost periphery was
fixed by an adhesive tape to manufacture a spirally coiled
electrode element.
[0084] The spirally coiled electrode element was accommodated in a
battery can made of iron and plated with nickel. The battery can
having diameter of 18 mm, height of 65 mm, inside diameter of 17.38
mm, and the thickness of 0.31 mm was used. A pair of insulating
plates were disposed on both the upper and lower surfaces of the
spirally coiled electrode element and a cathode lead made of
aluminum was drawn from the cathode current collector and connected
to a battery cover. Further, an anode lead made of nickel was drawn
from the anode current collector and welded to the battery can.
[0085] Nonaqueous electrolyte solution obtained by dissolving
LiPF.sub.6 in the mixed solvent of ethylene carbonate and dimethyl
carbonate of equal volume at the rate of 1 mole/1 was injected into
the battery can.
[0086] Then, the battery can was caulked through a gasket having a
surface to which asphalt was applied to fix the battery cover
thereto and hold an air-tightness in the battery. A cylindrical
nonaqueous electrolyte secondary battery was manufactured in such a
manner as described above.
Sample 2
[0087] A nonaqueous electrolyte secondary battery was manufactured
in the same manner as that of the Sample 1 except that the carbon
material of 0.3 wt % was included in the composite particles.
Sample 3
[0088] A nonaqueous electrolyte secondary battery was manufactured
in the same manner as that of the Sample 1 except that the carbon
material of 0.5 wt % was included in the composite particles.
Sample 4
[0089] A nonaqueous electrolyte secondary battery was manufactured
in the same manner as that of the Sample 1 except that the carbon
material of 1.0 wt % was included in the composite particles.
Sample 5
[0090] A nonaqueous electrolyte secondary battery was manufactured
in the same manner as that of the Sample 1 except that the carbon
material of 3.0 wt % was included in the composite particles.
Sample 6
[0091] A nonaqueous electrolyte secondary battery was manufactured
in the same manner as that of the Sample 1 except that the carbon
material of 5.0 wt % was included in the composite particles.
Sample 7
[0092] A nonaqueous electrolyte secondary battery was manufactured
in the same manner as that of the Sample 1 except that the carbon
material of 10.0 wt % was included in the composite particles.
Sample 8
[0093] A nonaqueous electrolyte secondary battery was manufactured
in the same manner as that of the Sample 1 except that the carbon
material of 15.0 wt % was included in the composite particles.
Sample 9
[0094] A nonaqueous electrolyte secondary battery was manufactured
in the same manner as that of the Sample 1 except that the carbon
material of 20.0 wt % was included in the composite particles.
Sample 10
[0095] A nonaqueous electrolyte secondary battery was manufactured
in the same manner as that of the Sample 1 except that the carbon
material of 30.0 wt % was included in the composite particles.
Sample 11
[0096] A nonaqueous electrolyte secondary battery was manufactured
in the same manner as that of the Sample 1 except that the carbon
material of 50.0 wt % was included in the composite particles.
Sample 12
[0097] A nonaqueous electrolyte secondary battery was manufactured
in the same manner as that of the Sample 1 except that the carbon
material of 70.0 wt % was included in the composite particles.
Sample 13
[0098] A nonaqueous electrolyte secondary battery was manufactured
in the same manner as that of the Sample 1 except that the carbon
material of 90.0 wt % was included in the composite particles.
Sample 14
[0099] A nonaqueous electrolyte secondary battery was manufactured
in the same manner as that of the Sample 1 except that metal
capable of electrochemically reacting with lithium was not used and
only spherical graphite (trade name: MCMB 6-28 produced by Osaka
Gas Chemicals Co., Ltd.) was used.
Sample 15
[0100] A nonaqueous electrolyte secondary battery was manufactured
in the same manner as that of the Sample 1 except that the carbon
material was not included in metal capable of electrochemically
reacting with lithium, that is, the composite particles were only
composed of Si.
[0101] The cyclic maintaining/retention ratios of the Samples 1 to
15 manufactured as described above were obtained. In order to
measure the cyclic maintaining/retention ratio, charging and
discharging cycles were repeated in which a constant-current and
constant-voltage charging operation was carried out under the
conditions of maximum voltage of 4.2 V, constant-current of 1 A and
charging time for 5 hours and a discharging operation was carried
out under constant-current of 1 A up to end voltage of 2.5 V.
Assuming that the discharging capacity of a first cycle was 100,
the discharging capacity of 50th cycle was represented by % as a
cyclic maintaining/retention ratio.
[0102] The initial capacity of each of the Samples 1 to 15 was
measured. Assuming that the initial capacity of the Sample 1 was 1,
the ratio of the initial capacity of each of the Samples 2 to 15
was represented as an initial capacity ratio.
[0103] The initial capacity ratios and the cyclic
maintaining/retention ratios of the Samples 1 to 15 are shown in
Table 1 illustrated below and FIG. 2.
TABLE-US-00001 TABLE 1 Contained Scale Shaped Carbon Graphite
Initial Material Conductive Cyclic Maintaining/ Capacity (wt %)
Agent (%) retention Ratio (%) Ratio Sample 1 0.1 50 11 1.00 Sample
2 0.3 50 15 1.03 Sample 3 0.5 50 32 1.05 Sample 4 1.0 50 68 1.09
Sample 5 3.0 50 81 1.11 Sample 6 5.0 50 84 1.11 Sample 7 10.0 50 90
1.10 Sample 8 15.0 50 93 1.06 Sample 9 20.0 50 94 1.02 Sample 10
30.0 50 94 0.98 Sample 11 50.0 50 90 0.91 Sample 12 70.0 50 80 0.73
Sample 13 90.0 50 70 0.45 Sample 14 100.0 50 95 0.35 Sample 15 0.0
50 9 0.99
[0104] It was understood from the results of the Table 1 and FIG. 2
that the Samples 1 to 14 using the composite particles having the
carbon material contained in the metallic material as the negative
active material of the anode showed more excellent cyclic
characteristics than that of the Sample 15 using the negative
active material of the anode composed of only metal capable of
electrochemically reacting with lithium.
[0105] The Sample 14 using the negative active material of the
anode including no metal capable of electrochemically reacting with
lithium and composed only of the carbon material showed an initial
capacity lower than those of the Samples 1 to 13 using the
composite particles including the metallic material.
[0106] It was apparent from the above-described results that the
anode included the composite particles having the carbon material
contained in the metallic material and metal capable of
electrochemically reacting with lithium in the nonaqueous
electrolyte solution was included as the metallic material so that
the nonaqueous electrolyte secondary battery in which a high
initial capacity was compatible with excellent cyclic
characteristics could be realized.
Experiment 2
Sample 16
[0107] A nonaqueous electrolyte secondary battery was manufactured
in the same manner as that of the Sample 1 except that acetylene
black (produced by Denki Kagaku Kogyo K. K.) of 10 wt % was used as
the carbon material contained in the composite particles. The
acetylene black is an aggregate of several hundred nm to several
thousand nm having fine particles of about several ten nm connected
in a string of beads.
Sample 17
[0108] A nonaqueous electrolyte secondary battery was manufactured
in the same manner as that of the Sample 1 except that scale type
graphite (trade name: KS-6 produced by Timcal Co., Ltd.) of 10 wt %
was used as the carbon material contained in the composite
particles. Sample 18
[0109] A nonaqueous electrolyte secondary battery was manufactured
in the same manner as that of the Sample 1 except that fibrous
graphite (trade name: VGCF produced by Showa Denko, K. K.) of 10 wt
% was used as the carbon material contained in the composite
particles. Sample 19
[0110] A nonaqueous electrolyte secondary battery was manufactured
in the same manner as that of the Sample 1 except that pitch-based
non-graphitizable carbon (trade name: Carbotron P produced by
Kureha Chemical Industry Co., Ltd.) of 10 wt % was used as the
carbon material contained in the composite particles. The
pitch-based non-graphitizable carbon has angular forms caused to be
minute to have an average diameter of about several m to several
ten m. Sample 20
[0111] A nonaqueous electrolyte secondary battery was manufactured
in the same manner as that of the Sample 1 except that the mixture
of scale type graphite (trade name: KS-6 produced by Timcal Co.,
Ltd.) and fibrous graphite (trade name: KS-6 produced by Timcal
Co., Ltd.) of 10 wt % having equal volume was used as the carbon
material contained in the composite particles.
[0112] The initial capacity ratios and the cyclic
maintaining/retention ratios of the Samples 16 to 20 manufactured
as mentioned above were obtained in the same manner as that of the
above Experiment 1. The results of the initial capacity ratios and
the cyclic maintaining/retention ratios of the Samples 16 to 20 are
shown in Table 2 together with the results of the Sample 7.
TABLE-US-00002 TABLE 2 Contained Scale Shaped Carbon Graphite
Cyclic Initial Material Conductive Maintaining/retention Capacity
(wt %) Agent (%) Ratio (%) Ratio Sample 7 10.0 50 90 1.10 Sample 16
10.0 50 91 1.05 Sample 17 10.0 50 92 1.07 Sample 18 10.0 50 93 1.08
Sample 19 10.0 50 94 1.04 Sample 20 10.0 50 93 1.09
[0113] As apparent from the Table 2, when any kind of materials of
acetylene black, graphite and non-graphitizable carbon was used as
the carbon material contained in the composite particles, the
nonaqueous electrolyte secondary battery having a high capacity and
excellent cyclic characteristics could be realized.
[0114] Further, it was understood that any of a spherical form, a
scale form and a fibrous form could be used as the form of the
carbon material contained in the composite particles and a
plurality of kinds of them could be mixed and used.
Experiment 3
Sample 21
[0115] Initially, Si powder of 20 parts by weight as metal capable
of electrochemically reacting with lithium was mixed with Cu powder
of 80 parts by weight as metal which did not electrochemically
react with lithium and the mixture was heated at 1000.degree. C.
and molten in an atmosphere of Ar.
[0116] Then, a carbon material of 0.1 wt % was added to the mixture
of Si and Cu in a molten state without changing the atmosphere and
they were mixed for some time. As the carbon material, spherical
graphite (trade name: MCMB 6-28 produced by Osaka Gas Chemicals
Co., Ltd.) was used.
[0117] Then, the mixture was atomized to the atmosphere of Ar to
obtain atomized powder.
[0118] Subsequently, the atomized powder was classified by 200
meshes and the classified product thus obtained was used as
composite particles.
[0119] A nonaqueous electrolyte secondary battery was manufacture
in the same manner as that of the Sample 1 except that the
composite particles obtained as described above were used as the
anode material.
[0120] The initial capacity ratio and the cyclic
maintaining/retention ratio of the Sample 21 manufactured as
mentioned above were obtained in a similar manner to that of the
above Experiment 1. The results of the initial capacity ratio and
the cyclic maintaining/retention ratio of the Sample 21 are shown
in Table 3 as well as the results of the Sample 10.
TABLE-US-00003 TABLE 3 Contained Scale Shaped Carbon Graphite
Cyclic Initial Material Conductive Maintaining/retention Capacity
(wt %) Agent (%) Ratio (%) Ratio Sample 10 30.0 50 94 0.98 Sample
21 30.0 50 95 0.98
[0121] As apparent from the Table 3, even when the metallic
material forming the composite particles was composed of the
mixture of the metal capable of electrochemically reacting with
lithium and the metal incapable of electrochemically reacting with
lithium, a nonaqueous electrolyte secondary battery having a high
capacity and excellent in its cyclic characteristics could be
realized.
Experiment 4
Sample 22
[0122] Composite particles were produced in the same manner as that
of the Sample 8. The composite particles and scale type graphite
(trade name: KS-44 produced by Timcal Co., Ltd.) were mixed in the
weight ratio 95:5. A nonaqueous electrolyte secondary battery was
manufactured in the same manner as that of the Sample 8 except that
an anode was manufactured by using the mixture.
Sample 23
[0123] Composite particles were produced in the same manner as that
of the Sample 8. The composite particles and scale type graphite
(trade name: KS-44 produced by Timcal Co., Ltd.) were mixed in the
weight ratio 85:15. A nonaqueous electrolyte secondary battery was
manufactured in the same manner as the Sample 8 except that an
anode was manufactured by using the mixture.
Sample 24
[0124] Composite particles were produced in the same manner as that
of the Sample 8. The composite particles and scale type graphite
(trade name: KS-44 produced by Timcal Co., Ltd.) were mixed in the
weight ratio 65:35. A nonaqueous electrolyte secondary battery was
manufactured in the same manner as that of the Sample 8 except that
an anode was manufactured by using the mixture.
Sample 25
[0125] Composite particles were produced in the same manner as that
of the Sample 8. The composite particles and scale type graphite
(trade name: KS-44 produced by Timcal Co., Ltd.) were mixed in the
weight ratio 25:75. A nonaqueous electrolyte secondary battery was
manufactured in the same manner as the Sample 8 except that an
anode was manufactured by using the mixture.
Sample 26
[0126] Composite particles were produced in the same manner as that
of the Sample 8. The composite particles and scale type graphite
(trade name: KS-44 produced by Timcal Co., Ltd.) were mixed in the
weight ratio 5:95. A nonaqueous electrolyte secondary battery was
manufactured in the same manner as that of the Sample 8 except that
an anode was manufactured by using the mixture.
[0127] The initial capacity ratios and the cyclic
maintaining/retention ratios of the Samples 22 to 26 manufactured
as mentioned above were obtained in a similar manner to that of the
above Experiment 1. The results of the initial capacity ratios and
the cyclic maintaining/retention ratios of the Samples 22 to 26 are
shown in Table 4 as well as the results of the Sample 8.
TABLE-US-00004 TABLE 4 Contained Scale Shaped Carbon Graphite
Cyclic Initial Material Conductive Maintaining/retention Capacity
(wt %) Agent (%) Ratio (%) Ratio Sample 22 15.0 5 75 1.33 Sample 23
15.0 15 81 1.22 Sample 24 15.0 35 94 1.15 Sample 8 15.0 50 93 1.06
Sample 25 15.0 75 94 0.88 Sample 26 15.0 95 94 0.45
[0128] As apparent from the Table 4, when the anode had the carbon
powder as well as the composite particles, the nonaqueous
electrolyte secondary battery having a high capacity and excellent
cyclic characteristics could be realized under various kinds of
mixture ratios.
Experiment 5
Sample 27
[0129] A nonaqueous electrolyte secondary battery was manufactured
in the same manner as that of the Sample 10 except that a carbon
material was added to Si in a molten state under the atmosphere of
air and they were mixed for some time, when composite particles
were produced.
[0130] The initial capacity ratio and the cyclic
maintaining/retention ratio of the Sample 27 manufactured as
mentioned above were obtained in a similar manner to that of the
above Experiment 1. The results of the initial capacity ratio and
the cyclic maintaining/retention ratio of the Sample 27 are shown
in Table 5 as well as the results of the Sample 10.
TABLE-US-00005 TABLE 5 Contained Scale Shaped Carbon Graphite
Cyclic Initial Material Conductive Maintaining/retention Capacity
(wt %) Agent (%) Ratio (%) Ratio Sample 10 30.0 50 94 0.98 Sample
27 30.0 50 92 0.98
[0131] It was understood from the results of the Table 5 that the
Sample 10 in which the carbon material was mixed with the metal
capable of electrochemically reacting with lithium in a molten
state under a non-oxidizing atmosphere showed a higher capacity and
a more excellent cyclic maintaining/retention ratio than those of
the Sample 27 in which the carbon material was mixed with the metal
capable of electrochemically reacting with lithium in air.
[0132] As apparent from the above-described results, at least a
part of a step of mixing the carbon material with metal capable of
electrochemically reacting with lithium and pelletizing the mixture
was carried out under the non-oxidizing atmosphere so that the
composite particles could be manufactured without oxidizing or
sintering the carbon material and a nonaqueous electrolyte
secondary battery having more excellent characteristics could be
manufactured.
Experiment 6
Sample 28
[0133] A nonaqueous electrolyte secondary battery was manufactured
in the same manner as that of the Sample 7 except that composite
particles were produced by further adding metallic carbide compound
(SiC) of 1 wt % as a carbon material to Si in a molten state.
Spherical graphite (trade name: MCMB 6-28 produced by Osaka Gas
Chemicals Co., Ltd.) and the metallic carbide compound (SiC) as the
carbon materials were added to Si in the molten state at the same
time.
Sample 29
[0134] A nonaqueous electrolyte secondary battery was manufactured
in the same manner as that of the Sample 7 except that composite
particles were produced by further adding metallic carbide compound
(SiC) of 3 wt % as a carbon material to Si in a molten state.
Spherical graphite (trade name: MCMB 6-28 produced by Osaka Gas
Chemicals Co., Ltd.) and the metallic carbide compound (SiC) as the
carbon materials were added to Si in the molten state at the same
time.
Sample 30
[0135] A nonaqueous electrolyte secondary battery was manufactured
in the same manner as that of the Sample 7 except that composite
particles were produced by further adding metallic carbide compound
(SiC) of 5 wt % as a carbon material to Si in a molten state.
Spherical graphite (trade name: MCMB 6-28 produced by Osaka Gas
Chemicals Co., Ltd.) and the metallic carbide compound (SiC) as the
carbon materials were added to Si in the molten state at the same
time.
Sample 31
[0136] A nonaqueous electrolyte secondary battery was manufactured
in the same manner as that of the Sample 7 except that composite
particles were produced by further adding metallic carbide compound
(SiC) of 10 wt % as a carbon material to Si in a molten state.
Spherical graphite (trade name: MCMB 6-28 produced by Osaka Gas
Chemicals Co., Ltd.) and the metallic carbide compound (SiC) as the
carbon materials were added to Si in the molten state at the same
time.
Sample 32
[0137] A nonaqueous electrolyte secondary battery was manufactured
in the same manner as that of the Sample 7 except that composite
particles were produced by further adding metallic carbide compound
(SiC) of 20 wt % as a carbon material to Si in a molten state.
Spherical graphite (trade name: MCMB 6-28 produced by Osaka Gas
Chemicals Co., Ltd.) and the metallic carbide compound (SiC) as the
carbon materials were added to Si in the molten state at the same
time.
Sample 33
[0138] A nonaqueous electrolyte secondary battery was manufactured
in the same manner as that of the Sample 7 except that composite
particles were produced by further adding metallic carbide compound
(SiC) of 40 wt % as a carbon material to Si in a molten state.
Spherical graphite (trade name: MCMB 6-28 produced by Osaka Gas
Chemicals Co., Ltd.) and the metallic carbide compound (SiC) as the
carbon materials were added to Si in the molten state at the same
time.
Sample 34
[0139] A nonaqueous electrolyte secondary battery was manufactured
in the same manner as that of the Sample 7 except that composite
particles were produced by further adding metallic carbide compound
(SiC) of 70 wt % as a carbon material to Si in a molten state.
Spherical graphite (trade name: MCMB 6-28 produced by Osaka Gas
Chemicals Co., Ltd.) and the metallic carbide compound (SiC) as the
carbon materials were added to Si in the molten state at the same
time.
Sample 35
[0140] A nonaqueous electrolyte secondary battery was manufactured
in the same manner as that of the Sample 7 except that composite
particles were produced by further adding metallic carbide compound
(SiC) of 90 wt % as a carbon material to Si in a molten state.
Spherical graphite (trade name: MCMB 6-28 produced by Osaka Gas
Chemicals Co., Ltd.) and the metallic carbide compound (SiC) as the
carbon materials were added to Si in the molten state at the same
time.
Sample 36
[0141] A nonaqueous electrolyte secondary battery was manufactured
in the same manner as that of the Sample 1 except that composite
particles were produced by adding only metallic carbide compound
(SiC) of 40 wt % as a carbon material to Si in a molten state.
[0142] The initial capacity ratios and the cyclic
maintaining/retention ratios of the Samples 28 to 36 manufactured
as mentioned above were obtained in a similar manner to that of the
above Experiment 1. The results of the initial capacity ratios and
the cyclic maintaining/retention ratios of the Samples 28 to 36 are
shown in Table 6.
TABLE-US-00006 TABLE 6 Composite Particle Metal Capable of
Contained Carbon Material Electrochemically Metallic Carbide
Reacting with Compound (SiC) Acetylene Black Lithium (wt %) (wt %)
(wt %) Sample 28 90 1 10 Sample 29 90 3 10 Sample 30 90 5 10 Sample
31 90 10 10 Sample 32 90 20 10 Sample 33 90 40 10 Sample 34 90 70
10 Sample 35 90 90 10 Sample 36 100 40 -- Scale Shaped Graphite
Cyclic Maintaining/retention Conductive Agent (%) Ratio (%) Sample
28 50 90 Sample 29 50 91 Sample 30 50 93 Sample 31 50 94 Sample 32
50 94 Sample 33 50 93 Sample 34 50 92 Sample 35 50 90 Sample 36 50
92
[0143] As apparent from the results of the Sample 36 in the Table
6, the nonaqueous electrolyte secondary battery excellent in its
cyclic characteristics could be realized by using the metallic
carbide compound as the carbon material to be contained in the
composite particles.
[0144] Further, as apparent from the results of the Samples 28 to
35, the mixture of materials such as the metallic carbide compound
and acetylene black could be used as the carbon material to be
contained in the composite particles.
INDUSTRIAL APPLICABILITY
[0145] Since composite particles include metal capable of
electrochemically reacting with lithium in a nonaqueous electrolyte
as a metallic material, an anode according to the present invention
can realize a high capacity. Further, the anode according to the
present invention can ensure an electronic conductivity in the
composite particles even. when the composite particles are caused
to be minute due to expansion and contraction upon electrochemical
reaction, because a carbon material is contained in the composite
particles so that the carbon material is interposed between the
minute particles. Thus, according to the present invention, there
can be provided the anode in which a high capacity is exhibited,
the rise of internal resistance in a battery due to the
deterioration of electrodes is suppressed and excellent
characteristics are realized, when the anode is used for a
nonaqueous electrolyte battery.
[0146] In a nonaqueous electrolyte secondary battery according to
the present invention, an anode includes composite particles having
a carbon material contained in a metallic material. Since the
composite particles include metal capable of electrochemically
reacting with lithium in nonaqueous electrolyte solution as the
metallic material, the nonaqueous electrolyte secondary battery
having a high capacity can be realized. Even when the composite
particles are caused to be minute, since the carbon material is
contained in the composite particles, the carbon material is
interposed between the minute particles to ensure an electronic
conductivity in the composite particles. As a result, even when
charging and discharging operations are repeated, the rise of
internal resistance in the battery due to the deterioration of
electrodes is suppressed. Accordingly, according to the present
invention, there can be provided the nonaqueous electrolyte
secondary battery in which a high capacity is shown, the rise of
internal resistance in the battery due to the deterioration of
electrodes is suppressed and excellent cyclic characteristics are
realized.
[0147] In a method for manufacturing an anode according to the
present invention, when composite particles are produced, at least
a part of a step of mixing a metallic material including metal
capable of electrochemically reacting with lithium in a nonaqueous
electrolyte with a carbon material and pelletizing the mixture is
carried out in a non-oxidizing atmosphere. Thus, the carbon
material is prevented from being oxidized or burnt. Therefore,
according to the present invention, can be manufactured the anode
capable of realizing a nonaqueous electrolyte secondary battery
having high capacity and excellent cyclic characteristics.
* * * * *