U.S. patent application number 15/108177 was filed with the patent office on 2016-11-10 for negative electrode active material for nonaqueous electrolyte secondary batteries and nonaqueous electrolyte secondary battery containing negative electrode active material.
This patent application is currently assigned to Sanyo Electric Co., Ltd.. The applicant listed for this patent is SANYO ELECTRIC CO., LTD.. Invention is credited to Tatsuya Akira, Yoshio Kato, Hiroshi Minami, Taizou Sunano.
Application Number | 20160329562 15/108177 |
Document ID | / |
Family ID | 56126242 |
Filed Date | 2016-11-10 |
United States Patent
Application |
20160329562 |
Kind Code |
A1 |
Akira; Tatsuya ; et
al. |
November 10, 2016 |
NEGATIVE ELECTRODE ACTIVE MATERIAL FOR NONAQUEOUS ELECTROLYTE
SECONDARY BATTERIES AND NONAQUEOUS ELECTROLYTE SECONDARY BATTERY
CONTAINING NEGATIVE ELECTRODE ACTIVE MATERIAL
Abstract
In a nonaqueous electrolyte secondary battery in which SiO.sub.x
is used as a negative electrode active material, initial
charge/discharge efficiency and cycle characteristics are improved.
Provided is a negative electrode active material, containing
particles made of SiO.sub.x (0.5.ltoreq.X.ltoreq.1.5), for
nonaqueous electrolyte secondary batteries. In the negative
electrode active material, amorphous carbon is stuck on carbon
coatings. The particles made of SiO.sub.x preferably have a size of
1 .mu.m to 15 .mu.m. Particles of amorphous carbon preferably have
a size of 0.01 .mu.m to 1 .mu.m. One hundred percent of the surface
of SiO.sub.x is preferably covered by the carbon coatings.
Inventors: |
Akira; Tatsuya; (Osaka,
JP) ; Minami; Hiroshi; (Osaka, JP) ; Sunano;
Taizou; (Osaka, JP) ; Kato; Yoshio; (Osaka,
JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SANYO ELECTRIC CO., LTD. |
Osaka |
|
JP |
|
|
Assignee: |
Sanyo Electric Co., Ltd.
Daito-shi, Osaka
JP
|
Family ID: |
56126242 |
Appl. No.: |
15/108177 |
Filed: |
December 12, 2014 |
PCT Filed: |
December 12, 2014 |
PCT NO: |
PCT/JP2015/006198 |
371 Date: |
June 24, 2016 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
Y02E 60/10 20130101;
B32B 2264/12 20130101; C09J 7/255 20180101; H01M 4/133 20130101;
C09J 2483/00 20130101; G06F 3/041 20130101; H01M 4/483 20130101;
H01M 10/0525 20130101; C09J 7/38 20180101; B32B 2264/104 20130101;
H01M 4/131 20130101; H01M 4/625 20130101; C09J 2467/006 20130101;
B32B 2457/10 20130101; B32B 15/20 20130101; B32B 2307/202 20130101;
H01M 2004/027 20130101; B32B 2264/108 20130101; H01M 4/621
20130101; B32B 15/16 20130101 |
International
Class: |
H01M 4/48 20060101
H01M004/48; H01M 4/62 20060101 H01M004/62; H01M 4/133 20060101
H01M004/133; H01M 10/0525 20060101 H01M010/0525; H01M 4/131
20060101 H01M004/131 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 16, 2014 |
JP |
2014-254384 |
Claims
1. A negative electrode active material for nonaqueous electrolyte
secondary batteries being a particulate negative electrode active
material used in nonaqueous electrolyte secondary batteries, the
negative electrode active material comprising: mother particles
made of SiO.sub.x (0.5.ltoreq.X.ltoreq.1.5); carbon coating layers
each covering at least one portion of the surface of a
corresponding one of the mother particles; and amorphous carbon
particles stuck on the carbon coating layers.
2. The negative electrode active material for nonaqueous
electrolyte secondary batteries according to claim 1, wherein the
mother particles have an average size of 1 .mu.m to 15 .mu.m and
the amorphous carbon particles have an average size of 0.01 .mu.m
to 1 .mu.m.
3. The negative electrode active material for nonaqueous
electrolyte secondary batteries according to claim 1, wherein 100%
of the surface of each of the mother particles is covered by a
corresponding one of the carbon coating layers.
4. A nonaqueous electrolyte secondary battery comprising: a
negative electrode containing the negative electrode active
material according to claim 1; a positive electrode containing a
positive electrode active material; a separator placed between the
positive electrode and the negative electrode; and a nonaqueous
electrolyte.
Description
TECHNICAL FIELD
[0001] The present invention relates to a negative electrode active
material for nonaqueous electrolyte secondary batteries and a
nonaqueous electrolyte secondary battery containing the negative
electrode active material.
BACKGROUND ART
[0002] Silicon (Si) and a silicon oxide represented by SiO.sub.x
have higher capacity per unit volume as compared to carbon
materials such as graphite and therefore have been investigated for
applications in negative electrode active materials. In particular,
SiO.sub.x has a smaller volume expansion coefficient as compared to
Si when SiO.sub.x stores Li during charge and therefore is expected
to be quickly commercialized. For example, Patent Literature 1
discloses SiO.sub.x having a carbon coating formed on the
surface.
CITATION LIST
Patent Literature
[0003] PTL 1: Japanese Published Unexamined Patent Application No.
2004-47404
SUMMARY OF INVENTION
Technical Problem
[0004] However, there is a problem in that a nonaqueous electrolyte
secondary battery in which SiO.sub.x or the like is used as a
negative electrode active material has poorer initial
charge/discharge efficiency and a larger reduction in capacity in
initial cycles as compared to the case where graphite is used as a
negative electrode active material.
Solution to Problem
[0005] A major cause of the problem is that the change in volume of
SiO.sub.x or the like during charge and discharge is larger than
that of graphite. The large change in volume of an active material
probably causes, for example, the reduction in electrical
conductivity of an active material layer, leading to the
deterioration of initial charge/discharge efficiency or the
like.
[0006] In order to solve the problem, a negative electrode active
material for nonaqueous electrolyte secondary batteries according
to the present invention is a particulate negative electrode active
material used in nonaqueous electrolyte secondary batteries. The
negative electrode active material includes mother particles made
of SiO.sub.x (0.5.ltoreq.X.ltoreq.1.5), carbon coating layers each
covering at least one portion of the surface of a corresponding one
of the mother particles, and amorphous carbon particles stuck on
the carbon coating layers.
[0007] A nonaqueous electrolyte secondary battery according to the
present invention includes a negative electrode containing the
negative electrode active material, a positive electrode, a
separator placed between the positive electrode and the negative
electrode, and a nonaqueous electrolyte.
Advantageous Effects of Invention
[0008] According to the present invention, in a nonaqueous
electrolyte secondary battery in which SiO.sub.x is used as a
negative electrode active material, cycle characteristics and
initial charge/discharge efficiency can be improved.
BRIEF DESCRIPTION OF DRAWINGS
[0009] FIG. 1 is a sectional view of a negative electrode which is
an example of an embodiment of the present invention.
[0010] FIG. 2 is a sectional view of a particle of a negative
electrode active material which is an example of an embodiment of
the present invention.
[0011] FIG. 3 is a first electron micrograph showing a cross
section of a negative electrode active material particle used in
Experiment 1.
[0012] FIG. 4 is a second electron micrograph showing a cross
section of a negative electrode active material particle used in
Experiment 1.
[0013] FIG. 5 is a graph showing results of the laser Raman
spectroscopic analysis of negative electrode active material
particles used in Experiment 1.
[0014] FIG. 6 is a graph showing results of the laser Raman
spectroscopic analysis of negative electrode active material
particles used in Experiment 4.
[0015] FIG. 7 is a graph showing results of the laser Raman
spectroscopic analysis of carbonaceous matter prepared by
heat-treating citric acid only.
[0016] FIG. 8 is a graph showing I.sub.V/I.sub.G values in FIGS. 5
to 7.
[0017] FIG. 9 is a third electron micrograph showing a cross
section of a negative electrode active material particle used in
Experiment 4.
DESCRIPTION OF EMBODIMENTS
[0018] Embodiments of the present invention are described below in
detail.
[0019] In this specification, the term "approximately **" is
intended to include completely the same things and those regarded
as substantially the same, as described using the term
"approximately the same" as an example. Drawings referred to in the
description of the embodiments are those schematically drawn.
Dimensional proportions of each component illustrated in the
drawings may possibly be different from those of an actual one.
Detailed dimensional proportions and the like should be judged in
consideration of descriptions below.
[0020] A nonaqueous electrolyte secondary battery which is an
example of an embodiment of the present invention includes a
positive electrode containing a positive electrode active material,
a negative electrode containing a negative electrode active
material, a nonaqueous electrolyte containing a nonaqueous solvent,
and a separator. An example of the nonaqueous electrolyte secondary
battery is a structure in which an electrode assembly formed by
winding the positive electrode, the negative electrode, and the
separator placed therebetween and the nonaqueous electrolyte are
housed in an enclosure.
(Positive Electrode)
[0021] The positive electrode is preferably composed of a positive
electrode current collector and a positive electrode active
material layer formed on the positive electrode current collector.
The positive electrode current collector used is, for example, a
conductive thin film, particularly metal or alloy foil which is
made of aluminium or the like and which is stable within the
potential range of the positive electrode or a film including a
metal surface layer made of aluminium or the like. The positive
electrode active material layer preferably contains a conductive
material and a conductive agent in addition to the positive
electrode active material.
[0022] The positive electrode active material is not particularly
limited and is preferably a lithium transition metal oxide. The
lithium transition metal oxide may contain a non-transition metal
such as Mg or Al. Examples of the lithium transition metal oxide
include lithium cobaltate, olivine-type lithium phosphates typified
by lithium iron phosphate, Ni--Co--Mn, Ni--Mn--Al, and Ni--Co--Al.
The positive electrode active material may contain one or more of
these compounds.
[0023] For the conductive material, carbon materials such as carbon
black, acetylene black, Ketjenblack, and graphite and mixtures of
two or more of the carbon materials can be used.
[0024] For the binding agent, polytetrafluoroethylene,
polyvinylidene fluoride, polyvinyl acetate, polyacrylonitrile,
polyvinyl alcohol, and mixtures of two or more of these compounds
can be used.
(Negative Electrode)
[0025] As exemplified in FIG. 1, the negative electrode 10
preferably includes a negative electrode current collector 11 and a
negative electrode active material layer 12 placed on the negative
electrode current collector 11. The negative electrode current
collector 11 used is, for example, a conductive thin film,
particularly metal or alloy foil which is made of copper or the
like and which is stable within the potential range of the negative
electrode or a film including a metal surface layer made of copper
or the like. The negative electrode active material layer 12
preferably contains a binding agent (not shown) in addition to the
negative electrode active material 13. The binding agent used may
be polytetrafluoroethylene or the like as is the case with the
positive electrode and is preferably styrene-butadiene rubber
(SBR), polyimide, or the like. The binding agent may be used in
combination with a thickening agent such as
carboxymethylcellulose.
[0026] As exemplified in FIG. 2, the negative electrode active
material 13 contains negative electrode active materials 13a
including mother particles 14 made of SiO.sub.x
(0.5.ltoreq.X.ltoreq.1.5), carbon coating layers 15 each covering
at least one portion of the surface of a corresponding one of the
mother particles 14, and amorphous carbon particles 16 stuck to the
surfaces of the carbon coating layers 15. The negative electrode
active material 13 may contain the negative electrode active
materials 13a only and preferably contain negative electrode active
materials 13b having a smaller change in volume during charge and
discharge than that of the negative electrode active materials 13a
in combination with the negative electrode active materials 13a
from the viewpoint of achieving both high capacity and enhanced
cycle characteristics. The negative electrode active materials 13b
are not particularly limited and are preferably a carbonaceous
active material such as graphite or hard carbon.
[0027] In the case of using the negative electrode active materials
13a and the negative electrode active materials 13b in combination,
when the negative electrode active materials 13b are graphite, the
mass ratio of the negative electrode active materials 13a to
graphite preferably ranges from 1:99 to 20:80. When the mass ratio
thereof is within the above range, both high capacity and enhanced
cycle characteristics are likely to be achieved. However, when the
percentage of the negative electrode active materials 13a with
respect to the mass of the negative electrode active material 13 is
less than 1% by mass, the merit of increasing the capacity by
adding the negative electrode active materials 13a is small.
[0028] In the negative electrode active materials 13a (hereinafter
referred to as the negative electrode active material particles
13a), the carbon coating layers 15 are placed on the surfaces of
the mother particles 14, which are made of SiO.sub.x
(0.5.ltoreq.X.ltoreq.1.5), and the amorphous carbon particles 16
are stuck to the surfaces of the carbon coating layers 15.
SiO.sub.x has a structure in which Si is dispersed in an amorphous
SiO.sub.2 matrix. The presence of dispersed Si can be confirmed by
observation using a transmission electron microscope (TEM).
[0029] In the nonaqueous electrolyte secondary battery, which
contains the negative electrode active material particles 13a, the
carbon coating layers 15 on the surfaces of the mother particles 14
can improve a disadvantage of SiO.sub.x, which has low electronic
conductivity, and the amorphous carbon particles 16, which are
stuck to the surfaces of the carbon coating layers 15, improve the
binding force between SiO.sub.x and a binder by an anchoring
effect. When particles stuck to the surfaces of the carbon coating
layers 15 are amorphous carbon particles, initial charge/discharge
efficiency and cycle characteristics are particularly improved. The
reason for this is as described below. In the case where highly
crystalline carbon typified by graphite or fine metal particles are
stuck to the surface of SiO.sub.x, a high-temperature treatment
step, an electroless plating step, or the like is necessary.
Treating SiO.sub.x at high temperature significantly reduces the
charge/discharge capacity because of the disproportionation
reaction of SiO.sub.x. In the case where the SiO.sub.x surface is
electrolessly plated, irregularities are unlikely to be formed on
the surfaces of particles and no sufficient anchoring effect is
obtained.
[0030] The fact that the amorphous carbon 16 is stuck to the
surfaces of the carbon coating layers 15 means that the amorphous
carbon 16 is attached to the surfaces of the carbon coating layers
15 even in the case of mixing with a solvent or the like when the
negative electrode is prepared. This is different from secondary
aggregation.
[0031] The mother particles 14 preferably have an average size of 1
.mu.m to 15 .mu.m and more preferably 4 .mu.m to 10 .mu.m. In this
specification, the term "average size" refers to the particle size
(volume-average particle size: Dv.sub.50) at a cumulative volume
percentage of 50% in the particle size distribution determined by a
laser diffraction/scattering method. Dv.sub.50 can be measured
using, for example, "LA-750" manufactured by HORIBA. When the
average size of the mother particles 14 is too small, the surface
area of the particles is too large and the amount of the mother
particles 14 reacting with an electrolyte solution is large, hence,
the capacity may possibly be reduced. However, when the average
size thereof is too large, the influence of the volume expansion of
SiO.sub.x during charge is large and therefore charge/discharge
characteristics may possibly be reduced.
[0032] The amorphous carbon particles 16 preferably have an average
size of 0.01 .mu.m to 1 .mu.m and more preferably 0.05 .mu.m to 0.8
.mu.m. When the average size of the amorphous carbon particles 16
is too small, surface irregularities of the carbon coating layers
15 on the mother particles 14 are small and therefore no sufficient
anchoring effect is likely to be obtained. However, when the
average size thereof is too large, the number of the amorphous
carbon particles 16 stuck on the carbon coating layers 15 is
limited and therefore no sufficient anchoring effect is likely to
be obtained.
[0033] The amorphous carbon particles 16 are preferably more than
0% to 15% by mass with respect to the mother particles 14 and more
preferably 2% to 8% by mass. When the amorphous carbon particles 16
are too few with respect to the mother particles 14, surface
irregularities of the carbon coating layers 15 on the mother
particles 14 are few and therefore no sufficient anchoring effect
is likely to be obtained. However, when the amorphous carbon
particles 16 are too many, the fraction of amorphous carbon in the
active material is large and the capacity is likely to be
reduced.
[0034] As a carbon material in the carbon coating layers 15, carbon
black, acetylene black, Ketjenblack, graphite, and mixtures of two
or more of these materials can be used as is the case with the
conductive material in the positive electrode active material
layer.
[0035] Each of the carbon coating layers 15 preferably covers 50%
to 100% of the surface of a corresponding one of the mother
particles 14 and more preferably 100%. In the present invention,
the fact that the surfaces of the mother particles 14 are covered
by the carbon coating layers 15 means that the surfaces of the
mother particles 14 are covered by the carbon coating layers 15
that have a thickness of at least 1 nm in the case where a cross
section of each particle is observed with a SEM.
[0036] The carbon coating layers 15 preferably have an average
thickness of 1 nm to 200 nm and more preferably 5 nm to 100 nm in
view of the ensuring of electrical conductivity and the diffusivity
of Li.sup.+ into SiO.sub.x forming the mother particles 14 or the
like. The coating layers 15 preferably have substantially a uniform
thickness over the entire area thereof. The average thickness of
the carbon coating layers 15 can be measured in such a manner that
cross sections of the negative electrode active material particles
13a are observed using a scanning electron microscope (SEM), a
transmission electron microscope (TEM), or the like. When the
thickness of the coating layers 15 is too small, the electrical
conductivity is reduced and it is difficult to uniformly cover the
mother particles 14. However, when the thickness of the coating
layers 15 is too large, the diffusivity of Li.sup.+ into the mother
particles 14 is inhibited and the capacity is likely to be reduced.
The percentage of the carbon coating layers with respect to
SiO.sub.x is preferably 10% by mass or less.
[0037] The carbon coating layers 15 can be formed by, for example,
a common process such as a CVD process, a sputtering process, or a
plating (electroplating or electroless plating) process. For
example, in the case where the coating layers 15 are formed on the
surfaces of SiO.sub.x particles by the CVD process using the carbon
material, for example, the SiO.sub.x particles and a hydrocarbon
gas are heated in a vapor phase and carbon produced by the
pyrolysis of the hydrocarbon gas is deposited on the SiO.sub.x
particles. The hydrocarbon gas used may be a methane gas or an
acetylene gas.
[0038] The negative electrode active materials 13a preferably have
a BET specific surface area of 1 m.sup.2/g to 30 m.sup.2/g and more
preferably 5 m.sup.2/g to 30 m.sup.2/g. When the BET specific
surface area thereof is too small, no sufficient irregularities are
formed on the SiO.sub.x particles and no sufficient anchoring
effect is likely to be obtained. However, when the BET specific
surface area thereof is too large, the amount of a binder attached
to the surface of SiO.sub.x is too large, the dispersibility of the
binder is reduced, and the adhesion of the negative electrode is
likely to be reduced.
[0039] The amorphous carbon particles 16 can be stuck to the carbon
coating layers 15 in such a manner that, for example, an aqueous
solution containing an organic acid catalyst and the SiO.sub.x
particles including the carbon coating layers are mixed together
and are subjected to hydrolysis and a polymerization reaction at
80.degree. C. to 120.degree. C., water is evaporated, and heat
treatment is then performed at 500.degree. C. to 800.degree. C. The
aqueous solution containing the organic acid catalyst and the
SiO.sub.x particles including the carbon coating layers may be
mixed with a lithium compound. Examples of the organic acid
catalyst include citric acid, malic acid, tartaric acid, lactic
acid, and glycolic acid. Examples of the lithium compound include
LiOH, Li.sub.2CO.sub.3, LiF, and LiCl.
[0040] SiO.sub.x forming the mother particles 14 may contain
lithium silicate (such as Li.sub.4SiO.sub.4, Li.sub.2SiO.sub.3,
Li.sub.2Si.sub.2O.sub.5, or Li.sub.8SiO.sub.6) in particles.
(Nonaqueous Electrolyte)
[0041] The following salts can be used as an electrolyte salt in
the nonaqueous electrolyte: for example, LiClO.sub.4, LiBF.sub.4,
LiPF.sub.6, LiAlCl.sub.4, LiSbF.sub.6, LiSCN, LiCF.sub.3SO.sub.3,
LiCF.sub.3CO.sub.2, LiAsF.sub.6, LiB.sub.10Cl.sub.10, lower
aliphatic lithium carboxylates, LiCl, LiBr, LiI, chloroborane
lithium, borates, imide salts, and the like. In particular,
LiPF.sub.6 is preferably used from the viewpoint of ionic
conductivity and electrochemical stability. Electrolyte salts may
be used alone or in combination. In 1 L of the nonaqueous
electrolyte, 0.8 mol to 1.5 mol of the electrolyte salt is
preferably contained.
[0042] For example, a cyclic carbonate, a linear carbonate, a
cyclic carboxylate, or the like is used as a solvent in the
nonaqueous electrolyte. Examples of the cyclic carbonate include
propylene carbonate (PC) and ethylene carbonate (EC). Examples of
the linear carbonate include diethyl carbonate (DEC), ethyl methyl
carbonate (EMC), and dimethyl carbonate (DMC). Examples of the
cyclic carboxylate include 7-butyrolactone (GBL) and
.gamma.-valerolactone (GVL). Nonaqueous solvents may be used alone
or in combination.
(Separator)
[0043] The separator used is a porous sheet having ionic
permeability and insulating properties. Examples of the porous
sheet include microporous thin films, woven fabrics, and nonwoven
fabrics. The separator is preferably made of a polyolefin such as
polyethylene or polypropylene.
EXAMPLES
[0044] The present invention is further described below with
reference to examples. The present invention is not limited to the
examples.
Examples
Experiment 1
(Preparation of Negative Electrode)
[0045] SiO.sub.x (X=0.93, an average primary particle size of 5.0
.mu.m) surface-coated with carbon was prepared. Coating was
performed by a CVD process. The percentage of carbon with respect
to SiO.sub.x was 10% by mass. The carbon coverage of the surface of
SiO.sub.x was 100%. The carbon coverage of the SiO.sub.x surface
was confirmed by a method below. A cross section of each SiO.sub.x
particle was exposed using an ion milling system (ex. IM4000)
manufactured by Hitachi High-Technologies Corporation and was
checked using a SEM and a backscattered electron image. The
interface between a carbon coating layer and SiO.sub.x in the
particle cross section was identified from the backscattered
electron image. The percentage of carbon coatings, having a
thickness of 1 nm or more, present on the surface of each SiO.sub.x
particle was calculated from the ratio of the sum of the lengths of
the interfaces between the carbon coatings having a thickness of 1
nm or more and SiO.sub.x to the perimeter of SiO.sub.x in the
particle cross section. The average of the percentages of the
carbon coatings on the surfaces of 30 of the SiO.sub.x particles
was calculated as a carbon coverage.
[0046] To 1,000 g of water, 0.5 moles of Li.sub.2CO.sub.3 was
added, followed by adding 0.2 moles of citric acid, whereby an
aqueous solution in which Li.sub.2CO.sub.3 was completely dissolved
was prepared. To the aqueous solution, 1 mole of the above
SiO.sub.x was added, followed by mixing. The mixed solution was
subjected to a dehydrocondensation reaction at 80.degree. C.,
followed by drying at 120.degree. C., whereby an intermediate was
obtained. The intermediate was heat-treated at 600.degree. C. for 5
hours in an Ar atmosphere. The SiO.sub.x was washed with pure
water. The BET specific surface area of the heat-treated and
water-washed SiO.sub.x particles was measured using Tristar II 3020
(manufactured by Shimadzu Corporation), resulting in that the BET
specific surface area was 20 m.sup.2/g. FIG. 3 shows a SEM image of
the heat-treated and water-washed SiO.sub.x particles. In FIG. 3,
it is observed that amorphous carbon is finely attached to a carbon
coating layer 15 or the surface of a crystalline carbon
particle.
[0047] The fact that amorphous carbon was stuck to the surface of
SiO.sub.x surface-coated with carbon was confirmed by a method
below. FIG. 4 shows a SEM image of the heat-treated and
water-washed SiO.sub.x particles that were atomized and dispersed
in a solvent using TK FILMIX (manufactured by PRIMIX Corporation).
Since amorphous carbon was present on the surface of a carbon
coating film after SiO.sub.x surface-coated with carbon was
atomized and was dispersed, the amorphous carbon was judged to be
stuck on the surface of the carbon coating film without being
secondarily aggregated or simply attached.
[0048] The fact that carbon stuck on the SiO.sub.x surface-coated
with carbon was amorphous carbon was confirmed by a method below.
FIG. 5 shows the laser Raman spectroscopic analysis of carbonaceous
matter (hereinafter referred to as a), measured using the Raman
spectrometer ARAMIS (manufactured by Shimadzu Corporation), present
on the surfaces of the heat-treated and water-washed SiO.sub.x
particles. A Raman spectrum supposed to be a mixture of two or more
types was observed. For spectrum interpretation, FIG. 6 shows
observation results of carbonaceous matter (hereinafter referred to
as .beta.) on the surfaces of untreated SiO.sub.x particles and
FIG. 7 shows observation results of carbonaceous matter
(hereinafter referred to as .gamma.) prepared by heat-treating
citric acid only. The untreated SiO.sub.x particles used were a
material used in Experiment 4 below. From the ratio R
(=I.sub.D/I.sub.G) of the intensity I.sub.D of a D band (a peak
appearing at 1,360 cm.sup.-1) used to evaluate carbon materials to
the intensity I of a G band (a peak appearing at 1,600 cm.sup.-1),
it can be confirmed that .beta. is carbonaceous matter with high
crystallinity and .gamma. is carbonaceous matter, such as soot,
having low crystallinity.
[0049] Next, for FIGS. 5 to 7, the intensity of a saddle portion
(minimum) between the G band and the D band was defined as I.sub.V,
I.sub.V/I.sub.G values were compared, and spectrum interpretation
was performed for a. Smoothing was appropriately performed. A base
line was linearly approximated at 800 cm.sup.-1 to 1,900 cm.sup.-1.
FIG. 8 graphically shows the I.sub.V/I.sub.G values. As is clear
from FIG. 8, a is a mixed component of .beta. and .gamma.. Thus, it
can be confirmed that carbon stuck on SiO.sub.x surface-coated with
carbon is amorphous carbon with low crystallinity.
[0050] SiO.sub.x and PAN (polyacrylonitrile) serving as a binder
were mixed at a mass ratio of 95:5, followed by adding NMP
(N-methyl-2-pyrrolidone) serving as a dilution solvent. This was
stirred using a mixer (ROBOMIX manufactured by PRIMIX Corporation),
whereby negative electrode mix slurry was prepared. The negative
electrode mix slurry was applied to a surface of copper foil such
that the mass per 1 m.sup.2 of a negative electrode mix layer was
25 g/m.sup.2. Next, this was dried at 105.degree. C. in air and was
rolled, whereby a negative electrode was prepared. The packing
density of the negative electrode mix layer was 1.50 g/ml.
(Preparation of Nonaqueous Electrolyte Solution)
[0051] To a solvent mixture prepared by mixing ethylene carbonate
(EC) and diethyl carbonate (DEC) at a volume ratio of 3:7, 1.0 mole
per liter of lithium hexafluorophosphate (LiPF.sub.6) was added,
whereby a nonaqueous electrolyte solution was prepared.
(Assembly of Battery)
[0052] An electrode assembly was prepared in an inert atmosphere
using the negative electrode equipped with a Ni tab at the outer
periphery thereof, lithium metal foil, and a polyethylene separator
placed between the negative electrode and the lithium metal foil.
The electrode assembly was put in a battery enclosure composed of
an aluminium laminate. Furthermore, the nonaqueous electrolyte
solution was poured into the battery enclosure. Thereafter, the
battery enclosure was sealed, whereby Battery A1 was prepared.
Experiment 2
[0053] Battery A2 was prepared in substantially the same manner as
that described in Experiment 1 except that the amount of added
citric acid was 0.18 moles. The BET specific surface area of
heat-treated and water-washed SiO.sub.x particles was measured
using Tristar II 3020, resulting in that the BET specific surface
area was 15 m.sup.2/g.
Experiment 3
[0054] Battery A2 was prepared in substantially the same manner as
that described in Experiment 1 except that the amount of added
citric acid was 0.25 moles. The BET specific surface area of
heat-treated and water-washed SiO.sub.x particles was measured
using Tristar II 3020, resulting in that the BET specific surface
area was 30 m.sup.2/g.
Experiment 4
[0055] Battery Z was prepared in substantially the same manner as
that described in Experiment 1 except that untreated SiO.sub.x was
used as a negative electrode active material (that is, SiO.sub.x
having no amorphous carbon particles on a carbon coating layer).
The BET specific surface area of SiO.sub.x particles was measured
using Tristar II 3020, resulting in that the BET specific surface
area was 5 m.sup.2/g. FIG. 9 shows a cross-sectional SEM image of
the SiO.sub.x particles. In FIG. 9, small particulates are carbon
particles with high crystallinity and are those remaining without
forming a layer when carbon coating layers 15 were formed.
Experiments
[0056] The above batteries were charged and discharged under
conditions below, followed by investigating the initial
charge/discharge efficiency given by Equation (1) below and the
tenth-cycle capacity retention given by Equation (2) below. The
results are shown in Table 1.
(Charge and Discharge Conditions)
[0057] After constant-current charge was performed at a current of
0.2 lt (4 mA) until the voltage reached 0 V, constant-current
charge was performed at a current of 0.05 lt (1 mA) until the
voltage reached 0 V. Next, after a rest was taken for 10 minutes,
constant-current discharge was performed at a current of 0.2 lt (4
mA) until the voltage reached 1.0 V.
(Equation for Calculating Initial Charge/Discharge Efficiency)
[0058] Initial charge/discharge efficiency (%)=(first-cycle
discharge capacity/first-cycle charge capacity).times.100 (1)
(Equation for Calculating Tenth-Cycle Capacity Retention)
[0059] Tenth-cycle capacity retention (%)=(tenth-cycle discharge
capacity/first-cycle discharge capacity).times.100 (2)
TABLE-US-00001 TABLE 1 Amorphous Amount carbon BET Initial of
particles specific charge/ citric on carbon surface discharge acid
coating area efficiency Capacity Batteries (mol) layers (m.sup.2/g)
(%) retention A1 0.2 Observed 20 74 52 A2 0.18 Observed 15 89 21 A3
0.25 Observed 30 71 Not measured Z -- Not observed 5 67 7
[0060] In Battery Z, in which no amorphous carbon particles are
placed on carbon coatings on the surfaces of SiO particles, it is
conceivable that no sufficient anchoring effect is obtained between
active material particles and a binder and the adhesion between
active materials is reduced.
[0061] However, in Batteries A1 to A3, since carbon coatings are
placed on the surfaces of SiO.sub.R particles and amorphous carbon
particles are stuck on the carbon coatings, it is conceivable that
the surfaces of the particles have irregularities sufficient to
obtain an anchoring effect between active material particles and a
binder and the adhesion between active materials is improved.
REFERENCE SIGNS LIST
[0062] 10 Negative electrode [0063] 11 Negative electrode current
collector [0064] 12 Negative electrode active material layer [0065]
13, 13a, 13b Negative electrode active material [0066] 14 Mother
particles [0067] 15 Carbon coating layers [0068] 16 Amorphous
carbon particles
* * * * *