CN104701502B - Lithium ion battery cathode material and preparation method thereof, and lithium ion battery - Google Patents
Lithium ion battery cathode material and preparation method thereof, and lithium ion battery Download PDFInfo
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 98
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000010406 cathode material Substances 0.000 title abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 134
- 239000000463 material Substances 0.000 claims abstract description 92
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 31
- 229910052737 gold Inorganic materials 0.000 claims abstract description 26
- 239000010931 gold Substances 0.000 claims abstract description 26
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 25
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052709 silver Inorganic materials 0.000 claims abstract description 15
- 239000004332 silver Substances 0.000 claims abstract description 15
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 86
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 56
- 239000002245 particle Substances 0.000 claims description 33
- 239000000725 suspension Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000005253 cladding Methods 0.000 claims description 17
- -1 gold ion Chemical class 0.000 claims description 14
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000479 mixture part Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 150000003057 platinum Chemical class 0.000 claims description 2
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 claims description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 171
- 239000010703 silicon Substances 0.000 abstract description 99
- 229910052710 silicon Inorganic materials 0.000 abstract description 99
- 239000000377 silicon dioxide Substances 0.000 abstract description 86
- 239000002131 composite material Substances 0.000 abstract description 53
- 229910052751 metal Inorganic materials 0.000 abstract description 14
- 239000002184 metal Substances 0.000 abstract description 14
- 239000011159 matrix material Substances 0.000 abstract description 10
- 230000003647 oxidation Effects 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- MSVOWLCCSIJLAG-UHFFFAOYSA-N [Si]=O.[Si]=O Chemical compound [Si]=O.[Si]=O MSVOWLCCSIJLAG-UHFFFAOYSA-N 0.000 abstract 1
- 238000007323 disproportionation reaction Methods 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 90
- 238000000498 ball milling Methods 0.000 description 24
- 239000000243 solution Substances 0.000 description 18
- 239000012298 atmosphere Substances 0.000 description 17
- 210000004027 cell Anatomy 0.000 description 15
- 229910052744 lithium Inorganic materials 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
- 239000010439 graphite Substances 0.000 description 11
- 229910002804 graphite Inorganic materials 0.000 description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 238000005245 sintering Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 150000003376 silicon Chemical class 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000011049 filling Methods 0.000 description 6
- 239000005543 nano-size silicon particle Substances 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 229910001961 silver nitrate Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 230000005518 electrochemistry Effects 0.000 description 4
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 4
- NTVYFDOMBHOLGP-UHFFFAOYSA-N gold nitric acid Chemical compound [Au].O[N+]([O-])=O NTVYFDOMBHOLGP-UHFFFAOYSA-N 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101100373011 Drosophila melanogaster wapl gene Proteins 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 229910004074 SiF6 Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 210000004483 pasc Anatomy 0.000 description 1
- 238000009829 pitch coating Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a lithium ion battery cathode material and a preparation method, and a lithium ion battery. A structure of the lithium ion battery cathode material is characterized in that a first mixture obtained by disproportionation of silicon oxide silicon monoxide is coated by one or more from silver, gold and platinum, the first mixture mainly comprises a composite material of silicon and silica, and the composite material of silicon and silica is a matrix material of the lithium ion battery cathode material. Metal silver, gold and platinum have good conductivity and are stable in air, and the conductivity can not be reduced due to oxidation. A conductive frame is formed by coating one or more of metal silver, gold and platinum on the first mixture for convenient electron transmission, problem of no conductivity of silicon in the first mixture and silica in the silica composite material can be made up, the lithium ion battery cathode material has good conductivity, so that cycle life as well as charge and discharge efficiency of the lithium ion battery made by the material can be increased.
Description
Technical field
The invention belongs to technical field of lithium ion is and in particular to a kind of lithium ion battery negative material and its preparation side
Method, lithium ion battery.
Background technology
At present, the lithium ion battery of production and application mainly adopts graphite negative electrodes material, but the theory of graphite embedding lithium capacity
For 372mAh/g, reality has reached 370mAh/g, therefore, graphite negative electrodes material almost no room for promotion on capacity.
Nearly more than ten years, various new high power capacity and high magnification negative material are developed, wherein silica-base material due to
Its high specific discharge capacity（The theoretical specific capacity of silicon is 4200mAh/g）And become study hotspot, but this material is embedding de-
Along with serious volumetric expansion and contraction during lithium, lead to the electroactive material powder of detached on electrode, ultimately result in appearance
Amount decay.In order to overcome the special capacity fade of silicon based anode material, usually by silicon and other inactive metals（As Fe, Al,
Cu etc.）Form alloy, such as Chinese patent CN03116070.0 discloses silicon aluminium alloy/carbon composite material used for lithium ion battery negative electrode
And preparation method thereof；Or material is evenly spread to formation composite in other activity or non-active material（As Si-C, Si-
TiN etc.）, as Chinese patent CN02112180.X discloses Si-C composite material and the system of used as negative electrode of Li-ion battery height ratio capacity
Preparation Method.More conventional method, is the one layer of amorphous carbon of Surface coating in silicon nanoparticle, such as CN200910027938.1
The composite negative pole material of a kind of half fluidised form pitch-coating nano-silicon and graphite is disclosed；CN200910037666.3 discloses a kind of drip
The preparation method of the composite negative pole material of blue or green cladding nano-silicon.
Although said method has done certain modification, above-mentioned silicium cathode material electrochemical performance for silicium cathode material
Still undesirable.
Content of the invention
The technical problem to be solved is for deficiency above-mentioned present in prior art, provides a kind of lithium ion
Cell negative electrode material and preparation method thereof, lithium ion battery, in this negative material, one or more of argentiferous, gold, platinum are one
Form conducting matrix grain outside the first mixture obtaining after silica disproportionated reaction, be easy to electric transmission.
Solve present invention problem and a kind of lithium ion battery negative material of offer, its structure are provided
It is that the first mixture obtaining after silicon monoxide disproportionated reaction is coated with one or more of silver, gold, platinum.
Preferably, the particle diameter of described silicon monoxide is 1000～15000 mesh.
Preferably, silver-colored, golden, platinum the gross mass of one or more of described first mixture outer cladding account for described lithium from
The 0.5～30% of sub- cell negative electrode material quality.
Preferably, described second mixture includes answering of partly unreacted silicon monoxide and silicon and silica
Condensation material, finds after testing：In the composite of silicon and silica, silicon is distributed in silica substrate, and described silicon
Particle diameter be nanoscale (1nm～50nm), silicon accounts for the 25～33% of the second mixture quality, and silica accounts for the second mixing
The 50～67% of amount of substance.
The present invention also provides a kind of preparation method of above-mentioned lithium ion battery negative material, comprises the following steps：
（1）Silicon monoxide obtains the second mixture after there is disproportionated reaction；
（2）One or more of silver salt, gold salt, platinum salt are added to the water with described second mixture and are suspended
Liquid, adds hydrofluoric acid, and described second mixture part is corroded and obtains the first mixture, and obtains in this first mixing beyond the region of objective existence
It is coated with the lithium ion battery negative material of one or more of silver, gold, platinum.
Preferably, described step（1）With described step（2）Between also include step（i）：By described second mixture mill
Become the particle that particle diameter is 1000～15000 mesh.
Preferably, described step（1）Described in the temperature of silicon monoxide disproportionated reaction be 700～1200 DEG C, the time is
0.5～24 hour.
Preferably, described step（2）Described in hydrofluoric acid addition according to every gram of metal in corresponding described suspension
Ion adds the hydrofluoric acid of the 5～15wt% of 10～40g.Directly the amount according to metal ion limits the amount of hydrofluoric acid, metal ion
When reacting with SiO, hydrofluoric acid is all enough, but the amount of hydrofluoric acid is much smaller than SiO in the second mixture2All remove
Amount.Here hydrofluoric acid simply plays a booster action, so that the reproducibility of SiO is brought into play.
Preferably, described step（2）Described in one of silver ion in suspension, gold ion, platinum ion or several
The total concentration planted is 0.0001～0.01mol/L.
Preferably, described step（2）Described in the amount of the second mixture described in suspension be 5～30g/ml.
The present invention also provides a kind of lithium ion battery, and its negative pole includes above-mentioned lithium ion battery negative material.
The structure of the lithium ion battery negative material in the present invention is that first obtaining after silicon monoxide disproportionated reaction mixes
Compound is coated with one or more of silver, gold, platinum, and the first mixture mainly includes the composite of silicon and silica,
And the composite of this silicon and silica is the matrix material of lithium ion battery negative material.Argent, gold, platinum electric conductivity are relatively
Good, and sufficiently stable in atmosphere, its electric conductivity will not be reduced because of oxidation.The first mixture outer cladding argent,
One or more of gold, platinum define conducting matrix grain, are easy to electric transmission, compensate for the silicon in the first mixture and titanium dioxide
Silica in the composite of silicon does not have the problem of electric conductivity so that this lithium ion battery negative material has leads well
Electrically, thus improve cycle life and the efficiency for charge-discharge of the lithium ion battery made using this material.
Silver, gold, the electric conductivity of platinum are far above amorphous carbon, graphite etc., and are rich in ductility, can be with lithium ion battery
Volume Changes of active material particle in the first mixture in negative material in charge and discharge process and stretch accordingly or
Shrink.Therefore, in one or more of the first mixture outer cladding silver, gold, platinum, lithium-ion electric on the one hand can effectively be increased
Pond negative material electric conductivity；On the other hand due to the ductility of metal material, this structure can be kept under Volume Changes
Stability, is conducive to extending the cycle life of ion cathode material lithium.
The raw material that in the present invention, the preparation method of lithium ion battery negative material is used is easy to get, the letter of preparation method technique
Single.
Specific embodiment
For making those skilled in the art more fully understand technical scheme, with reference to specific embodiment to this
Invention is described in further detail.
Embodiment 1
The present embodiment provides a kind of preparation method of lithium ion battery negative material, comprises the following steps：
（1）By silicon monoxide powder（Particle diameter is 2000 mesh）It is placed in crucible, and put in atmosphere furnace, in argon gas atmosphere
It is warmed up to 800 DEG C under protection, heats 24 hours at such a temperature, silicon monoxide occurs disproportionated reaction to generate silicon and silica
Composite, because silicon monoxide can be reunited after high temperature sintering, so the particle diameter of the second mixture finally giving
Larger, this second mixture includes the composite of partly unreacted silicon monoxide and silicon and silica.After testing
Find：In the composite of silicon and silica, silicon is distributed in silica substrate, and the particle diameter of described silicon is nanoscale
8nm, silicon accounts for the 32% of the first mixture quality, and silica accounts for the 64% of the first mixture quality.
（2）Second mixture is added in ball grinder, adds the ball milling pearl of the weight of 4 times of second mixture（Large and small
Ball milling pearl is according to 1:1 ratio adds）.Ball grinder is placed on planetary ball mill, by second under 300 revs/min of rotating speed
Mixture ball milling 12 hours, this second mixture ball milling is become the particle that particle diameter is 5000 mesh.
（3）Above-mentioned second mixture is added to the water, adds appropriate silver nitrate solution, obtain suspension, wherein, this hangs
In supernatant liquid, the amount of the second mixture is 10g/ml, and the concentration of the silver ion in suspension is 0.01mol/L.Then in 30W/cm2
The sound intensity ultrasonic under conditions of ultrasonication so that the second mixture is fully dispersed and mix with silver nitrate solution, stirring
The enough hydrofluoric acid solutions of lower dropping, and the addition of hydrofluoric acid adds 10g according to every gram of silver ion in corresponding described suspension
5wt% hydrofluoric acid, silver ion according to following equation react, M in equationn+For Ag+, certain M can also represent Jin Huo
Platinum.
Mn++0.5nSiO+3nHF→M↓+0.5nH2SiF6+0.5nH2O+nH+
Second mixture part is corroded and obtains the first mixture, and obtains being coated with argent in this first mixture
Lithium ion battery negative material.Wherein, the quality of the argent of the first mixture outer cladding accounts for lithium ion battery negative material
Quality 0.5%.
By the preparation method in this enforcement, in the first mixture outer cladding obtaining after silicon monoxide disproportionated reaction
Silver, this preparation method is with respect to directly by the first mixture after silicon monoxide disproportionated reaction directly and after argent dry mixed
Carry out calcination again and prepare lithium ion battery negative material comparing, the preparation method in the present embodiment is in the first mixture outer cladding silver
More uniform.And due in the present embodiment first mixture outer cladding silver chemical reaction be direct by the silver ion in solution
With the oxidation Asia pasc reaction in the second mixture, the contact surface of both reactions is exactly outer in the sub- silicon of the oxidation in the second mixture
Surface, so the silver generating after reaction is also in the outer surface of former second mixture, and is in close contact, due in the second mixture
Become the first mixture, so i.e. silver is closely coated on the appearance of the first mixture after the partial reaction that the sub- silicon of oxidation occurs
Face.
By gained lithium ion battery negative material respectively with conductive agent acetylene black, binding agent PVDF according to mass ratio 80: 10:
10 mixing, use NMP（1-Methyl-2-Pyrrolidone）This mixture is modulated into slurry, is coated uniformly on Copper Foil, 100 DEG C true
Empty dry 24 hours, prepared experimental cell pole piece.It is to electrode with lithium piece, electrolyte is the LiPF6 solution of 1mol/L, solvent
For EC（Ethyl carbonate ester）+DMC（Dimethyl carbonate）（Volume ratio 1: 1）, barrier film is celgard2400 film, full of argon gas
It is assembled into CR2025 type button cell in the glove box of atmosphere.
The charge-discharge performance test of the button cell that lithium ion battery negative material manufactured in the present embodiment is made：First
Secondary specific discharge capacity is 1556mAh/g, and after circulating 100 times, specific discharge capacity is 809mAh/g.
The present embodiment provides a kind of lithium ion battery, and its negative pole includes above-mentioned lithium ion battery negative material.
The structure of the lithium ion battery negative material in the present embodiment is first obtaining after silicon monoxide disproportionated reaction
Mixture is coated with silver, and the first mixture mainly includes the composite of silicon and silica, and this silicon and silica
Composite is the matrix material of lithium ion battery negative material.The composite of this silicon and silica is passed through by silicon monoxide
High temperature disproportionated reaction generates, and silicon therein is nano-silicon.In the composite of silicon and silica, silicon accounts for about 1/3rd
Quality, silica accounts for about 2/3rds quality.In the composite of silicon and silica, silicon is distributed in silica
In, during embedding de- lithium, the silica in the composite of silicon and silica can stop silicon grain repeatedly embedding de-
Electrochemistry sintering is occurred to reunite during lithium；And silica makes to form good skeleton between silicon grain and silicon grain and props up
Support can buffer the volumetric expansion of silicon well, reduces the cubical expansivity of whole silica composite, effectively reduces silica multiple
The capacity attenuation speed of condensation material.Argent is the best material of electric conductivity in all metals, and argent foot in atmosphere
Enough stable, its electric conductivity will not be reduced because of oxidation.Define conducting matrix grain in the argent of the first mixture outer cladding, be easy to
Electric transmission, compensate for the silica in the silicon in the first mixture and the composite of silica does not have asking of electric conductivity
Inscribe so that this lithium ion battery negative material has good electric conductivity, thus improve the lithium ion made using this material
The cycle life of battery and efficiency for charge-discharge.
Embodiment 2
The present embodiment provides a kind of preparation method of lithium ion battery negative material, comprises the following steps：
（1）By silicon monoxide powder（Particle diameter is 1000 mesh）It is placed in crucible, and put in atmosphere furnace, in argon gas atmosphere
It is warmed up to 1200 DEG C under protection, heats 0.5 hour at such a temperature, silicon monoxide occurs disproportionated reaction to generate silicon and silica
Composite, because silicon monoxide can be reunited after high temperature sintering, so the grain of the second mixture finally giving
Footpath is larger, and this second mixture includes the composite of partly unreacted silicon monoxide and silicon and silica.Through inspection
Survey and find：In the composite of silicon and silica, silicon is distributed in silica substrate, and the particle diameter of described silicon is nanometer
Level 10nm, silicon accounts for the 30% of the first mixture quality, and silica accounts for the 60% of the first mixture quality.
（2）Second mixture is added in ball grinder, adds the ball milling pearl of the weight of 4 times of second mixture（Large and small
Ball milling pearl is according to 1:1 ratio adds）.Ball grinder is placed on planetary ball mill, by second under 300 revs/min of rotating speed
Mixture ball milling 12 hours, this second mixture ball milling is become the particle that particle diameter is 1000 mesh.
（3）Above-mentioned second mixture is added to the water, adds appropriate nitric acid gold solution, obtain suspension, wherein, this hangs
In supernatant liquid, the amount of the second mixture is 20g/ml, and the concentration of the gold ion in suspension is 0.001mol/L.Then in 30W/cm2
The sound intensity ultrasonic under conditions of ultrasonic so that the second mixture is fully dispersed and mix with nitric acid gold solution, stir lower
The hydrofluoric acid solution of the amount of filling up, and the addition of hydrofluoric acid adds 20g's according to every gram of gold ion in corresponding described suspension
The hydrofluoric acid of 10wt%.Second mixture part is corroded and obtains the first mixture, and obtains being coated with this first mixture
The lithium ion battery negative material of metallic gold.Wherein, the quality of the metallic gold of the first mixture outer cladding accounts for lithium ion battery and bears
The 15% of the quality of pole material.
Method according to preparing button cell in embodiment 1, the lithium ion battery negative material being obtained using the present embodiment
Make button cell, and charge-discharge performance test is carried out to this battery：First discharge specific capacity has reached 1352mAh/g,
After circulating 100 times, specific discharge capacity is 732mAh/g.
The present embodiment provides a kind of lithium ion battery, and its negative pole includes above-mentioned lithium ion battery negative material.
The structure of the lithium ion battery negative material in the present embodiment is first obtaining after silicon monoxide disproportionated reaction
Mixture is coated with gold, and the first mixture mainly includes the composite of silicon and silica, and this silicon and silica
Composite is the matrix material of lithium ion battery negative material.The composite of this silicon and silica is passed through by silicon monoxide
High temperature disproportionated reaction generates, and silicon therein is nano-silicon.In the composite of silicon and silica, silicon accounts for about 1/3rd
Quality, silica accounts for about 2/3rds quality.In the composite of silicon and silica, silicon is distributed in silica
In, during embedding de- lithium, the silica in the composite of silicon and silica can stop silicon grain repeatedly embedding de-
Electrochemistry sintering is occurred to reunite during lithium；And silica makes to form good skeleton between silicon grain and silicon grain and props up
Support can buffer the volumetric expansion of silicon well, reduces the cubical expansivity of whole silica composite, effectively reduces silica multiple
The capacity attenuation speed of condensation material.The electric conductivity of metallic gold is good, and metallic gold is sufficiently stable in atmosphere, will not be because of oxidation
And reduce its electric conductivity.Define conducting matrix grain in the metallic gold of the first mixture outer cladding, be easy to electric transmission, compensate for
Silica in the composite of the silicon in one mixture and silica does not have the problem of electric conductivity so that this lithium-ion electric
Pond negative material has good electric conductivity, thus improve the cycle life of the lithium ion battery made using this material and filling
Discharging efficiency.
Embodiment 3
The present embodiment provides a kind of preparation method of lithium ion battery negative material, comprises the following steps：
（1）By silicon monoxide powder（Particle diameter is 10000 mesh）It is placed in crucible, and put in atmosphere furnace, in argon gas atmosphere
Protection under be warmed up to 1100 DEG C, heat 12 hours at such a temperature, silicon monoxide occurs disproportionated reaction to generate silicon and titanium dioxide
The composite of silicon, because silicon monoxide can be reunited after high temperature sintering, so the second mixture finally giving
Particle diameter is larger, and this second mixture includes the composite of partly unreacted silicon monoxide and silicon and silica.Warp
Detection finds：In the composite of silicon and silica, silicon is distributed in silica substrate, and the particle diameter of described silicon is to receive
Meter level 1nm, silicon accounts for the 27% of the first mixture quality, and silica accounts for the 54% of the first mixture quality.
（2）Second mixture is added in ball grinder, adds the ball milling pearl of the weight of 4 times of second mixture（Large and small
Ball milling pearl is according to 1:1 ratio adds）.Ball grinder is placed on planetary ball mill, by second under 300 revs/min of rotating speed
Mixture ball milling 12 hours, this second mixture ball milling is become the particle that particle diameter is 8000 mesh.
（3）Above-mentioned second mixture is added to the water, adds appropriate platinum chloride solution, obtain suspension, wherein, this hangs
In supernatant liquid, the amount of the second mixture is 30g/ml, and the concentration of the platinum ion in suspension is 0.005mol/L.Then in 30W/cm2
The sound intensity ultrasonic under conditions of ultrasonic so that the second mixture is fully dispersed and mix with platinum chloride solution, stir lower
The hydrofluoric acid solution of the amount of filling up, and the addition of hydrofluoric acid adds 40g's according to every gram of platinum ion in corresponding described suspension
The hydrofluoric acid of 8wt%.Second mixture part is corroded and obtains the first mixture, and obtains being coated with this first mixture
The lithium ion battery negative material of metal platinum.Wherein, the quality of the metal platinum of the first mixture outer cladding accounts for lithium ion battery and bears
The 30% of the quality of pole material.
Method according to preparing button cell in embodiment 1, the lithium ion battery negative material being obtained using the present embodiment
Make button cell, and charge-discharge performance test is carried out to this battery：First discharge specific capacity has reached 1415mAh/g,
After circulating 100 times, specific discharge capacity is 746mAh/g.
The present embodiment provides a kind of lithium ion battery, and its negative pole includes above-mentioned lithium ion battery negative material.
The structure of the lithium ion battery negative material in the present embodiment is first obtaining after silicon monoxide disproportionated reaction
Mixture is coated with platinum, and the first mixture mainly includes the composite of silicon and silica, and this silicon and silica
Composite is the matrix material of lithium ion battery negative material.The composite of this silicon and silica is passed through by silicon monoxide
High temperature disproportionated reaction generates, and silicon therein is nano-silicon.In the composite of silicon and silica, silicon accounts for about 1/3rd
Quality, silica accounts for about 2/3rds quality.In the composite of silicon and silica, silicon is distributed in silica
In, during embedding de- lithium, the silica in the composite of silicon and silica can stop silicon grain repeatedly embedding de-
Electrochemistry sintering is occurred to reunite during lithium；And silica makes to form good skeleton between silicon grain and silicon grain and props up
Support can buffer the volumetric expansion of silicon well, reduces the cubical expansivity of whole silica composite, effectively reduces silica multiple
The capacity attenuation speed of condensation material.The electric conductivity of metal platinum is good, and metal platinum is sufficiently stable in atmosphere, will not be because of oxidation
And reduce its electric conductivity.Define conducting matrix grain in the metal platinum of the first mixture outer cladding, be easy to electric transmission, compensate for
Silica in the composite of the silicon in one mixture and silica does not have the problem of electric conductivity so that this lithium-ion electric
Pond negative material has good electric conductivity, thus improve the cycle life of the lithium ion battery made using this material and filling
Discharging efficiency.
Embodiment 4
The present embodiment provides a kind of preparation method of lithium ion battery negative material, comprises the following steps：
（1）By silicon monoxide powder（Particle diameter is 15000 mesh）It is placed in crucible, and put in atmosphere furnace, in argon gas atmosphere
Protection under be warmed up to 700 DEG C, heat 5 hours at such a temperature, silicon monoxide occurs disproportionated reaction to generate silicon and silica
Composite, because silicon monoxide can be reunited after high temperature sintering, so the grain of the second mixture finally giving
Footpath is larger, and this second mixture includes the composite of partly unreacted silicon monoxide and silicon and silica.Through inspection
Survey and find：In the composite of silicon and silica, silicon is distributed in silica substrate, and the particle diameter of described silicon is nanometer
Level 50nm, silicon accounts for the 25% of the first mixture quality, and silica accounts for the 50% of the first mixture quality.
（2）Second mixture is added in ball grinder, adds the ball milling pearl of the weight of 4 times of second mixture（Large and small
Ball milling pearl is according to 1:1 ratio adds）.Ball grinder is placed on planetary ball mill, by second under 300 revs/min of rotating speed
Mixture ball milling 12 hours, this second mixture ball milling is become the particle that particle diameter is 15000 mesh.
（3）Above-mentioned second mixture is added to the water, adds appropriate silver nitrate and the mixed solution of nitric acid gold（Mixing is molten
In liquid, the amount of the material of silver ion and gold ion is than for 1:1）, obtain suspension, wherein, the amount of the second mixture in this suspension
For 5g/ml, the silver ion in suspension and the total concentration of gold ion are 0.008mol/L.Then in 30W/cm2The sound intensity ultrasonic
Under conditions of ultrasonic so that the second mixture fully dispersed and with silver nitrate and nitric acid gold mixed solution mix, stirring
The enough hydrofluoric acid solutions of lower dropping, and the addition of hydrofluoric acid is according to every gram of gold ion or silver ion in corresponding described suspension
Add the hydrofluoric acid of the 12wt% of 30g.Second mixture part is corroded and obtains the first mixture, and obtains in this first mixing
Beyond the region of objective existence is coated with the lithium ion battery negative material of metal platinum.Wherein, the quality of the metal platinum of the first mixture outer cladding accounts for lithium
The 5% of the quality of ion battery cathode material.
Method according to preparing button cell in embodiment 1, the lithium ion battery negative material being obtained using the present embodiment
Make button cell, and charge-discharge performance test is carried out to this battery：First discharge specific capacity has reached 1379mAh/g,
After circulating 100 times, specific discharge capacity is 698mAh/g.
The present embodiment provides a kind of lithium ion battery, and its negative pole includes above-mentioned lithium ion battery negative material.
Embodiment 5
The present embodiment provides a kind of preparation method of lithium ion battery negative material, comprises the following steps：
（1）By silicon monoxide powder（Particle diameter is 8000 mesh）It is placed in crucible, and put in atmosphere furnace, in argon gas atmosphere
It is warmed up to 950 DEG C under protection, heats 6 hours at such a temperature, silicon monoxide occurs disproportionated reaction to generate silicon and silica
Composite, because silicon monoxide can be reunited after high temperature sintering, so the particle diameter of the second mixture finally giving
Larger, this second mixture includes the composite of partly unreacted silicon monoxide and silicon and silica.After testing
Find：In the composite of silicon and silica, silicon is distributed in silica substrate, and the particle diameter of described silicon is nanoscale
25nm, silicon accounts for the 26% of the first mixture quality, and silica accounts for the 52% of the first mixture quality.
（2）Second mixture is added in ball grinder, adds the ball milling pearl of the weight of 4 times of second mixture（Large and small
Ball milling pearl is according to 1:1 ratio adds）.Ball grinder is placed on planetary ball mill, by second under 300 revs/min of rotating speed
Mixture ball milling 12 hours, this second mixture ball milling is become the particle that particle diameter is 10000 mesh.
（3）Above-mentioned second mixture is added to the water, adds appropriate silver nitrate solution, obtain suspension, wherein, this hangs
In supernatant liquid, the amount of the second mixture is 5g/ml, and the concentration of the silver ion in suspension is 0.001mol/L.Then in 30W/cm2
The sound intensity ultrasonic under conditions of ultrasonic so that the second mixture is fully dispersed and mix with silver nitrate solution, stir lower
The hydrofluoric acid solution of the amount of filling up, and the addition of hydrofluoric acid adds 10g's according to every gram of silver ion in corresponding described suspension
The hydrofluoric acid of 13wt%.Second mixture part is corroded and obtains the first mixture, and obtains being coated with this first mixture
The lithium ion battery negative material of argent.Wherein, the quality of the argent of the first mixture outer cladding accounts for lithium ion battery and bears
The 20% of the quality of pole material.
Method according to preparing button cell in embodiment 1, the lithium ion battery negative material being obtained using the present embodiment
Make button cell, and charge-discharge performance test is carried out to this battery：First discharge specific capacity has reached 1423mAh/g,
After circulating 100 times, specific discharge capacity is 872mAh/g.
The present embodiment provides a kind of lithium ion battery, and its negative pole includes above-mentioned lithium ion battery negative material.
Embodiment 6
The present embodiment provides a kind of preparation method of lithium ion battery negative material, comprises the following steps：
（1）By silicon monoxide powder（Particle diameter is 12000 mesh）It is placed in crucible, and put in atmosphere furnace, in argon gas atmosphere
Protection under be warmed up to 1000 DEG C, heat 1 hour at such a temperature, silicon monoxide occurs disproportionated reaction to generate silicon and silica
Composite, because silicon monoxide can be reunited after high temperature sintering, so the grain of the second mixture finally giving
Footpath is larger, and this second mixture includes the composite of partly unreacted silicon monoxide and silicon and silica.Through inspection
Survey and find：In the composite of silicon and silica, silicon is distributed in silica substrate, and the particle diameter of described silicon is nanometer
Level 6nm, silicon accounts for the 31% of the first mixture quality, and silica accounts for the 62% of the first mixture quality.
（2）Second mixture is added in ball grinder, adds the ball milling pearl of the weight of 4 times of second mixture（Large and small
Ball milling pearl is according to 1:1 ratio adds）.Ball grinder is placed on planetary ball mill, by second under 300 revs/min of rotating speed
Mixture ball milling 12 hours, this second mixture ball milling is become the particle that particle diameter is 12000 mesh.
（3）Above-mentioned second mixture is added to the water, adds appropriate platinum chloride solution, obtain suspension, wherein, this hangs
In supernatant liquid, the amount of the second mixture is 15g/ml, and the concentration of the platinum ion in suspension is 0.002mol/L.Then in 30W/cm2
The sound intensity ultrasonic under conditions of ultrasonic so that the second mixture is fully dispersed and mix with platinum chloride solution, stir lower
The hydrofluoric acid solution of the amount of filling up, and the addition of hydrofluoric acid adds 40g's according to every gram of platinum ion in corresponding described suspension
The hydrofluoric acid of 15wt%.Second mixture part is corroded and obtains the first mixture, and obtains being coated with this first mixture
The lithium ion battery negative material of metal platinum.Wherein, the quality of the metal platinum of the first mixture outer cladding accounts for lithium ion battery and bears
The 10% of the quality of pole material.
Method according to preparing button cell in embodiment 1, the lithium ion battery negative material being obtained using the present embodiment
Make button cell, and charge-discharge performance test is carried out to this battery：First discharge specific capacity has reached 1579mAh/g,
After circulating 100 times, specific discharge capacity is 1015mAh/g.
The present embodiment provides a kind of lithium ion battery, and its negative pole includes above-mentioned lithium ion battery negative material.
Embodiment 7
The present embodiment provides a kind of lithium ion battery, and its negative pole contains the lithium ion battery described in the above embodiments 1～6
Negative material and graphite, wherein, the quality of lithium ion battery negative material accounts for the mixing of lithium ion battery negative material and graphite
The 20% of thing gross mass.
Lithium ion battery in the present embodiment, during embedding de- lithium, the silica in negative pole can stop silicon grain from existing
Occur electrochemistry sintering to reunite during repeatedly embedding de- lithium, and silica makes to be formed very between silicon grain and silicon grain
Good skeletal support can buffer the volumetric expansion of silicon grain well, and then effectively alleviates the whole negative pole material of lithium ion battery
The capacity attenuation of material；Graphite in negative pole does not almost have bulk effect.
Efficiency is less than 80% to the lithium ion battery negative material of embodiment 1～6 preparation first, and existing business graphite
Efficiency is more than 85% to negative material first, and efficiency is more than 95% to high-end graphite cathode material first.By above-described embodiment 1～embodiment
The lithium ion battery negative material of 6 preparations is jointly negative as lithium ion battery with the high-end graphite cathode material in the present embodiment
Pole material, the efficiency first of this mixing negative material is more than 92%, and embedding lithium specific capacity is 540mAh/g first, puts after circulating 100 times
Electric specific capacity is 485mAh/g.
It is understood that the embodiment of above principle being intended to be merely illustrative of the present and the exemplary enforcement adopting
Mode, but the invention is not limited in this.For those skilled in the art, in the essence without departing from the present invention
In the case of god and essence, various modifications and improvement can be made, these modifications and improvement are also considered as protection scope of the present invention.
Claims (7)
1. a kind of preparation method of lithium ion battery negative material is it is characterised in that comprise the following steps：
(1) silicon monoxide obtains the second mixture after there is disproportionated reaction；
(2) one or more of silver salt, gold salt, platinum salt are added to the water with described second mixture and obtain suspension, then
Add hydrofluoric acid, the addition of described hydrofluoric acid according to every gram of metal ion in corresponding described suspension add 10～40g 5～
The hydrofluoric acid of 15wt%, described second mixture part is corroded and obtains the first mixture, and obtains in this first mixing beyond the region of objective existence
It is coated with the lithium ion battery negative material of one or more of silver, gold, platinum.
2. the preparation method of lithium ion battery negative material according to claim 1 is it is characterised in that described step (1)
Also include step (i) and described step (2) between：Described second mixture is worn into the particle that particle diameter is 1000～15000 mesh.
3. the preparation method of lithium ion battery negative material according to claim 1 is it is characterised in that described step (1)
Described in silicon monoxide disproportionated reaction temperature be 700～1200 DEG C, the time be 0.5～24 hour.
4. the preparation method of lithium ion battery negative material according to claim 1 is it is characterised in that described step (2)
Described in the total concentration of one or more of silver ion in suspension, gold ion, platinum ion be 0.0001～0.01mol/
L.
5. the preparation method of lithium ion battery negative material according to claim 1 is it is characterised in that described step (2)
Described in the amount of the second mixture described in suspension be 5～30g/ml.
6. the preparation method of lithium ion battery negative material according to claim 1 is it is characterised in that described first mixes
Beyond the region of objective existence cladding silver-colored, golden, platinum the gross mass of one or more account for described lithium ion battery negative material quality 0.5～
30%.
7. a kind of lithium ion battery is it is characterised in that its negative pole includes the lithium-ion electric described in claim 1～6 any one
The negative material that the preparation method of pond negative material prepares.
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| CN110444733B (en) * | 2019-08-22 | 2020-09-29 | 中南大学 | Lithium ion battery photoreduction silver modified nano silicon cathode and preparation method thereof |
| CN112670467B (en) * | 2020-11-23 | 2022-08-26 | 深圳石墨烯创新中心有限公司 | Preparation method of lithium ion battery silicon oxide/carbon/graphite negative electrode material |
| CN115000392B (en) * | 2022-07-18 | 2023-06-30 | 湖北亿纬动力有限公司 | Composite anode material and preparation method and application thereof |
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| CN102709537A (en) * | 2012-07-03 | 2012-10-03 | 清华大学 | Preparation method of silicon-silver composite anode material of lithium ion battery and reaction kettle |
| CN103236525A (en) * | 2013-05-06 | 2013-08-07 | 奇瑞汽车股份有限公司 | Silicon carbon composite material, preparation method thereof as well as lithium ion battery |
| CN103259001A (en) * | 2013-05-06 | 2013-08-21 | 奇瑞汽车股份有限公司 | Silica composite material as well as preparation method thereof and lithium ion battery |
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| CN103236525A (en) * | 2013-05-06 | 2013-08-07 | 奇瑞汽车股份有限公司 | Silicon carbon composite material, preparation method thereof as well as lithium ion battery |
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