CN110148730A - A kind of Gao Shouxiao long-life silicon based anode material and its preparation method and application - Google Patents
A kind of Gao Shouxiao long-life silicon based anode material and its preparation method and application Download PDFInfo
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- CN110148730A CN110148730A CN201910453138.XA CN201910453138A CN110148730A CN 110148730 A CN110148730 A CN 110148730A CN 201910453138 A CN201910453138 A CN 201910453138A CN 110148730 A CN110148730 A CN 110148730A
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 44
- 239000010703 silicon Substances 0.000 title claims abstract description 44
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000010405 anode material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 111
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium Ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- 239000002322 conducting polymer Substances 0.000 claims abstract description 12
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 9
- 238000005253 cladding Methods 0.000 claims abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 34
- 239000007789 gas Substances 0.000 claims description 28
- 238000001354 calcination Methods 0.000 claims description 20
- 239000011734 sodium Substances 0.000 claims description 19
- 229910052786 argon Inorganic materials 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 238000002242 deionisation method Methods 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 12
- 239000010439 graphite Substances 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 8
- 238000006722 reduction reaction Methods 0.000 claims description 8
- 229910052754 neon Inorganic materials 0.000 claims description 7
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon(0) Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N Ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000005336 cracking Methods 0.000 claims description 6
- 229960003638 dopamine Drugs 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 238000005554 pickling Methods 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021382 natural graphite Inorganic materials 0.000 claims description 4
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 claims description 4
- 150000003233 pyrroles Chemical class 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium(0) Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- QJBTZWUJJBSGPI-UHFFFAOYSA-K iron(3+);chloride;sulfate Chemical compound [Cl-].[Fe+3].[O-]S([O-])(=O)=O QJBTZWUJJBSGPI-UHFFFAOYSA-K 0.000 claims description 2
- 229910052743 krypton Inorganic materials 0.000 claims description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton(0) Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon(0) Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001345 alkine derivatives Chemical class 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000000977 initiatory Effects 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000011780 sodium chloride Substances 0.000 claims 1
- 229910021384 soft carbon Inorganic materials 0.000 claims 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 abstract description 29
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 239000002923 metal particle Substances 0.000 abstract description 3
- 238000002203 pretreatment Methods 0.000 abstract description 3
- 239000012495 reaction gas Substances 0.000 abstract description 3
- 239000011247 coating layer Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 16
- 238000010792 warming Methods 0.000 description 15
- 238000007599 discharging Methods 0.000 description 14
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 7
- 229910021383 artificial graphite Inorganic materials 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 229910001290 LiPF6 Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PAZHGORSDKKUPI-UHFFFAOYSA-N Lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229960002163 hydrogen peroxide Drugs 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052912 lithium silicate Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N 2-Pyrrolidone Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling Effects 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000002427 irreversible Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- -1 polyethylene pyrrole Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052904 quartz Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—BASIC 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—BASIC 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
-
- H—ELECTRICITY
- H01—BASIC 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—BASIC 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—BASIC 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
-
- H—ELECTRICITY
- H01—BASIC 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
-
- H—ELECTRICITY
- H01—BASIC 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
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—BASIC 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
-
- 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
Abstract
The invention discloses a kind of Gao Shouxiao long-life silicon based anode materials and its preparation method and application to make SiO that the Si/SiO that disproportionated reaction obtains relatively uniform silicon wafer particle size occur by high temperature pre-treatment2Material, then in CO2Na restores part SiO under atmosphere2Material coulombic efficiency for the first time is improved, CO is selected2SiO can be reduced as reaction gas2The gibbs free energy change reacted with Na carries out reaction quickly under the conditions of relatively mild.The carbon coating layer for being formed by chemical vapor deposition even compact improves the electronic conductivity of material, reduces material resistance.Secondary conducting polymer cladding improves the interface performance of material, further increases the cyclical stability of material.And the poor defect of improvement polymer conductivity is modified by high conductivity nano-metal particle.Lithium ion battery made of material prepared by the present invention, the specific capacity of battery, for the first time coulombic efficiency and cyclical stability are improved, and have fabulous application prospect.
Description
Technical field
The present invention relates to a kind of lithium ion battery material more particularly to a kind of Gao Shouxiao long-life silicon based anode materials
And its preparation method and application.
Background technique
With the development of electric car and portable electrical appliance, the demand of lithium ion battery with high energy density also increasingly increases
Add.Conventional graphite negative material theoretical specific capacity only has 372mAh/g, is difficult to meet the market demand.The gram volume for the first time of silicon materials
For 4200mAh/g, embedding lithium platform is higher, and earth's crust storage is abundant, and the advantages such as environmentally friendly gradually cause the extensive pass of researcher
Note.
However the volume expansion of silicon is up to 300%, in cyclic process, not only results in the conductive charcoal network of silicon and surrounding
Separation forms " dead silicon ", it is peeling-off with collector to also result in silicon.Secondly, biggish volume expansion also results in surface
SEI film constantly recombinates destruction, keeps SEI film more and more thicker, constantly the Li of consumption anode+, coulombic efficiency reduction.Finally, biggish
The phase leads to silicon materials dusting after cycling for volume expansion, and these problems eventually lead to cycle performance and sharply deteriorate.
Due to the above problem, part attention is transferred on the sub- silicon of oxidation by academia and industrial circle.Compared with nano-silicon,
It aoxidizes sub- silicon and although sacrifices portion capacity, but its expansion is relatively small (~100%), and generated in charge and discharge process
By-product lithia, lithium metasilicate, lithium metasilicate etc. can provide buffer function, greatly improve the cycle performance of material.But
The electric conductivity of material is relatively poor, and head effect is lower.Lee D J[Lee D J,Ryou M H,Lee J N,et
al.Nitrogen-doped carbon coating for a high-performance SiO anode in lithium-
Ion batteries [J] .Electrochemistry Communications, 2013,34:98-101.] etc. it is mixed by liquid phase
Conjunction+high temperature cabonization mode prepares nitrogen-doped carbon coated Si O material, and the material circulation is relatively preferable, but first effect is relatively low.Jee
[Yom J H, Sun W H, Cho S M, the et al.Improvement of irreversible behavior of such as HoYom
SiO anodes for lithium ion batteries by a solid state reaction at high
Temperature [J] .Journal of Power Sources, 2016,311:159-166.] by by SiO and lithium metal into
Row solid phase reaction is carrying out carbon coating, is preparing Gao Shouxiao silicon based anode material, the method increase material coulombic efficiency for the first time,
But the cycle performance of material is relatively poor, comparatively harsh to synthesis condition due to using lithium metal as reactant, exists
Security risk, and there is the risk for producing gas during battery is closed and starched.
Summary of the invention
To overcome defect of the existing technology, the object of the present invention is to provide a kind of Gao Shouxiao long-life silicon-based anode materials
Material and its preparation method and application.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of preparation method of Gao Shouxiao long-life silicon based anode material, comprising the following steps:
S1, the sub- silicon of oxidation are calcined under inert gas protection, obtain calcining materials；By high-temperature calcination pre-treatment,
SiO occurs disproportionated reaction and obtains the Si/SiO for having relatively uniform silicon wafer particle size2Material.
S2, calcining materials and metal Na after mixing, in CO2Reduction reaction is carried out in atmosphere, obtains reducing material；?
CO2Part SiO is heat-treated by Na under atmosphere2, improve the coulombic efficiency for the first time of material, and the remaining SiO not being reduced2
Material circulation stability can be improved with the volume expansion of padded coaming.CO2SiO can be reduced as reaction gas2It is reacted with Na
Gibbs free energy change, make reaction quickly carried out under the conditions of relatively mild.
S3, reducing material are after pickling impurity removal, then wash to neutrality, obtain dried material after dry；Acid processing is main
Remove the Na of unreacted Na and reaction generation2O and Na2CO3Deng.
S4, dried material is placed in inert gas, is passed through cracking performance gas and carries out chemical vapor deposition, obtains carbon coating
Material；The cladding carbon-coating even compact being prepared by chemical vapor deposition, can significantly improve the electronic conductivity of material；
S5, carbon encapsulated material is dispersed in deionization water-alcohol system, surfactant, high conductivity nanogold is added
Category and polymer monomer are simultaneously uniformly mixed, and initiator is then added and carries out auto polymerization reaction, obtains conducting polymer packet after drying
Cover material；By coating one layer of conducting polymer in material outer layer, improves the interface performance of material, further increase material circulation
Performance；In addition, overcoming the relatively poor (phase of conducting polymer performance by the way that high conductivity nano metal is added in the polymer
For carbon material) defect, further increase the electron conduction of material, improve the coulombic efficiency for the first time and circulation of material
Service life.
S6, it after conducting polymer covering material is broken into powdery granule, is mixed with graphite and obtains high first effect longevity
Order silicon based anode material.Since graphite electronic conductivity is higher, matter is soft, can further buffer the volume expansion of silica-base material,
Therefore it is mixed by demand to obtain the silicon based anode material of Gao Shouxiao long-life.
Further, in step sl, the median particle diameter for aoxidizing sub- silicon is 5 μm~7 μm；The inert gas is helium
At least one of gas, neon, argon gas, Krypton, xenon；The calcining is carried out in rotary furnace, and the rotary furnace turns
Speed is 0.25r/min~1r/min；The temperature of the calcining is 800 DEG C~1200 DEG C, and the time is 0.5h~6h.With other sintering
Equipment is compared, and revolution furnace temperature is more uniform.
Further, in step s 2, the calcining materials, metal Na and CO2Molar ratio be 2:(4~1): 1；CO2It rubs
You are calculated with gas flow rate multiplied by reduction reaction constant temperature time amount；The temperature of reduction reaction is 200 DEG C~800 DEG C, time 1h
~12h.Reduction reaction is carried out in rotary furnace, and rotary furnace revolving speed is 0.25r/min~1r/min.
Further, in step s3, acid used in the pickling is one or more of hydrochloric acid, sulfuric acid, nitric acid, acid
Mass fraction be 10%~50%；Pickling time is 0.5h~3h.
Further, in step s 4, the volume ratio of the inert gas and cracking performance gas is 5:1~1:1, chemical gas
Mutually the time of deposition is 0.5h~6h, and chemical vapor deposition is carried out in rotary furnace, and the revolving speed of the rotary furnace is
0.25r/min~1r/min；The cracking performance gas is methane or its homologue, acetylene or its homologue, benzene or its homologue
At least one of,
Further, in step s 5, the deionization water-alcohol system be deionization water-methanol, deionization water-ethanol,
One kind of deionized water-propyl alcohol, deionized water-isopropanol and deionization water-methanol；The surfactant is polyethylene pyrrole
At least one of pyrrolidone, lauryl sodium sulfate or neopelex；The high conductivity nano metal be Ag,
At least one of Au, Cu, the median particle diameter of the high conductivity nano metal are 10nm~200nm；The polymer monomer
For at least one of pyrroles, dopamine, acrylonitrile or aniline；The initiator is hydrogen peroxide, iron chloride or ammonium persulfate
At least one of.The addition of surfactant can improve the compatibility between material and polymer monomer, promote reaction
It carries out.
Further, in step s 6, the broken median particle diameter of conducting polymer covering material is 5 μm~7 μm,
The mass fraction that the graphite accounts for Gao Shouxiao long-life silicon based anode material is 0%~95%.
Further, in step s 6, the graphite be natural graphite, it is artificial graphite, carbonaceous mesophase spherules, hard carbon, soft
At least one of carbon, the median particle diameter of the graphite are 10 μm~20 μm.
It is another object of the present invention to provide the Gao Shouxiao long-life silicon-based anodes as made from above-mentioned preparation method
Material.
Third object of the present invention is to provide above-mentioned Gao Shouxiao long-life silicon based anode material in lithium ion battery
Application.Silica-base material of the invention is prepared into lithium ion battery as negative electrode material, electricity is carried out to lithium ion battery obtained
The test of chemical property, the specific capacity of lithium ion battery obtained, first effect and cyclical stability are improved.
Compared with prior art, the invention has the benefit that
(1) present invention, first by high temperature pre-treatment, makes SiO that disproportionated reaction acquisition occur relatively equal using SiO as raw material
The Si/SiO of even silicon wafer particle size2Material, then in CO2Na restores part SiO under atmosphere2Improve material coulombic efficiency for the first time,
The SiO that residue is not reduced2Material circulation stability can be improved with the volume expansion of padded coaming.Select CO2As reaction gas
Body can reduce SiO2The gibbs free energy change reacted with Na carries out reaction quickly under the conditions of relatively mild.It is aided with again
The carbon coating layer that chemical vapor deposition (CVD) forms even compact improves the electronic conductivity of material, reduces material resistance.Pass through
Secondary conducting polymer cladding improves the interface performance of material, further increases the cyclical stability of material.The present invention utilizes stone
The properties such as black electronic conductivity is higher, and matter is soft mix it with silica-base material, so as to further buffer the body of silica-base material
Product expansion, is prepared Gao Shouxiao long-life silicon based anode material.
(2) high conductivity nano metal is added in the experiment for preparing secondary conducting polymer covering material in the present invention, with
Improve the polymer conductivity defect poor compared with carbon material, further increases the electron conduction of material, improve material for the first time
Coulombic efficiency and cycle life.And simple process, it is easy to amplify production.
(3) lithium ion battery is made using material prepared by the present invention as negative electrode material, to lithium ion battery obtained into
The test of row chemical property, the specific capacity of lithium ion battery obtained, for the first time coulombic efficiency and cyclical stability are mentioned
Height has fabulous application prospect.
Detailed description of the invention
Fig. 1 is the SEM figure of silicon based anode material prepared by embodiment 1；
Fig. 2 is first charge-discharge of the battery under 0.1C current density made of the material of embodiment 1 and the preparation of comparative example 1
Curve；
Fig. 3 is first charge-discharge of the battery under 0.1C current density made of the material of embodiment 2 and the preparation of comparative example 2
Curve；
Fig. 4 is full battery of the battery under 1C/1C current density made of the material of embodiment 2 and the preparation of comparative example 2
Cycle performance curve.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention will be further explained.Obviously, described embodiment is this
Invention a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art exist
Every other embodiment obtained under the premise of creative work is not made, shall fall within the protection scope of the present invention.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection scope.
Except there is a special instruction, the various reagents used in the present invention, raw material be can commodity commercially or
Person can the product as made from well known method.
Embodiment 1
3kg SiO is placed in the rotary furnace under argon atmosphere protection, 800 DEG C of processing 6h are warming up to 10 DEG C/min, it should
In the process, furnace body keeps 0.25r/min, and room temperature discharges to obtain calcining materials.Then by calcining materials, metal Na according to 2:4's
Ratio is uniformly mixed, and is subsequently added to CO2In rotary furnace under atmosphere protection, 10 DEG C/min is warming up to 600 DEG C of processing 6h (constant temperature
Guarantee Na:SiO:CO in the process2Molar ratio is 2:4:1), during being somebody's turn to do, furnace body keeps 0.25r/min, and room temperature discharging is gone back
Raw material.Above-mentioned reducing material is placed in 10% dilute hydrochloric acid solution, 0.5h is impregnated, is then filtered, and use deionization
Water washing filter cake 3 times are neutrality to filtrate PH, are then dried in 60 DEG C of dryings.Take the dry complete material of 3kg
It is placed in the rotary furnace under argon atmosphere protection, is warming up to 800 DEG C with 10 DEG C/min, flow velocity is according to argon gas at this time: acetylene=5:1
Ratio be passed through acetylene and argon gas, react 6h, then stop being passed through acetylene, argon gas flow velocity is constant, in entire sintering process
In, furnace body revolving speed keeps 0.25r/min, room temperature discharging.Take above-mentioned product 1.95kg, 0.05kg copper nanoparticle (10nm) and
200mL pyrroles's (Py) monomer and 0.02kg polyvinylpyrrolidone are dispersed in 5L deionization water-ethanol, are slowly added dropwise
Enter the FeCl of 3L 0.5mol/L3Solution carries out polymerization reaction 2h, then carries out washing drying.Material after drying is placed in machine
It in tool mill, is crushed and carries out de-agglomerated, obtain the silicon based anode material that D50 is 6 μm.
Fig. 1 is the SEM figure of silicon based anode material prepared by embodiment 1, it is found that granular size is comparatively uniform,
About 6 μm of particle or so.By the silicon based anode material of preparation: SP:LA133=8:1:1 ratio carries out conjunction slurry, coating, assembling
CR2016 button cell, electrolyte use 1mol/L LiPF6EC+DMC solution, and carry out electrochemical property test.As a result such as
Shown in Fig. 2, under the current density of 0.1C, the first discharge specific capacity of battery made of material prepared by embodiment 1 is
1754mAh/g, charge specific capacity 1486mAh/g, coulombic efficiency is 84.7% for the first time.
Comparative example 1
By commercialized SiO/C material: SP:LA133=8:1:1 ratio carries out conjunction slurry, coating, assembling CR2016 button electricity
Pond, electrolyte use 1mol/L LiPF6EC+DMC solution, and carry out electrochemical property test.As a result as shown in Fig. 2,
Under 0.1C current density, the first discharge specific capacity of battery made of material prepared by comparative example 1 is 2189mAh/g, charge ratio
Capacity is 1593mAh/g, and coulombic efficiency is 72.8% for the first time.It is compared by embodiment 1 and comparative example 1 it can be found that embodiment 1
The coulombic efficiency for the first time of battery made of the material being prepared is greatly improved.
Embodiment 2
3kg SiO is placed in the rotary furnace under neon atmosphere protection, 1200 DEG C of processing 0.5h are warming up to 10 DEG C/min, it should
In the process, furnace body keeps 1r/min, and room temperature discharging obtains calcining materials.Then by calcining materials, metal Na according to 2:4 ratio
Example is uniformly mixed, and is subsequently added to CO2In rotary furnace under atmosphere protection, 10 DEG C/min is warming up to 200 DEG C of processing 12h (constant temperature
Guarantee Na:SiO:CO in the process2Molar ratio is 2:1:1), during being somebody's turn to do, furnace body keeps 1r/min, room temperature discharging.By above-mentioned object
Material is placed in 50% dilution heat of sulfuric acid, is impregnated 3h, is then filtered, and filter cake 3 times is washed with deionized to filtrate PH
For neutrality, then it is dried in 60 DEG C of dryings.The dry complete material of 3kg is taken to be placed in returning under neon atmosphere protection
In converter, be warming up to 1200 DEG C with 10 DEG C/min, flow velocity is according to neon at this time: acetylene=5:1 ratio is passed through acetylene and neon
Gas reacts 0.5h, then stops being passed through acetylene, and neon flow velocity is constant, and in entire sintering process, furnace body revolving speed keeps 1r/
Min, room temperature discharging.Take above-mentioned product 1.95kg, 0.05kg copper nanoparticle (10nm) and 200mL pyrroles's (Py) monomer and 0.02kg
Neopelex is dispersed in 5L deionization water-ethanol, and the FeCl into 3L 0.5mol/L is slowly added dropwise3Solution
Polymerization reaction 2h is carried out, washing drying is then carried out.Material after drying is placed in mechanical mill, is crushed and carries out de-agglomerated, obtain
The silicon based anode material that D50 is 6 μm is obtained, the material and artificial graphite are mixed according to the ratio of 1:3, wherein used artificial
Graphite D50 is 15 μm, obtains Gao Shouxiao long-life silicon based anode material.
By the Gao Shouxiao long-life silicon based anode material of preparation: SP:LA133=8:1:1 ratio carries out conjunction slurry, coating, group
CR2016 button cell is filled, electrolyte uses 1mol/L LiPF6EC+DMC solution, and carry out electrochemical property test, test
As a result as shown in figure 3, the first discharge specific capacity of battery made of material prepared by embodiment 2 is 684.6mAh/g, charge ratio
Capacity is 604.8mAh/g, and coulombic efficiency is 88.3% for the first time.It is anode with NCM622, material prepared by embodiment 2 is cathode,
It is soft that the processes such as conjunction slurry, coating, roll-in, cutting, cross cutting, lamination, welding electrode ear, top side seal, baking, fluid injection assembling 7Ah is carried out respectively
Packet battery after forming and capacity dividing, carries out normal temperature circulation test, as a result as shown in figure 4, current full battery under 1C/1C current density
Circulation 516 weeks, capacity retention ratio 91.2%.
Comparative example 2
By commercialized SiO/C/ graphite material: SP:LA133=8:1:1 ratio carries out conjunction slurry, coating, assembles CR2016
Button cell, electrolyte use 1mol/L LiPF6EC+DMC solution, and carry out electrochemical property test.As a result such as Fig. 3 institute
Show, under 0.1C current density, the first discharge specific capacity of battery made of material prepared by comparative example 2 is 721.2mAh/g,
Charge specific capacity is 608.2mAh/g, and coulombic efficiency is 84.3% for the first time.It can be with by embodiment 2 in Fig. 3 and the comparison of comparative example 2
It was found that the coulombic efficiency for the first time of battery made of the material that the present invention is prepared is greatly improved.It is with NCM622
Anode, the commercialization SiO/C/ graphite in comparative example 2 are cathode, carry out respectively conjunction slurry, coating, roll-in, cutting, cross cutting, lamination,
The processes such as welding electrode ear, top side seal, baking, fluid injection assemble 7Ah soft-package battery, after forming and capacity dividing, carry out under 1C/1C current density
Normal temperature circulation test, as a result as shown in figure 4, full battery recycles 516 weeks at present, capacity retention ratio 85.7%.By real in Fig. 4
Apply example 2 and comparative example 2 comparison it can be found that material by polymer overmold and high conductivity nano-metal particle modification after,
The cycle performance of material promotes about 6%, and stability is improved, this is because polymer overmold can improve the boundary of material
Face performance, while the modification of high conductivity nano-metal particle can make up the conducting polymer electric conductivity defect poor compared with carbon material
Reason.
Embodiment 3
3kg SiO is placed in the rotary furnace under argon atmospher protection, 900 DEG C of processing 3h, the mistake are warming up to 10 DEG C/min
Cheng Zhong, furnace body keep 0.5r/min, and room temperature discharging obtains calcining materials.Then by calcining materials, metal Na according to 2:4 ratio
Example is uniformly mixed, and is subsequently added to CO2In rotary furnace under atmosphere protection, 10 DEG C/min is warming up to 400 DEG C of processing 1h (constant temperature mistakes
Guarantee Na:SiO:CO in journey2Molar ratio is 2:2:1), during being somebody's turn to do, furnace body keeps 0.5r/min, room temperature discharging.By above-mentioned object
Material is placed in 10% dilute hydrochloric acid solution, is impregnated 0.5h, is then filtered, and filter cake 3 times is washed with deionized to filtrate
PH is neutrality, is then dried in 60 DEG C of dryings.The dry complete material of 3kg is taken to be placed under argon atmosphere protection
In rotary furnace, be warming up to 900 DEG C with 10 DEG C/min, flow velocity is according to argon gas at this time: methane=5:1 ratio is passed through methane and argon gas
Gas reacts 6h, then stops being passed through acetylene, and argon gas flow velocity is constant, and in entire sintering process, furnace body revolving speed keeps 0.5r/
Min, room temperature discharging.Take above-mentioned product 1.95kg, 0.05kg nano-silver powder (100nm) and 200mL aniline (ANi) monomer and
0.02kg lauryl sodium sulfate is dispersed in 5L deionized water-propyl alcohol, and the FeCl into 3L 0.5mol/L is slowly added dropwise3
Solution carries out polymerization reaction 2h, then carries out washing drying.Material after drying is placed in mechanical mill, it is broken to carry out solution group
It is poly-, the silicon based anode material that D50 is 5 μm is obtained, the material and carbonaceous mesophase spherules are mixed according to the ratio of 1:2,
In artificial graphite D50 used be 10 μm, obtain Gao Shouxiao long-life silicon based anode material.
Embodiment 4
3kg SiO is placed in the rotary furnace under argon atmospher protection, 900 DEG C of processing 3h, the mistake are warming up to 10 DEG C/min
Cheng Zhong, furnace body keep 0.5r/min, and room temperature discharging obtains calcining materials.Then by calcining materials, metal Na according to 2:4 ratio
Example is uniformly mixed, and is subsequently added to CO2In rotary furnace under atmosphere protection, 10 DEG C/min is warming up to 600 DEG C of processing 4h (constant temperature mistakes
Guarantee Na:SiO:CO in journey2Molar ratio is 2:2:1), during being somebody's turn to do, furnace body keeps 0.5r/min, room temperature discharging.By above-mentioned object
Material is placed in 10% dilute hydrochloric acid solution, is impregnated 0.5h, is then filtered, and filter cake 3 times is washed with deionized to filtrate
PH is neutrality, is then dried in 60 DEG C of dryings.The dry complete material of 3kg is taken to be placed under argon atmosphere protection
In rotary furnace, be warming up to 900 DEG C with 10 DEG C/min, flow velocity is according to argon gas at this time: acetylene=5:1 ratio is passed through acetylene and argon gas
Gas reacts 6h, then stops being passed through acetylene, and argon gas flow velocity is constant, and in entire sintering process, furnace body revolving speed keeps 0.5r/
Min, room temperature discharging.Take above-mentioned product 1.95kg, 0.05kg nano-gold powder (10nm) and 200mL dopamine (DA) monomer and
0.02kg polyvinylpyrrolidone is dispersed in 5L deionized water-isopropanol, is slowly added dropwise into 5L 0.1M ammonium persulfate
Solution carries out polymerization reaction 2h, then carries out washing drying.Material after drying is placed in mechanical mill, it is broken to carry out solution group
It is poly-, the silicon based anode material that D50 is 7 μm is obtained, the material and natural graphite are mixed according to the ratio of 1:4, wherein institute
It is 20 μm with artificial graphite D50, obtains Gao Shouxiao long-life silicon based anode material.
Embodiment 5
3kg SiO is placed in the rotary furnace under argon atmospher protection, 900 DEG C of processing 3h, the mistake are warming up to 10 DEG C/min
Cheng Zhong, furnace body keep 0.5r/min, and room temperature discharging obtains calcining materials.Then by calcining materials, metal Na according to 2:4 ratio
Example is uniformly mixed, and is subsequently added to CO2In rotary furnace under atmosphere protection, 10 DEG C/min is warming up to 600 DEG C of processing 12h (constant temperature
Guarantee Na:SiO:CO in the process2Molar ratio is 2:4:1), during being somebody's turn to do, furnace body keeps 0.5r/min, room temperature discharging.It will be above-mentioned
Material is placed in 10% dilute hydrochloric acid solution, is impregnated 0.5h, is then filtered, and is washed with deionized filter cake 3 times and is extremely filtered
Liquid PH is neutrality, is then dried in 60 DEG C of dryings.The dry complete material of 3kg is taken to be placed under argon atmosphere protection
Rotary furnace in, be warming up to 900 DEG C with 10 DEG C/min, flow velocity is according to argon gas at this time: acetylene=5:1 ratio is passed through acetylene and argon
Gas gas reacts 6h, then stops being passed through acetylene, and argon gas flow velocity is constant, and in entire sintering process, furnace body revolving speed is kept
0.5r/min, room temperature discharging.Take above-mentioned product 1.95kg, 0.05kg copper nanoparticle (10nm) and 200mL dopamine (DA) monomer
With with 0.02kg neopelex, be dispersed in 5L deionized water-isopropanol, be slowly added dropwise into 5L mass fraction
Polymerization reaction 2h is carried out for 10% hydrogenperoxide steam generator, then carries out washing drying.Material after drying is placed in mechanical mill,
It is broken to carry out de-agglomerated, obtain the silicon based anode material that D50 is 7 μm, by the material and natural graphite according to 5:95 ratio into
Row mixing obtains Gao Shouxiao long-life silicon based anode material wherein artificial graphite D50 used is 20 μm.
Claims (10)
1. a kind of preparation method of Gao Shouxiao long-life silicon based anode material, it is characterised in that: the following steps are included:
S1, the sub- silicon of oxidation are calcined under inert gas protection, obtain calcining materials；
S2, calcining materials and metal Na after mixing, in CO2Reduction reaction is carried out in atmosphere, obtains reducing material；
After pickling impurity removal, washing to neutrality obtains dried material after dry for S3, reducing material；
S4, dried material is placed in inert gas, is passed through cracking performance gas and carries out chemical vapor deposition, obtains carbon coating material
Material；
S5, carbon encapsulated material is dispersed in deionization water-alcohol system, be added surfactant, high conductivity nano metal and
Polymer monomer is simultaneously uniformly mixed, and initiator is then added and carries out auto polymerization reaction, and conducting polymer cladding material is obtained after dry
Material；
S6, it after conducting polymer covering material is broken into powdery granule, is mixed with graphite and obtains Gao Shouxiao long-life silicon
Base negative electrode material.
2. preparation method according to claim 1, it is characterised in that: in step sl, the intermediate value grain for aoxidizing sub- silicon
Diameter is 5 μm~7 μm；The inert gas is at least one of helium, neon, argon gas, Krypton, xenon；It is described calcining be
It is carried out in rotary furnace, the revolving speed of the rotary furnace is 0.25r/min~1r/min；The temperature of the calcining be 800 DEG C~
1200 DEG C, the time is 0.5h~6h.
3. preparation method according to claim 1, it is characterised in that: in step s 2, the calcining materials, metal Na with
CO2Molar ratio be 2:(4~1): 1；The temperature of the reduction reaction is 200 DEG C~800 DEG C, and the time is 1h~12h, and reduction is anti-
Should be carried out in rotary furnace, rotary furnace revolving speed is 0.25r/min~1r/min.
4. preparation method according to claim 1, it is characterised in that: in step s3, acid used in the pickling is salt
One or more of acid, sulfuric acid, nitric acid, sour mass fraction are 10%~50%；Pickling time is 0.5h~3h.
5. preparation method according to claim 1, it is characterised in that: in step s 4, the inert gas and cracking performance
The volume ratio of gas is 5:1~1:1, and the time of chemical vapor deposition is 0.5h~6h, and chemical vapor deposition is in rotary furnace
It carries out, the revolving speed of the rotary furnace is 0.25r/min~1r/min；The cracking performance gas is methane or its homologue, second
At least one of alkynes or its homologue, benzene or its homologue.
6. preparation method according to claim 1, it is characterised in that: in step s 5, the deionization water-alcohol system is
Deionization water-methanol, deionization water-ethanol, deionized water-propyl alcohol, deionized water-isopropanol and deionization water-methanol
It is a kind of；The surfactant be polyvinylpyrrolidone, lauryl sodium sulfate or neopelex at least
It is a kind of；The high conductivity nano metal is at least one of Ag, Au, Cu, the intermediate value grain of the high conductivity nano metal
Diameter is 10nm~200nm；The polymer monomer is at least one of pyrroles, dopamine, acrylonitrile or aniline；The initiation
Agent is at least one of hydrogen peroxide, iron chloride or ammonium persulfate.
7. preparation method according to claim 1, it is characterised in that: in step s 6, the conducting polymer coats material
Expect that broken median particle diameter is 5 μm~7 μm, the mass fraction that the graphite accounts for Gao Shouxiao long-life silicon based anode material is
0%~95%.
8. preparation method according to claim 1, it is characterised in that: in step s 6, the graphite is natural graphite, people
At least one of graphite, carbonaceous mesophase spherules, hard carbon, soft carbon are made, the median particle diameter of the graphite is 10 μm~20 μm.
9. Gao Shouxiao long-life silicon based anode material made from preparation method a method as claimed in any one of claims 1-8.
10. application of the Gao Shouxiao long-life silicon based anode material as claimed in claim 9 in lithium ion battery.
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