CN116864643A - Silicon-based composite material, preparation method and battery - Google Patents
Silicon-based composite material, preparation method and battery Download PDFInfo
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- CN116864643A CN116864643A CN202310907331.2A CN202310907331A CN116864643A CN 116864643 A CN116864643 A CN 116864643A CN 202310907331 A CN202310907331 A CN 202310907331A CN 116864643 A CN116864643 A CN 116864643A
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 118
- 239000010703 silicon Substances 0.000 title claims abstract description 118
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 48
- 239000000463 material Substances 0.000 claims abstract description 35
- 239000010405 anode material Substances 0.000 claims abstract description 26
- 239000013354 porous framework Substances 0.000 claims abstract description 18
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 14
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 238000005056 compaction Methods 0.000 claims abstract description 6
- 239000007773 negative electrode material Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 238000005229 chemical vapour deposition Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000003575 carbonaceous material Substances 0.000 claims description 9
- 239000011246 composite particle Substances 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 9
- 239000007784 solid electrolyte Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000011247 coating layer Substances 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 3
- 229920001940 conductive polymer Polymers 0.000 claims description 3
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 3
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims description 3
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 3
- 239000005052 trichlorosilane Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 5
- 238000007086 side reaction Methods 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 16
- 239000012298 atmosphere Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 11
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000013067 intermediate product Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000006183 anode active material Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- -1 alumina Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
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- 238000002156 mixing Methods 0.000 description 3
- 229910021392 nanocarbon Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
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- 238000005406 washing Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007833 carbon precursor Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
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- 238000010998 test method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000002227 LISICON Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical group [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910002064 alloy oxide Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
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- 239000002223 garnet Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
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- 238000005342 ion exchange Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/36—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
- 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
- H01M4/625—Carbon or graphite
-
- 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
Abstract
The invention provides a silicon-based composite material, a preparation method and a battery, and particularly relates to the technical field of secondary batteries. The silicon-based anode material comprises a plurality of silicon-based composite material particles, wherein the silicon-based composite material particles comprise spherical porous framework materials and silicon nano particles distributed in pores of the spherical porous framework materials, the sphericity of the silicon-based composite material particles is more than or equal to 0.85, and the specific surface area of the silicon-based composite material is 0.1m 2 /g‑1m 2 And/g. The silicon-based composite material provided by the invention has the advantages of regular particle shape, higher sphericity, smaller specific surface area, improved material concentration, uniform material dispersion and reduced side reaction. In addition, high sphericity is beneficial to avoiding particlesThe particles are crushed and pulverized in the rolling process, so that the compressive strength and the compaction density are improved, the interface of the composite material particle body is further optimized by the smaller specific surface area, and the high-temperature cycle performance and the high-temperature storage performance of the silicon-based anode material are improved.
Description
Technical Field
The invention relates to the technical field of secondary batteries, in particular to a silicon-based composite material, a preparation method and a battery.
Background
While sales of new energy automobiles are continuously increased, large devices such as new energy automobiles and the like provide higher-rate charge and discharge requirements for lithium ion batteries, and currently used anode and cathode materials cannot meet the requirements. In order to improve the performance of the lithium ion battery, it is definitely the most convenient and efficient to improve the electrochemical performance of the negative electrode. Silicon has a larger theoretical specific capacity (4200 mAh/g), an order of magnitude higher than the specific capacity (372 mAh/g) of the graphite-based negative electrode material, and a lower lithium intercalation potential. The silicon has low reactivity with electrolyte, is rich in reserves in crust, has low price, and is an ideal choice for the cathode material of a new generation of lithium ion batteries.
Under the condition of high addition amount, the existing novel silicon-carbon structure product has the problems of high-temperature circulation and high-temperature storage performance degradation, and is characterized by phenomena of gas production of a high-temperature storage battery, high-temperature circulation water jump and the like.
In general, the high-temperature performance of the battery is accelerated (but incomplete) of the low-temperature performance, and particularly, the positive electrode is extremely unstable in a high-temperature and high-lithium removal state in a high-nickel system, and has high activity due to metal ion dissolution and free oxygen dissolution; meanwhile, the negative electrode is in a low potential state for a long time, active lithium ions are consumed by the reduction reaction of the electrolyte, and finally inorganic lithium salt is generated, so that a large number of side reactions, SEI decomposition, regeneration and the like are caused; and the high temperature increases the reduction reaction rate of the electrolyte, so that a great deal of active lithium ions are lost.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a silicon-based composite material, which solves the problems of poor battery processing performance and poor high-temperature cycle performance under the condition of high silicon-based composite material addition ratio in the prior art.
The second object of the present invention is to provide a method for preparing a silicon-based composite material.
It is a further object of the present invention to provide a battery.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the first aspect of the invention provides a silicon-based composite material, comprising a plurality of silicon-based composite material particles, wherein the silicon-based composite material particles comprise spherical porous framework materials and silicon nano particles distributed in pores of the spherical porous framework materials, the sphericity of the silicon-based composite material particles is more than or equal to 0.85, and the specific surface area of the silicon-based composite material is 0.1m 2 /g-1m 2 /g。
Further, in the particle size distribution of the silicon-based composite particles, 0 < (DV, 90-DV, 10)/DV, 50 is less than or equal to 1, and preferably 0.5-0.8.
Further, the particle size distribution of the silicon-based composite material satisfies:
(1) DV,10 is 4.5 μm-6.0 μm;
(2) DV,50 is 8.0 μm-15.0 μm;
(3) DV,99 is 20.0 μm-30.0 μm.
Further, the silicon-based anode material has a powder compaction density of 0.8g/cm under a pressure of 1 ton 3 -2.0g/cm 3 。
Further, the skeleton density of the silicon-based anode material is 1.2g/cm 3 -2.1g/cm 3 Preferably 1.4g/cm 3 -1.8g/cm 3 。
Further, the silicon nanoparticles are amorphous silicon, and the particle size of the silicon nanoparticles is 0.4nm-10nm, preferably 0.4nm-2nm.
Preferably, the silicon content in the silicon-based composite particles is from 5wt.% to 95wt.%.
Preferably, the spherical porous framework material comprises at least one of spherical porous carbon, spherical porous metal framework, and spherical porous metal oxide framework.
Further, the silicon-based composite particles also have a coating layer, and the material of the coating layer comprises at least one of solid electrolyte, conductive polymer, carbonaceous material, metal, alloy and metal oxide.
The second aspect of the invention provides a preparation method of the silicon-based anode material, which comprises the following steps: providing a spherical porous framework material, taking a silicon source as a deposition gas, and depositing silicon nano particles in pores of the spherical porous framework material by a chemical vapor deposition method to obtain the silicon-based anode material.
Further, the silicon source includes at least one of monosilane, disilane, trichlorosilane, and dichlorosilane.
Preferably, the chemical vapor deposition is performed under inert gas protection.
Preferably, the temperature of the chemical vapor deposition is 200-1000 ℃ and the time is 0.1-100 h.
A third aspect of the present invention provides a battery comprising a positive electrode and a negative electrode, the negative electrode comprising a negative electrode active material, the negative electrode active material being the silicon-based negative electrode material or the silicon-based negative electrode material being obtained according to the preparation method.
Compared with the prior art, the invention has at least the following beneficial effects:
the silicon-based composite material provided by the invention has the advantages of regular particle shape, higher sphericity, smaller specific surface area, improved material concentration, uniform material dispersion and reduced side reaction. In addition, the high sphericity is favorable for avoiding crushing and pulverization of particles in the rolling process, improving compressive strength and compaction density, further optimizing the interface of a composite material particle body by the smaller specific surface area, and improving the high-temperature cycle performance and the high-temperature storage performance of the silicon-based anode material.
The preparation method provided by the invention has the advantages of continuous process, high degree of mechanization and strong controllability, and is suitable for large-scale industrial production.
The battery provided by the invention has the advantages that the silicon-based composite material with better service performance is used, and the cycle performance and stability of the secondary battery are further improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
Fig. 1 is an SEM image of the silicon-based composite material obtained in example 2.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to embodiments and examples, but it will be understood by those skilled in the art that the following embodiments and examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
As analyzed in the background art of the invention, the large volume expansion of silicon is the biggest problem limiting the industrialized application of the silicon-based negative electrode, and the chemical vapor deposition of the silicon-containing precursor is carried out on the porous matrix, so that silicon nano particles are dispersed and filled in the pore structure of the porous matrix, and the volume expansion of silicon in the charging and discharging processes can be effectively relieved. However, the inventor finds that the shape of the silicon-based composite material particles influences the full play of the performance of the composite material, and when the irregularly-shaped silicon-based composite material particles are used as a negative electrode material, the multi-edge angle can cause the continuous generation of a Solid Electrolyte Interface (SEI) film, consume active lithium in the battery and cause capacity attenuation and poor circulation; in addition, when the negative electrode is manufactured, the tip stress at the corner results in poor pressure resistance, and is easily crushed in the rolling process.
The first aspect of the invention provides a silicon-based composite material comprising a plurality of silicon-based composite material particles, the silicon-based composite material particles comprising a spherical porous framework material and silicon nanoparticles distributed in pores of the spherical porous framework material, the sphericity of the silicon-based composite material particlesMore than or equal to 0.85, the specific surface area of the silicon-based composite material is 0.1m 2 /g-1m 2 /g。
The silicon-based composite material provided by the invention has the advantages of regular particle shape, higher sphericity, smaller specific surface area, improved material concentration, uniform material dispersion and reduced side reaction. In some embodiments of the present invention, the sphericity of the silicon-based composite is typically, but not limited to, 0.85, 0.87, 0.90, 0.93, 0.95, 0.98 or 1. The high sphericity is favorable for avoiding crushing and pulverization of particles in the rolling process, and the compressive strength and the compaction density are improved. When the sphericity of the silicon-based composite material particles is less than 0.85, the surfaces of the silicon-based composite material particles have more edges and corners, the compressive capacity of the edges and corners in the rolling process is poor, the composite material is easy to crush under the action of tip stress, and when the silicon-based composite material particles are used as a negative electrode material, the edges and corners can lead to continuous generation of a Solid Electrolyte Interface (SEI) film, consume active lithium in the battery, and lead to capacity attenuation and poor circulation.
In some embodiments of the present invention, the specific surface area of the silicon-based composite material is typically, but not limited to, 0.1m 2 /g、0.2m 2 /g、0.3m 2 /g、0.4m 2 /g、0.5m 2 /g、0.6m 2 /g、0.7m 2 /g、0.8m 2 /g、0.9m 2 /g or 1m 2 And/g. The interface of the composite material particle body is further optimized by the smaller specific surface area, and the high-temperature cycle performance and the high-temperature storage performance of the silicon-based anode material are improved.
Further, in the particle size distribution of the silicon-based composite particles, 0 < (DV, 90-DV, 10)/DV, 50 is less than or equal to 1, and preferably 0.5-0.8. The particles in this range have better concentration and more uniform particle size.
In some embodiments of the invention, (DV, 90-DV, 10)/DV, 50 is typically, but not limited to, 0.2, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1.
Further, the particle size distribution of the silicon-based composite material satisfies:
(1) DV,10 is 4.5 μm-6.0 μm;
(2) DV,50 is 8.0 μm-15.0 μm;
(3) DV,99 is 20.0 μm-30.0 μm.
Further, the silicon-based anode material has a powder compaction density of 0.8g/cm under a pressure of 1 ton 3 -2.0g/cm 3 。
Further, the skeleton density of the silicon-based anode material is 1.2g/cm 3 -2.1g/cm 3 Preferably 1.4g/cm 3 -1.8g/cm 3 。
In some embodiments of the present invention, the skeletal density of the silicon-based composite material is typically, but not limited to, 1.2g/cm 3 、1.3g/cm 3 、1.4g/cm 3 、1.5g/cm 3 、1.6g/cm 3 、1.7g/cm 3 、1.8g/cm 3 、1.9g/cm 3 、2.0g/cm 3 Or 2.1g/cm 3 。
Further, the silicon nanoparticles are amorphous silicon, and the particle size of the silicon nanoparticles is 0.4nm-10nm, preferably 0.4nm-2nm.
Preferably, the silicon content in the silicon-based composite particles is from 5wt.% to 95wt.%; in some embodiments of the present invention, the silicon content is typically, but not limited to, 5wt.%, 15wt.%, 25wt.%, 35wt.%, 45wt.%, 55wt.%, 65wt.%, 75wt.%, 85wt.%, or 95wt.%.
Preferably, the spherical porous framework material comprises at least one of spherical porous carbon, spherical porous metal framework (e.g., spherical copper foam) and spherical porous metal oxide framework (e.g., spherical porous titanium oxide, spherical porous aluminum oxide).
Further, the silicon-based composite particles are further provided with a coating layer, and the material of the coating layer comprises at least one of solid electrolyte (such as LISICON type solid electrolyte, nasicon type solid electrolyte, perovskite type solid electrolyte, garnet type solid electrolyte or sulfide solid electrolyte), conductive polymer (such as polyethylene oxide, carboxymethyl cellulose, polyacrylic acid or polyacrylonitrile), carbonaceous material (such as carbon fiber, carbon nano tube, graphite, graphene or amorphous carbon), metal simple substance or alloy (such as lithium, magnesium, copper, nickel, aluminum or silver), and metal oxide (such as alumina, zinc oxide, magnesium oxide, zirconium oxide or titanium oxide).
The second aspect of the invention provides a preparation method of the silicon-based anode material, which comprises the following steps: providing a spherical porous framework material, taking a silicon source as a deposition gas, and depositing silicon nano particles in pores of the spherical porous framework material by a chemical vapor deposition method to obtain the silicon-based anode material.
In some embodiments, the sphericity of the spherical porous skeletal material is ≡ 0.85, e.g., 0.85, 0.87, 0.90, 0.93, 0.95, 0.98, 1, etc. The spherical porous framework material may be selected from commercial specification products or prepared by methods known in the art, such as hydrothermal, solvothermal, electrochemical deposition, powder metallurgy, molten metal, ion exchange.
The preparation method provided by the invention has the advantages of continuous process, high degree of mechanization and strong controllability, and is suitable for large-scale industrial production.
Further, the silicon source includes at least one of monosilane, disilane, trichlorosilane, and dichlorosilane.
Preferably, the chemical vapor deposition is performed under the protection of an inert gas, wherein the inert gas comprises one or more of nitrogen, argon and helium. In the mixed gas containing the silicon source and the inert gas, the volume content of the silicon source is 1-50%.
Preferably, the temperature of the chemical vapor deposition is 200-1000 ℃ and the time is 0.1-100 h.
A third aspect of the present invention provides a battery comprising a positive electrode and a negative electrode, the negative electrode comprising a negative electrode active material, the negative electrode active material being the silicon-based negative electrode material or the silicon-based negative electrode material being obtained according to the preparation method.
The battery provided by the invention has the advantages that the silicon-based composite material with better service performance is used, and the cycle performance and stability of the secondary battery are further improved.
The invention is further illustrated by the following specific examples and comparative examples, however, it should be understood that these examples are for the purpose of illustration only in greater detail and should not be construed as limiting the invention in any way. The raw materials used in the examples and comparative examples of the present invention were conducted under conventional conditions or conditions recommended by the manufacturer, without specifying the specific conditions. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The present example provides a silicon-based composite material, which was prepared by selecting a spherical porous carbon material (model BK2021012903, north Korea nanotechnology Co., ltd.) having a sphericity of 0.98 for commercial use as a base material, placing the spherical porous carbon material in an atmosphere furnace, and heating under N 2 Heating from room temperature to 600-1000 ℃ at 2-5 ℃/min in the atmosphere; 5-30% SiH 4 -N 2 Maintaining the mixed atmosphere at 600-1000 ℃ for 10-50 h; and at N 2 Naturally cooling under protection; obtaining the spherical silicon-based composite material.
Example 2
The embodiment provides a silicon-based composite material, and the preparation method comprises the following steps:
respectively dissolving spherical calcium carbonate and asphalt in a certain mass ratio in tetrahydrofuran, uniformly stirring the two solutions, placing the two solutions in a reaction kettle, preserving heat for 8 hours at 260 ℃, cooling, washing with hydrochloric acid, and drying to obtain the spherical porous carbon precursor. The spherical porous carbon precursor is subjected to constant temperature heat treatment at 1000 ℃ for 10 hours under an inert atmosphere of nitrogen or argon, and then is exposed to an oxygen-containing environment such as CO at a high temperature of 1100 DEG C 2 Gas or H 2 And (3) activating in O steam to obtain the spherical porous carbon material with the sphericity of 0.9.
Placing the prepared spherical porous carbon material in an atmosphere furnace, and adding N into the furnace 2 Heating from room temperature to 600-1000 ℃ at 2-5 ℃/min in the atmosphere; 5-30% SiH 4 -N 2 Maintaining the mixed atmosphere at 600-1000 ℃ for 10-50 h; and at N 2 Naturally cooling under protection; obtaining the spherical silicon-based composite material. SEM was performed on the silicon-based composite material, and the resulting image was as shown in FIG. 1.
Example 3
Acetylene is used as a carbon source, acetylene gas is introduced into a tube furnace at a certain (80-120 mL/min) rate, the temperature is raised to 600-900 ℃ at a heating rate of 5-10 ℃/min, the synthesis time is 1-5 h, the nano carbon spheres are prepared, the nano carbon spheres and KOH are fully and uniformly mixed according to a certain proportion (2-4:1), the nano carbon spheres and KOH are placed into the tube furnace for heat activation treatment, the temperature is raised to 800-1000 ℃ at a heating rate of 2-5 ℃/min in a nitrogen atmosphere, the temperature is kept for 2-4 h, and the intermediate product is obtained after cooling. Washing the intermediate product to be neutral by deionized water, treating the intermediate product by excessive concentrated nitric acid in an oil bath pot at 80-100 ℃ for 2-5 hours, washing the intermediate product again to be neutral, and drying the intermediate product at 80 ℃ for 12 hours to obtain the spherical porous carbon material with the sphericity of 0.85.
Placing the prepared spherical porous carbon material in an atmosphere furnace, and adding N into the furnace 2 Heating from room temperature to 600-1000 ℃ at 2-5 ℃/min in the atmosphere; 5-30% SiH 4 -N 2 Maintaining the mixed atmosphere at 600-1000 ℃ for 10-50 h; and at N 2 Naturally cooling under protection; obtaining the spherical silicon-based composite material.
Example 4
The embodiment provides a silicon-based composite material, and the preparation method comprises the following steps:
1. mixing aluminum hydroxide and pure water, adding the mixture into a ball mill, ball-milling for 8 hours to obtain aluminum hydroxide slurry, mixing the aluminum hydroxide slurry with ammonium bicarbonate, adding a quantitative polyvinyl alcohol aqueous solution, stirring uniformly at a high speed, drying and granulating the mixed slurry through a spray dryer, and roasting the granulated powder at 750 ℃ for 6 hours to obtain the spherical porous alumina material with the sphericity of 0.85.
2. The prepared spherical porous alumina material is placed in an atmosphere furnace and is treated by N 2 Heating from room temperature to 600-1000 ℃ at 2-5 ℃/min in the atmosphere; 5-30% SiH 4 -N 2 Maintaining the mixed atmosphere at 600-1000 ℃ for 10-50 h; and at N 2 Naturally cooling under protection; obtaining the spherical silicon-based composite material.
Example 5
This example provides a silicon-based composite material, which is different from example 1 in that a spherical silicon-based composite material is surface-coated with N 2 Heating to 800 ℃ at 2 ℃/min in the atmosphere, and heating to 50% C 2 H 2 -N 2 And (3) maintaining the mixture for 0.5h to obtain the carbon-coated spherical silicon-based composite material and the carbon coating layerIs 10nm thick. The rest of the method and the raw materials are the same as those in the example 1, and are not repeated here.
Comparative example 1
This comparative example provides a silicon-based composite material, which is different from example 1 in that the base material is porous carbon (model ZLD-2, st. Sank group, inc.) of commercial gravel structure, the sphericity is 0.65, and the remaining raw materials and steps are the same as example 1, and are not repeated here.
Comparative examples 2 to 3
This comparative example provides a silicon-based composite material, which is different from example 2 in that the particle size distribution of particles is controlled and regulated by controlling the inflow rate of acetylene and the heating temperature and time; the deposition amount of silicon particles in the pores is adjusted by controlling the flow rate of the silane gas, the deposition temperature and the deposition time, so as to adjust the specific surface area of the material, and the rest raw materials and steps are the same as those in example 2, and are not repeated here.
Test example 1
Physical and chemical parameters of the silicon-based composite materials obtained in examples 1 to 5 and comparative examples 1 to 3 were measured. The sphericity of the particles is calculated by the equivalent diameter of the particles by a sedimentation method and the equivalent diameter by a laser diffraction method, and the specific method belongs to the public knowledge in the field and is not repeated.
The specific surface area of the particles was measured by a specific surface area analyzer.
The particle size was measured by a laser particle size analyzer.
The compacted density of the particles was measured by a compacted densitometer and maintained at a pressure of 1t for 10s to obtain compacted density test data.
The skeleton density was measured by helium specific gravity.
The true density of the particles was measured by a full-automatic true density meter.
TABLE 1 physicochemical parameters of the silicon-based composite materials obtained in examples 1 to 5 and comparative examples 1 to 3
The physicochemical parameters of the anode materials of examples 1 to 5 and comparative examples 1 to 3 are shown in table 1, and it can be seen that the materials of the spherical particles have a more uniform particle size distribution and a smaller specific surface area than those of the gravel (irregular) particles.
Test example 2
The silicon-based anode materials provided in the above examples and comparative examples are used as anode active materials, anode pieces are prepared respectively, a CR2032 type button cell is prepared by a conventional method, and electrical performance tests are performed on the cells. The specific test method comprises the following steps:
(1) And (3) half-cell assembly: CR2032 button cell is assembled in a glove box, a metal lithium sheet is used as a counter electrode, a polypropylene microporous membrane is used as a diaphragm, and electrolyte is LiPF 6 Dissolved in a mixture of Ethyl Carbonate (EC) and diethyl carbonate (DEC) (volume ratio EC: dec=1:1), wherein LiPF 6 The concentration was 1mol/L.
The battery was tested for charge and discharge using a blue-electric (LAND) battery test system.
(2) Cyclic gram capacity and first time efficiency test: after CR2032 type buckling and standing for 6 hours, discharging to 0.005V at 0.05C, and discharging to 0.005V at 0.01C; standing for 5min, and charging to 1.5V at constant current of 0.05C; the first lithium removal gram capacity is the gram capacity (or called mass specific capacity) of the electrode material, and the ratio of the first lithium removal capacity to the first lithium intercalation capacity is the first coulombic efficiency of the battery.
The silicon-based anode materials provided in the above examples and comparative examples were used as anode active materials, and a soft-pack battery was prepared and tested for electrical properties using a conventional method from a pole piece containing the anode active materials. The soft package battery is prepared in a dehumidification room with the dew point of-45 ℃. The battery is subjected to charge-discharge cyclic test by a blue-blog (LANBTS) battery test system, and the specific test method comprises the following steps:
(1) Manufacturing a positive plate: and uniformly stirring and mixing the anode active material CNM811, the conductive agent SuperP, the binder PVDF and the solvent NMP according to the mass ratio of 92:3:5:150, uniformly coating the mixture on an anode current collector, and then drying the mixture at 80 ℃ to obtain the anode plate.
(2) Manufacturing a negative plate: the silicon-based composite materials prepared in the examples and the comparative examples are mixed with graphite according to a certain proportion to obtain a negative electrode active material, the conductive agent SuperP, the binder polyacrylic acid and the solvent deionized water are uniformly mixed according to a mass ratio of 95:1:4:120, uniformly coated on a negative electrode current collector, and then dried at 100 ℃ to obtain the negative electrode sheet.
(3) And separating the positive plate and the negative plate through square lamination and using a polypropylene isolating film to prepare battery cores, packaging the battery cores into an aluminum plastic bag, injecting electrolyte with corresponding capacity into the aluminum plastic bag, and vacuum sealing to obtain the soft package battery. The electrolyte is a mixed solution of EC and DEC of LiPF6, wherein the concentration of LiPF6 is 1mol/L, and the volume ratio of EC to DEC is 1:1.
(4) The chemical composition comprises the following components: forming a battery after filling and sealing, standing in a constant temperature box at 25 ℃ for 12 hours, then charging to 3.3V at a constant current of 0.02C, standing for 30min, charging to 3.8V at a constant current of 0.025C, standing for 10min, and charging to 4.2V at a constant current of 0.33C; and vacuumizing and shearing the air bag of the formed battery, then carrying out capacity division, charging to 4.45V at a constant current of 0.33C, standing for 10min, discharging to 3V at a constant current of 1C, standing for 10min, discharging to 3V at a constant current of 0.33C, and ending the capacity division. The ratio of the discharge capacity divided by the charge capacity in the formation of the soft pack battery into the capacity is the first efficiency of the battery.
(5) And (3) 25 ℃ cycle test: placing the battery in a constant temperature box at 25 ℃, charging to 4.45V at a constant current of 1C, and charging to 0.1C at a constant voltage of 4.45V; after standing for 10min, discharging the 1C constant current to 3.0V, standing for 10min, repeating the above charging and discharging steps until the discharge capacity is lower than 80% of the first-cycle discharge capacity, and stopping to obtain the cycle number, namely the cycle life of the soft-package battery; the record has a 100-cycle capacity retention rate.
(6) And (3) cycle test at 45 ℃: the cells were placed in a 45℃incubator and the other steps were cycled at 25 ℃.
Table 2 kinetic properties of silicon-based composites prepared in examples and comparative examples
As is clear from Table 2, the silicon contents in each of examples and comparative examples were about 50%, and thus the gram capacities were not greatly different, but the silicon-based materials obtained in examples 1 to 5 had higher initial coulombic efficiency and better cycle performance, particularly high-temperature cycle performance, than those of comparative example 1 having an irregular shape and comparative examples 2 to 3 having a relatively high specific surface area and low particle concentration.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. A silicon-based anode material is characterized by comprising a plurality of silicon-based composite material particles, wherein the silicon-based composite material particles comprise spherical porous framework materials and silicon nano particles distributed in pores of the spherical porous framework materials, the sphericity of the silicon-based composite material particles is more than or equal to 0.85, and the specific surface area of the silicon-based composite material is 0.1m 2 /g-1m 2 /g。
2. The silicon-based anode material according to claim 1, wherein 0 < (DV, 90-DV, 10)/DV, 50 is equal to or less than 1, preferably 0.5-0.8, in the particle size distribution of the silicon-based composite particles.
3. The silicon-based anode material according to claim 1, wherein the particle size distribution of the silicon-based composite material satisfies:
(1) DV,10 is 4.5 μm-6.0 μm;
(2) DV,50 is 8.0 μm-15.0 μm;
(3) DV,99 is 20.0 μm-30.0 μm.
4. The silicon-based anode material according to claim 1, wherein the silicon-based anode materialThe powder compaction density of the material at a pressure of 1 ton was 0.8g/cm 3 -2.0g/cm 3 。
5. The silicon-based anode material according to claim 1, wherein the skeletal density of the silicon-based anode material is 1.2g/cm 3 -2.1g/cm 3 Preferably 1.4g/cm 3 -1.8g/cm 3 。
6. The silicon-based anode material according to claim 1, wherein the silicon nanoparticles are amorphous silicon, the particle size of the silicon nanoparticles is 0.4nm-10nm, preferably 0.4nm-2nm;
preferably, the silicon content in the silicon-based composite particles is from 5wt.% to 95wt.%;
preferably, the spherical porous framework material comprises at least one of spherical porous carbon, spherical porous metal framework, and spherical porous metal oxide framework.
7. The silicon-based anode material according to claim 1, wherein the silicon-based composite particles further have a coating layer, and the material of the coating layer includes at least one of a solid electrolyte, a conductive polymer, a carbonaceous material, a metal, an alloy, and a metal oxide.
8. A method for producing the silicon-based anode material according to any one of claims 1 to 7, comprising: providing a spherical porous framework material, taking a silicon source as a deposition gas, and depositing silicon nano particles in pores of the spherical porous framework material by a chemical vapor deposition method to obtain the silicon-based anode material.
9. The method of preparing according to claim 8, wherein the silicon source comprises at least one of monosilane, disilane, trichlorosilane, and dichlorosilane;
preferably, the chemical vapor deposition is performed under inert gas protection;
preferably, the temperature of the chemical vapor deposition is 200-1000 ℃ and the time is 0.1-100 h.
10. A battery comprising a positive electrode and a negative electrode, the negative electrode comprising a negative electrode active material comprising the silicon-based negative electrode material of any one of claims 1-7 or the silicon-based negative electrode material obtained according to the production method of any one of claims 8-9.
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