CN115732636B - Silicon negative electrode material, silicon negative electrode sheet and application thereof - Google Patents
Silicon negative electrode material, silicon negative electrode sheet and application thereof Download PDFInfo
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- CN115732636B CN115732636B CN202211171620.2A CN202211171620A CN115732636B CN 115732636 B CN115732636 B CN 115732636B CN 202211171620 A CN202211171620 A CN 202211171620A CN 115732636 B CN115732636 B CN 115732636B
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 202
- 239000010703 silicon Substances 0.000 title claims abstract description 202
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 202
- 239000007773 negative electrode material Substances 0.000 title claims description 29
- 239000002245 particle Substances 0.000 claims abstract description 109
- 239000010405 anode material Substances 0.000 claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 claims abstract description 51
- 239000002184 metal Substances 0.000 claims abstract description 51
- 239000007788 liquid Substances 0.000 claims abstract description 40
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 239000000084 colloidal system Substances 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000003763 carbonization Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims description 76
- 238000003756 stirring Methods 0.000 claims description 52
- 229920002472 Starch Polymers 0.000 claims description 46
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 45
- 235000019698 starch Nutrition 0.000 claims description 44
- 239000008107 starch Substances 0.000 claims description 44
- 238000002156 mixing Methods 0.000 claims description 40
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- 239000000843 powder Substances 0.000 claims description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 238000005245 sintering Methods 0.000 claims description 27
- 238000007710 freezing Methods 0.000 claims description 23
- 230000008014 freezing Effects 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 22
- -1 titanium dioxide modified SiOx Chemical class 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 239000011267 electrode slurry Substances 0.000 claims description 18
- 239000004408 titanium dioxide Substances 0.000 claims description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 17
- 229910001416 lithium ion Inorganic materials 0.000 claims description 17
- 239000011230 binding agent Substances 0.000 claims description 16
- 239000006258 conductive agent Substances 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 11
- 239000001099 ammonium carbonate Substances 0.000 claims description 11
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 11
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 11
- 239000006229 carbon black Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 238000012216 screening Methods 0.000 claims description 9
- 239000011863 silicon-based powder Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000006004 Quartz sand Substances 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 6
- 239000011022 opal Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000004113 Sepiolite Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 238000010306 acid treatment Methods 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 125000005341 metaphosphate group Chemical group 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 229910052624 sepiolite Inorganic materials 0.000 claims description 3
- 235000019355 sepiolite Nutrition 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
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- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 79
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 10
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 239000011258 core-shell material Substances 0.000 abstract description 8
- 230000008859 change Effects 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 4
- 239000011247 coating layer Substances 0.000 abstract description 4
- 238000007599 discharging Methods 0.000 abstract description 4
- 239000002210 silicon-based material Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 56
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 28
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 27
- 239000000391 magnesium silicate Substances 0.000 description 27
- 229910052919 magnesium silicate Inorganic materials 0.000 description 27
- 235000019792 magnesium silicate Nutrition 0.000 description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 26
- 239000002131 composite material Substances 0.000 description 26
- 239000007789 gas Substances 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 229910052786 argon Inorganic materials 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 239000011572 manganese Substances 0.000 description 11
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 229920001155 polypropylene Polymers 0.000 description 10
- 229910013716 LiNi Inorganic materials 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229920002261 Corn starch Polymers 0.000 description 8
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 8
- 229910021383 artificial graphite Inorganic materials 0.000 description 8
- 239000008120 corn starch Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 238000011049 filling Methods 0.000 description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- 229920003048 styrene butadiene rubber Polymers 0.000 description 8
- 238000004804 winding Methods 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
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- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229920002239 polyacrylonitrile Polymers 0.000 description 4
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- 229920000573 polyethylene Polymers 0.000 description 4
- 229920001592 potato starch Polymers 0.000 description 4
- 238000011085 pressure filtration Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 3
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
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- 244000017020 Ipomoea batatas Species 0.000 description 2
- 235000002678 Ipomoea batatas Nutrition 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
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- QTHKJEYUQSLYTH-UHFFFAOYSA-N [Co]=O.[Ni].[Li] Chemical compound [Co]=O.[Ni].[Li] QTHKJEYUQSLYTH-UHFFFAOYSA-N 0.000 description 2
- OGCCXYAKZKSSGZ-UHFFFAOYSA-N [Ni]=O.[Mn].[Li] Chemical compound [Ni]=O.[Mn].[Li] OGCCXYAKZKSSGZ-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000000665 guar gum Substances 0.000 description 2
- 235000010417 guar gum Nutrition 0.000 description 2
- 229960002154 guar gum Drugs 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
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- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 238000001420 photoelectron spectroscopy Methods 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920001690 polydopamine Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229940100486 rice starch Drugs 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 229940005550 sodium alginate Drugs 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
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- 235000010643 Leucaena leucocephala Nutrition 0.000 description 1
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- 238000005562 fading Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
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Classifications
-
- 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 application discloses a silicon anode material, a silicon anode sheet and application thereof, wherein the silicon anode material has a double-layer coated core-shell structure, siOx particles are used as an inner core to ensure high specific capacity and lower volume change, a modified titanium dioxide layer is used as a first coating layer to improve the electronic conductivity of the material, and a uniformly coated metal colloidal liquid carbonization layer is used as a second coating layer to improve the ionic conductivity of the material. Meanwhile, the modified titanium dioxide layer is treated by weak acid and high-temperature hydrogen gas, is rich in porous and weak hydrogen bonds, is easy to uniformly coat with metal colloid liquid, the carbonized layer of the metal colloid liquid is of a porous structure, the conductive carbon layer is exposed through pores with a certain aperture, the problem that the coating of the carbonized layer reduces the electronic conductivity is avoided, and the porous structure can further buffer the volume expansion of a silicon material in the charging and discharging processes, so that the material has a longer cycle life.
Description
Technical Field
The application relates to a silicon anode material, a silicon anode sheet and application thereof, and belongs to the technical field of lithium ion batteries.
Background
In order to meet the increasing demand for batteries with rapid charge and discharge capability for ultra-high energy density, next-generation high energy density secondary batteries are required to develop batteries (LIBs) with high safety, large-scale applications, low cost (such as electric vehicles and hybrid electric vehicles), which require high capacity electrode materials with long cycle life and excellent rate performance. Since the silicon anode material has a theoretical specific capacity of 4200 mAh/g and exhibits a relatively low operating voltage (about 0.4v vs. li+/Li), silicon is the second most abundant element in the crust. These advantages make silicon one of the most commercially valuable negative electrode materials for next generation high energy density lithium ion batteries.
However, silicon particles are subject to pulverization and fall from the current collector during lithiation, resulting in a delithiation process due to the large change in volume (> 300%), resulting in loss of electrical contact between particles. At the same time, it may lead to repeated formation of solid electrolyte interfaces at the electrode surface. This is the main reason for the fast capacity fade of the silicon anode and the poor cycle performance.
The volume expansion in the lithium intercalation reaction of the silicon oxygen anode material (SiOx) is small compared to the pure silicon anode material, but it is not negligible, exceeding 180% volume change. The development of coping strategies such as core-shell cladding structures, hollow structures and the like can improve the larger volume expansion of the silicon-oxygen anode material under high current density, however, in most research and development: when lithium is intercalated in the first circle, on the basis of improving the conductivity of the material by doping elements in the silicon-oxygen anode material, the thickness of the core-shell cladding structure layer is not uniform, the expansion stress applied to the structure in all directions is different, the damage to the material structure is large, and the thinner part of the core-shell structure layer is easier to crack after multiple charge and discharge; in addition, the core-shell coating structure itself can generate overlarge volume change in the redox reaction of charge and discharge, the core-shell coating structure can crack and expose the silicon oxide particles in the core-shell coating structure, so that the charge and discharge cycle life of the prepared battery is shortened, and the capacity retention rate is drastically reduced.
Disclosure of Invention
In order to solve the technical problems, the application provides a silicon anode material, a silicon anode sheet and application thereof, siOx particles are taken as an inner core, a metal colloidal liquid carbonization layer is uniformly coated on the SiOx particles, the SiOx particles can be modified, and the metal colloidal liquid carbonization layer is uniformly coated after a titanium dioxide layer is coated.
The first object of the application is to provide a silicon anode material, which comprises SiOx particles, wherein x is more than or equal to 0 and less than 2, and a metal colloidal solution carbonization layer coated on the SiOx particles, wherein the metal colloidal solution is obtained by the following steps: and mixing and heating the starch dispersion liquid and the metal solution to form a colloidal liquid, and performing freezing, thermal gelatinization, stirring and cooling circulation treatment for 2-10 times to obtain the metal colloidal liquid.
Further, the freezing is performed at-20-0 ℃, the thermal forming glue is performed at 50-100 ℃, and the cooling is performed at 20-30 ℃.
In the application, when starch dispersion liquid and metal solution are mixed and heated to form colloidal liquid, the surface of starch particles in the solution becomes rough due to continuous heating, and the heating and melting can destroy hydrogen bonds among starch molecules, most of starch is disintegrated and loses particle morphology, starch shows adhesion aggregation phenomenon, if the starch particles are directly coated on the surfaces of SiOx particles, aggregation is caused, and the thickness of a starch aggregation coating structure layer is different.
Further, the mass ratio of the starch to the metal is 1000: 1-150.
Further, the starch dispersion liquid and the metal solution are heated and mixed uniformly at 50-100 ℃.
Further, the metal solution is at least one of silicate, metasilicate, sulfate, chloride, nitrate, phosphate and metaphosphate containing calcium, manganese, magnesium, aluminum, nickel and zinc.
Further, the starch dispersion liquid is prepared by dispersing starch in one or more mixed solvents of ethanol, methanol, propanol, toluene and water.
Further, the SiOx particles are prepared by the following method: mixing a silicon-containing substance and Si powder according to a proportion of 1-50: mixing 5-30 mass percent, heating at 800-1400 ℃, condensing and agglomerating silicon-containing steam generated by heating, crushing and screening the blocks to obtain SiOx particles.
Further, the particle size of the SiOx particles is 1.5-24 μm.
Further, the silicon-containing substance is at least one of silicon dioxide particles, white carbon black, opal, sepiolite, high-purity quartz sand and diatomite.
Further, the SiOx particles are titanium dioxide modified SiOx particles, and are prepared by the following steps:
(1) According to the mass: volume: the volume is 1-8: 100: 0.2-0.8 of modified SiOx particles, glycerol dispersant and tetrabutyl titanate are added, stirred and dispersed, then ammonium carbonate accounting for 1-20% of the mass of the SiOx particles is added, and the mixture is heated and reacted for 4-12 hours at the temperature of 30-70 ℃, the solvent is removed, and the black powder is obtained after drying;
(2) And (3) performing weak acid treatment on the black powder, washing, and press-filtering, and sintering in an inert gas containing not more than 2% of hydrogen in volume ratio at 350-800 ℃ for 30 min-12 h to obtain the titanium dioxide modified SiOx particles.
Further, 10-120 g of black powder is added into 1L of 1-8wt% acetic acid for stirring for 8-15 min.
In the application, titanium dioxide is adopted to modify SiOx particles, a titanium dioxide layer is formed on the surfaces of the SiOx particles, the expansion rate of the titanium dioxide layer in the lithium ion deintercalation process is very low, the modified titanium dioxide layer is treated by weak acid and high-temperature hydrogenation gas, is rich in porous and weak hydrogen bonds, is easy for uniform coating of metal colloid, and is also in a porous structure, the conductive carbon layer is exposed by pores with a certain pore diameter, so that the problem that the electron conductivity is reduced by coating of the titanium dioxide layer and the carbonization layer is avoided, and the porous structure can further buffer the volume expansion of silicon materials in the charge-discharge process, so that the materials have longer cycle life.
During the preparation process, the ammonium carbonate is added to slow the hydrolysis rate of tetrabutyl titanate; while the hydrogen high temperature treatment can change the conductivity of the titanium dioxide layer.
Further, the starch is at least one of potato starch, sweet potato starch, tapioca starch, mung bean starch, pea starch, wheat starch, corn starch, soybean starch and rice starch.
Further, the valence state of the silicon in the silicon anode material comprises zero valenceSilicon in the state, +1-valent state, +2-valent state, +3-valent state, +4-valent state, the contents of which are respectively referred to as Si 0 、Si 1 、Si 2 、Si 3 、Si 4 The total Si content is recorded as Si Total (S) The following relation is satisfied:
Si 0 /Si total (S) ≥Si 2 /Si Total (S) ≥Si 1 /Si Total (S) ；
And/or Si 0 /Si Total (S) ≥Si 2 /Si Total (S) ≥Si 3 /Si Total (S) ；
And/or Si 0 /Si Total (S) ≥Si 2 /Si Total (S) ≥Si 4 /Si Total (S) 。
Further, the ratio of the silicon content of each valence state is calculated as: (1) The silicon anode material is subjected to X-ray (XPS) photoelectron spectroscopy test to obtain XPS spectrum: (2) Si2p fitting peaks are obtained through the position of the binding energy 104.29 e V, the peaks in the Si2p spectrum are further fitted by five peaks with the binding energy of 100 e V, 102.3e V, 103.5 e V, 104.1e V and 104.6 e V, the five peaks respectively correspond to zero-valent silicon peaks, +1-valent silicon peaks, +2-valent silicon peaks, +3-valent silicon peaks, +4-valent silicon peaks, and the proportion of the silicon with different valence states is determined according to the areas of the silicon peaks with different valence states in the XPS spectrum, and the Si2p fitting peaks comprise: total Si content Total (S) The total area of five peaks is zero-valent silicon, +1-valent silicon, +2-valent silicon, +3-valent silicon and +4-valent silicon peaks, si 0 、Si 1 、Si 2 、Si 3 、Si 4 The peak areas of the silicon are respectively zero-valent silicon, +1-valent silicon, +2-valent silicon, +3-valent silicon and +4-valent silicon.
Further, the thickness of the carbonized layer of the metal colloid is 3-120 nm. More preferably 5 to 50 nm, still more preferably 8 to 25nm.
Further, the thickness of the titanium dioxide layer is 3-120 nm. More preferably 5 to 50 nm, still more preferably 8 to 25nm.
Further, the median particle diameter D50 of the silicon anode material is 3.0-18.0 mu m. More preferably 5.2 to 11.5 μm, still more preferably 5.5 to 8.3 μm.
Further, the siliconThe specific surface area of the anode material is 0.4-4.8 m 2 Preferably 1.05 to 2.4 m per gram 2 /g。
Further, the inert gas is at least one of helium (He), neon (Ne), argon (Ar) and krypton (Kr).
The second object of the present application is to provide a preparation method of the silicon anode material, comprising the following steps:
s1, preparing SiOx particles;
s2, mixing and heating the starch dispersion liquid and the metal solution to form a colloidal liquid, and performing freezing, thermalization to form gel, stirring and cooling circulation treatment for 2-10 times to obtain the metal colloidal liquid;
s3, adding 2-100 g of metal colloid liquid into 1kg of SiOx particles, uniformly stirring, drying to obtain SiOx particles containing a metal colloid liquid layer, sintering at 500-1100 ℃ for 10 min-10 h under the condition of inert gas, annealing, and grinding to obtain the silicon anode material.
The third object of the application is to provide a silicon negative electrode sheet comprising a negative electrode current collector and a positive and/or negative silicon-containing negative electrode layer on the negative electrode current collector, wherein the silicon-containing negative electrode layer is prepared by the following method: the silicon anode material, the binder and the conductive agent are mixed according to the mass ratio of 85-100: 0.1 to 9: and 0.1-12, mixing, adding a solvent, stirring to obtain negative electrode slurry, and coating the negative electrode slurry on the front surface and/or the back surface of a negative electrode current collector to obtain the silicon-containing negative electrode layer.
Further, graphite can be added into the silicon anode material for mixing, so that the composition ratio of the silicon anode in the silicon anode material can be adjusted.
Further, the graphite is obtained by surface coating, oxidation, halogenation or element doping treatment of natural graphite and artificial graphite.
Further, the binder is one or more binders of polyvinylidene fluoride, chitosan, acacia, xanthan gum binder, guar gum, carboxymethyl cellulose, sodium carboxymethyl cellulose, lithium carboxymethyl cellulose, styrene butadiene rubber, polyacrylic acid, polyaniline and sodium alginate, or one or more binders obtained by crosslinking or one or more binders obtained by copolymerizing.
Further, the conductive agent is one or more of carbon black, graphite powder, graphene, conductive carbon powder, carbon metal composite powder, carbon nanofiber, composite carbon nanofiber and conductive composite carbon microfiber.
Further, the silicon anode material, the binder and the conductive agent are prepared from the following components in percentage by mass: 0.1-2: 0.1-3, 85-88: 2-5: 3-6, 85-88: 5-8: 6-9, 85-88: 8-9: 9-12, 88-92: 0.1-2: 0.1-3, 88-92: 2-5: 3-6, 88-92: 5-8: 6-9, 88-92: 8-9: 9-12, 82-95: 0.1-2: 0.1-3, 82-95: 2-5: 3-6, 82-95: 5-8: 6-9, 82-95: 8-9: 9-12, 95-100: 0.1-2: 0.1-3, 95-100: 2-5: 3-6, 95-100: 5-8: 6-9 or 95-100: 8-9: 9-12.
The fourth object of the application is to provide a lithium ion battery prepared by adopting the silicon anode material or the silicon anode sheet.
Further, the lithium ion battery is prepared by the following method: and winding the silicon negative plate, the isolating film and the positive plate to obtain a battery cell, and filling the battery cell with a battery shell and injecting electrolyte to obtain the lithium ion battery.
Further, the diaphragm is at least one of polyethylene, polypropylene, polyamide fiber, polyacrylonitrile, glass fiber, ceramic fiber, polyvinylidene fluoride membrane, composite polyethylene coated with aluminum oxide, zirconium dioxide, silicon dioxide, ceramic and polydopamine, composite polyamide fiber, composite polypropylene, composite polyacrylonitrile and composite polyvinylidene fluoride diaphragm.
Further, the positive electrode active material in the positive electrode sheet is one or more of lithium cobalt nickel oxide, lithium manganese nickel oxide, lithium nickel cobalt aluminate, manganese-rich lithium nickel cobalt aluminate, lithium nickel cobalt manganate, lithium iron phosphate, lithium cobalt oxide and lithium manganese iron phosphate.
The beneficial effects of the application are as follows:
the silicon anode material provided by the application has a double-layer coated core-shell structure, wherein SiOx particles are used as an inner core to ensure high specific capacity and lower volume change, a modified titanium dioxide layer is used as a first coating layer to improve the electronic conductivity of the material, and a uniformly coated metal colloidal liquid carbonization layer is used as a second coating layer to improve the ionic conductivity of the material. Meanwhile, the modified titanium dioxide layer is treated by weak acid and high-temperature hydrogen gas, is rich in porous and weak hydrogen bonds, is easy to uniformly coat with metal colloid liquid, the carbonized layer of the metal colloid liquid is of a porous structure, the conductive carbon layer is exposed through pores with a certain aperture, the problem that the coating of the carbonized layer reduces the electronic conductivity is avoided, and the porous structure can further buffer the volume expansion of a silicon material in the charging and discharging processes, so that the material has a longer cycle life.
The modified titanium dioxide layer and the uniformly coated metal colloidal solution carbonization layer have smaller difference in expansion force of charging and lithium intercalation and shrinkage stress of discharging and lithium removal in all directions of SiOx particles, damage to the modified titanium dioxide layer and the uniformly coated metal colloidal solution carbonization layer is reduced, the modified titanium dioxide layer and the uniformly coated metal colloidal solution carbonization layer can be kept stable, and the battery capacity retention rate after repeated charging and discharging is over 80 percent.
Detailed Description
The present application will be further described with reference to specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the present application and practice it.
The application provides a silicon anode material, which comprises SiOx particles and a metal colloid carbonization layer coated on the SiOx particles, wherein the metal colloid is obtained by the following steps: mixing and heating the starch dispersion liquid and the metal solution to form a colloidal liquid, freezing at-20-0 ℃, performing thermal forming to form gel at 50-100 ℃, stirring, and performing cooling circulation treatment for 2-10 times at room temperature to obtain the metal colloidal liquid.
In the application, when starch dispersion liquid and metal solution are mixed and heated to form colloidal liquid, the surface of starch particles in the solution becomes rough due to continuous heating, and the heating and melting can destroy hydrogen bonds among starch molecules, most of starch is disintegrated and loses particle morphology, starch shows adhesion aggregation phenomenon, if the starch particles are directly coated on the surfaces of SiOx particles, aggregation is caused, and the thickness of a starch aggregation coating structure layer is different.
The mass ratio of the starch to the metal is 1000: 1-150, wherein the starch dispersion liquid and the metal solution are heated and mixed uniformly at 50-100 ℃.
Wherein the metal solution is at least one of silicate, metasilicate, sulfate, chloride, nitrate, phosphate and metaphosphate containing calcium, manganese, magnesium, aluminum, nickel and zinc.
Wherein, the starch dispersion liquid is prepared by dispersing starch in one or more mixed solvents of ethanol, methanol, propanol, toluene and water.
Wherein the starch is at least one of potato starch, sweet potato starch, tapioca starch, mung bean starch, pea starch, wheat starch, corn starch, soybean starch and rice starch.
The SiOx particles of the application are prepared by the following method: mixing a silicon-containing substance and Si powder according to a proportion of 1-50: mixing 5-30 mass percent, heating at 800-1400 ℃, condensing and agglomerating silicon-containing steam generated by heating, crushing and screening the blocks to obtain SiOx particles. The silicon-containing substance is at least one of silicon dioxide particles, white carbon black, opal, sepiolite, high-purity quartz sand and diatomite.
The preparation of the SiOx particles further comprises the modification of the SiOx particles by the following steps:
(1) According to the mass: volume: the volume is 1-8: 100: 0.2-0.8 of modified SiOx particles, glycerol dispersant and tetrabutyl titanate are added, stirred and dispersed, then ammonium carbonate accounting for 1-20% of the mass of the SiOx particles is added, and the mixture is heated and reacted for 4-12 hours at the temperature of 30-70 ℃, the solvent is removed, and the black powder is obtained after drying;
(2) Adding 10-120 g of black powder into 1L of 1-8wt% acetic acid, stirring for 8-15 min, performing weak acid treatment, washing, press filtering, sintering in an inert gas containing hydrogen with the volume ratio of not more than 2%, and obtaining titanium dioxide modified SiOx particles at 350-800 ℃.
In the application, titanium dioxide is adopted to modify SiOx particles, a titanium dioxide layer is formed on the surfaces of the SiOx particles, the expansion rate of the titanium dioxide layer in the lithium ion deintercalation process is very low, the modified titanium dioxide layer is treated by weak acid and high-temperature hydrogenation gas, is rich in porous and weak hydrogen bonds, is easy for uniform coating of metal colloid, and is also in a porous structure, the conductive carbon layer is exposed by pores with a certain pore diameter, so that the problem that the electron conductivity is reduced by coating of the titanium dioxide layer and the carbonization layer is avoided, and the porous structure can further buffer the volume expansion of silicon materials in the charge-discharge process, so that the materials have longer cycle life.
During the preparation process, the ammonium carbonate is added to slow the hydrolysis rate of tetrabutyl titanate; while the hydrogen high temperature treatment can change the conductivity of the titanium dioxide layer.
The valence state of the silicon in the silicon anode material of the application comprises zero-valence silicon, +1-valence silicon, +2-valence silicon, +3-valence silicon and +4-valence silicon, and the corresponding valence state silicon content is respectively recorded as Si 0 、Si 1 、Si 2 、Si 3 、Si 4 The total Si content is recorded as Si Total (S) The following relation is satisfied:
Si 0 /Si total (S) ≥Si 2 /Si Total (S) ≥Si 1 /Si Total (S) ；
And/or Si 0 /Si Total (S) ≥Si 2 /Si Total (S) ≥Si 3 /Si Total (S) ；
And/or Si 0 /Si Total (S) ≥Si 2 /Si Total (S) ≥Si 4 /Si Total (S) 。
The silicon content ratio of each valence state is calculated as follows: (1) The silicon anode material is subjected to X-ray (XPS) photoelectron spectroscopy test to obtain XPS spectrum: (2) Si2p fitting peaks are obtained through the position of the binding energy 104.29 e V, the peaks in Si2p spectra are fitted by five peaks with the binding energy of 100 e V, 102.3e V, 103.5 e V, 104.1e V and 104.6 e V, the peaks respectively correspond to zero-valent silicon peaks, +1-valent silicon peaks, +2-valent silicon peaks, +3-valent silicon peaks and +4-valent silicon peaks, and the proportion of the silicon with different valences is determined according to the areas of the silicon peaks with different valences in XPS spectra, and the Si2p fitting peaks comprise: total Si content Total (S) The total area of five peaks is zero-valent silicon, +1-valent silicon, +2-valent silicon, +3-valent silicon and +4-valent silicon peaks, si 0 、Si 1 、Si 2 、Si 3 、Si 4 The peak areas of the silicon are respectively zero-valent silicon, +1-valent silicon, +2-valent silicon, +3-valent silicon and +4-valent silicon.
Further, the thickness of the carbonized layer of the metal colloid is 3-120 nm. More preferably 5 to 50 nm, still more preferably 8 to 25nm.
Further, the thickness of the titanium dioxide layer is 3-120 nm. More preferably 5 to 50 nm, still more preferably 8 to 25nm.
Further, the median particle diameter D50 of the silicon anode material is 3.0-18.0 mu m. More preferably 5.2 to 11.5 μm, still more preferably 5.5 to 8.3 μm.
Further, the specific surface area of the silicon anode material is 0.4-4.8 m 2 Preferably 1.05 to 2.4 m per gram 2 /g。
The application also provides a preparation method of the silicon anode material, which comprises the following steps:
s1, preparing SiOx particles;
s2, mixing and heating the starch dispersion liquid and the metal solution to form a colloidal liquid, and performing freezing, thermalization to form gel, stirring and cooling circulation treatment for 2-10 times to obtain the metal colloidal liquid;
s3, adding 2-100 g of metal colloid liquid into 1kg of SiOx particles, uniformly stirring, drying to obtain SiOx particles containing a metal colloid liquid layer, sintering at 500-1100 ℃ for 10 min-10 h under the condition of inert gas, annealing, and grinding to obtain the silicon anode material.
The application also provides a silicon negative plate, which comprises a negative current collector and a silicon-containing negative electrode layer on the front and/or back of the negative current collector, wherein the silicon-containing negative electrode layer is prepared by the following method: the silicon anode material, the binder and the conductive agent are mixed according to the mass ratio of 85-100: 0.1 to 9: and 0.1-12, mixing, adding water, stirring to obtain negative electrode slurry, and coating the negative electrode slurry on the front surface and/or the back surface of the negative electrode current collector to obtain the silicon-containing negative electrode layer.
The silicon negative electrode material can be mixed with graphite for adjusting the component ratio of the silicon negative electrode in the silicon negative electrode material.
Wherein the graphite is obtained by surface coating, oxidation, halogenation or element doping treatment of natural graphite and artificial graphite.
The adhesive is one or more adhesives obtained by crosslinking one or more adhesives or one or more adhesives obtained by copolymerizing one or more adhesives, wherein the adhesive is polyvinylidene fluoride, chitosan, arabic gum, a xanthan gum adhesive, guar gum, carboxymethyl cellulose, sodium carboxymethyl cellulose, lithium carboxymethyl cellulose, styrene butadiene rubber, polyacrylic acid, polyaniline and sodium alginate.
The conductive agent is one or more of carbon black, graphite powder, graphene, conductive carbon powder, carbon metal composite powder, carbon nanofiber, composite carbon nanofiber and conductive composite carbon microfiber.
The silicon anode material, the binder and the conductive agent are prepared from the following components in percentage by mass: 0.1-2: 0.1-3, 85-88: 2-5: 3-6, 85-88: 5-8: 6-9, 85-88: 8-9: 9-12, 88-92: 0.1-2: 0.1-3, 88-92: 2-5: 3-6, 88-92: 5-8: 6-9, 88-92: 8-9: 9-12, 82-95: 0.1-2: 0.1-3, 82-95: 2-5: 3-6, 82-95: 5-8: 6-9, 82-95: 8-9: 9-12, 95-100: 0.1-2: 0.1-3, 95-100: 2-5: 3-6, 95-100: 5-8: 6-9 or 95-100: 8-9: 9-12.
The application also provides a lithium ion battery prepared from the silicon anode material or the silicon anode sheet.
The lithium ion battery is prepared by the following steps: and winding the silicon negative plate, the isolating film and the positive plate to obtain a battery cell, and filling the battery cell with a battery shell and injecting electrolyte to obtain the lithium ion battery.
The diaphragm is at least one of polyethylene, polypropylene, polyamide fiber, polyacrylonitrile, glass fiber, ceramic fiber, polyvinylidene fluoride membrane, composite polyethylene coated with aluminum oxide, zirconium dioxide, silicon dioxide, ceramic and polydopamine, composite polyamide fiber, composite polypropylene, composite polyacrylonitrile and composite polyvinylidene fluoride diaphragm.
The positive electrode plate comprises a positive electrode plate, wherein the positive electrode active material in the positive electrode plate is one or more of lithium cobalt nickel oxide, lithium manganese nickel oxide, lithium nickel cobalt aluminate, manganese-rich lithium nickel cobalt aluminate, lithium nickel cobalt manganate, lithium iron phosphate, lithium cobalt oxide and lithium manganese iron phosphate.
The application is further illustrated by the following examples:
example 1:
1. the preparation method of the silicon anode material comprises the following steps:
(1) Mixing opal and Si powder according to a mass ratio of 4:10, heating in a heating furnace at 960 ℃, condensing and agglomerating silicon-containing steam generated by heating, crushing and screening the blocks to obtain SiOx particles;
(2) Dispersing corn starch in ethanol, mixing to obtain a mixed solution, adding magnesium silicate solution, stirring (the mass ratio of starch to magnesium silicate is 1000:10), drying, heating at 65 ℃ and mixing uniformly to obtain magnesium silicate colloidal solution, transferring the magnesium silicate colloidal solution to a freezing chamber, freezing at-10 ℃, heating to gel at 65 ℃ in a heating pot, stirring, cooling at room temperature, and repeating the steps of freezing-heating to gel-stirring-cooling at room temperature for 5 times to obtain magnesium silicate colloidal solution containing hydrogen bonds with magnesium silicate uniformly distributed;
(3) 15g of magnesium silicate colloidal solution is added according to 1kg of modified SiOx particles, the mixture is stirred uniformly, and is dried by a spray drying/heating furnace, so as to obtain SiOx particles with magnesium silicate colloidal solution layer, and the SiOx particles are sent into a sintering furnace under argon gas, sintered for 5 hours at 680 ℃, annealed and ball-milled to obtain the silicon anode material.
The SiOx particles in step (2) are further modified before being treated by magnesium silicate colloidal fluid: (1) feeding SiOx particles into a reaction kettle, adding glycerol dispersant and tetrabutyl titanate (according to the mass g: volume mL: 4:100:0.4), stirring, dispersing, adding ammonium carbonate accounting for 3% of the mass of the SiOx particles, heating at 45 ℃ for reaction for 6 hours, performing pressure filtration, and drying the obtained solid substance to remove glycerol to obtain black powder; (2) adding 1L of 3wt% acetic acid into 100g of black powder, stirring for 10min, carrying out weak acidification, washing and filter pressing, conveying to a sintering furnace, introducing mixed gas (98% argon gas and 2 hydrogen%), and sintering at 500 ℃ for 2h to obtain modified SiOx particles.
2. Silicon negative electrode plate made of silicon negative electrode material: comprising a negative electrode current collector and a positive and/or negative silicon-containing negative electrode layer on the negative electrode current collector
Preparing a front side and a back side silicon-containing anode layer: mixing a silicon negative electrode material, a binder styrene butadiene rubber, a conductive agent (composite carbon nanofiber and carbon black are mixed according to a mass ratio of 1:2:3), adding solvent water and stirring to obtain a negative electrode slurry, and coating the negative electrode slurry on the front surface of a negative electrode current collector to obtain a silicon-containing negative electrode layer on the front surface and the back surface.
3. Silicon negative electrode sheet application: silicon negative plate, aluminum oxide coated composite polypropylene isolating film, nickel cobalt lithium manganate (LiNi) 0.87 Co 0.02 Mn 0.11 And O) winding the positive plate to obtain a battery core, and filling the battery core with a battery shell and injecting electrolyte to obtain the lithium ion battery.
Example 2:
1. the preparation method of the silicon anode material comprises the following steps:
(1) Mixing opal and Si powder according to a mass ratio of 4:10, heating in a heating furnace at 960 ℃, condensing and agglomerating silicon-containing steam generated by heating, crushing and screening the blocks to obtain SiOx particles;
(2) Dispersing corn starch in ethanol, mixing to obtain a mixed solution, adding magnesium silicate solution, stirring (the mass ratio of starch to magnesium silicate is 1000:15), drying, heating at 65 ℃ and mixing uniformly to obtain magnesium silicate colloidal solution, transferring the magnesium silicate colloidal solution to a freezing chamber, freezing at-10 ℃, heating to gel at 65 ℃ in a heating pot, stirring, cooling at room temperature, and repeating the steps of freezing-heating to gel-stirring-cooling at room temperature for 5 times to obtain magnesium silicate colloidal solution containing hydrogen bonds with magnesium silicate uniformly distributed;
(3) 15g of magnesium silicate colloidal solution is added according to 1kg of modified SiOx particles, the mixture is stirred uniformly, and is dried by a spray drying/heating furnace, so as to obtain SiOx particles with magnesium silicate colloidal solution layer, and the SiOx particles are sent into a sintering furnace under argon gas, sintered for 5 hours at 680 ℃, annealed and ball-milled to obtain the silicon anode material.
The SiOx particles in step (2) are further modified before being treated by magnesium silicate colloidal fluid: (1) feeding SiOx particles into a reaction kettle, adding glycerol dispersing agent and tetrabutyl titanate (according to the mass g: volume mL: 4:100:0.6), stirring, dispersing, adding ammonium carbonate accounting for 3% of the mass of the SiOx particles, heating at 45 ℃ for reaction for 6 hours, performing pressure filtration, and drying the obtained solid substance to remove glycerol to obtain black powder; (2) adding 1L of 3wt% acetic acid into 100g of black powder, stirring for 10min, carrying out weak acidification, washing and filter pressing, conveying to a sintering furnace, introducing mixed gas (98% argon gas and 2 hydrogen%), and sintering at 500 ℃ for 2h to obtain modified SiOx particles.
2. Silicon negative electrode plate made of silicon negative electrode material: comprising a negative electrode current collector and a positive and/or negative silicon-containing negative electrode layer on the negative electrode current collector
Preparing a front side and a back side silicon-containing anode layer: mixing a silicon negative electrode material, a binder styrene butadiene rubber, a conductive agent (composite carbon nanofiber and carbon black are mixed according to a mass ratio of 1:2:3), adding solvent water and stirring to obtain a negative electrode slurry, and coating the negative electrode slurry on the front surface of a negative electrode current collector to obtain a silicon-containing negative electrode layer on the front surface and the back surface.
3. Silicon negative electrode sheet application: silicon negative plate, aluminum oxide coated composite polypropylene isolating film, nickel cobalt lithium manganate (LiNi) 0.87 Co 0.02 Mn 0.11 And O) winding the positive plate to obtain a battery core, and filling the battery core with a battery shell and injecting electrolyte to obtain the lithium ion battery.
Example 3:
1. the preparation method of the silicon anode material comprises the following steps:
(1) Mixing opal and Si powder according to a mass ratio of 4:10, heating in a heating furnace at 960 ℃, condensing and agglomerating silicon-containing steam generated by heating, crushing and screening the blocks to obtain SiOx particles;
(2) Dispersing corn starch in ethanol, mixing to obtain a mixed solution, adding magnesium silicate/aluminum silicate solution, stirring (the mass ratio of starch to magnesium silicate is 1000:25), drying, heating at 65deg.C, and mixing uniformly to obtain magnesium silicate colloidal solution, transferring the magnesium silicate colloidal solution to a freezing chamber, freezing at-10deg.C, heating to 65 deg.C in a heating pot for gelatinization, stirring, cooling at room temperature, and repeating the steps of freezing-heating to gelatinization-stirring-cooling at room temperature for 5 times to obtain magnesium silicate colloidal solution containing hydrogen bonds with magnesium silicate uniformly distributed;
(3) 15g of magnesium silicate colloidal solution is added according to 1kg of modified SiOx particles, the mixture is stirred uniformly, and is dried by a spray drying/heating furnace, so as to obtain SiOx particles with magnesium silicate colloidal solution layer, and the SiOx particles are sent into a sintering furnace under argon gas, sintered for 5 hours at 680 ℃, annealed and ball-milled to obtain the silicon anode material.
The SiOx particles in step (2) are further modified before being treated by magnesium silicate colloidal fluid: (1) feeding SiOx particles into a reaction kettle, adding glycerol dispersing agent and tetrabutyl titanate (according to the mass g: volume mL: 4:100:0.8), stirring, dispersing, adding ammonium carbonate accounting for 3% of the mass of the SiOx particles, heating at 45 ℃ for reaction for 6 hours, performing pressure filtration, and drying the obtained solid substance to remove glycerol to obtain black powder; (2) adding 1L of 3wt% acetic acid into 100g of black powder, stirring for 10min, carrying out weak acidification, washing and filter pressing, conveying to a sintering furnace, introducing mixed gas (98% argon gas and 2 hydrogen%), and sintering at 500 ℃ for 2h to obtain modified SiOx particles.
2. Silicon negative electrode plate made of silicon negative electrode material: comprising a negative electrode current collector and a positive and/or negative silicon-containing negative electrode layer on the negative electrode current collector
Preparing a front side and a back side silicon-containing anode layer: mixing a silicon negative electrode material, a binder styrene butadiene rubber, a conductive agent (composite carbon nanofiber and carbon black are mixed according to a mass ratio of 1:2:3), adding solvent water and stirring to obtain a negative electrode slurry, and coating the negative electrode slurry on the front surface of a negative electrode current collector to obtain a silicon-containing negative electrode layer on the front surface and the back surface.
3. Silicon negative electrode sheet application: silicon negative plate, aluminum oxide coated composite polypropylene isolating film, nickel cobalt lithium manganate (LiNi) 0.87 Co 0.02 Mn 0.11 And O) winding the positive plate to obtain a battery core, and filling the battery core with a battery shell and injecting electrolyte to obtain the lithium ion battery.
Example 4:
1. the preparation method of the silicon anode material comprises the following steps:
(1) Mixing high-purity quartz sand and Si powder according to the mass ratio of 5:15, heating in a heating furnace at 1060 ℃, condensing and agglomerating silicon-containing steam generated by heating, crushing and screening the blocks to obtain SiOx particles;
(2) Dispersing corn starch in ethanol, mixing to obtain a mixed solution, adding an aluminum silicate solution, stirring (the mass ratio of starch to aluminum silicate is 1000:2), drying, heating at 70 ℃ and mixing uniformly to obtain an aluminum silicate colloidal solution, transferring the aluminum silicate colloidal solution to a freezing chamber, freezing at-10 ℃, heating to gel at 70 ℃ in a heating pot, stirring, cooling at room temperature, and repeating the steps of freezing, heating to gel, stirring and cooling at room temperature for 5 times to obtain an aluminum silicate colloidal solution containing hydrogen bonds with aluminum silicate uniformly distributed;
(3) Adding 40g of aluminum silicate colloidal solution into 1kg of modified SiOx particles, uniformly stirring, spray drying/heating in a heating furnace to obtain SiOx particles with aluminum silicate colloidal solution layer, sending argon gas into a sintering furnace, sintering at 540 ℃ for 5h, annealing, and ball milling to obtain the silicon anode material.
The SiOx particles in step (2) are further modified before being treated by the aluminum silicate colloidal solution: (1) feeding SiOx particles into a reaction kettle, adding glycerol dispersant and tetrabutyl titanate (according to the mass g: volume mL: 5:100:0.4), stirring, dispersing, adding 8% ammonium carbonate of the mass of SiOx particles, heating at 55 ℃ for reaction for 6h, press-filtering, drying the obtained solid substance, and removing glycerol to obtain black powder; (2) adding 1L of 3wt% acetic acid into 100g of black powder, stirring for 10min, carrying out weak acidification, washing and filter pressing, conveying to a sintering furnace, introducing mixed gas (98% argon gas and 2 hydrogen%), and sintering at 600 ℃ for 2h to obtain modified SiOx particles.
2. Silicon negative electrode plate made of silicon negative electrode material: comprising a negative electrode current collector and a positive and/or negative silicon-containing negative electrode layer on the negative electrode current collector
Preparing a front side and a back side silicon-containing anode layer: mixing a silicon negative electrode material and artificial graphite spheres (the silicon negative electrode material and the artificial graphite spheres are mixed according to the mass ratio of 3:7), a binder styrene butadiene rubber, a conductive agent (the composite carbon nanofiber and the carbon black are mixed according to the mass ratio of 1:2) according to the mass ratio of 96:1.2:1.8, adding solvent water and stirring to obtain negative electrode slurry, and coating the negative electrode slurry on the front surface of a negative electrode current collector to obtain the silicon-containing negative electrode layers on the front surface and the back surface.
3. Silicon negative electrode sheet application: silicon negative plate, aluminum oxide coated composite polypropylene isolating film, nickel cobalt lithium manganate (LiNi) 0.87 Co 0.02 Mn 0.11 O/ LiNi 0.82 Co 0.08 Mn 0.10 And O) winding the positive plate to obtain a battery core, and filling the battery core with a battery shell and injecting electrolyte to obtain the lithium ion battery.
Example 5:
1. the preparation method of the silicon anode material comprises the following steps:
(1) Mixing high-purity quartz sand and Si powder according to the mass ratio of 5:15, heating in a heating furnace at 1060 ℃, condensing and agglomerating silicon-containing steam generated by heating, crushing and screening the blocks to obtain SiOx particles;
(2) Dispersing corn starch in ethanol, mixing to obtain a mixed solution, adding an aluminum silicate solution, stirring (the mass ratio of starch to aluminum silicate is 1000:5), drying, heating at 70 ℃ and mixing uniformly to obtain an aluminum silicate colloidal solution, transferring the aluminum silicate colloidal solution to a freezing chamber, freezing at-10 ℃, heating to gel at 70 ℃ in a heating pot, stirring, cooling at room temperature, and repeating the steps of freezing, heating to gel, stirring and cooling at room temperature for 5 times to obtain an aluminum silicate colloidal solution containing hydrogen bonds with aluminum silicate uniformly distributed;
(3) Adding 40g of aluminum silicate colloidal solution into 1kg of modified SiOx particles, uniformly stirring, spray drying/heating in a heating furnace to obtain SiOx particles with aluminum silicate colloidal solution layer, sending argon gas into a sintering furnace, sintering at 540 ℃ for 5h, annealing, and ball milling to obtain the silicon anode material.
The SiOx particles in step (2) are further modified before being treated by the aluminum silicate colloidal solution: (1) feeding SiOx particles into a reaction kettle, adding glycerol dispersant and tetrabutyl titanate (according to the mass g: volume mL: 5:100:0.6), stirring, dispersing, adding 8% ammonium carbonate of the mass of SiOx particles, heating at 55 ℃ for reaction for 6h, press-filtering, drying the obtained solid substance, and removing glycerol to obtain black powder; (2) adding 1L of 3wt% acetic acid into 100g of black powder, stirring for 10min, carrying out weak acidification, washing and filter pressing, conveying to a sintering furnace, introducing mixed gas (98% argon gas and 2 hydrogen%), and sintering at 600 ℃ for 2h to obtain modified SiOx particles.
2. Silicon negative electrode plate made of silicon negative electrode material: comprising a negative electrode current collector and a positive and/or negative silicon-containing negative electrode layer on the negative electrode current collector
Preparing a front side and a back side silicon-containing anode layer: mixing a silicon negative electrode material and artificial graphite spheres (the silicon negative electrode material and the artificial graphite spheres are mixed according to the mass ratio of 3:7), a binder styrene butadiene rubber, a conductive agent (the composite carbon nanofiber and the carbon black are mixed according to the mass ratio of 1:2) according to the mass ratio of 96:1.2:1.8, adding solvent water and stirring to obtain negative electrode slurry, and coating the negative electrode slurry on the front surface of a negative electrode current collector to obtain the silicon-containing negative electrode layers on the front surface and the back surface.
3. Silicon negative electrode sheet application: silicon negative plate, aluminum oxide coated composite polypropylene isolating film, nickel cobalt lithium manganate (LiNi) 0.87 Co 0.02 Mn 0.11 O/ LiNi 0.82 Co 0.08 Mn 0.10 And O) winding the positive plate to obtain a battery core, and filling the battery core with a battery shell and injecting electrolyte to obtain the lithium ion battery.
Example 6:
1. the preparation method of the silicon anode material comprises the following steps:
(1) Mixing high-purity quartz sand and Si powder according to the mass ratio of 5:15, heating in a heating furnace at 1060 ℃, condensing and agglomerating silicon-containing steam generated by heating, crushing and screening the blocks to obtain SiOx particles;
(2) Dispersing corn starch in ethanol, mixing to obtain a mixed solution, adding an aluminum silicate solution, stirring (the mass ratio of starch to aluminum silicate is 1000:6), drying, heating at 70 ℃ and mixing uniformly to obtain an aluminum silicate colloidal solution, transferring the aluminum silicate colloidal solution to a freezing chamber, freezing at-10 ℃, heating to gel at 70 ℃ in a heating pot, stirring, cooling at room temperature, and repeating the steps of freezing, heating to gel, stirring and cooling at room temperature for 5 times to obtain an aluminum silicate colloidal solution containing hydrogen bonds with aluminum silicate uniformly distributed;
(3) Adding 40g of aluminum silicate colloidal solution into 1kg of modified SiOx particles, uniformly stirring, spray drying/heating in a heating furnace to obtain SiOx particles with aluminum silicate colloidal solution layer, sending argon gas into a sintering furnace, sintering at 540 ℃ for 5h, annealing, and ball milling to obtain the silicon anode material.
The SiOx particles in step (2) are further modified before being treated by the aluminum silicate colloidal solution: (1) feeding SiOx particles into a reaction kettle, adding glycerol dispersant and tetrabutyl titanate (according to the mass g: volume mL: 5:100:0.8), stirring, dispersing, adding ammonium carbonate, heating at 55 ℃ for reaction for 6 hours, performing pressure filtration, drying the obtained solid substance, and removing glycerol to obtain black powder; (2) adding 1L of 3wt% acetic acid into 100g of black powder, stirring for 10min, carrying out weak acidification, washing and filter pressing, conveying to a sintering furnace, introducing mixed gas (98% argon gas and 2 hydrogen%), and sintering at 600 ℃ for 2h to obtain modified SiOx particles.
2. Silicon negative electrode plate made of silicon negative electrode material: comprising a negative electrode current collector and a positive and/or negative silicon-containing negative electrode layer on the negative electrode current collector
Preparing a front side and a back side silicon-containing anode layer: mixing a silicon negative electrode material and artificial graphite spheres (the silicon negative electrode material and the artificial graphite spheres are mixed according to the mass ratio of 3:7), a binder styrene butadiene rubber, a conductive agent (the composite carbon nanofiber and the carbon black are mixed according to the mass ratio of 1:2) according to the mass ratio of 96:1.2:1.8, adding solvent water and stirring to obtain negative electrode slurry, and coating the negative electrode slurry on the front surface of a negative electrode current collector to obtain the silicon-containing negative electrode layers on the front surface and the back surface.
3. Silicon negative electrode sheet application: silicon negative plate, aluminum oxide coated composite polypropylene isolating film, nickel cobalt lithium manganate (LiNi) 0.87 Co 0.02 Mn 0.11 O/ LiNi 0.82 Co 0.08 Mn 0.10 And O) winding the positive plate to obtain a battery core, and filling the battery core with a battery shell and injecting electrolyte to obtain the lithium ion battery.
Comparative example 1:
the difference from example 3 is that the metal gum is not subjected to the cycle of freezing-heating to gum-forming-stirring-cooling.
Comparative example 2:
the difference from example 3 is that the SiOx particles have not been subjected to a modification treatment.
Examples, comparative examples test:
1. powder resistance, silicon pole piece expansion at 100 soc%:
measuring the powder resistance of the silicon anode materials obtained in examples 1-6 and comparative examples 1-4 by using a membrane internal resistance meter; the thickness scale measures the thickness of the negative electrode sheet after tabletting of examples 1-6 and comparative examples 1-4, the thickness of the negative electrode sheet of the battery under 100soc%, and the expansion rate of the negative electrode sheet= (thickness of the negative electrode sheet under 100soc% and the thickness of the negative electrode sheet during compaction)/the thickness of the negative electrode sheet during compaction is 100%.
2. And (3) electrical property detection:
at normal temperature of 25 ℃, the initial and cut-off voltages are 2.8V, 4.25V, 1C is charged to 4.25V, then 4.25V constant voltage is charged until the current is reduced to 0.05C, 0.2C is discharged to 2.8V, and the 100 th circle, 600 th circle capacity retention rate and DCR growth rate of the battery at 25 ℃ are recorded.
TABLE 1 Pole piece case
Table 1 the powder resistances of the silicon anode materials of examples 1 to 6 were 0.145 Ω, 0.156 Ω, 0.153 Ω, 0.120 Ω, 0.118 Ω, 0.152 Ω, respectively, and the powder resistances of the silicon anode materials of examples 1 to 6 were between 0.118 and 0.156 Ω, respectively, and the powder resistances of comparative example 1 and comparative example 2 were 0.151 and 0.214, respectively, and the powder resistances of comparative example 2 were high; compared with the test results of examples 1-6, the silicon anode pole piece expansion rate of comparative examples 1-2 is higher, which indicates that SiOx particles are not modified, the pole piece expansion rate is higher, and the structural performance of the anode piece is poor.
The 100 th round, 300 th round and 700 th round of the battery of the examples 1 to 6 have capacity retention rates of 87.4 to 89.1%, 84.4 to 86.2%, 81.9 to 82.7%, and the 100 th round, 300 th round and 700 th round of the comparative examples 1 to 2 have capacity retention rates of 85.4 to 86.0%, 76.9 to 82.4% and 73.8 to 75.1%, respectively, wherein the battery of the comparative example 1 decays rapidly, which may coat uneven SiOx particles, the structure of the silicon negative electrode material is unstable, and cracking occurs, which means that the coating uniformity of the silicon negative electrode material can be improved during the cycle of freezing-heating gel-stirring-cooling treatment, and mechanical properties, tensile strength and elasticity can be improved, and capacity fading can be effectively reduced.
The above-described embodiments are merely preferred embodiments for fully explaining the present application, and the scope of the present application is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present application, and are intended to be within the scope of the present application. The protection scope of the application is subject to the claims.
Claims (11)
1. The silicon anode material is characterized by comprising SiOx particles, wherein x is more than or equal to 0 and less than 2, and a metal colloid carbonization layer coated on the SiOx particles, wherein the metal colloid is obtained by the following steps of: mixing and heating the starch dispersion liquid and the metal solution to form a colloidal liquid, and performing freezing, thermalization to form a gel, stirring and cooling circulation treatment for 2-10 times to obtain the metal colloidal liquid;
the SiOx particles are titanium dioxide modified SiOx particles and are prepared by the following steps:
(1) According to the mass: volume: the volume is 1-8: 100: adding unmodified SiOx particles, glycerol dispersant and tetrabutyl titanate into 0.2-0.8 g/mL/mL, stirring and dispersing, adding ammonium carbonate accounting for 1-20% of the mass of the SiOx particles, heating and reacting for 4-12 h at 30-70 ℃, removing the solvent, and drying to obtain black powder;
(2) And (3) carrying out weak acid treatment on the black powder, washing, and press-filtering, and then sintering in an inert gas containing not more than 2% of hydrogen in volume ratio at 350-800 ℃ to obtain titanium dioxide modified SiOx particles.
2. The silicon negative electrode material according to claim 1, wherein the freezing is performed at-20 to 0 ℃, the thermal forming glue is performed at 50 to 100 ℃, and the cooling is performed at 20 to 30 ℃.
3. The silicon negative electrode material according to claim 1, wherein the mass ratio of starch to metal is 1000: 1-150.
4. The silicon negative electrode material according to claim 1, wherein the temperature at which the starch dispersion and the metal solution are mixed and heated is 50 to 100 ℃.
5. The silicon negative electrode material according to claim 1, wherein the metal solution is at least one of silicate, metasilicate, sulfate, chloride, nitrate, phosphate, and metaphosphate containing calcium, manganese, magnesium, aluminum, nickel, and zinc.
6. The silicon negative electrode material according to claim 1, wherein the SiOx particles are prepared by: mixing a silicon-containing substance and Si powder according to a proportion of 1-50: mixing 5-30 mass percent, heating at 800-1400 ℃, condensing and agglomerating silicon-containing steam generated by heating, crushing and screening the blocks to obtain SiOx particles.
7. The silicon negative electrode material according to claim 6, wherein the silicon-containing substance is at least one of silica particles, white carbon black, opal, sepiolite, high-purity quartz sand, and diatomaceous earth.
8. The silicon negative electrode material according to claim 1, wherein the weakly acidic treatment is carried out by adding 10 to 120g of black powder to 1L of 1 to 8wt% acetic acid and stirring for 8 to 15 min.
9. A method for producing a silicon anode material according to any one of claims 1 to 8, comprising the steps of:
s1, preparing SiOx particles;
s2, mixing and heating the starch dispersion liquid and the metal solution to form a colloidal liquid, and performing freezing, thermalization to form gel, stirring and cooling circulation treatment for 2-10 times to obtain the metal colloidal liquid;
s3, adding 2-100 g of metal colloid liquid into 1kg of SiOx particles, uniformly stirring, drying to obtain SiOx particles containing a metal colloid liquid layer, sintering at 500-1100 ℃ for 10 min-10 h under the condition of inert gas, annealing, and grinding to obtain the silicon anode material.
10. The silicon negative plate is characterized by comprising a negative current collector and a silicon-containing negative electrode layer on the front side and/or the back side of the negative current collector, wherein the silicon-containing negative electrode layer is prepared by the following method: the silicon anode material, the binder and the conductive agent according to any one of claims 1-8, wherein the mass ratio is 85-100: 0.1 to 9: and 0.1-12, mixing, adding a solvent, stirring to obtain negative electrode slurry, and coating the negative electrode slurry on the front surface and/or the back surface of a negative electrode current collector to obtain the silicon-containing negative electrode layer.
11. A lithium ion battery prepared by using the silicon anode material according to any one of claims 1 to 8 or the silicon anode sheet according to claim 10.
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