CN116344787A - Novel composite material for secondary lithium ion battery, preparation method and application - Google Patents
Novel composite material for secondary lithium ion battery, preparation method and application Download PDFInfo
- Publication number
- CN116344787A CN116344787A CN202111584164.XA CN202111584164A CN116344787A CN 116344787 A CN116344787 A CN 116344787A CN 202111584164 A CN202111584164 A CN 202111584164A CN 116344787 A CN116344787 A CN 116344787A
- Authority
- CN
- China
- Prior art keywords
- composite material
- solution phase
- electrolysis
- lithium ion
- ion battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 97
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 102
- 150000003839 salts Chemical class 0.000 claims abstract description 54
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 45
- 150000001875 compounds Chemical class 0.000 claims abstract description 42
- 239000011159 matrix material Substances 0.000 claims abstract description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 33
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- 229910052796 boron Inorganic materials 0.000 claims abstract description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 18
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 7
- 230000008021 deposition Effects 0.000 claims abstract description 5
- 238000010000 carbonizing Methods 0.000 claims abstract description 4
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 4
- 238000004945 emulsification Methods 0.000 claims abstract description 4
- 238000007711 solidification Methods 0.000 claims abstract description 3
- 230000008023 solidification Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 94
- 239000007789 gas Substances 0.000 claims description 86
- 229920005989 resin Polymers 0.000 claims description 53
- 239000011347 resin Substances 0.000 claims description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 50
- 238000007740 vapor deposition Methods 0.000 claims description 48
- 239000010439 graphite Substances 0.000 claims description 44
- 229910002804 graphite Inorganic materials 0.000 claims description 44
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 29
- 239000004005 microsphere Substances 0.000 claims description 27
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 26
- 239000003921 oil Substances 0.000 claims description 22
- 235000019198 oils Nutrition 0.000 claims description 22
- -1 siloxane compound Chemical class 0.000 claims description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 21
- 229910052786 argon Inorganic materials 0.000 claims description 21
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 229920001568 phenolic resin Polymers 0.000 claims description 16
- 239000005011 phenolic resin Substances 0.000 claims description 16
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 16
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 15
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 15
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 14
- 235000021355 Stearic acid Nutrition 0.000 claims description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 13
- 239000000839 emulsion Substances 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 13
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 13
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 13
- 238000004321 preservation Methods 0.000 claims description 13
- 239000008117 stearic acid Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- LTEHWCSSIHAVOQ-UHFFFAOYSA-N tripropyl borate Chemical compound CCCOB(OCCC)OCCC LTEHWCSSIHAVOQ-UHFFFAOYSA-N 0.000 claims description 12
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 11
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 11
- 239000008158 vegetable oil Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 229930182478 glucoside Natural products 0.000 claims description 9
- 239000002736 nonionic surfactant Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 9
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 7
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 7
- 239000000194 fatty acid Substances 0.000 claims description 7
- 229930195729 fatty acid Natural products 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 239000007773 negative electrode material Substances 0.000 claims description 7
- 239000001103 potassium chloride Substances 0.000 claims description 7
- 235000011164 potassium chloride Nutrition 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000005062 Polybutadiene Substances 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 229920005546 furfural resin Polymers 0.000 claims description 6
- 229920002857 polybutadiene Polymers 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- 229950008882 polysorbate Drugs 0.000 claims description 6
- 229920000136 polysorbate Polymers 0.000 claims description 6
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 claims description 4
- 239000005662 Paraffin oil Substances 0.000 claims description 4
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 239000002480 mineral oil Substances 0.000 claims description 4
- 235000010446 mineral oil Nutrition 0.000 claims description 4
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 claims description 4
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000787 lecithin Substances 0.000 claims description 3
- 229940067606 lecithin Drugs 0.000 claims description 3
- 235000010445 lecithin Nutrition 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 229960004274 stearic acid Drugs 0.000 claims description 3
- 238000004804 winding Methods 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 23
- 229910052710 silicon Inorganic materials 0.000 description 23
- 239000010703 silicon Substances 0.000 description 22
- 239000006185 dispersion Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- 229910021642 ultra pure water Inorganic materials 0.000 description 10
- 239000012498 ultrapure water Substances 0.000 description 10
- ADKPKEZZYOUGBZ-UHFFFAOYSA-N [C].[O].[Si] Chemical compound [C].[O].[Si] ADKPKEZZYOUGBZ-UHFFFAOYSA-N 0.000 description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- 239000001294 propane Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 239000002153 silicon-carbon composite material Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 239000005543 nano-size silicon particle Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 239000011856 silicon-based particle Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a novel composite material for a secondary lithium ion battery, a preparation method and application thereof. The composite material is as follows: inside is spherical porous hard carbon material with hollow holes, and inside the holes, products of decomposition and deposition of gas containing silicon oxide and one or more gaseous compounds containing C, N, B, P element are deposited, wherein the products comprise SiOx particles; x ranges from 0 to 1.5, and the value of x is controlled through molten salt electrolysis; the porous hard carbon material is obtained by preparing a hard carbon matrix through double emulsion method solidification and then carbonizing.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a novel composite material for a secondary lithium ion battery, a preparation method and application thereof.
Background
Silicon-based materials are typical representatives of the negative electrode materials of the new generation of high-capacity lithium ion batteries, and have become hot spots for theoretical and application research in recent years. The nano silicon-based negative electrode material has the advantages of unique surface effect, unique size effect and the like, can greatly improve the cycle performance of silicon serving as a negative electrode, and is expected to solve the bottleneck problem of limiting the silicon negative electrode to be a substitute for a commercial graphite negative electrode. However, silicon-based negative electrodes also face many challenges such as large volume expansion during charge and discharge, low conductivity, and unstable Solid Electrolyte Interface (SEI) films, etc. Currently, the preparation of silicon-carbon composite materials can improve the problems faced by silicon-based cathodes to a certain extent. Silicon and carbon are mixed, mixed with a precursor of pyrolytic carbon of an organic substance, carbonized and crushed to obtain the silicon-carbon composite material, as in patent CN 1913200A. However, the method cannot meet the uniform dispersion of the silicon and carbon materials in the preparation process, so that the silicon-carbon anode material cannot fully exert the advantages.
Disclosure of Invention
The embodiment of the invention provides a novel composite material for a secondary lithium ion battery, and a preparation method and application thereof. The nanometer SiOx and one or more gaseous compounds containing C, N, B, P elements in the composite material are uniformly distributed in the pores of the spherical porous carbon through vapor deposition, and then the pores are reduced through molten salt electrolysis, so that the range of x in the SiOx is controlled. The porous structure can limit the size and uniform dispersion of the deposited nano SiOx, reduce the expansion effect and avoid the problem of electrical contact deterioration caused by SiOx pulverization; on the other hand, the large-size hole in the center provides a larger buffer space for the expansion of the SiOx material, so that the whole structure of the composite material is not easily damaged by the expansion, and the structure of the composite material can be kept unchanged under the condition that the SiOx fully performs lithium intercalation and deintercalation reaction, thereby improving the electrochemical performance of the battery. And under the multi-element compounding, C and N are favorable for improving the cycle performance of the material, and B and P are favorable for improving the multiplying power performance of the material.
In a first aspect, an embodiment of the present invention provides a novel composite material for a secondary lithium ion battery, where the composite material is: a spherical porous hard carbon material having hollow pores inside, and inside the pores, a silicon oxide-containing gas and one or more gaseous compounds containing any one element of C, N, B, P are deposited to decompose the deposited product, including SiOx particles; x ranges from 0 to 1.5, and the value of x is controlled through molten salt electrolysis;
The porous hard carbon material is obtained by preparing a hard carbon matrix through double emulsion method solidification and then carbonizing.
Preferably, the silicon oxide content in the composite material accounts for 1-70 wt%.
Preferably, the particle size of the composite material ranges from 1um to 100um, and the average pore diameter of the pores ranges from 0.1nm to 10nm; the size of the hollow hole is 0.5-80 um.
Preferably, the hard carbon matrix of the spherical porous hard carbon material is one or a combination of a plurality of phenolic resin, epoxy resin, furfural resin or polybutadiene resin;
the silicon-oxygen-containing gas is a siloxane compound, comprising: a combination of one or more of trimethoxysilane, tetramethoxysilane, triethoxysilane, and tetraethoxysilane;
the gaseous compound containing the C element comprises: one or more of acetylene, methane, propylene, ethylene, propane, and gaseous ethanol;
the gaseous compound containing N element comprises: one or more of nitrogen, ammonia, urea, and melamine;
the gaseous compound containing B element comprises: one or more of diborane, trimethyl borate, tripropyl borate, and boron tribromide;
The gaseous compound containing the P element comprises: phosphine and/or phosphorus oxychloride.
In a second aspect, an embodiment of the present invention provides a method for preparing the novel composite material for a secondary lithium ion battery according to the first aspect, where the preparation method includes:
step one: adopting pure oil as a first solution phase; dissolving resin in a corresponding solvent, and adding a nonionic surfactant and a curing agent to prepare a second solution phase; taking oil containing surfactant as a third solution phase; slowly adding the first solution phase into the second solution phase, stirring for 0.5-1 hour, adding the stirred mixed solution into the third solution phase, stirring to obtain the required emulsion, continuously stirring while heating to 80-130 ℃, preserving heat for 1-24 hours until the resin is solidified, and forming hollow resin microspheres, and then centrifugally cleaning and drying;
step two: introducing a pore-forming air source into the hollow resin microspheres at 600-1000 ℃ for 1-10 hours, and performing pore-forming treatment on the hollow resin microspheres to obtain a porous hard carbon matrix material; wherein the pore-forming gas source is one or the combination of two of carbon dioxide or water vapor; the air flow of the pore-forming air source is 2L/min-20L/min;
Step three: vapor deposition is carried out on the porous hard carbon matrix material to obtain composite material powder; the gas source of the vapor deposition comprises a silicon oxide-containing gas and one or more gaseous compounds containing any element C, N, B, P;
step four: placing the dried salt into a crucible, and winding and suspending two graphite sheets on the crucible by conductive wires respectively to serve as pre-electrolysis electrodes; argon is introduced, the gas flow rate is 0.5-2L/min, the temperature is raised to 800-900 ℃ at the heating rate of 2-10 ℃/min, and two graphite sheets are placed after heat preservation for half an hour; applying constant voltage of 2.5-3.0V between two graphite sheets for pre-electrolysis for 1-2 hours; after the pre-electrolysis is finished, continuously heating to 900-1000 ℃, and lifting two graphite sheets from molten salt to be suspended; putting composite material powder, applying constant voltage of 2.2-3.0V between two electrodes of molten salt electrolysis, and starting electrolysis for 5-20 hours; and after the electrolysis is finished, taking out the electrolyzed sample, washing with water, placing the sample in a blast drying box, and drying at 50-80 ℃ for 8-20 hours to obtain the novel composite material for the secondary lithium ion battery.
Preferably, the protective gas for vapor deposition is one or the combination of two of nitrogen and argon, the flow rate is 1-5L/min, the gas flow rate of the gaseous compound is 0.5-10L/min, and the flow rate of the silicon-oxygen-containing gas is 0.5-10L/min; the vapor deposition temperature is 500-1500 ℃, and the vapor deposition time is 1-20 hours.
Preferably, the dried salt comprises: one or more of calcium chloride, magnesium chloride, sodium chloride and potassium chloride;
the resin comprises: one or a combination of a plurality of phenolic resin, epoxy resin, furfural resin or polybutadiene resin;
the solvent comprises: one or more of ethanol, acetone and toluene;
the oils include: a combination of one or more of vegetable oil, paraffin oil, mineral oil, etc.;
the nonionic surfactant includes: one or more of alkyl glucosides, fatty acid glycerides, fatty acid sorbitan, polysorbate;
the curing agent comprises: a combination of one or more of trimethylhexamethylenediamine, ethylenediamine, and m-xylylenediamine;
the surfactant comprises one or a combination of more of stearic acid, sodium dodecyl benzene sulfonate, lecithin and the like;
the silicon-oxygen-containing gas is a siloxane compound, comprising: a combination of one or more of trimethoxysilane, tetramethoxysilane, triethoxysilane, and tetraethoxysilane;
the gaseous compound containing the C element comprises: one or more of acetylene, methane, propylene, ethylene, propane, and gaseous ethanol;
The gaseous compound containing N element comprises: one or more of nitrogen, ammonia, urea, and melamine;
the gaseous compound containing B element comprises: one or more of diborane, trimethyl borate, tripropyl borate, and boron tribromide;
the gaseous compound containing the P element comprises: phosphine and/or phosphorus oxychloride.
Preferably, the first solution phase, in mass fraction: second solution phase: third solution phase= (0, 30% ] (0, 50% ];
the second solution phase comprises the following components in percentage by mass: solvent: curing agent: nonionic surfactant= (0, 80% ] (0, 90% ]: [0, 30% ] (0, 20% ];
the third solution phase comprises oil in mass fraction: surfactant= (0, 90% ] (0, 30% ]).
In a third aspect, an embodiment of the present invention provides a negative electrode material for a lithium battery, including the novel composite material for a secondary lithium ion battery according to the first aspect.
In a fourth aspect, an embodiment of the present invention provides a lithium ion battery, where the lithium ion battery includes the novel composite material for a secondary lithium ion battery described in the first aspect.
The embodiment of the invention provides a novel composite material for a secondary lithium ion battery. The nanometer SiOx and one or more gaseous compounds containing C, N, B, P elements in the composite material are uniformly distributed in the pores of the spherical porous carbon through vapor deposition, and then the pores are reduced through molten salt electrolysis, so that the range of x in the SiOx is controlled. The porous structure can limit the size of the nano SiOx after deposition and the size of the reduced nano silicon, control uniform dispersion, reduce expansion effect and avoid the problem of electrical contact deterioration caused by SiOx pulverization; on the other hand, the large-size hole in the center provides a larger buffer space for the expansion of the SiOx material, so that the whole structure of the composite material is not easily damaged by the expansion, and the structure of the composite material can be kept unchanged under the condition that the SiOx fully performs lithium intercalation and deintercalation reaction, thereby improving the electrochemical performance of the battery. And under the multi-element compounding, C and N are favorable for improving the cycle performance of the material, and B and P are favorable for improving the multiplying power performance of the material.
Drawings
The technical scheme of the embodiment of the invention is further described in detail through the drawings and the embodiments.
FIG. 1 is a flow chart of a method of preparing a novel composite material for a secondary lithium ion battery according to an embodiment of the present invention;
fig. 2 is a Scanning Electron Microscope (SEM) image of a cut surface of the novel composite material for a secondary lithium ion battery prepared in example 1 of the present invention.
Detailed Description
The invention is further illustrated by the drawings and the specific examples, which are to be understood as being for the purpose of more detailed description only and are not to be construed as limiting the invention in any way, i.e. not intended to limit the scope of the invention.
The novel composite material for the secondary lithium ion battery is provided with a spherical porous hard carbon material with hollow holes inside, and a product of decomposition and deposition of a silicon-oxygen-containing gas and one or more gaseous compounds containing C, N, B, P elements is deposited inside the holes, wherein the product comprises SiOx particles; x ranges from 0 to 1.5, and the value of x is controlled through molten salt electrolysis;
the porous hard carbon material is prepared by solidifying a hard carbon matrix through a double emulsion method and then carbonizing. The hard carbon matrix of the spherical porous hard carbon material is one or a combination of a plurality of phenolic resin, epoxy resin, furfural resin or polybutadiene resin.
The silicon content of the composite material is 1-70wt%.
The particle size of the composite material ranges from 1um to 100um, and the average pore diameter of the pores ranges from 0.1nm to 10nm; the size of the hollow hole is 0.5 um-80 um.
The flow of the preparation method of the novel composite material for the secondary lithium ion battery is shown in the figure 1, and the preparation method comprises the following steps:
step 1: adopting pure oil as a first solution phase; dissolving resin in a corresponding solvent, and adding a nonionic surfactant and a curing agent to prepare a second solution phase; taking oil containing surfactant as a third solution phase; slowly adding the first solution phase into the second solution phase, stirring for 0.5-1 hour, adding the stirred mixed solution into the third solution phase, stirring to obtain the required emulsion, continuously stirring while heating to 80-130 ℃, preserving heat for 1-24 hours until the resin is solidified, and forming hollow resin microspheres, and then centrifugally cleaning and drying;
the first solution phase comprises the following components in mass fraction: second solution phase: third solution phase= (0, 30% ] (0, 50% ];
in the second solution phase, resin: solvent: curing agent: nonionic surfactant= (0, 80% ] (0, 90% ]: [0, 30% ] (0, 20% ];
In the third solution phase, oils, in mass fraction: surfactant= (0, 90% ] (0, 30% ]).
The resin comprises: one or a combination of a plurality of phenolic resin, epoxy resin, furfural resin or polybutadiene resin;
the solvent comprises: one or more of ethanol, acetone and toluene;
the oils include: a combination of one or more of vegetable oil, paraffin oil, mineral oil, etc.;
the nonionic surfactant includes: one or more of alkyl glucosides, fatty acid glycerides, fatty acid sorbitan, polysorbate;
the curing agent comprises: a combination of one or more of trimethylhexamethylenediamine, ethylenediamine, and m-xylylenediamine;
the surfactant comprises one or more of stearic acid, sodium dodecyl benzene sulfonate, lecithin, etc.
Step 2: introducing a pore-forming air source into the hollow resin microspheres at 600-1000 ℃ for 1-10 hours, and performing pore-forming treatment on the hollow resin microspheres to obtain a porous hard carbon matrix material;
wherein the pore-forming gas source is one or the combination of two of carbon dioxide or water vapor; the air flow of the pore-forming air source is 2L/min-20L/min;
Step 3: vapor deposition is carried out on the porous hard carbon matrix material to obtain composite material powder;
wherein the gas source for vapor deposition comprises a silicon-oxygen-containing gas and one or more gaseous compounds containing any element C, N, B, P;
the protective gas for vapor deposition is one or the combination of two of nitrogen and argon, the flow rate is 1-5L/min, the gas flow rate of the gaseous compound is 0.5-10L/min, and the flow rate of the silicon-oxygen-containing gas is 0.5-10L/min; the vapor deposition temperature is 500-1500 ℃, and the vapor deposition time is 1-20 hours.
Specifically, the silicon-oxygen-containing gas is a siloxane compound, comprising: a combination of one or more of trimethoxysilane, tetramethoxysilane, triethoxysilane, and tetraethoxysilane;
the gaseous compound containing C element comprises: one or more of acetylene, methane, propylene, ethylene, propane, and gaseous ethanol;
the gaseous compound containing N element comprises: one or more of nitrogen, ammonia, urea, and melamine;
the gaseous compound containing B element comprises: one or more of diborane, trimethyl borate, tripropyl borate, and boron tribromide;
the gaseous compound containing the P element comprises: phosphine and/or phosphorus oxychloride.
Step 4: carrying out molten salt electrolysis on the composite material powder to prepare a novel composite material for the secondary lithium ion battery;
the method specifically comprises the following steps: placing the dried salt into a crucible, and winding and suspending two graphite sheets on the crucible by conductive wires respectively to serve as pre-electrolysis electrodes; argon is introduced, the gas flow rate is 0.5-2L/min, the temperature is raised to 800-900 ℃ at the heating rate of 2-10 ℃/min, and two graphite sheets are placed after heat preservation for half an hour; applying constant voltage of 2.5-3.0V between two graphite sheets for pre-electrolysis for 1-2 hours; after the pre-electrolysis is finished, continuously heating to 900-1000 ℃, and lifting two graphite sheets from molten salt to be suspended; putting composite material powder, applying constant voltage of 2.2-3.0V between two electrodes of molten salt electrolysis, and starting electrolysis for 5-20 hours; and after the electrolysis is finished, taking out the electrolyzed sample, washing with water, placing the sample in a blast drying box, and drying at 50-80 ℃ for 8-20 hours to obtain the novel composite material for the secondary lithium ion battery.
The dried salt comprises: one or more of calcium chloride, magnesium chloride, sodium chloride and potassium chloride.
The novel composite material for the secondary lithium ion battery, which is prepared by the invention, can be used as a negative electrode material of the lithium ion battery.
In order to better understand the technical scheme provided by the invention, the following specific processes for preparing the novel composite material for the secondary lithium ion battery by applying the method provided by the embodiment of the invention, and the method and the battery characteristics for applying the novel composite material to the lithium ion secondary battery are respectively described in a plurality of specific examples.
Example 1
The embodiment provides a preparation method of a novel composite material for a secondary lithium ion battery, which comprises the following steps:
step 1: dissolving phenolic resin in alcohol by using vegetable oil as a first solution phase, adding polysorbate and ethylenediamine to prepare a second solution phase, using oil containing stearic acid as a third solution phase, slowly adding the first solution phase into the second solution phase, stirring for 1 hour, adding the stirred mixed solution into the third solution phase, stirring to obtain a required emulsion, continuously stirring while heating to 130 ℃, preserving heat for 14 hours until the resin is solidified, and centrifuging, cleaning and drying after hollow resin microspheres are formed;
step 2: performing pore-forming treatment on the cleaned hollow resin microspheres, wherein an air source is water vapor, the pore-forming temperature is 1000 ℃ and the duration is 1 hour, and a porous hard carbon matrix of 11.5um is obtained;
Step 3: taking nitrogen as a shielding gas, wherein the flow rate is 1L/min, taking the porous hard carbon matrix obtained in the step 2 as a substrate, taking trimethoxysilane containing silicon oxygen as a silicon source, and introducing methane containing a compound of C element into a reaction container in a gas form, and performing vapor deposition to obtain composite material powder; wherein the gas flow rate is 0.5L/min, and the gas flow rate of methane is 0.5L/min. The temperature of vapor deposition was 500 ℃, and the time of vapor deposition was 20 hours.
Step 4: molten salt electrolysis: the dried anhydrous calcium chloride is placed in a crucible, and two graphite sheets wound by 0.2mm molybdenum wires are respectively wound by conductive wires and suspended above the crucible to serve as a pre-electrolysis electrode. Argon is introduced, the gas flow rate is 0.5L/min, the temperature is raised to 800 ℃ at the heating rate of 2 ℃/min, and after half an hour of heat preservation, two graphite sheets are placed. A constant voltage of 2.5V was applied between the two graphite sheets for pre-electrolysis for 1 hour. And (3) after the pre-electrolysis is finished, lifting the pre-electrolysis electrode from molten salt to be suspended, continuously heating the crucible to 900 ℃, and putting the composite material powder prepared in the step (3). The distance between the electrodes was 2cm, a constant voltage of 2.2V was applied between the electrodes, and electrolysis was started for 20 hours. After the electrolysis is completed, taking out the electrolyzed sample, and performing ultrasonic washing for 3 times by using ultrapure water to remove the fused salt attached to the surface of the sample. The washed sample was dried at 50℃for 8 hours. Obtaining the novel silica composite material with small size and high dispersion and hollow holes inside.
Fig. 2 is an SEM image of a cut surface of the novel composite material for a secondary lithium ion battery prepared in example 1 of the present invention. From the tangential SEM, it can be seen that a large void exists in the central region of the interior of the material, providing a larger buffer space for the expansion of silicon on the basis of the abundance of voids.
The obtained material was used as a negative electrode material.
The obtained anode material, conductive additive carbon black and adhesive (1:1 sodium cellulose and styrene butadiene rubber) are mixed according to the proportion of 95:2:3, weighing. The slurry preparation was performed in a beater at room temperature. And uniformly coating the prepared slurry on the copper foil. Drying at 50deg.C for 2 hr in a forced air drying oven, cutting into 8×8mm pole pieces, and vacuum drying at 100deg.C for 10 hr in a vacuum drying oven. And transferring the dried pole piece into a glove box for standby use to assemble a battery.
The simulated cell was assembled in a glove box containing a high purity Ar atmosphere using metallic lithium as the counter electrode, 1 mole LiPF 6 The solution in Ethylene Carbonate (EC)/dimethyl carbonate (DMC) was used as an electrolyte to assemble a battery. The constant current charge and discharge mode test was performed using a charge and discharge meter with a discharge cutoff voltage of 0.005V and a charge cutoff voltage of 1.5V, and the charge and discharge test was performed at a C/10 current density. The test results are recorded in table 1.
Example 2
The embodiment provides a preparation method of a novel composite material for a secondary lithium ion battery, which comprises the following steps:
step 1: dissolving phenolic resin in alcohol by using vegetable oil as a first solution phase, adding alkyl glucoside and ethylenediamine to prepare a second solution phase, using oil containing stearic acid as a third solution phase, slowly adding the first solution phase into the second solution phase, stirring for 1 hour, adding the stirred mixed solution into the third solution phase, stirring to obtain a required emulsion, continuously stirring while heating to 130 ℃, preserving heat for 5 hours until the resin is solidified, and centrifuging, cleaning and drying after hollow resin microspheres are formed;
step 2: performing pore-forming treatment on the cleaned hollow resin microspheres, wherein the adopted air source is water vapor, the pore-forming temperature is 1000 ℃ and the pore-forming time is 8 hours, so as to obtain a 16.1um porous hard carbon matrix;
step 3: taking argon as a shielding gas, wherein the flow rate is 1.5L/min, taking the porous hard carbon matrix obtained in the step 2 as a substrate, taking tetramethoxy silane containing silicon oxygen as a silicon source, and introducing ammonia gas containing N element compound into a reaction container in a gas form, and performing vapor deposition to obtain composite material powder; wherein the flow rate of the tetramethoxysilane gas is 0.8L/min, and the flow rate of the ammonia-containing gas is 0.8L/min. The temperature of vapor deposition was 600 ℃, and the time of vapor deposition was 12.5 hours.
Step 4: molten salt electrolysis: the dried anhydrous sodium chloride is put into a crucible, and two graphite sheets wound by copper wires with the diameter of 0.3mm are respectively wound by conductive wires and suspended on the crucible to serve as a pre-electrolysis electrode. Argon is introduced, the gas flow rate is 1L/min, the temperature is raised to 850 ℃ at the heating rate of 3 ℃/min, and after half an hour of heat preservation, two graphite sheets are placed. A constant voltage of 2.6V was applied between the two graphite sheets for pre-electrolysis for 2 hours. And (3) after the pre-electrolysis is finished, lifting the pre-electrolysis electrode from molten salt to be suspended, continuously heating the crucible to 950 ℃, and putting the composite material powder prepared in the step (3). The distance between the electrodes was 3cm, a constant voltage of 2.3V was applied between the electrodes, and electrolysis was started for 18 hours. After the electrolysis is completed, taking out the electrolyzed sample, and performing ultrasonic washing for 4 times by using ultrapure water to remove the fused salt attached to the surface of the sample. The washed sample was dried at 55℃for 9 hours. And obtaining the small-size high-dispersion silicon-oxygen-carbon composite material.
The electrochemical properties of the assembled button cell were evaluated under the same test conditions as in example 1, and are recorded in table 1.
Example 3
The embodiment provides a preparation method of a novel composite material for a secondary lithium ion battery, which comprises the following steps:
step 1: dissolving phenolic resin in alcohol by using vegetable oil as a first solution phase, adding polysorbate and trimethyl hexamethylenediamine to prepare a second solution phase, using oil containing stearic acid as a third solution phase, slowly adding the first solution phase into the second solution phase, stirring for 1 hour, adding the stirred mixed solution into the third solution phase, stirring to obtain a required emulsion, continuously stirring, heating to 100 ℃, preserving heat for 4 hours until the resin is solidified, and centrifuging, cleaning and drying after hollow resin microspheres are formed;
step 2: performing pore-forming treatment on the porous hard carbon matrix obtained in the step 2 as a substrate, wherein the adopted air source is water vapor, the pore-forming temperature is 1000 ℃ and the duration is 1-10 hours, so as to obtain a 11.3um porous hard carbon matrix;
step 3: taking nitrogen as a shielding gas, wherein the flow rate is 2L/min, taking the porous hard carbon matrix obtained in the step 2 as a substrate, taking silicon-oxygen-containing gas triethoxysilane as a silicon source, and a compound tripropyl borate containing B element as a gas, and introducing the gas into a reaction container for vapor deposition to obtain composite material powder; wherein the gas flow rate of triethoxysilane is 1L/min, and the gas flow rate of tripropyl borate is 1L/min. The temperature of vapor deposition was 700 ℃, and the time of vapor deposition was 10 hours.
Step 4: molten salt electrolysis: the dried anhydrous magnesium chloride is placed into a crucible, and two graphite sheets wound by an iron wire with the diameter of 0.4mm are respectively wound by a conductive wire and suspended on the crucible to serve as a pre-electrolysis electrode. Argon is introduced, the gas flow rate is 2L/min, the temperature is raised to 900 ℃ at the heating rate of 4 ℃/min, and after half an hour of heat preservation, two graphite sheets are placed. A constant voltage of 2.7V was applied between the two graphite sheets for pre-electrolysis for 2 hours. And (3) after the pre-electrolysis is finished, lifting the pre-electrolysis electrode from molten salt to be suspended, continuously heating the crucible to 1000 ℃, and putting the composite material powder prepared in the step (3). The distance between the electrodes was 4cm, a constant voltage of 2.4V was applied between the electrodes, and electrolysis was started for 18 hours. After the electrolysis is completed, taking out the electrolyzed sample, and performing ultrasonic washing for 5 times by using ultrapure water to remove the fused salt attached to the surface of the sample. The washed sample was dried at 60℃for 10 hours. And obtaining the small-size high-dispersion silicon-oxygen-carbon composite material.
The electrochemical properties of the assembled button cell were evaluated under the same test conditions as in example 1, and are recorded in table 1.
Example 4
The embodiment provides a preparation method of a novel composite material for a secondary lithium ion battery, which comprises the following steps:
step 1: dissolving phenolic resin in alcohol by using vegetable oil as a first solution phase, adding polysorbate and ethylenediamine to prepare a second solution phase, using oil containing stearic acid as a third solution phase, slowly adding the first solution phase into the second solution phase, stirring for 1 hour, adding the stirred mixed solution into the third solution phase, stirring to obtain a required emulsion, continuously stirring while heating to 85 ℃, preserving heat for 4 hours until the resin is solidified, and centrifuging, cleaning and drying after hollow resin microspheres are formed;
step 2: placing the dried sample into a reaction device, heating to 1300 ℃, preserving heat for 6 hours, and performing high-temperature carbonization treatment on the dried sample to obtain a porous hard carbon matrix with the diameter of 12.8 microns;
step 3: performing pore-forming treatment on the porous hard carbon matrix obtained in the step 2 as a substrate, wherein an air source is carbon dioxide, the pore-forming temperature is 900 ℃ and the duration is 5 hours;
step 4: taking argon as a shielding gas, wherein the flow rate is 2.5L/min, taking the product obtained in the step 3 as a substrate, taking tetraethoxysilane containing silicon oxygen as a silicon source, and a compound phosphorus oxychloride containing P element, introducing the silicon source and the compound phosphorus oxychloride into a reaction container in a gas form, and performing vapor deposition to obtain composite material powder; wherein the flow rate of tetraethoxysilane gas is 1.25L/min, and the flow rate of phosphorus oxychloride gas compound gas is 1.25L/min. The temperature of vapor deposition was 800 ℃, and the time of vapor deposition was 8 hours.
Step 5: molten salt electrolysis: the dried anhydrous potassium chloride is placed in a crucible, and two graphite sheets wound by 0.5mm molybdenum wires are respectively wound by conductive wires and suspended above the crucible to serve as pre-electrolysis electrodes. Argon is introduced, the gas flow rate is 2L/min, the temperature is raised to 850 ℃ at the heating rate of 5 ℃/min, and after half an hour of heat preservation, two graphite sheets are placed. A constant voltage of 2.8V was applied between the two graphite sheets for pre-electrolysis for 2 hours. And (3) after the pre-electrolysis is finished, lifting the pre-electrolysis electrode from molten salt to be suspended, continuously heating the crucible to 1000 ℃, and putting the composite material powder prepared in the step (3). The distance between the electrodes was 5cm, a constant voltage of 2.5V was applied between the electrodes, and electrolysis was started for 20 hours. After the electrolysis is completed, taking out the electrolyzed sample, and performing ultrasonic washing for 6 times by using ultrapure water to remove the fused salt attached to the surface of the sample. The washed sample was dried at 65℃for 12 hours. And obtaining the small-size high-dispersion silicon-oxygen-carbon composite material.
The electrochemical properties of the assembled button cell were evaluated under the same test conditions as in example 1, and are recorded in table 1.
Example 5
The embodiment provides a preparation method of a novel composite material for a secondary lithium ion battery, which comprises the following steps:
step 1: dissolving phenolic resin in alcohol by using vegetable oil as a first solution phase, adding alkyl glucoside and ethylenediamine to prepare a second solution phase, using oil containing stearic acid as a third solution phase, slowly adding the first solution phase into the second solution phase, stirring for 1 hour, adding the stirred mixed solution into the third solution phase, stirring to obtain a required emulsion, continuously stirring while heating to 100 ℃, preserving heat for 10 hours until the resin is solidified, and centrifuging, cleaning and drying after hollow resin microspheres are formed;
step 2: performing pore-forming treatment on the cleaned hollow resin microspheres, wherein an air source is carbon dioxide, the pore-forming temperature is 1000 ℃ and the duration is 6 hours, and a 15.3um porous hard carbon matrix is obtained;
step 3: taking nitrogen as a shielding gas, the flow rate is 3L/min, taking the porous hard carbon matrix obtained in the step 2 as a substrate, taking trimethoxysilane and tetramethoxysilane containing silicon oxygen as silicon sources, and introducing gaseous compounds methane, ammonia, trimethyl borate and phosphorus oxychloride containing C, N, B and P elements into a reaction container in the form of gases for vapor deposition to obtain composite material powder; wherein, the gas flow rates of trimethoxysilane and tetramethoxysilane are 1L/min, and the gas flow rates of methane, ammonia, trimethyl borate and phosphorus oxychloride are 0.5L/min. The temperature of vapor deposition was 900 ℃ and the time of vapor deposition was 5 hours.
Step 4: molten salt electrolysis: the dried anhydrous calcium chloride and sodium chloride are placed in a crucible, and two graphite sheets wound by 0.6mm molybdenum wires are respectively wound by conductive wires and suspended above the crucible to serve as pre-electrolysis electrodes. Argon is introduced, the gas flow rate is 1L/min, the temperature is raised to 800 ℃ at the heating rate of 6 ℃/min, and after half an hour of heat preservation, two graphite sheets are placed. A constant voltage of 2.9V was applied between the two graphite sheets for pre-electrolysis for 1 hour. And (3) after the pre-electrolysis is finished, lifting the pre-electrolysis electrode from molten salt to be suspended, continuously heating the crucible to 900 ℃, and putting the composite material powder prepared in the step (3). The distance between the electrodes was 6cm, a constant voltage of 2.6V was applied between the electrodes, and electrolysis was started for 15 hours. After the electrolysis is completed, taking out the electrolyzed sample, and performing ultrasonic washing for 7 times by using ultrapure water to remove the fused salt attached to the surface of the sample. The washed sample was dried at 70℃for 12 hours. And obtaining the small-size high-dispersion silicon-oxygen-carbon composite material.
The electrochemical properties of the assembled button cell were evaluated under the same test conditions as in example 1, and are recorded in table 1.
Example 6
The embodiment provides a preparation method of a novel composite material for a secondary lithium ion battery, which comprises the following steps:
step 1: dissolving phenolic resin in alcohol by taking paraffin oil as a first solution phase, adding alkyl glucoside and ethylenediamine to prepare a second solution phase, taking oil containing stearic acid as a third solution phase, slowly adding the first solution phase into the second solution phase, stirring for 1 hour, adding the stirred mixed solution into the third solution phase, stirring to obtain a required emulsion, continuously stirring, heating to 130 ℃, preserving heat for 5 hours until the resin is solidified, and centrifuging, cleaning and drying after hollow resin microspheres are formed;
step 2: performing pore-forming treatment on the cleaned hollow resin microspheres, wherein an air source is carbon dioxide, the pore-forming temperature is 1000 ℃ and the duration is 5 hours, and a 11.3um porous hard carbon matrix is obtained;
step 3: taking argon as a shielding gas, wherein the flow rate is 3.5L/min, taking the porous hard carbon matrix obtained in the step 2 as a substrate, taking trimethoxysilane and triethoxysilane containing silicon oxygen as silicon sources, and introducing gaseous compounds including C, N, B and P elements such as propylene, urea, tripropyl borate and phosphine into a reaction container in the form of gases for vapor deposition to obtain composite material powder; wherein, the gas flow rates of trimethoxysilane and triethoxysilane are 1.25L/min, and the gas flow rates of propylene, urea, tripropyl borate and phosphine gaseous compounds are 0.6L/min. The temperature of vapor deposition was 1000℃and the time of vapor deposition was 4 hours.
Step 4: molten salt electrolysis: the dried anhydrous calcium chloride and potassium chloride are placed in a crucible, and two graphite sheets wound by copper wires with the thickness of 0.7mm are respectively wound by conductive wires and suspended above the crucible to serve as pre-electrolysis electrodes. Argon is introduced, the gas flow rate is 1L/min, the temperature is raised to 900 ℃ at the heating rate of 6 ℃/min, and after half an hour of heat preservation, two graphite sheets are placed. A constant voltage of 2.9V was applied between the two graphite sheets for pre-electrolysis for 1 hour. And (3) after the pre-electrolysis is finished, lifting the pre-electrolysis electrode from molten salt to be suspended, continuously heating the crucible to 1000 ℃, and putting the composite material powder prepared in the step (3). The distance between the electrodes was 2cm, a constant voltage of 2.7V was applied between the electrodes, and electrolysis was started for 10 hours. After the electrolysis is completed, taking out the electrolyzed sample, and performing ultrasonic washing for 8 times by using ultrapure water to remove the fused salt attached to the surface of the sample. The washed sample was dried at 50℃for 16 hours. And obtaining the small-size high-dispersion silicon-oxygen-carbon composite material.
The electrochemical properties of the assembled button cell were evaluated under the same test conditions as in example 1, and are recorded in table 1.
Example 7
The embodiment provides a preparation method of a novel composite material for a secondary lithium ion battery, which comprises the following steps:
step 1: dissolving phenolic resin in alcohol by using vegetable oil as a first solution phase, adding alkyl glucoside and ethylenediamine to prepare a second solution phase, using oil containing stearic acid as a third solution phase, slowly adding the first solution phase into the second solution phase, stirring for 1 hour, adding the stirred mixed solution into the third solution phase, stirring to obtain a required emulsion, continuously stirring while heating to 130 ℃, preserving heat for 12 hours until the resin is solidified, and centrifuging, cleaning and drying after hollow resin microspheres are formed;
step 2: performing pore-forming treatment on the cleaned hollow resin microspheres, wherein the adopted air source is water vapor, the pore-forming temperature is 800 ℃ and the duration is 5 hours, so as to obtain a 10.8um porous hard carbon matrix;
step 3: taking nitrogen as a shielding gas, the flow rate is 4L/min, taking the porous hard carbon matrix obtained in the step 2 as a substrate, taking trimethoxy silane, tetramethoxy silane and triethoxy silane containing silicon oxygen as silicon sources, and introducing propane, hydrazine, diborane and phosphine containing C, N, B and P elements into a reaction container in a gas form for vapor deposition to obtain composite material powder; wherein, the gas flow rates of trimethoxy silane, tetramethoxy silane and triethoxy silane are all 1.3L/min, and the gas flow rates of propane, hydrazine, diborane and phosphine are all 0.5L/min. The temperature of vapor deposition was 1100 ℃, and the time of vapor deposition was 2.5 hours.
Step 4: molten salt electrolysis: the dried anhydrous calcium chloride and magnesium chloride are placed in a crucible, and two graphite sheets wound by an iron wire with the diameter of 0.8mm are respectively wound by a conductive wire and suspended on the crucible to serve as pre-electrolysis electrodes. Argon is introduced, the gas flow rate is 1L/min, the temperature is raised to 800 ℃ at the heating rate of 8 ℃/min, and after half an hour of heat preservation, two graphite sheets are placed. A constant voltage of 2.5V was applied between the two graphite sheets for pre-electrolysis for 1 hour. And (3) after the pre-electrolysis is finished, lifting the pre-electrolysis electrode from molten salt to be suspended, continuously heating the crucible to 900 ℃, and putting the composite material powder prepared in the step (3). The distance between the electrodes was 4cm, a constant voltage of 2.8V was applied between the electrodes, and electrolysis was started for 8 hours. After the electrolysis is completed, taking out the electrolyzed sample, and performing ultrasonic washing for 5 times by using ultrapure water to remove the fused salt attached to the surface of the sample. The washed sample was dried at 60℃for 14 hours. And obtaining the small-size high-dispersion silicon-oxygen-carbon composite material.
The electrochemical properties of the assembled button cell were evaluated under the same test conditions as in example 1, and are recorded in table 1.
Example 8
The embodiment provides a preparation method of a novel composite material for a secondary lithium ion battery, which comprises the following steps:
step 1: dissolving phenolic resin in alcohol by using mineral oil as a first solution phase, adding alkyl glucoside and ethylenediamine to prepare a second solution phase, using oil containing stearic acid as a third solution phase, slowly adding the first solution phase into the second solution phase, stirring for 1 hour, adding the stirred mixed solution into the third solution phase, stirring to obtain a required emulsion, continuously stirring, heating to 130 ℃, preserving heat for 12 hours until the resin is solidified, and centrifuging, cleaning and drying after hollow resin microspheres are formed;
step 2: performing pore-forming treatment on the cleaned hollow resin microspheres, wherein an air source is carbon dioxide, the pore-forming temperature is 900 ℃ and the duration is 6 hours, and a 12.5um porous hard carbon matrix is obtained;
step 3: taking argon as a shielding gas, the flow rate is 4.5L/min, taking the porous hard carbon matrix obtained in the step 2 as a substrate, taking trimethoxy silane, tetramethoxy silane and tetraethoxy silane containing silicon oxygen as silicon sources, and adding ethanol, nitrogen, trimethyl borate and phosphorus oxychloride containing C, N, B and P elements into a reaction container in a gas form, and performing vapor deposition to obtain composite material powder; wherein, the gas flow rates of trimethoxysilane, tetramethoxysilane and tetraethoxysilane are all 1.7L/min, and the gas flow rates of ethanol, nitrogen, trimethyl borate and phosphorus oxychloride are all 1.25L/min. The temperature of vapor deposition was 1200 ℃, and the time of vapor deposition was 2 hours.
Step 4: molten salt electrolysis: the dried anhydrous sodium chloride and magnesium chloride were placed in a crucible, and two graphite sheets wound with 1mm molybdenum wire were wound with conductive wire and suspended on the crucible, respectively, as pre-electrolysis electrodes. Argon is introduced, the gas flow rate is 2L/min, the temperature is raised to 900 ℃ at the heating rate of 5 ℃/min, and after half an hour of heat preservation, two graphite sheets are placed. A constant voltage of 2.5V was applied between the two graphite sheets for pre-electrolysis for 1.5 hours. And (3) after the pre-electrolysis is finished, lifting the pre-electrolysis electrode from molten salt to be suspended, continuously heating the crucible to 1000 ℃, and putting the composite material powder prepared in the step (3). The distance between the electrodes was 5cm, a constant voltage of 2.5V was applied between the electrodes, and electrolysis was started for 7 hours. After the electrolysis is completed, taking out the electrolyzed sample, and performing ultrasonic washing for 5 times by using ultrapure water to remove the fused salt attached to the surface of the sample. The washed sample was dried at 60℃for 18 hours. And obtaining the small-size high-dispersion silicon-oxygen-carbon composite material.
The electrochemical properties of the assembled button cell were evaluated under the same test conditions as in example 1, and are recorded in table 1.
Example 9
The embodiment provides a preparation method of a novel composite material for a secondary lithium ion battery, which comprises the following steps:
step 1: dissolving phenolic resin in alcohol by using vegetable oil as a first solution phase, adding fatty acid sorbitan and m-xylylenediamine to prepare a second solution phase, using oil containing stearic acid as a third solution phase, slowly adding the first solution phase into the second solution phase, stirring for 1 hour, adding the stirred mixed solution into the third solution phase, stirring to obtain a required emulsion, continuously stirring, heating to 80 ℃, preserving heat for 5 hours until the resin is solidified, and centrifuging, cleaning and drying after hollow resin microspheres are formed;
step 2: carrying out pore-forming treatment on the cleaned hollow resin microspheres, wherein an air source is a combination of two of carbon dioxide and water vapor, the pore-forming temperature is 1000 ℃ at 20L/min, and the duration is 2 hours, so as to obtain a 9.3um porous hard carbon matrix;
step 3: taking nitrogen as a shielding gas, the flow rate is 5L/min, taking the porous hard carbon matrix obtained in the step 2 as a substrate, taking tetramethoxysilane, triethoxysilane and tetraethoxysilane containing silicon oxygen as silicon sources, and adding compounds containing C, N, B and P elements such as ethylene, propane, urea, melamine, tripropyl borate, boron tribromide, phosphine and phosphorus oxychloride into a reaction container in a gas form, and performing vapor deposition to obtain composite material powder; wherein, the gas flow rates of tetramethoxysilane, triethoxysilane and tetraethoxysilane are all 2.7L/min, and the gas flow rates of ethylene, propane, urea, melamine, tripropyl borate, boron tribromide, phosphine and phosphorus oxychloride gaseous compounds are all 1L/min. The temperature of vapor deposition was 1400℃and the time of vapor deposition was 1.25 hours.
Step 4: molten salt electrolysis: the dried anhydrous sodium chloride and potassium chloride are placed in a crucible, and two graphite sheets wound by 0.9mm molybdenum wires are respectively wound by conductive wires and suspended above the crucible to serve as pre-electrolysis electrodes. Argon is introduced, the gas flow rate is 2L/min, the temperature is raised to 800 ℃ at the heating rate of 5 ℃/min, and after half an hour of heat preservation, two graphite sheets are placed. A constant voltage of 2.8V was applied between the two graphite sheets for pre-electrolysis for 1 hour. And (3) after the pre-electrolysis is finished, lifting the pre-electrolysis electrode from molten salt to be suspended, continuously heating the crucible to 900 ℃, and putting the composite material powder prepared in the step (3). The distance between the electrodes was 6cm, a constant voltage of 2.8V was applied between the electrodes, and electrolysis was started for 6 hours. After the electrolysis is completed, taking out the electrolyzed sample, and performing ultrasonic washing for 6 times by using ultrapure water to remove the fused salt attached to the surface of the sample. The washed sample was dried at 75℃for 18 hours. And obtaining the small-size high-dispersion silicon-oxygen-carbon composite material.
The electrochemical properties of the assembled button cell were evaluated under the same test conditions as in example 1, and are recorded in table 1.
Example 10
The embodiment provides a preparation method of a novel composite material for a secondary lithium ion battery, which comprises the following steps:
step 1: dissolving phenolic resin in alcohol by using vegetable oil as a first solution phase, adding alkyl glucoside and ethylenediamine to prepare a second solution phase, using oil containing stearic acid as a third solution phase, slowly adding the first solution phase into the second solution phase, stirring for 1 hour, adding the stirred mixed solution into the third solution phase, stirring to obtain a required emulsion, continuously stirring, heating to 130 ℃, preserving heat for 10 hours until the resin is solidified, and centrifuging, cleaning and drying after hollow resin microspheres are formed;
step 2: performing pore-forming treatment on the cleaned hollow resin microspheres, wherein an air source is oxygen, the pore-forming temperature is 800 ℃ and the duration is 6 hours, and a 16.2um porous hard carbon matrix is obtained;
step 3: taking argon as a shielding gas, the flow rate is 5L/min, taking the porous hard carbon matrix obtained in the step 2 as a substrate, taking trimethoxysilane, triethoxysilane and tetraethoxysilane containing silicon oxygen as silicon sources, and introducing acetylene, propane, ammonia, hydrazine, tripropyl borate, boron tribromide, phosphine and phosphorus oxychloride containing C, N, B and P elements into a reaction container in a gas form for vapor deposition to obtain composite material powder; wherein, the gas flow rates of trimethoxysilane, triethoxysilane and tetraethoxysilane are all 3.3L/min, and the gas flow rates of acetylene, propane, ammonia, hydrazine, tripropyl borate, boron tribromide, phosphine and phosphorus oxychloride gaseous compounds are all 1.3L/min. The temperature of vapor deposition was 1500 ℃, and the time of vapor deposition was 1 hour.
Step 4: molten salt electrolysis: the dried anhydrous calcium chloride, sodium chloride and potassium chloride were placed in a crucible, and two graphite sheets wound with 1mm molybdenum wire were wound with conductive wires and suspended on the crucible, respectively, as pre-electrolysis electrodes. Argon is introduced, the gas flow rate is 2L/min, the temperature is increased by 900 ℃ at the heating rate of 10 ℃/min, and after half an hour of heat preservation, two graphite sheets are placed. A constant voltage of 3.0V was applied between the two graphite sheets for pre-electrolysis for 2 hours. And (3) after the pre-electrolysis is finished, lifting the pre-electrolysis electrode from molten salt to be suspended, continuously heating the crucible to 1000 ℃, and putting the composite material powder prepared in the step (3). The distance between the electrodes was 6cm, a constant voltage of 3.0V was applied between the electrodes, and electrolysis was started for 5 hours. After the electrolysis is completed, taking out the electrolyzed sample, and performing ultrasonic washing for 8 times by using ultrapure water to remove the fused salt attached to the surface of the sample. The washed sample was dried at 80℃for 20 hours. And obtaining the small-size high-dispersion silicon-oxygen-carbon composite material.
The electrochemical properties of the assembled button cell were evaluated under the same test conditions as in example 1, and are recorded in table 1.
For better comparison, we prepared a comparative sample as follows.
Comparative example 1
The comparative example provides a preparation method of a silicon-carbon composite material in the prior art, which comprises the following steps:
(1) Adding silicon particles, carbon source precursor polyvinylpyrrolidone, graphite and antioxidant citric acid into an ethanol system, and sanding according to the mass ratio of 1:1:1:0.1 to obtain a dispersion liquid.
(2) And (3) carrying out spray drying on the dispersion liquid to obtain silicon carbon powder.
(3) And then carrying out gas phase cladding on the powder to finally obtain the silicon-carbon composite material.
The electrochemical properties of the assembled button cell were evaluated under the same test conditions as in example 1, and are recorded in table 1.
TABLE 1
As can be seen from comparison of comparative examples and examples, the novel composite material for the secondary lithium ion battery provided by the invention has higher specific capacity and first effect. Meanwhile, the first effect of the material can be further improved by regulating and controlling the deposition time, temperature, gas flow rate and molten salt electrolysis time. The invention scientifically sets the gas flow rate and the temperature in the preparation process, and avoids the phenomenon that silane is decomposed too fast due to the too high gas flow rate and the too high temperature and is directly deposited on the surface of the carbon matrix, thereby influencing the performance of the battery. Meanwhile, incomplete decomposition of silane caused by too low temperature is avoided, and the capacity of the battery is prevented from being influenced. The invention scientifically sets the molten salt electrolysis time in the preparation, and can reduce partial silica particles into nano silicon particles through further electrolysis, further increase the buffer space and simultaneously improve the specific capacity of the material by utilizing the silicon particles. The invention scientifically sets the molten salt electrolysis time in the preparation, and when the molten salt electrolysis time is shorter, the silicon oxide content is more, so that the charging specific capacity is smaller and the coulomb efficiency is lower. When the electrolysis time exceeds a certain time, the volume expansion of the silicon is more obvious due to the more content of the silicon, so that the coulomb efficiency of the silicon starts to be reduced, and when the volume effect of the silicon exceeds a reserved buffer space, the structure of the composite material is damaged, and the coulomb efficiency and the cycle stability are influenced.
The embodiment of the invention provides a novel composite material for a secondary lithium ion battery. The nanometer SiOx and one or more gaseous compounds containing C, N, B, P elements in the composite material are uniformly distributed in the pores of the spherical porous carbon through vapor deposition, and then the pores are reduced through molten salt electrolysis, so that the range of x in the SiOx is controlled. The porous structure can limit the size and uniform dispersion of the deposited nano SiOx, reduce the expansion effect and avoid the problem of electrical contact deterioration caused by SiOx pulverization; on the other hand, the large-size hole in the center provides a larger buffer space for the expansion of the SiOx material, so that the whole structure of the composite material is not easily damaged by the expansion, and the structure of the composite material can be kept unchanged under the condition that the SiOx fully performs lithium intercalation and deintercalation reaction, thereby improving the electrochemical performance of the battery. And, through multielement recombination, the specific capacity and the first cycle efficiency are further improved.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The novel composite material for the secondary lithium ion battery is characterized in that the composite material is as follows: inside is spherical porous hard carbon material with hollow holes, and inside the holes, products of decomposition and deposition of gas containing silicon oxide and one or more gaseous compounds containing C, N, B, P element are deposited, wherein the products comprise SiOx particles; x ranges from 0 to 1.5, and the value of x is controlled through molten salt electrolysis;
the porous hard carbon material is obtained by preparing a hard carbon matrix through double emulsion method solidification and then carbonizing.
2. The composite of claim 1, wherein the silica content of the composite is 1wt% to 70wt%.
3. The composite material of claim 1, wherein the composite material has a particle size in the range of 1um to 100um and an average pore size of pores in the range of 0.1nm to 10nm; the size of the hollow hole is 0.5-80 um.
4. The composite material according to claim 1, wherein the hard carbon matrix of the spherical porous hard carbon material is one or a combination of a plurality of phenolic resin, epoxy resin, furfural resin or polybutadiene resin;
the silicon-oxygen-containing gas is a siloxane compound, comprising: a combination of one or more of trimethoxysilane, tetramethoxysilane, triethoxysilane, and tetraethoxysilane;
The gaseous compound containing the C element comprises: one or more of acetylene, methane, propylene, ethylene, propane, and gaseous ethanol;
the gaseous compound containing N element comprises: one or more of nitrogen, ammonia, urea, and melamine;
the gaseous compound containing B element comprises: one or more of diborane, trimethyl borate, tripropyl borate, and boron tribromide;
the gaseous compound containing the P element comprises: phosphine and/or phosphorus oxychloride.
5. A method for preparing the novel composite material for a secondary lithium ion battery as claimed in any one of claims 1 to 4, characterized in that the preparation method comprises the following steps:
step one: adopting pure oil as a first solution phase; dissolving resin in a corresponding solvent, and adding a nonionic surfactant and a curing agent to prepare a second solution phase; taking oil containing surfactant as a third solution phase; slowly adding the first solution phase into the second solution phase, stirring for 0.5-1 hour, adding the stirred mixed solution into the third solution phase, stirring to obtain the required emulsion, continuously stirring while heating to 80-130 ℃, preserving heat for 1-24 hours until the resin is solidified, and forming hollow resin microspheres, and then centrifugally cleaning and drying;
Step two: introducing a pore-forming air source into the hollow resin microspheres at 600-1000 ℃ for 1-10 hours, and performing pore-forming treatment on the hollow resin microspheres to obtain a porous hard carbon matrix material; wherein the pore-forming gas source is one or the combination of two of carbon dioxide or water vapor; the air flow of the pore-forming air source is 2L/min-20L/min;
step three: vapor deposition is carried out on the porous hard carbon matrix material to obtain composite material powder; the gas source of the vapor deposition comprises a silicon oxide-containing gas and one or more gaseous compounds containing any element C, N, B, P;
step four: placing the dried salt into a crucible, and winding and suspending two graphite sheets on the crucible by conductive wires respectively to serve as pre-electrolysis electrodes; argon is introduced, the gas flow rate is 0.5-2L/min, the temperature is raised to 800-900 ℃ at the heating rate of 2-10 ℃/min, and two graphite sheets are placed after heat preservation for half an hour; applying constant voltage of 2.5-3.0V between two graphite sheets for pre-electrolysis for 1-2 hours; after the pre-electrolysis is finished, continuously heating to 900-1000 ℃, and lifting two graphite sheets from molten salt to be suspended; putting composite material powder, applying constant voltage of 2.2-3.0V between two electrodes of molten salt electrolysis, and starting electrolysis for 5-20 hours; and after the electrolysis is finished, taking out the electrolyzed sample, washing with water, placing the sample in a blast drying box, and drying at 50-80 ℃ for 8-20 hours to obtain the novel composite material for the secondary lithium ion battery.
6. The method according to claim 5, wherein the protective gas for vapor deposition is one or a combination of nitrogen and argon, the flow rate is 1-5L/min, the gas flow rate of the gaseous compound is 0.5-10L/min, and the flow rate of the silicon-oxygen-containing gas is 0.5-10L/min; the vapor deposition temperature is 500-1500 ℃, and the vapor deposition time is 1-20 hours.
7. The method according to claim 5, wherein,
the dried salt comprises: one or more of calcium chloride, magnesium chloride, sodium chloride and potassium chloride;
the resin comprises: one or a combination of a plurality of phenolic resin, epoxy resin, furfural resin or polybutadiene resin;
the solvent comprises: one or more of ethanol, acetone and toluene;
the oils include: a combination of one or more of vegetable oil, paraffin oil, mineral oil, etc.;
the nonionic surfactant includes: one or more of alkyl glucosides, fatty acid glycerides, fatty acid sorbitan, polysorbate;
the curing agent comprises: a combination of one or more of trimethylhexamethylenediamine, ethylenediamine, and m-xylylenediamine;
The surfactant comprises one or a combination of more of stearic acid, sodium dodecyl benzene sulfonate, lecithin and the like;
the silicon-oxygen-containing gas is a siloxane compound, comprising: a combination of one or more of trimethoxysilane, tetramethoxysilane, triethoxysilane, and tetraethoxysilane;
the gaseous compound containing the C element comprises: one or more of acetylene, methane, propylene, ethylene, propane, and gaseous ethanol;
the gaseous compound containing N element comprises: one or more of nitrogen, ammonia, urea, and melamine;
the gaseous compound containing B element comprises: one or more of diborane, trimethyl borate, tripropyl borate, and boron tribromide;
the gaseous compound containing the P element comprises: phosphine and/or phosphorus oxychloride.
8. The method of claim 5, wherein the first solution phase comprises, by mass fraction: second solution phase: third solution phase= (0, 30% ] (0, 50% ];
the second solution phase comprises the following components in percentage by mass: solvent: curing agent: nonionic surfactant= (0, 80% ] (0, 90% ]: [0, 30% ] (0, 20% ];
The third solution phase comprises oil in mass fraction: surfactant= (0, 90% ] (0, 30% ]).
9. A negative electrode material of a lithium ion battery, which is characterized in that the negative electrode material of the lithium ion battery comprises the novel composite material for a secondary lithium ion battery according to any one of the claims 1-4.
10. A lithium ion battery, characterized in that the lithium ion battery comprises the novel composite material for a secondary lithium ion battery according to any one of the above claims 1-4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111584164.XA CN116344787A (en) | 2021-12-22 | 2021-12-22 | Novel composite material for secondary lithium ion battery, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111584164.XA CN116344787A (en) | 2021-12-22 | 2021-12-22 | Novel composite material for secondary lithium ion battery, preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116344787A true CN116344787A (en) | 2023-06-27 |
Family
ID=86891689
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111584164.XA Pending CN116344787A (en) | 2021-12-22 | 2021-12-22 | Novel composite material for secondary lithium ion battery, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116344787A (en) |
-
2021
- 2021-12-22 CN CN202111584164.XA patent/CN116344787A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111326723B (en) | Silicon-carbon composite negative electrode material for lithium ion battery and preparation method thereof | |
| US11929484B2 (en) | Compound, preparation method therefore, and use in lithium ion secondary battery | |
| CN106848199B (en) | Nano-silicon/porous carbon composite anode material of lithium ion battery and preparation method and application thereof | |
| EP3890070A1 (en) | Silicon-oxygen composite negative electrode material and method for preparation thereof and lithium-ion battery | |
| CN102522534B (en) | Silicon-carbon composite material with high specific capacity, preparation method of silicon-carbon composite material, lithium ion battery anode material and lithium ion battery | |
| CN111710845A (en) | Silica composite negative electrode material, preparation method thereof and lithium ion battery | |
| CN111477849B (en) | Preparation method of porous Si/SiC/C material and negative electrode material | |
| CN103311522A (en) | Silicon/carbon composite microsphere negative electrode material as well as preparation method and application for same | |
| CN108281634A (en) | A kind of method and its application of graphene coated graphite negative material of lithium ion battery | |
| CN108923037B (en) | Silicon-rich SiOx-C material and preparation method and application thereof | |
| CN111048764A (en) | Silicon-carbon composite material and preparation method and application thereof | |
| CN113764642A (en) | Lithium-silicon oxide-containing composite negative electrode material, preparation method thereof and lithium ion battery | |
| CN112349899A (en) | Silicon-based composite negative electrode material, preparation method thereof and lithium ion battery | |
| CN102983317A (en) | Silicon-based composite material and preparation method thereof, silicon-carbon composite material and lithium ion battery | |
| WO2023115860A1 (en) | Composite material for secondary lithium-ion battery, and preparation method therefor and use thereof | |
| CN109659486A (en) | Preparation method, cathode and the lithium ion battery of negative electrode of lithium ion battery | |
| CN115360355B (en) | Three-dimensional net-shaped structure composite material for lithium battery and preparation method and application thereof | |
| CN111403708A (en) | Lithium ion battery silicon monoxide composite negative electrode material and preparation method thereof, and lithium ion battery | |
| CN110323440A (en) | A kind of preparation method of graphene/carbon-silicon nano composite anode material | |
| CN118398780A (en) | Silicon-oxygen negative electrode material, preparation method thereof and secondary battery | |
| CN116706013A (en) | Composite negative electrode material, preparation method thereof and lithium ion battery | |
| CN110890540A (en) | Fluorine-containing silicon monoxide negative electrode material and preparation method and application thereof | |
| CN114784253B (en) | Silicon-carbon oxide composite negative electrode material for secondary battery, preparation and application | |
| CN115566169A (en) | Silica composite material, negative pole piece, lithium ion battery and preparation method thereof | |
| CN111384379A (en) | Graphene-coated porous silicon composite material, battery, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |