CN116995220A - 一种硅碳负极材料及其制备和应用 - Google Patents
一种硅碳负极材料及其制备和应用 Download PDFInfo
- Publication number
- CN116995220A CN116995220A CN202311251928.2A CN202311251928A CN116995220A CN 116995220 A CN116995220 A CN 116995220A CN 202311251928 A CN202311251928 A CN 202311251928A CN 116995220 A CN116995220 A CN 116995220A
- Authority
- CN
- China
- Prior art keywords
- silicon
- carbon
- negative electrode
- lithium
- boric acid
- 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.)
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Links
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000007773 negative electrode material Substances 0.000 title claims description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 95
- 239000010405 anode material Substances 0.000 claims abstract description 60
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 56
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 47
- 239000010703 silicon Substances 0.000 claims abstract description 47
- 239000002245 particle Substances 0.000 claims abstract description 46
- -1 boric acid compound Chemical class 0.000 claims abstract description 40
- 238000010438 heat treatment Methods 0.000 claims abstract description 37
- 239000007789 gas Substances 0.000 claims abstract description 35
- 229920000642 polymer Polymers 0.000 claims abstract description 32
- 239000004327 boric acid Substances 0.000 claims abstract description 30
- 239000011159 matrix material Substances 0.000 claims abstract description 30
- 238000000151 deposition Methods 0.000 claims abstract description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000010000 carbonizing Methods 0.000 claims abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 46
- 229910002804 graphite Inorganic materials 0.000 claims description 22
- 239000010439 graphite Substances 0.000 claims description 22
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 16
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 229910021538 borax Inorganic materials 0.000 claims description 14
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 14
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 11
- 238000004132 cross linking Methods 0.000 claims description 11
- 238000011065 in-situ storage Methods 0.000 claims description 11
- 239000005011 phenolic resin Substances 0.000 claims description 11
- 229920001568 phenolic resin Polymers 0.000 claims description 11
- 229920006037 cross link polymer Polymers 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 8
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000391 magnesium silicate Substances 0.000 claims description 4
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 4
- 235000019792 magnesium silicate Nutrition 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 239000012756 surface treatment agent Substances 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 claims description 2
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 claims description 2
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- NEXSMEBSBIABKL-UHFFFAOYSA-N hexamethyldisilane Chemical compound C[Si](C)(C)[Si](C)(C)C NEXSMEBSBIABKL-UHFFFAOYSA-N 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- HZRMTWQRDMYLNW-UHFFFAOYSA-N lithium metaborate Chemical compound [Li+].[O-]B=O HZRMTWQRDMYLNW-UHFFFAOYSA-N 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- LOCZQLKNTOXJDV-UHFFFAOYSA-N magnesium;oxido(oxo)borane Chemical compound [Mg+2].[O-]B=O.[O-]B=O LOCZQLKNTOXJDV-UHFFFAOYSA-N 0.000 claims description 2
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000009719 polyimide resin Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- JVUYWILPYBCNNG-UHFFFAOYSA-N potassium;oxido(oxo)borane Chemical compound [K+].[O-]B=O JVUYWILPYBCNNG-UHFFFAOYSA-N 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 239000005049 silicon tetrachloride Substances 0.000 claims description 2
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 claims description 2
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005052 trichlorosilane Substances 0.000 claims description 2
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 claims description 2
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 claims description 2
- VEDJZFSRVVQBIL-UHFFFAOYSA-N trisilane Chemical compound [SiH3][SiH2][SiH3] VEDJZFSRVVQBIL-UHFFFAOYSA-N 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 56
- 229910052757 nitrogen Inorganic materials 0.000 description 28
- 239000000243 solution Substances 0.000 description 21
- 230000008021 deposition Effects 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 238000003763 carbonization Methods 0.000 description 10
- 238000000498 ball milling Methods 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000011889 copper foil Substances 0.000 description 8
- 238000012216 screening Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 125000005619 boric acid group Chemical group 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000004804 winding Methods 0.000 description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
- 239000004020 conductor Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 239000006256 anode slurry Substances 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 229910052743 krypton Inorganic materials 0.000 description 3
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229910052754 neon Inorganic materials 0.000 description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000011115 styrene butadiene Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002109 single walled nanotube Substances 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- YWJVFBOUPMWANA-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YWJVFBOUPMWANA-UHFFFAOYSA-H 0.000 description 1
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- JVZGJLAPJLXQKT-UHFFFAOYSA-N lithium iron(2+) manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Fe+2].[Mn+2].[Li+].[Ni+2] JVZGJLAPJLXQKT-UHFFFAOYSA-N 0.000 description 1
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000009702 powder compression Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
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- 229910001415 sodium ion Inorganic materials 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
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Abstract
本发明属于电池技术领域,具体涉及一种硅碳负极材料及其制备和应用。所述硅碳负极材料的制备方法,包括以下步骤:在非活性气氛下,对硼酸化合物交联的聚合物进行碳化处理,得到一次碳颗粒;在所述一次碳颗粒的表面沉积硅,得到沉积硅碳基体;将所述沉积硅碳基体与表面处理剂、分散剂混合后,在非活性气体与氧气的混合气氛下,加热处理,得到所述硅碳负极材料。本发明通过内部碳结构来增强硅碳负极材料的强度;引入含硼酸基团,提高了锂离子在碳结构中的扩散动力学;同时通过微氧化结构表面硅氧层以及增加表面处理剂,增强硅碳负极材料的强度。
Description
技术领域
本发明属于电池技术领域,具体涉及一种硅碳负极材料及其制备和应用。
背景技术
锂离子电池(LIB)因其在能量密度、功率密度和循环寿命等方面的优势,已成为主要的化学电源。在负极材料方面,硅负极材料被认为是下一代锂离子电池负极的最具潜力的替代材料。其具有传统石墨负极材料近10倍的理论比容量(4200mAh/g);同时硅元素原料来源很广泛,非常适合大规模的生产和应用。
沉积型硅碳负极材料是一种极具发展前景的锂离子电池硅负极材料,纳米尺度的硅团簇沉积分散在碳材料中,可提供较高的可逆容量(>1500mAh/g),且在首次循环过程中,硅基体部分会原位形成锂硅并被碳材料的多孔碳结构包围,起到缓冲体积膨胀和隔绝纳米硅团簇与电解液的直接接触的双重作用,降低了锂化时的体积膨胀和电解液消耗过大的负面作用,提高了材料的电性能。但由于多孔碳结构内部孔隙较多,碳结构强度较小,导致硅碳负极材料容易被压碎,因此负极电极上的材料容易在压片后开裂,导致负极电极的电性能下降。
因此,仍然需要探索有效的方法来实现沉积型硅碳负极材料结构强度,提高压片抗开裂、避免粉碎。
发明内容
本发明旨在解决上述问题,提供了一种硅碳负极材料及其制备和应用,能够有效提高材料结构强度,从而避免压片开裂、粉碎。
按照本发明的技术方案,所述硅碳负极材料的制备方法,包括以下步骤,
S1:在非活性气氛下,对硼酸化合物交联的聚合物进行碳化处理,得到一次碳颗粒;
所述硼酸化合物交联的聚合物由聚合物与硼酸化合物溶液加热交联得到,所述硼酸化合物溶液的溶剂中包含醇类和/或醇胺类化合物;
S2:在所述一次碳颗粒的表面沉积硅,得到沉积硅碳基体;
S3:将所述沉积硅碳基体与表面处理剂、分散剂混合后,在非活性气体与氧气的混合气氛下,于300~800℃加热处理,得到所述硅碳负极材料;
所述表面处理剂选自锂盐、镁盐和铝盐中的一种或多种。
进一步的,所述非活性气氛选自氮气、氦气、氖气、氩气、氪气和氙气等中的一种或多种。
进一步的,所述聚合物选自聚乙二醇、聚乙烯醇树脂、聚酰亚胺树脂、酚醛树脂和环氧树脂中的一种或多种;
所述硼酸化合物选自多硼酸锂、多硼酸、多硼酸钾、多硼酸酯、多硼酸钠、多硼酸镁、多硼酸铝、硼酸锂、硼酸、硼酸钾、硼酸酯、硼酸钠、硼酸镁、硼酸铝、偏硼酸锂、偏硼酸、偏硼酸钾、偏硼酸酯、偏硼酸钠、偏硼酸镁和偏硼酸铝中的一种或多种。
进一步的,所述聚合物和硼酸化合物的质量比为1:0.05~1.2。
进一步的,加热交联的温度为40~95℃,时间为1~4h。
具体的,所述硼酸化合物交联的聚合物的制备方法如下:向聚合物中加入硼酸化合物溶液,在40~95℃下交联1~4h,得到硼酸化合物交联的聚合物。
进一步的,所述硼酸化合物溶液中硼酸化合物的浓度为0.2~20wt%;所述硼酸化合物溶液中的溶剂为醇类和/或醇胺类化合物与水的混合溶液,溶剂中,醇类和醇胺类化合物的浓度之和可以为30-60wt%。
具体的,所述醇类化合物可以为酒精、丙三醇、甲醇等中的一种或多种,醇胺类化合物可以为三乙醇胺。
进一步的,所述步骤S1中,碳化处理的温度为600~1200℃,时间为1~5h,升温速率为2~20℃/min;碳化处理后还包括降温、破碎、筛分的步骤。
进一步的,所述步骤S2的具体操作为:在300~980℃下,向所述一次碳颗粒中通入气态硅源与非活性气体的混合气体,沉积硅20min~5h,得到沉积硅碳基体。
进一步的,所述步骤S2中,沉积硅时,反应容器内的压力≤2Kpa。
进一步的,所述气态硅源选自甲硅烷、乙硅烷、丙硅烷、二甲基硅烷、六甲基二硅烷、二氯二氢硅、三氯氢硅、四氯化硅和四氟化硅中的一种或多种(部分液态硅源加热后成气态硅源);所述非活性气体选自氮气、氦气、氖气、氩气、氪气和氙气等中的一种或多种;
通入所述气态硅源与所述非活性气体的气流比为0.1~1:0.005~1。
进一步的,所述表面处理剂选自硅酸锂、硅酸镁、硅酸铝、碳酸锂、氢氧化锂、氢氧化镁、铝酸锂、氯化锂和草酸锂中的一种或多种;
所述分散剂选自甲醇、乙醇、异丙醇、正丙醇、正丁醇、异丁醇和丙二醇中的一种或多种。
进一步的,所述步骤S3中,沉积硅碳基体、表面处理剂和分散剂的质量比为1:0.001~0.08:0.025~0.8。
进一步的,所述步骤S3中,加热处理前还包括球磨的步骤,球磨时间为20min~150min。
本发明的第二方面提供了上述制备方法制得的硅碳负极材料。
进一步的,所述硅碳负极材料的颗粒大小为2~55μm,其包括内部的多孔碳结构以及沉积在所述多孔碳结构表面的硅层,所述硅层的表面微氧化形成原位的硅氧。
进一步的,所述硅碳负极材料满足以下条件:
包括碳、硅、氧、硼元素;
碳含量在28~80%;
比表面积在0.75~16m2/g;
孔隙率1.2~32%;
距离0.02~1.5μm的表面区域存在硅氧(SiOx,0<x≤2)成分,硅氧成分包裹内部的硅碳成分(硅层和多孔碳结构);
距离0.02~1.5μm的表面区域存在硅酸镁和/或锂和/或铝成分,硅酸镁和/或锂和/或铝成分包裹内部的硅碳成分;
距离硅碳负极材料内部中心的0~R/4区域的C/O的元素原子比例>距离硅碳负极材料内部中心的3R/4~R区域的C/O的元素原子比例,R为硅碳负极材料内部中心距离边缘的最小的长度。
本发明的第三方面提供了一种负极片,包括负极集流体和负极活性物质层,所述负极活性物质层包含负极活性物质,所述负极活性物包括石墨负极材料和上述硅碳负极材料。
进一步的,所述石墨负极材料为人造石墨、天然石墨的至少一种。
进一步的,所述负极活性物中,石墨负极材料的占比为35~98%。
本发明的第四方面提供了一种二次用电装置,包括上述负极片。
进一步的,所述二次用电装置为锂离子电池、钠离子电池或超级电容器。
本发明的技术方案相比现有技术具有以下优点:本发明通过构建多级结构来提高(沉积硅)硅碳负极材料的强度,其中,
(1)通过内部碳结构来增强硅碳负极材料的强度:硼酸基团与聚合物以及溶剂的羟基基团形成稳定的硼酸酯类化合物,增加了硼酸基团与聚合物的融合,硼酸酯类化合物在聚合物内形成硼酸桥连结构,聚合物碳化后,增加一次颗粒内部碳结构稳定性和强度;此外含硼酸基团的引入,增加了P-O、P-C键,P-O、P-C键,可以在硅颗粒与碳结构之间建立高导电性和持久的连接,提高了锂离子在碳结构中的扩散动力学;
(2)通过微氧化结构的表面硅氧层以及增加表面处理剂,增强硅碳负极材料的强度:一方面表面微氧化使得硅碳基体表面硅形成原位的硅氧层,硅氧层具有电化学惰性,能有效缓冲因锂离子嵌入导致的硅体积膨胀而开裂;另一方面通过向沉积硅碳基体加入表面处理剂,提高沉积硅碳基体表面硅酸锂(镁、铝),可以稳定沉积硅碳基体表面的机械结构。
附图说明
图1为实施例3所得硅碳负极材料的EDS电子图像图。
图2为实施例3所得硅碳负极材料的EDS扫描硅含量分布图。
图3为实施例3所得硅碳负极材料的EDS扫描碳含量分布图。
图4为实施例3所得硅碳负极材料的EDS扫描硼含量分布图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步说明,以使本领域的技术人员可以更好地理解本发明并能予以实施,但所举实施例不作为对本发明的限定。
本发明提供了一种硅碳负极材料的制备方法,包括以下步骤,
(1)一次碳颗粒:
向聚合物加入其质量的0.05~1.2的硼酸化合物溶液(含量在0.2~20wt%硼酸化合物溶于45wt%三乙醇胺的丙三醇溶液中)、搅拌,在40~95℃下交联1~4h,得到硼酸化合物交联的聚合物;
硼酸化合物交联的聚合物送至加热炉中,加热炉中通入非活性气体(氮气、氦气、氖气、氩气、氪气、氙气等气体),升温速率在2~20℃/min至温度为600~1200℃,碳化停留1~5h,降温、破碎、筛分,得到多孔结构的一次碳颗粒;
(2)一次碳颗粒硅沉积:
一次碳颗粒送至流化床中,流化床的温度控制在300~980℃,通入非活性气体排除空气,流化床内部沉积腔压力≤2Kpa,通入气态硅源与非活性气体的混合气体(气流比为0.1~1:0.005~1)进行沉积硅20min~5h得到沉积硅碳基体;
(3)沉积硅碳基体表面包覆:
沉积硅碳基体、表面处理剂、分散剂按质量比1:0.001~0.08:0.025~0.8加入球磨机中,球磨20min~150min;再送至300~800℃的加热炉中,通入非活性气体与氧气的混合气体(非活性气体、氧气体积比=10:0.002~0.1),进行处理1~8h(致使沉积硅碳基体表面微氧化形成原位的硅氧),至颗粒大小2~55μm,得到硅碳负极材料。
所得硅碳负极材料可以用于制备负极电极/极片,具体如下:
硅碳负极材料+石墨负极材料、导电材料、粘结物质置于搅拌机的槽中,搅拌15~90min,加水至槽中硅碳负极材料+石墨负极材料的含量在40~65%为止,继续搅拌60~300min,调黏度在1.0~6Pa.s之间,得到负极浆料,将负极浆料涂覆在负极集流体上,70~115℃下干燥除去水分、压片、分切,即为负极电极。
具体的,石墨负极材料占比为硅硅负极材料、石墨负极材料总和的35~98%;硅碳负极材料+石墨负极材料、导电材料、粘结物质按照质量百分比分别为85~99.6wt%、0.2~7wt%、0.2~8.0wt%;
压片后的负极电极压实密度在0.80~1.80g/cm3,厚度在35~500μm,负极电极压上的硅碳负极材料+石墨负极材料单位面积重量为80~300g/m2。
优选的,导电材料为导电炭黑、乙炔黑、石墨、石墨烯、碳微米线、碳纳米线、碳微米管、碳纳米管中的至少一种;
粘结物质为聚丙烯腈、聚偏氟乙烯、聚乙烯醇、羧甲基纤维素、羧甲基纤维素锂、羧甲基纤维素锂、聚甲基丙烯酰、聚丙烯酸、聚丙烯酸锂、聚丙烯酸锂、羧甲基纤维素、苯乙烯-丁二烯基橡胶、氟基橡胶、乙烯丙烯二烯等;
负极集流体为铜箔、多孔铜箔、泡沫镍/铜箔、镀锌铜箔、镀镍铜箔、涂炭铜箔、镍箔、钛箔中的一种。
所得极片可以用于二次用电装置,如电池,具体如下:
将正极电极、隔离膜、负极电极依次叠卷绕、贴胶固定、卷绕得到裸电芯、超声焊接极耳,裸电芯放入铝(钢/铁/镍)壳、90~120℃下干燥除去水分、注入电解液、封装,即得二次用电装置。
优选的,正极片中的正极活性物质为镍锰酸锂、镍钴锰酸锂、镍钴铝酸锂、磷酸钒锂、钴酸锂、磷酸铁锰锂、镍铁锰酸锂中的至少一种;
隔离膜为聚乙烯、聚丙烯、聚磺酰、聚丙烯腈、聚乙烯醇、聚芳醚砜、聚偏氟乙烯、聚丙二酸中的至少一种。
实施例1:
1、硅碳负极材料制备:
(1)一次碳颗粒:向聚合物酚醛树脂中加入其质量的0.01的硼酸锂溶液(含量在15wt%硼酸锂溶于45wt%三乙醇胺溶液中)、搅拌,在60℃下交联2h,得到硼酸锂交联的聚合物;硼酸锂交联的聚合物送至加热炉中,加热炉中通入氮气,升温速率在3℃/min至温度为1100℃,碳化停留4h、降温、破碎、筛分,所得产物为一次碳颗粒(内部为多孔碳结构);
(2)一次碳颗粒硅沉积:一次碳颗粒送至流化床中,流化床的温度控制在580℃,通入氮气排除空气,流化床内部沉积腔压力≤200pa,以15L/min的流速通入甲硅烷和氮气的混合气体(气流比为0.5:0.15),沉积硅45min,得到沉积硅碳基体;
(3)沉积硅碳基体表面包覆:沉积硅碳基体、铝酸锂、正丙醇(质量比1:0.02:0.2)加入球磨机中、球磨100min,再送至500℃的加热炉中,通入混合气体(氮气、氧气体积比=10:0.005),进行处理2h(使得使沉积硅碳基体表面微氧化形成原位的硅氧),至颗粒大小2~55μm,得到硅碳负极材料。
2、硅碳负极材料应用:
(1)混合:硅碳负极材料+石墨负极材料(10wt%的硅碳负极材料+90wt%的石墨负极材料)、导电材料(70wt%的导电炭黑、30wt%单壁碳纳米管组成)、粘结物质(25wt%的羧甲基纤维素钠、25wt%的苯乙烯-丁二烯基橡胶、50wt%的聚丙烯酸组成)按照质量百分比分为95wt%、1.8wt%、3.2wt%置于搅拌机的槽中,搅拌60min、加水至槽中硅碳负极材料+石墨负极材料的含量固含量在55%,继续搅拌140min,调黏度在4Pa.s,得到负极浆料,将负极浆料涂覆在负极集流体涂炭铜箔正反面上,90~95℃下干燥除去水分、压片、分切,即为负极电极(压片后的负极电极压实密度在1.61g/cm3,厚度在129μm,负极电极压上的硅碳负极材料+石墨负极材料单位面积重量为95g/m2)。
(2)制电池:将正极电极(将镍钴锰酸锂LiNi0.81Co0.06Mn0.13涂覆在涂炭铝箔正反面上,厚度为128μm,面密度为0.019g/cm2)、9μm聚乙烯隔离膜、负极电极依次叠卷绕、贴胶固定、卷绕得到裸电芯、超声焊接极耳,裸电芯放入铝壳、100℃下干燥除去水分、注入电解液于铝壳、封装,即得二次用电装置。
实施例2:
与实施例1区别在于硅碳负极材料制备,具体如下:
(1)一次碳颗粒:向聚合物酚醛树脂加入其质量的0.015的硼酸锂溶液(含量在15wt%硼酸锂溶于45wt%三乙醇胺溶液中)、搅拌,60℃下交联2h,得到硼酸锂交联的聚合物;硼酸锂交联的聚合物送至加热炉中,加热炉中通入氮气,升温速率在3℃/min至温度为1100℃,碳化停留4h、降温、破碎、筛分,所得产物为一次碳颗粒(内部为多孔碳结构);
(2)一次碳颗粒硅沉积:一次碳颗粒送至流化床中,流化床的温度控制在580℃,通入氮气排除空气,流化床内部沉积腔压力≤200pa,以15L/min的流速通入甲硅烷和氮气的混合气体(气流比为0.5:0.15),进行沉积硅45min得到沉积硅碳基体;
(3)沉积硅碳基体表面包覆:沉积硅碳基体、铝酸锂、正丙醇(质量比1:0.03:0.2)加入球磨机中、球磨100min,再送至500℃的加热炉中,通入混合气体(氮气、氧气体积比=10:0.005),进行处理2h(使得使沉积硅碳基体表面微氧化形成原位的硅氧),至颗粒大小2~55μm,得到硅碳负极材料。
实施例3:
与实施例1区别在于硅碳负极材料制备,具体如下:
(1)一次碳颗粒:向聚合物酚醛树脂加入其质量的0.02的硼酸锂溶液(含量在15wt%硼酸锂溶于45wt%三乙醇胺溶液中)、搅拌,在60℃下交联2h,得到硼酸锂交联的聚合物;硼酸锂交联的聚合物送至加热炉中,加热炉中通入氮气,升温速率在3℃/min至温度为1100℃,碳化停留4h、降温、破碎、筛分,所得产物为一次碳颗粒(内部为多孔碳结构);
(2)一次碳颗粒硅沉积:一次碳颗粒送至流化床中,流化床的温度控制在580℃,通入氮气排除空气,流化床内部沉积腔压力≤200pa,以15L/min的流速通入甲硅烷和氮气的混合气体(气流比为0.5:0.15),进行沉积硅20min~5h得到沉积硅碳基体;
(3)沉积硅碳基体表面包覆:沉积硅碳基体、铝酸锂、正丙醇(质量比1:0.03:0.2)加入球磨机中、球磨90min,再送至500℃的加热炉中,通入混合气体(氮气、氧气体积比=10:0.005),进行处理2h(使得使沉积硅碳基体表面微氧化形成原位的硅氧),至颗粒大小2~55μm,得到硅碳负极材料。
所得硅碳负极材料的EDS(X射线能谱仪)电子图像如图1所示,EDS扫描硅、碳、硼含量分布图分别如图2-4所示,可以看出硅、碳、硼均匀分布于硅碳负极材料中。
实施例4:
1、硅碳负极材料制备:
(1)一次碳颗粒:向聚合物酚醛树脂加入其质量的0.01的硼酸钠溶液(含量在15wt%硼酸钠溶于45wt%三乙醇胺溶液中)、搅拌,在65℃下交联2h,得到硼酸钠交联的聚合物;硼酸钠交联的聚合物送至加热炉中,加热炉中通入氮气,升温速率在3℃/min至温度为1050℃,碳化停留4h、降温、破碎、筛分,所得产物为一次碳颗粒(内部为多孔碳结构);
(2)一次碳颗粒硅沉积:一次碳颗粒送至流化床中,流化床的温度控制在650℃,通入氮气排除空气,流化床内部沉积腔压力≤200pa,以12L/min的流速通入甲硅烷和氮气的混合气体(气流比为0.45:0.15),进行沉积硅35min得到沉积硅碳基体;
(3)沉积硅碳基体表面包覆:沉积硅碳基体、硅酸铝、正丙醇(质量比1:0.01:0.2)加入球磨机中、球磨90min,再送至550℃的加热炉中,通入混合气体(氮气、氧气体积比=10:0.008),进行处理2h(使得使沉积硅碳基体表面微氧化形成原位的硅氧),至颗粒大小2~55μm,得到硅碳负极材料。
2、硅碳负极材料应用:
(1)混合:硅碳负极材料+石墨负极材料(20wt%的硅碳负极材料+80wt%的石墨负极材料)、导电材料(70wt%的导电炭黑、30wt%单壁碳纳米管组成)、粘结物质(25wt%的羧甲基纤维素钠,25wt%的苯乙烯-丁二烯基橡胶,50wt%的聚丙烯酸组成)按照质量百分比分为95wt%、1.8wt%、3.2wt%置于搅拌机的槽中,搅拌60min、以加水至槽中硅碳负极材料+石墨负极材料的固含量在53%,继续搅拌120min,调黏度在4Pa.s,得到负极浆料,将负极浆料涂覆在负极集流体涂炭铜箔正反面上,90~95℃下干燥除去水分、压片、分切,即为负极电极(压片后的负极电极压实密度在1.60g/cm3,厚度在124μm,负极电极压上的硅碳负极材料+石墨负极材料单位面积重量为86g/m2)。
(2)制电池:将正极电极(将镍钴锰酸锂LiNi0.81Co0.06Mn0.13涂覆在涂炭铝箔正反面上,厚度为128μm,面密度为0.019g/cm2)、9μm聚乙烯隔离膜、负极电极依次叠卷绕、贴胶固定、卷绕得到裸电芯、超声焊接极耳,裸电芯放入铝壳、100℃下干燥除去水分、注入电解液于铝壳、封装,即得二次用电装置。
实施例5:
与实施例4区别在于硅碳负极材料制备,具体如下:
(1)一次碳颗粒:向聚合物酚醛树脂加入其质量的0.015的硼酸钠溶液(含量在15wt%硼酸钠溶于45wt%三乙醇胺溶液中)、搅拌,在65℃下交联2h,得到硼酸钠交联的聚合物;硼酸钠交联的聚合物送至加热炉中,加热炉中通入氮气,升温速率在3℃/min至温度为1050℃,碳化停留4h、降温、破碎、筛分,所得产物为一次碳颗粒(内部为多孔碳结构);
(2)一次碳颗粒硅沉积:一次碳颗粒送至流化床中,流化床的温度控制在650℃,通入氮气排除空气,流化床内部沉积腔压力≤200pa,以12L/min的流速通入甲硅烷和氮气的混合气体(气流比为0.45:0.15),进行沉积硅35min得到沉积硅碳基体;
(3)沉积硅碳基体表面包覆:沉积硅碳基体、硅酸铝、正丙醇(质量比1:0.02:0.2)加入球磨机中、球磨90min,再送至550℃的加热炉中,通入混合气体(氮气、氧气体积比=10:0.008),进行处理2h(使得使沉积硅碳基体表面微氧化形成原位的硅氧),至颗粒大小2~55μm,得到硅碳负极材料。
实施例6:
与实施例4区别在于硅碳负极材料制备,具体如下:
(1)一次碳颗粒:向聚合物酚醛树脂加入其质量的0.02的硼酸钠溶液(含量在15wt%硼酸钠溶于45wt%三乙醇胺溶液中)、搅拌,在65℃下交联2h,得到硼酸钠交联的聚合物;硼酸钠交联的聚合物送至加热炉中,加热炉中通入氮气,升温速率在3℃/min至温度为1050℃,碳化停留4h、降温、破碎、筛分,所得产物为一次碳颗粒(内部为多孔碳结构);
(2)一次碳颗粒硅沉积:一次碳颗粒送至流化床中,流化床的温度控制在650℃,通入氮气排除空气,流化床内部沉积腔压力≤200pa,以12L/min的流速通入甲硅烷和氮气的混合气体(气流比为0.45:0.15),进行沉积硅35min得到沉积硅碳基体;
(3)沉积硅碳基体表面包覆:沉积硅碳基体、铝酸锂、正丙醇(质量比1:0.03:0.2)加入球磨机中、球磨90min,再送至550℃的加热炉中,通入混合气体(氮气、氧气体积比=10:0.008),进行处理2h(使得使沉积硅碳基体表面微氧化形成原位的硅氧),至颗粒大小2~55μm,得到硅碳负极材料。
对比例1:
与实施例1区别在于:硅碳负极材料制备中,步骤(1)酚醛树脂没加硼酸锂溶液,与酚醛树脂进行交联。
对比例2:
与实施例1区别在于:硅碳负极材料制备中,步骤(2)球磨机中没加铝酸锂。
对比例3:
与实施例1区别在于:硅碳负极材料制备中,步骤(3)中仅通入氮气(没有混入氧气),没有进行沉积硅碳基体表面微氧化处理。
结果分析:
(1)粉末抗压性能测定:23℃下,用激光粒度仪测试各个实施例、对比例的硅碳负极材料的D10,再经过压力器55MPa压5min,测试各个实施例、对比例粉末的D10,记录压前后的D10,其结果如表1所示。
表1
压前D10/μm | 压后D10/μm | |
实施例1 | 3.14 | 2.89 |
实施例2 | 3.16 | 2.93 |
实施例3 | 3.15 | 2.87 |
实施例4 | 3.16 | 2.93 |
实施例5 | 3.19 | 2.95 |
实施例6 | 3.10 | 2.91 |
对比例1 | 3.13 | 2.82 |
对比例2 | 3.08 | 2.88 |
对比例3 | 3.18 | 2.89 |
结果显示:通过硼酸基团与聚合物的融合,硼酸酯类化合物在聚合物内形成硼酸桥连结构,聚合物碳化后,增加一次颗粒内部碳结构稳定性和强度,因此相对于实施例来说,对比例1中,酚醛树脂没加硼酸锂溶液,导致硅碳负极材料的结构强度降低,经过压力器55MPa压5min后,其D10更低,小颗粒更多。
(2)将各实施例、对比例的二次用电装置在高温化成、分容后,在25℃室温下进行起始2.8V、截止电压4.25V的0.5C充电/1C放电循环测试,记录100、600周时容量保持率,其结果如表2所示。
表2
100周容量保持率 | 600周容量保持率 | |
实施例1 | 93.7% | 85.5% |
实施例2 | 93.0% | 84.9% |
实施例3 | 92.9% | 85.8% |
实施例4 | 93.0% | 84.9% |
实施例5 | 92.0% | 85.7% |
实施例6 | 91.9% | 86.2% |
对比例1 | 91.1% | 84.0% |
对比例2 | 90.6% | 82.4% |
对比例3 | 91.7% | 81.5% |
结果显示:通过微氧化结构的表面硅氧层以及增加表面处理剂,有效缓冲因锂离子嵌入导致的硅体积膨胀而开裂、稳定沉积硅碳基体表面的机械结构,有助于提高材料的电性能。因此,实施例1~6的100周、600周容量保持率均不同程度优于对比例2、3的100周、600周容量保持率。
显然,上述实施例仅仅是为清楚地说明所作的举例,并非对实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引申出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (10)
1.一种硅碳负极材料的制备方法,其特征在于,包括以下步骤,
S1:在非活性气氛下,对硼酸化合物交联的聚合物进行碳化处理,得到一次碳颗粒;
所述硼酸化合物交联的聚合物由聚合物与硼酸化合物溶液加热交联得到,所述硼酸化合物溶液中的溶剂包含醇类和/或醇胺类化合物;
S2:在所述一次碳颗粒的表面沉积硅,得到沉积硅碳基体;
S3:将所述沉积硅碳基体与表面处理剂、分散剂混合后,在非活性气体与氧气的混合气氛下,于300~800℃加热处理,得到所述硅碳负极材料;
所述表面处理剂选自锂盐、镁盐和铝盐中的一种或多种。
2.如权利要求1所述的制备方法,其特征在于,所述聚合物选自聚乙二醇、聚乙烯醇树脂、聚酰亚胺树脂、酚醛树脂和环氧树脂中的一种或多种;
所述硼酸化合物选自多硼酸锂、多硼酸、多硼酸钾、多硼酸酯、多硼酸钠、多硼酸镁、多硼酸铝、硼酸锂、硼酸、硼酸钾、硼酸酯、硼酸钠、硼酸镁、硼酸铝、偏硼酸锂、偏硼酸、偏硼酸钾、偏硼酸酯、偏硼酸钠、偏硼酸镁和偏硼酸铝中的一种或多种。
3.如权利要求1或2所述的制备方法,其特征在于,所述聚合物和硼酸化合物的质量比为1:0.05~1.2。
4.如权利要求1所述的制备方法,其特征在于,所述步骤S2的具体操作为:在300~980℃下,向所述一次碳颗粒中通入气态硅源与非活性气体的混合气体,沉积硅20min~5h,得到沉积硅碳基体。
5.如权利要求4所述的制备方法,其特征在于,所述气态硅源选自甲硅烷、乙硅烷、丙硅烷、二甲基硅烷、六甲基二硅烷、二氯二氢硅、三氯氢硅、四氯化硅和四氟化硅中的一种或多种;
通入所述气态硅源与所述非活性气体的气流比为0.1~1:0.005~1。
6.如权利要求1所述的制备方法,其特征在于,所述表面处理剂选自氧化亚硅、硅酸锂、硅酸镁、硅酸铝、碳酸锂、氢氧化锂、氢氧化镁、铝酸锂、氯化锂和草酸锂中的一种或多种;
所述分散剂选自甲醇、乙醇、异丙醇、正丙醇、正丁醇、异丁醇和丙二醇中的一种或多种。
7.如权利要求1或6所述的制备方法,其特征在于,所述步骤S3中,沉积硅碳基体、表面处理剂和分散剂的质量比为1:0.001~0.08:0.025~0.8。
8.一种权利要求1-7中任一项所述的制备方法制得的硅碳负极材料,其特征在于,所述硅碳负极材料包括,内部的多孔碳结构以及沉积在所述多孔碳结构表面的硅层,所述硅层的表面微氧化形成原位的硅氧层。
9.一种负极片,包括负极集流体和负极活性物质层,所述负极活性物质层包含负极活性物质,其特征在于,所述负极活性物包括石墨负极材料和权利要求8所述的硅碳负极材料。
10.一种二次用电装置,其特征在于,包括权利要求9所述的负极片。
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