CN116960333A - Negative electrode material, preparation method and application thereof - Google Patents
Negative electrode material, preparation method and application thereof Download PDFInfo
- Publication number
- CN116960333A CN116960333A CN202310154456.2A CN202310154456A CN116960333A CN 116960333 A CN116960333 A CN 116960333A CN 202310154456 A CN202310154456 A CN 202310154456A CN 116960333 A CN116960333 A CN 116960333A
- Authority
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- China
- Prior art keywords
- silicon
- carbon
- anode material
- negative electrode
- mass
- Prior art date
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- Pending
Links
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000010703 silicon Substances 0.000 claims abstract description 178
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 178
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 175
- 239000010405 anode material Substances 0.000 claims description 159
- 239000003575 carbonaceous material Substances 0.000 claims description 109
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 33
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 31
- 229910052698 phosphorus Inorganic materials 0.000 claims description 31
- 239000011574 phosphorus Substances 0.000 claims description 31
- 239000011148 porous material Substances 0.000 claims description 29
- 229910001415 sodium ion Inorganic materials 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 25
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 17
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 17
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 12
- 229910052785 arsenic Inorganic materials 0.000 claims description 12
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 12
- 229910052796 boron Inorganic materials 0.000 claims description 12
- 239000011593 sulfur Substances 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 230000001681 protective effect Effects 0.000 claims description 11
- 229910052711 selenium Inorganic materials 0.000 claims description 11
- 239000011669 selenium Substances 0.000 claims description 11
- 230000002209 hydrophobic effect Effects 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 229910021385 hard carbon Inorganic materials 0.000 description 36
- 238000000034 method Methods 0.000 description 18
- 239000002245 particle Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 230000009286 beneficial effect Effects 0.000 description 10
- 229940091258 selenium supplement Drugs 0.000 description 10
- 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 7
- 238000009830 intercalation Methods 0.000 description 7
- 230000002687 intercalation Effects 0.000 description 7
- 239000011229 interlayer Substances 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 240000007594 Oryza sativa Species 0.000 description 6
- 235000007164 Oryza sativa Nutrition 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 235000009566 rice Nutrition 0.000 description 6
- 230000002411 adverse Effects 0.000 description 5
- 238000009831 deintercalation Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 244000060011 Cocos nucifera Species 0.000 description 4
- 235000013162 Cocos nucifera Nutrition 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 description 3
- 239000005539 carbonized material Substances 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 229910021384 soft carbon Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 description 2
- 241000609240 Ambelania acida Species 0.000 description 2
- 244000144725 Amygdalus communis Species 0.000 description 2
- 235000011437 Amygdalus communis Nutrition 0.000 description 2
- 235000017060 Arachis glabrata Nutrition 0.000 description 2
- 244000105624 Arachis hypogaea Species 0.000 description 2
- 235000010777 Arachis hypogaea Nutrition 0.000 description 2
- 235000018262 Arachis monticola Nutrition 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 235000014698 Brassica juncea var multisecta Nutrition 0.000 description 2
- 235000006008 Brassica napus var napus Nutrition 0.000 description 2
- 240000000385 Brassica napus var. napus Species 0.000 description 2
- 235000006618 Brassica rapa subsp oleifera Nutrition 0.000 description 2
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241001070941 Castanea Species 0.000 description 2
- 235000014036 Castanea Nutrition 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 240000007049 Juglans regia Species 0.000 description 2
- 235000009496 Juglans regia Nutrition 0.000 description 2
- CHQMXRZLCYKOFO-UHFFFAOYSA-H P(=O)([O-])([O-])F.[V+5].[Na+].P(=O)([O-])([O-])F.P(=O)([O-])([O-])F Chemical compound P(=O)([O-])([O-])F.[V+5].[Na+].P(=O)([O-])([O-])F.P(=O)([O-])([O-])F CHQMXRZLCYKOFO-UHFFFAOYSA-H 0.000 description 2
- 244000082204 Phyllostachys viridis Species 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- 240000006711 Pistacia vera Species 0.000 description 2
- 235000003447 Pistacia vera Nutrition 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 description 2
- 235000020224 almond Nutrition 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 2
- 239000010905 bagasse Substances 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000007833 carbon precursor Substances 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- -1 i.e. Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- 235000020232 peanut Nutrition 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 235000020233 pistachio Nutrition 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 description 2
- 235000011009 potassium phosphates Nutrition 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003346 selenoethers Chemical class 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 235000011008 sodium phosphates Nutrition 0.000 description 2
- 229960001471 sodium selenite Drugs 0.000 description 2
- 235000015921 sodium selenite Nutrition 0.000 description 2
- 239000011781 sodium selenite Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 235000019794 sodium silicate Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 235000020238 sunflower seed Nutrition 0.000 description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 2
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 235000020234 walnut Nutrition 0.000 description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052704 radon Inorganic materials 0.000 description 1
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The application provides a negative electrode material and a preparation method and application thereof. According to the negative electrode material provided by the application, the element A and the element silicon are synergistic, so that the stability, the multiplying power performance, the conductivity, the specific capacity, the first efficiency and the cycle performance of the negative electrode material are improved, and the electronic impedance rate of the negative electrode material is reduced.
Description
Technical Field
The application relates to the technical field of batteries, in particular to a negative electrode material and a preparation method and application thereof.
Background
Sodium ion batteries are one of the emerging secondary batteries. The sodium ion battery with the excellent performance, which is obtained by replacing lithium with sodium, can solve the problem of large-scale electricity storage application of lithium electricity, and has wide market prospect. The existing sodium ion battery generally uses hard carbon as a negative electrode material, wherein the hard carbon has a highly disordered structure, large interlayer spacing and more defects, so that sodium ions with larger radius can be conveniently embedded and extracted. However, the hard carbon has higher specific surface area, is easy to absorb moisture and oxygen, and has more side reactions, so that the first coulombic efficiency is lower; however, if the specific surface area of the hard carbon is directly reduced, the capacity of the hard carbon is reduced, so that the improvement of the overall performance of the sodium ion battery is limited.
Disclosure of Invention
The application provides a negative electrode material, a preparation method and application thereof, and aims to simultaneously improve the first effect and specific capacity of the negative electrode material.
In a first aspect, the present application provides a negative electrode material, the negative electrode material comprising a carbon-based material doped with an element a and a silicon element, the element a being a nonmetallic element, the silicon element being greater than the element a.
On one hand, the A element and the silicon element can increase the interlayer spacing of the carbon-based material, and when the anode material is applied to an ion battery, the carbon-based material with larger interlayer spacing is beneficial to the intercalation and deintercalation of sodium ions with larger volume, and is beneficial to the improvement of ion mobility, thereby being beneficial to the rapid charge/discharge process, and being beneficial to the improvement of the specific capacity of the anode material, particularly, the A element can also increase the active site of the anode material and improve the capacity of the anode material. Meanwhile, the silicon element can also play a supporting role on the carbon-based material, so that the collapse of the carbon-based material is prevented, and the stability of the anode material is improved.
On the other hand, the multiplying power performance and the conductivity of the anode material are improved by co-doping the element A and the element silicon, and the element silicon can be filled into the pores of the carbon-based material, so that the specific surface area and the electronic impedance of the anode material are further reduced, and the specific capacity, the first coulombic efficiency and the cycle performance are simultaneously improved.
On the other hand, the relative content of the element A and the silicon element is regulated and controlled in the application, namely, the content of the silicon element in the anode material is larger than that of the element A, and the element A and the silicon element cooperate to jointly improve the electrochemical performance of the battery, so that the capacity of the anode material can be greatly improved, the electronic impedance rate of the anode material can be reduced, and the anode material is prevented from expanding in the charge and discharge process.
In one embodiment, the a element includes at least one of nitrogen, phosphorus, sulfur, boron, arsenic, selenium.
In one embodiment, at least a portion of the elemental silicon bonds with the carbon-based material to form silicon carbide.
In one embodiment, the mass ratio of the element A to the silicon element is 0.01 to 10%.
In one embodiment, the ratio of the sum of the mass of the a element and the silicon element to the mass of the carbon-based material is 0.1 to 15%.
In one embodiment, the ratio of the sum of the mass of the a element and the silicon element to the mass of the carbon-based material is 0.5 to 10%.
In one embodiment, the ratio of the sum of the mass of the a element and the silicon element to the mass of the carbon-based material is 1 to 5%.
In one embodiment, the negative electrode material satisfies the following conditions between D10, D50, and D90: D10/D50 is more than or equal to 0.03, and D90/D50 is less than or equal to 2.00.
In one embodiment, the negative electrode material has a D10 of 0.1 to 3 μm, a D50 of 3 to 6 μm, and a D90 of 6 to 12 μm.
In one embodiment, the carbon-based material has pores, at least a portion of the a element and at least a portion of the silicon element filling into the pores.
In one embodiment, the mass ratio of the a element to the total a element located within the pores is greater than or equal to 1/2.
In one embodiment, the mass ratio of the elemental silicon to total elemental silicon within the pores is greater than or equal to 1/2.
In one embodiment, the negative electrode material has a hydrophobic contact angle of 90 to 180 °.
In one embodiment, the specific surface area of the negative electrode material is 1-35 m 2 /g。
In one embodiment, the negative electrode material has a tap density of 0.74 to 1.50g/cm 3 。
In a second aspect, the present application provides a method for preparing a negative electrode material, the method comprising:
heating a carbon source to 300-500 ℃ in a protective gas atmosphere to obtain a solid I;
mixing the solid I with a silicon source in a protective gas atmosphere, and heating to 900-1400 ℃ to obtain a solid II;
And under the atmosphere of protective gas, mixing the solid II with the source A, and heating to 300-700 ℃ to obtain the anode material.
In one embodiment, the carbon source comprises a biomass feedstock comprising at least one of rice hulls, peanut hulls, pistachio hulls, walnut hulls, chestnut hulls, almond hulls, sunflower seed hulls, pine cones, rice, coconut shells, bamboo, corn cobs, canola straw, and bagasse.
In one embodiment, the silicon source comprises at least one of elemental silicon, silicon dioxide, silicic acid, sodium silicate, silicon tetrafluoride, silicon oxide, silicate esters, silicon nitride, and silane.
In one embodiment, the source a comprises at least one of hydrazine hydrate, ammonia, ethylenediamine, urea, sodium vanadium phosphate, sodium vanadium fluorophosphate, phosphoric acid, sodium dihydrogen phosphate, sodium phosphate, potassium phosphate, ammonium dihydrogen phosphate, thiourea, sulfur oxide, thioacetamide, boron tribromide, boron trichloride, trimethyl borate, arsenic trioxide, arsenite, normal arsenate, meta arsenite, pyroarsenite, selenide, sodium selenite, selenate.
In a third aspect, the application provides a negative electrode sheet, which comprises the negative electrode material or the negative electrode material prepared by the preparation method of the negative electrode material.
In a fourth aspect, the present application provides a secondary battery comprising a positive electrode tab, a separator, and a negative electrode tab as described above.
In one embodiment, the secondary battery is a sodium ion battery, the first charge specific capacity of the sodium ion battery is 250-480 mAh/g, and the first coulombic efficiency is 50-89%.
Drawings
In order to more clearly describe the technical solution in the embodiments of the present application, the drawings required to be used in the embodiments of the present application will be described below.
Fig. 1 is an XRD pattern of the negative electrode material provided in example 2 of the present application.
Detailed Description
The following description of the technical solutions according to the embodiments of the present application will be given with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, but not all embodiments.
The terms "first," "second," and the like herein are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present application, unless otherwise indicated, the meaning of "a plurality" is two or more.
Furthermore, herein, the terms "upper," "lower," and the like, are defined with respect to the orientation in which the structure is schematically disposed in the drawings, and it should be understood that these directional terms are relative concepts, which are used for descriptive and clarity with respect thereto and which may be varied accordingly with respect to the orientation in which the structure is disposed.
For convenience of understanding, the following description will explain and describe related technical terms related to the embodiments of the present application.
Hard carbon: refers to a carbon material which is difficult to graphitize and is generally not graphitizable at temperatures above 2800 ℃.
Specific surface area: refers to the total area of the material per unit mass.
Sodium ion batteries are one of the emerging secondary batteries. The sodium ion battery with the excellent performance, which is obtained by replacing lithium with sodium, can solve the problem of large-scale electricity storage application of lithium electricity, and has wide market prospect. The existing sodium ion battery generally uses hard carbon as a negative electrode material, wherein the hard carbon has a highly disordered structure, large interlayer spacing and more defects, so that sodium ions with larger radius can be conveniently embedded and extracted. However, the hard carbon has a high specific surface area, is easy to absorb moisture and oxygen, has more side reactions, and has low initial coulombic efficiency, so that the improvement of the overall performance of the sodium ion battery is limited.
The application provides a negative electrode material, which comprises a carbon-based material, wherein the carbon-based material is doped with an element A and a silicon element, the element A is a nonmetallic element, and the content of the silicon element is larger than that of the element A.
Wherein the anode material is particulate, the anode material may include a plurality of carbon-based material particles, each of the carbon-based material particles being doped with an element a and an element silicon, as an example. The anode material 1 can be used for preparing a battery anode. The negative electrode material 1 is a carrier of ions and electrons during the charge and discharge of the battery, and determines energy storage and release. In one embodiment, the anode material 1 is applied to a sodium ion battery.
The carbon-based material is a material mainly composed of carbon. In one embodiment, the carbon-based material comprises at least one of hard carbon, soft carbon, activated carbon, graphite. In one embodiment, the carbon-based material is one of hard carbon, soft carbon, activated carbon, and graphite. In one embodiment, the carbon-based material comprises at least two of hard carbon, soft carbon, activated carbon, graphite.
In one embodiment, the carbon-based material is hard carbon. Hard carbon has the characteristics of larger interlayer spacing, high sodium storage capacity and the like. The hard carbon is used as a carbon-based material, so that the performance of the anode material can be improved.
In the application, the carbon-based material is doped with an element A and a silicon element, wherein the element A is a nonmetallic element except silicon. Doping of the carbon-based material with the a element is understood to mean that the a element is dispersed inside the carbon-based material, or that the a element is dispersed to the outer surface of the carbon-based material, and is also understood to mean that the a element is dispersed inside and outside the carbon-based material. Likewise, doping of the carbon-based material with elemental silicon may be understood as the dispersion of elemental silicon into the interior of the carbon-based material, or the dispersion of elemental silicon into the exterior surface of the carbon-based material, and may be understood as the dispersion of elemental silicon into the interior and exterior surfaces of the carbon-based material.
The carbon-based material is doped with the A element and the silicon element, on one hand, the A element and the silicon element can increase the interlayer spacing of the carbon-based material, and when the anode material is applied to an ion battery, the carbon-based material with larger interlayer spacing is beneficial to the intercalation and deintercalation of sodium ions with larger volume, and is beneficial to the improvement of ion mobility, thereby being beneficial to the rapid charge/discharge process, and being beneficial to the improvement of the specific capacity of the anode material, and particularly, the A element can also increase the active site of the anode material and improve the capacity of the anode material. On the other hand, the silicon element can also play a supporting role on the carbon-based material, so that the collapse of the carbon-based material is prevented, and the stability of the anode material is improved.
If the carbon-based material is not doped, i.e. the carbon-based material is not doped with element a and element silicon, for example, undoped hard carbon is used as a negative electrode material, the hard carbon is mainly prepared from high polymer materials such as coconut shells, starch, resin and the like, and the high polymer generates pores in the pyrolysis process, so that the hard carbon has higher specific surface area, is easy to absorb moisture and oxygen, has more side reactions and has lower initial coulomb efficiency. In the application, the specific capacity and stability of the cathode material are improved by doping the carbon-based material.
If the carbon-based material is doped with only the a element, the carbon-based material is doped with only the phosphorus element, the capacity improvement range of the anode material is limited by the phosphorus doping, the impedance of the anode material is increased after the phosphorus doping, and the power performance of the anode material is reduced due to the larger electronic impedance. If the carbon-based material is doped with silicon element only, the anode material is easily expanded due to too much silicon content in the anode material in the charging and discharging process of the battery, so that the safety performance and the cycle performance of the battery are affected.
In the application, firstly, the carbon-based material is doped with the element A and the silicon element simultaneously, the multiplying power performance and the conductivity of the anode material are improved by the co-doping of the element A and the silicon element, and the silicon element can be filled into the pores of the carbon-based material, so that the electronic impedance rate of the anode material is further reduced, and the specific capacity, the first efficiency and the cycle performance are improved. And secondly, the relative content of the element A and the silicon element is regulated and controlled, namely, the content of the silicon element in the anode material is larger than that of the element A, and the element A and the silicon element cooperate to jointly improve the electrochemical performance of the battery, so that the capacity of the anode material can be greatly improved, the electronic impedance rate of the anode material can be reduced, and the anode material is prevented from expanding in the charge and discharge process.
In the application, the relative doping amounts of the A element and the silicon element are not selected arbitrarily, and when the carbon-based material is doped with the A element and the silicon element, the properties of the A element and the silicon element and the influence on the carbon-based material are fully considered, so that the performance of the anode material is improved to the greatest extent, and the adverse influence on the anode material is reduced. For example, the capacity of the anode material is increased by the element a to a limited extent, the impedance of the anode material may be increased, the capacity of the anode material may be increased by the element silicon than the element a, and the electron impedance of the anode material may be reduced by the element silicon, but the anode material may be easily expanded due to the excessive content of the element silicon. In the application, the element A and the silicon element are doped at the same time, and the content of the silicon element can be reduced by adding a small amount of the element A, so that the anode material is not easy to expand while the capacity is improved, and the performance of the anode material is more excellent.
It is to be noted that the content of the silicon element in the present application means the mass of the silicon element in the negative electrode material per unit mass, and the content of the a element means the mass of the a element in the negative electrode material per unit mass, that is, the content in the present application means the mass content. In other embodiments, the content may also refer to molar content.
In one embodiment, the element a and the element silicon are uniformly doped in the carbon-based material.
In one embodiment, the element a and the element silicon may also be non-uniformly doped in the carbon-based material.
In one embodiment, the silicon element is uniformly doped in the carbon-based material, and the A element is non-uniformly doped in the carbon-based material; or the element A is uniformly doped in the carbon-based material, and the element silicon is non-uniformly doped in the carbon-based material.
In one embodiment, the element a includes at least one of nitrogen, phosphorus, sulfur, boron, arsenic, selenium. The nitrogen, phosphorus, sulfur, boron, arsenic, selenium and other elements can improve the capacity of the anode material.
In one embodiment, the element a comprises one of nitrogen, phosphorus, sulfur, boron, arsenic, selenium. The element A is a single element, so that the preparation of the anode material is facilitated.
In one embodiment, the element a is nitrogen. In one embodiment, the element a is a phosphorus element. In one embodiment, the element a is elemental sulfur. In one embodiment, the element a is boron. In one embodiment, the element a is an arsenic element. In one embodiment, the element a is elemental selenium.
In one embodiment, the element a includes two of nitrogen, phosphorus, sulfur, boron, arsenic, selenium. Illustratively, in one embodiment, the element a consists of a nitrogen element and a phosphorus element. In one embodiment, the element a consists of boron and phosphorus. In one embodiment, the element a consists of elemental selenium and elemental sulfur. In one embodiment, the element a consists of an arsenic element and a phosphorus element. In one embodiment, the element a consists of nitrogen and arsenic. In one embodiment, the element a consists of elemental sulfur and elemental phosphorus.
In one embodiment, the element a comprises three, four, five or six of nitrogen, phosphorus, sulfur, boron, arsenic, selenium. Illustratively, in one embodiment, the element a consists of elemental nitrogen, elemental sulfur, and elemental phosphorus. In one embodiment, the element a is composed of nitrogen, sulfur, selenium, and phosphorus. In one embodiment, the element a is composed of nitrogen, sulfur, selenium, boron, and phosphorus. In one embodiment, the element a is composed of nitrogen, sulfur, selenium, boron, arsenic, and phosphorus.
In one embodiment, at least a portion of the elemental silicon bonds with the carbon-based material to form silicon carbide. In the negative electrode material, at least part of silicon element exists in the form of silicon carbide, at least part of silicon element forms a covalent bond with carbon in the carbon-based material, on one hand, the silicon element and the carbon-based material are bonded to form silicon carbide, the conductivity of the silicon carbide is superior to that of simple substance silicon, and the silicon element exists in the form of silicon carbide, so that the conductivity of the negative electrode material is improved. On the other hand, a strong bond is formed between the silicon element and the carbon-based material, and the binding force between the silicon element and the carbon-based material is enhanced, so that the silicon element is not easy to fall off from the carbon-based material, and the effects of improving the stability of the anode material, improving the specific capacity of the anode material and the like are better ensured.
In one embodiment, 1/3 and more of the silicon element is bonded to the carbon-based material to form silicon carbide.
In one embodiment, 1/2 and more of the silicon element is bonded to the carbon-based material to form silicon carbide.
In one embodiment, 2/3 and more of the silicon element is bonded to the carbon-based material to form silicon carbide.
In one embodiment, all of the silicon element in the negative electrode material bonds to the carbon-based material to form silicon carbide.
In one embodiment, a portion of the elemental silicon is bonded to the carbon-based material to form silicon carbide, and another portion of the elemental silicon is present as elemental silicon, silicon dioxide, or the like.
In one embodiment, the element a may also be bonded to carbon in the carbon-based material.
In one embodiment, both the silicon element and the a element may form weak bonds or strong bonds with the carbon-based material.
In one embodiment, the mass ratio of the element A to the element silicon is 0.01 to 10%. If the relative content of the element a in the carbon-based material is too large, and the mass of the element a and the silicon element is greater than 10% by way of example, the capacity of the anode material is limited after the element a and the silicon element are doped. If the relative content of the silicon element in the carbon-based material is too large, and the mass ratio of the element A to the silicon element is smaller than 0.01% by way of example, too much silicon content in the anode material easily causes the anode material to expand, thereby affecting the safety performance and the cycle performance of the battery.
In the embodiment, the relative content of the element A and the silicon element is regulated, so that the mass ratio of the element A to the silicon element in the anode material is more than or equal to 0.01% and less than or equal to 10%, and in the range, the element A and the silicon element cooperate to jointly improve the electrochemical performance of the battery, so that the capacity of the anode material can be greatly improved, the electronic impedance rate of the anode material can be reduced, and the anode material is prevented from expanding in the charge and discharge process.
In one embodiment, the mass ratio of the element A to the element silicon is 0.05 to 10%.
In one embodiment, the mass ratio of the element A to the element silicon is 0.1 to 10%.
In one embodiment, the mass ratio of the element A to the element silicon is 0.5 to 10%.
In one embodiment, the mass ratio of the element A to the element silicon is 1 to 10%.
In one embodiment, the mass ratio of the element A to the element silicon is 2 to 10%.
In one embodiment, the mass ratio of the element A to the element silicon is 3 to 10%.
In one embodiment, the mass ratio of the element A to the element silicon is 4 to 10%.
In one embodiment, the mass ratio of the element A to the element silicon is 5 to 10%.
In one embodiment, the mass ratio of the element A to the element silicon is 6 to 10%.
In one embodiment, the mass ratio of the element A to the element silicon is 7 to 10%.
In one embodiment, the mass ratio of the element A to the element silicon is 8 to 10%.
In one embodiment, the mass ratio of the element A to the element silicon is 9 to 10%.
In one embodiment, the mass ratio of the element A to the element silicon is 0.01 to 9%.
In one embodiment, the mass ratio of the element A to the element silicon is 0.01 to 7%.
In one embodiment, the mass ratio of the element A to the element silicon is 0.01 to 5%.
In one embodiment, the mass ratio of the element A to the element silicon is 0.01 to 3%.
In one embodiment, the mass ratio of the element A to the element silicon is 0.01 to 1%.
In one embodiment, the mass ratio of the a element to the silicon element may be 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%.
In one embodiment, the ratio of the sum of the mass of the element a and the mass of the element silicon to the mass of the carbon-based material is 0.1 to 15%. The doping amount of the element a and the silicon affects the performance of the anode material, and if the doping amount of the element a and the silicon is too small, and the ratio of the sum of the mass of the element a and the mass of the silicon to the mass of the carbon-based material is less than 0.1% by way of example, the content of the element a and the silicon is too small, the improvement of the rate capability, the conductivity, the specific capacity, the first efficiency and the cycle performance of the anode material is not obviously promoted. If the doping amount of the element A and the silicon element is too much, the ratio of the sum of the mass of the element A and the mass of the silicon element to the mass of the carbon-based material is more than 15%, and the larger doping amount of the element A and the silicon element improves the processing difficulty of the anode material and influences the energy density of the battery so as to reduce the gram capacity of the battery, and meanwhile, excessive element A and silicon element also possibly occupy sodium intercalation sites of sodium ions, so that the capacity of the anode material is reduced.
In the application, the ratio of the sum of the mass of the element A and the mass of the silicon to the mass of the carbon-based material is more than or equal to 0.1 percent and less than or equal to 5 percent, and the doping amount of the element A and the silicon is controlled within a proper range, so that the purposes of improving the rate capability, the conductivity, the specific capacity, the first efficiency and the cycle performance of the anode material can be achieved, the stability of the anode material can be ensured, and the binding force of the element A and the silicon with the carbon-based material can be enhanced.
In one embodiment, the ratio of the sum of the mass of the element a and the mass of the element silicon to the mass of the carbon-based material is 0.5 to 15%.
In one embodiment, the ratio of the sum of the mass of the element a and the mass of the element silicon to the mass of the carbon-based material is 1 to 15%.
In one embodiment, the ratio of the sum of the mass of the element a and the mass of the element silicon to the mass of the carbon-based material is 2 to 15%.
In one embodiment, the ratio of the sum of the mass of the element a and the mass of the element silicon to the mass of the carbon-based material is 3 to 15%.
In one embodiment, the ratio of the sum of the mass of the element a and the mass of the element silicon to the mass of the carbon-based material is 4 to 15%.
In one embodiment, the ratio of the sum of the mass of the element a and the mass of the element silicon to the mass of the carbon-based material is 5 to 15%.
In one embodiment, the ratio of the sum of the mass of the element a and the mass of the element silicon to the mass of the carbon-based material is 8 to 15%.
In one embodiment, the ratio of the sum of the mass of the element a and the mass of the element silicon to the mass of the carbon-based material is 10 to 15%.
In one embodiment, the ratio of the sum of the mass of the element a and the mass of the element silicon to the mass of the carbon-based material is 12 to 15%.
In one embodiment, the ratio of the sum of the mass of the element a and the mass of the element silicon to the mass of the carbon-based material is 0.1 to 10%.
In one embodiment, the ratio of the sum of the mass of the element a and the mass of the element silicon to the mass of the carbon-based material is 0.1 to 5%.
In one embodiment, the ratio of the sum of the mass of the element a and the mass of the element silicon to the mass of the carbon-based material is 0.1 to 4%.
In one embodiment, the ratio of the sum of the mass of the element a and the mass of the element silicon to the mass of the carbon-based material is 0.1 to 3%.
In one embodiment, the ratio of the sum of the mass of the element a and the mass of the element silicon to the mass of the carbon-based material is 0.1 to 2%.
In one embodiment, the ratio of the sum of the mass of the element a and the mass of the silicon element to the mass of the carbon-based material is 0.1 to 1%.
In one embodiment, the ratio of the sum of the mass of the element a and the mass of the element silicon to the mass of the carbon-based material is 0.5 to 10%.
In one embodiment, the ratio of the sum of the mass of the element a and the mass of the element silicon to the mass of the carbon-based material is 1 to 5%.
In an embodiment, the ratio of the sum of the mass of the a element and the mass of the silicon element to the mass of the carbon-based material may be 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15%.
In one embodiment, D10 and D50 of the negative electrode material satisfy: D10/D50 is more than or equal to 0.03. Wherein D10 is the particle size corresponding to the case where the cumulative particle size distribution percentage in the negative electrode material reaches 10%, and D50 is the particle size corresponding to the case where the cumulative particle size distribution percentage in the negative electrode material reaches 50%.
If the particle size of the anode material is too small, the anode material is easy to agglomerate, and the intercalation and deintercalation of sodium ions are affected; if the particle size of the anode material is too large, the dispersibility of the anode material is poor, so that the preparation of the anode piece is affected due to the fact that the slurry of the anode material is not easy to prepare. In the application, the ratio of D10 to D50 of the anode material is more than or equal to 0.03, the particle size distribution of the anode material is moderate, and the anode material is beneficial to preparation while ensuring rapid intercalation and deintercalation of sodium ions.
In one embodiment, the D50 and D90 of the negative electrode material satisfy: D90/D50 is less than or equal to 2.00. Wherein D90 is the particle size corresponding to the cumulative particle size distribution percentage of the negative electrode material reaching 90%. The particle size of the anode material is too large or too small, which can have adverse effects on the performance and the preparation process of the anode material, and in the application, the ratio of D50 to D90 of the anode material is less than or equal to 2, so that the performance and the processing convenience of the anode material are improved.
In one embodiment, the negative electrode material satisfies between D50, D10, and D90: D10/D50 is more than or equal to 0.03, and D90/D50 is less than or equal to 2.00. The performance and the processing convenience of the anode material are improved.
In one embodiment, the D10 of the negative electrode material is 0.1 to 3 μm. The particle size of the anode material is too large or too small, which can have adverse effects on the performance and the preparation process of the anode material, and in the application, the D10 of the anode material is controlled within the range of 0.1-3 mu m, so that the performance and the processing convenience of the anode material are improved.
In one embodiment, D10 of the negative electrode material may be 0.1 μm, 0.12 μm, 0.14 μm, 0.15 μm, 0.18 μm, 0.2 μm, 0.22 μm, 0.25 μm, 0.26 μm, 0.28 μm, or 3 μm.
In one embodiment, the D50 of the negative electrode material is 3 to 6 μm. The particle size of the anode material is too large or too small, which can have adverse effects on the performance and the preparation process of the anode material, and in the application, the D50 of the anode material is controlled within the range of 3-6 mu m, so that the performance and the processing convenience of the anode material are improved.
In one embodiment, the D50 of the negative electrode material may be 3 μm, 3.2 μm, 3.4 μm, 3.5 μm, 3.8 μm, 4 μm, 4.2 μm, 4.5 μm, 4.6 μm, 4.8 μm, 5 μm, 5.2 μm, 5.5 μm, 5.6 μm, 5.8 μm, or 6 μm.
In one embodiment, the D90 of the negative electrode material is 6 to 12 μm. The particle size of the anode material is too large or too small, which can have adverse effects on the performance and the preparation process of the anode material, and in the application, the D90 of the anode material is controlled within the range of 6-12 mu m, so that the performance and the processing convenience of the anode material are improved.
In one embodiment, the D90 of the negative electrode material may be 6 μm, 6.2 μm, 6.4 μm, 6.5 μm, 6.8 μm, 7 μm, 7.2 μm, 7.5 μm, 7.6 μm, 7.8 μm, 8 μm, 8.2 μm, 8.5 μm, 8.6 μm, 8.8 μm, 9 μm, 9.2 μm, 9.5 μm, 9.6 μm, 9.8 μm, 10 μm, 10.2 μm, 10.5 μm, 10.6 μm, 10.8 μm, 11 μm, 11.2 μm, 11.5 μm, 11.6 μm, 11.8 μm or 12 μm.
In one embodiment, the carbon-based material has pores, and at least a portion of the element a fills the pores.
In one embodiment, the carbon-based material has pores, and at least a portion of the silicon element fills the pores.
In one embodiment, the carbon-based material has pores, at least a portion of the element a and at least a portion of the element silicon filling the pores. It can be understood that the hard carbon is mainly prepared from high-molecular polymer materials such as coconut shell, starch, resin and the like, and the high-molecular polymer generates pores in the pyrolysis process, so that the hard carbon has higher specific surface area, is easy to absorb moisture and oxygen, has more side reactions and has lower initial coulombic efficiency. According to the embodiment, at least part of the A element and at least part of the silicon element are filled into the pores, so that the specific surface area of the carbon-based material can be effectively reduced, and the first coulombic efficiency of the battery is improved. In addition, because the silicon-based anode material has very high specific capacity, the silicon element is used as a doping substance, so that the specific capacity of the anode material can be effectively ensured and even improved without being influenced by the reduction of the specific surface area.
In one embodiment, a portion of the a element fills the pores and another portion of the a element is located within the framework of the carbon-based material.
In one embodiment, a portion of the elemental silicon fills the pores and another portion of the elemental silicon is located within the framework of the carbon-based material.
In one embodiment, the mass ratio of the element A to the total element A located within the pores is greater than or equal to 1/2. Most of the A element in the anode material is positioned in the pores of the carbon-based material, so that the first coulomb efficiency of the battery can be improved better.
In one embodiment, the mass ratio of the element A to the total element A located within the pores is greater than or equal to 2/3.
In one embodiment, the mass ratio of the element A to the total element A located within the pores is greater than or equal to 4/5.
In one embodiment, the mass ratio of elemental silicon to total elemental silicon within the pores is greater than or equal to 1/2. Most of silicon elements in the cathode material are positioned in pores of the carbon-based material, so that the first coulombic efficiency of the battery can be improved better.
In one embodiment, the mass ratio of elemental silicon to total elemental silicon within the pores is greater than or equal to 2/3.
In one embodiment, the mass ratio of elemental silicon to total elemental silicon within the pores is greater than or equal to 4/5.
In one embodiment, the negative electrode material has a hydrophobic contact angle of 90 to 180 °. The hydrophobic contact angle is also called as a hydrophobic contact angle or a hydrophobic contact angle, when the hydrophobic contact angle is 90-180 degrees, the negative electrode material is not easy to be wetted by water, and the larger the hydrophobic contact angle is, the smaller the wettability of the negative electrode material is. In the application, the hydrophobic contact angle of the anode material is set to be 90-180 degrees, so that the anode material is not easy to react with water vapor in the environment, and the stability of the anode material is improved; on the other hand, the negative electrode material can be ensured to be fully contacted with the electrolyte, and the ion mobility is improved, so that the rapid charge/discharge process is facilitated, and the specific capacity of the negative electrode material is improved.
In one embodiment, the specific surface area of the anode material is 1 to 35m 2 And/g. The specific surface area of the anode material affects the performance of the anode material, and if the specific surface area of the anode material is too large, the initial coulombic efficiency of the battery is low. If the specific surface area of the negative electrode material is too small, the intercalation and deintercalation of sodium ions are not facilitated, the capacity of the negative electrode material is affected, and the capacity of the negative electrode material is reduced. In the application, the specific surface area of the anode material 1 is controlled within the range of 1-35m2/g, so that the capacity of the anode material can be increased while the first coulombic efficiency of the battery is ensured to be improved.
In one embodiment, the specific surface area of the anode material is 5 to 35m 2 /g。
In one embodiment, the specific surface area of the anode material is 10 to 35m 2 /g。
In one embodiment, the specific surface area of the anode material is 15-35 m 2 /g。
In one embodiment, the specific surface area of the anode material is 20 to 35m 2 /g。
In one embodiment, the specific surface area of the anode material is 25 to 35m 2 /g。
In one embodiment, the specific surface area of the anode material is 30 to 35m 2 /g。
In one embodiment, the specific surface area of the anode material is 1 to 30m 2 /g。
In one embodiment, the specific surface area of the anode material is 1 to 25m 2 /g。
In one embodiment, the specific surface area of the anode material is 1 to 20m 2 /g。
In one embodiment, the specific surface area of the anode material is 1-15 m 2 /g。
In one embodiment, the specific surface area of the anode material is 1 to 10m 2 /g。
In one embodiment, the specific surface area of the anode material is 1 to 5m 2 /g。
In an embodiment, the specific surface area of the anode material may be 1m 2 /g、2m 2 /g、5m 2 /g、8m 2 /g、10m 2 /g、12m 2 /g、15m 2 /g、17m 2 /g、20m 2 /g、22m 2 /g、24m 2 /g、25m 2 /g、26m 2 /g、28m 2 /g、30m 2 /g or 35m 2 /g。
In one embodiment, the negative electrode material has a tap density of 0.74 to 1.50g/cm 3 . Tap density refers to the density of the negative electrode material after compaction. In the application, the tap density of the cathode material is controlled to be 0.74-1.50 g/cm 3 In the range, the first coulombic efficiency and capacity of the anode material are improved.
In one embodiment, the negative electrode material has a tap density of 0.75 to 1.50g/cm 3 。
In one embodiment, the negative electrode material has a tap density of 0.8 to 1.50g/cm 3 。
In one embodiment, the negative electrode material has a tap density of 0.9 to 1.50g/cm 3 。
In one embodiment, the negative electrode material has a tap density of 1 to 1.50g/cm 3 。
In one embodiment, the negative electrode material has a tap density of 1.2 to 1.50g/cm 3 。
In one embodiment, the negative electrode material has a tap density of 0.74 to 1.4g/cm 3 。
In one embodiment, the negative electrode material has a tap density of 0.74 to 1g/cm 3 。
In one embodiment, the negative electrode material has a tap density of 0.74 to 0.9g/cm3.
In one embodiment, the negative electrode material has a tap density of 0.74 to 0.8g/cm3.
In one embodiment, the negative electrode material has a tap density of 0.74g/cm 3 、0.78g/cm 3 、0.8g/cm 3 、0.85g/cm 3 、0.9g/cm 3 、0.95g/cm 3 、1.1g/cm 3 、1.15g/cm 3 、1.2g/cm 3 、1.25g/cm 3 、1.3g/cm 3 、1.35g/cm 3 、1.4g/cm 3 、1.45g/cm 3 Or 1.5g/cm 3 。
The application provides a preparation method of a negative electrode material, which comprises the following steps of S1, S2 and S3:
step S1, heating a carbon source to 300-500 ℃ in a protective gas atmosphere to obtain a solid I;
step S2, mixing the solid I with a silicon source in a protective gas atmosphere, and heating to 900-1400 ℃ to obtain a solid II;
And step S3, mixing the solid II with the source A in a protective gas atmosphere, and heating to 300-700 ℃ to obtain the anode material.
In step S1, the carbon source is heated at a relatively low temperature to remove water in the carbon source, so as to obtain a pre-carbonized material, i.e., solid i, where carbonization of the solid i is relatively insufficient. In the step S2, the solid I and the silicon source are continuously mixed and then heated to a higher temperature, so that on one hand, the solid I is completely carbonized, on the other hand, the silicon source reacts with carbon in the solid I to generate silicon carbide so as to form a solid II, at the moment, the solid II is a carbon-based material doped with silicon element, at the moment, the silicon element in the solid II is doped in the form of silicon carbide, and the solid II is undoped with the element A. And step S3, uniformly mixing the solid II with the A source, and heating in the middle-low temperature range to dope the A element into the solid II, namely the carbon-based material, so as to obtain the anode material.
The preparation method of the anode material provided by the application can save energy, has a simple process, and is convenient for large-scale preparation of the anode material.
In one embodiment, the shielding gas comprises at least one of nitrogen, carbon dioxide, helium, neon, argon, krypton, xenon, radon.
In one embodiment, the shielding gas used in step S1, step S2 and step S3 is the same. The same protective gas is used, so that the preparation process of the anode material is simpler.
In other embodiments, the shielding gas used in step S1, step S2, and step S3 may be different.
In one embodiment, the heating time for heating the carbon source is 3 to 5 hours.
In one embodiment, the heating time for heating the solid I is 3 to 10 hours.
In one embodiment, the heating time for heating the mixture of solids II and source A is from 1 to 6 hours.
In one embodiment, the carbon source comprises a biomass feedstock comprising at least one of rice hulls, peanut hulls, pistachio hulls, walnut hulls, chestnut hulls, almond hulls, sunflower seed hulls, pine cones, rice, coconut hulls, bamboo, corn cobs, canola straw, and bagasse. Biomass raw materials are used as carbon sources, so that the energy is saved and the environment is protected.
In one embodiment, the silicon source comprises at least one of elemental silicon, silicon dioxide, silicic acid, sodium silicate, silicon tetrafluoride, silicon oxide, silicate esters, silicon nitride, and silane.
In one embodiment, the source a comprises a nitrogen source comprising at least one of hydrazine hydrate, ammonia, ethylenediamine, urea.
In one embodiment, the source a comprises a phosphorus source comprising at least one of sodium vanadium phosphate, sodium vanadium fluorophosphate, phosphoric acid, sodium dihydrogen phosphate, sodium phosphate, potassium phosphate, ammonium dihydrogen phosphate.
In one embodiment, the source a comprises a sulfur source comprising at least one of thiourea, sulfur oxides, thioacetamide.
In one embodiment, the source a comprises a boron source comprising at least one of boron tribromide, boron trichloride, trimethyl borate.
In one embodiment, the source a comprises a source of arsenic comprising at least one of arsenic trioxide, arsenite, meta-arsenite, and pyroarsenite.
In one embodiment, the source a comprises a selenium source comprising at least one of selenide, sodium selenite, selenate.
It is noted that the negative electrode material is not prepared strictly in the order of steps S1, S2 and S3, and the preparation steps in the present application may include more or fewer preparation steps. For example, if the carbon source contains a silicon source, the silicon source may be added little or no more in the subsequent steps.
The application provides a negative electrode plate, which comprises the negative electrode material or the negative electrode plate comprises the negative electrode material prepared by the preparation method of the negative electrode material.
The application provides a secondary battery, which comprises a positive electrode plate, a diaphragm and a negative electrode plate.
In one embodiment, the secondary battery is a sodium ion battery.
In one embodiment, the first charge specific capacity of the sodium ion battery is 250-480 mAh/g.
In one embodiment, the first coulombic efficiency of the sodium ion battery is 50-89%.
In order to illustrate the beneficial effects of the method of the present application, the present application is also described in the following examples and comparative examples.
Example 1
Embodiment 1 provides a negative electrode material, the negative electrode material comprises phosphorus element and silicon element, the phosphorus element accounts for 0.1 percent of the mass of the silicon element, the ratio of the sum of the mass of the phosphorus element and the mass of the silicon element to the mass of the carbon-based material is 0.1 percent, the silicon element in the negative electrode material exists in the form of silicon carbide, d10/d50=0.03 and d90/d50=1.00 of the negative electrode material.
The preparation method of the anode material provided in the embodiment 1 comprises the following steps:
(1) Crushing rice hulls, then placing the crushed rice hulls in a tube furnace, introducing nitrogen as a protective gas, heating to 350 ℃, and carbonizing for 2 hours to obtain a pre-carbonized material.
(2) 3g of pre-carbonized material is taken, 2.99mg of silicon dioxide is added for high-temperature sintering at 1000 ℃ for 6 hours, and the hard carbon precursor doped with silicon element is obtained.
(3) Adding 0.003mg of phosphoric acid into the hard carbon precursor, uniformly mixing to obtain a mixture, sintering at 450 ℃ for 3 hours, cooling, and further crushing to obtain the phosphorus-and silicon-doped hard carbon anode material.
The specific surface area of the hard carbon anode material is 7m by BET (Brunauer-Emmett-Teller) specific surface area test 2 /g。
Example 2
The anode material provided in example 2 is different from that in example 1 in that, in the anode material provided in example 2, the ratio of the sum of the mass of phosphorus element and silicon element to the mass of the carbon-based material is 10%.
The specific surface area of the hard carbon anode material is 4m by BET specific surface area test 2 /g。
Example 3
The anode material provided in example 3 is different from that in example 1 in that, in the anode material provided in example 3, the ratio of the sum of the mass of phosphorus element and silicon element to the mass of the carbon-based material is 5%.
The specific surface area of the hard carbon anode material is 5m by BET specific surface area test 2 /g。
Example 4
The anode material provided in example 4 is different from that in example 1 in that in the anode material provided in example 4, d10/d50=1 and d90/d50=2.00 of the anode material.
The BET specific surface area of the hard carbon anode material is measuredSpecific surface area of 8m 2 /g。
Example 5
The anode material provided in example 5 is different from the anode material in example 1 in that a silicon source is added in step (3), and in the anode material provided in example 5, silicon elements in the anode material are all present in the form of silicon dioxide.
The specific surface area of the hard carbon anode material is 7m by BET specific surface area test 2 /g。
Comparative example 1
The anode material provided in comparative example 1 is different from that in example 1 in that in the anode material provided in comparative example 1, only phosphorus element was doped, and silicon element was not doped.
The specific surface area of the hard carbon anode material is 45m by BET specific surface area test 2 /g。
Comparative example 2
The anode material provided in comparative example 2 is different from that in example 1 in that in the anode material provided in comparative example 2, only silicon element was doped, and phosphorus element was not doped.
The specific surface area of the hard carbon anode material is 47m according to BET specific surface area test 2 /g。
Comparative example 3
The anode material provided in comparative example 3 is different from that in example 1 in that in the anode material provided in comparative example 3, the content of silicon element is smaller than the content of phosphorus element, and silicon element accounts for 0.1% by mass of phosphorus element.
The specific surface area of the hard carbon anode material is 55m according to BET specific surface area test 2 /g。
The negative electrode materials provided in examples 1 to 5 and the negative electrode materials provided in comparative examples 1 to 3 described above were assembled into a negative electrode tab and a sodium ion battery, respectively, as follows:
negative pole piece: the negative electrode material was mixed with carboxymethyl cellulose (CMC), SBR and SP according to 95.8:1.2:2: mixing, ball milling and stirring according to the mass ratio of 1 to obtain negative electrode slurry, coating the negative electrode slurry on the surface of a copper foil, and vacuum drying overnight at 110 ℃ to obtain a negative electrode plate;
positive pole piece: metal sodium sheet;
electrolyte solution: ethylene carbonate and ethylmethyl carbonate were mixed in a 3:7 volume ratio and added with NaPF 6 Forming electrolyte, naPF 6 The concentration of (2) is 1mol/L;
a diaphragm: a polypropylene microporous separator;
sodium ion battery assembly: and assembling the button type sodium ion battery in an inert atmosphere glove box according to the assembling sequence of the negative electrode plate, the diaphragm, the electrolyte and the positive electrode plate.
The electrochemical properties of each of the sodium ion batteries assembled in the above sodium ion battery examples were respectively subjected to the performance test as in table 1, and the test results are shown in table 1 below:
TABLE 1 Performance test results
As shown in fig. 1, from the XRD spectrum of the anode material of example 2, it can be seen that 2-Theta is a characteristic diffraction of SiC of about 35.65 °, 41.46 °, 60.03 °, 71.86 °, 75.61 °, indicating that elemental silicon has been successfully incorporated into the hard carbon material and is present in the form of silicon carbide.
From the test results of the above examples 1 to 5 and comparative examples 1 to 3, it can be seen that the capacity and the first coulombic efficiency of the hard carbon anode material obtained by carbonization are greatly improved through the low-temperature carbonization, silicon doping, high-temperature carbonization, and phosphorus doping processes. In the high-rate test, compared with comparative examples 1-3 of the hard carbon anode material which is not treated by the method, the anode material prepared by the method has more excellent electrochemical performance. In summary, the application adopts the co-doping of phosphorus and silicon, which not only can increase the sodium intercalation active site of the sodium battery, reduce the specific surface area and improve the capacity of the whole battery, but also can support the hard carbon skeleton and prevent the collapse of the hard carbon structure in the high-rate charge and discharge process.
The above details of the negative electrode material, the preparation method and the application thereof provided by the embodiment of the present application, and specific examples are applied to illustrate the principle and the embodiment of the present application, and the above description of the embodiment is only used to help understand the method and the core idea of the present application; meanwhile, as those skilled in the art will have variations in specific embodiments and application scope in light of the ideas of the present application, the present description should not be construed as limiting the present application.
Claims (13)
1. The negative electrode material is characterized by comprising a carbon-based material, wherein the carbon-based material is doped with an element A and a silicon element, the element A is a nonmetallic element, and the content of the silicon element is greater than that of the element A.
2. The anode material according to claim 1, wherein the a element includes at least one of nitrogen, phosphorus, sulfur, boron, arsenic, and selenium.
3. The anode material of claim 1, wherein at least a portion of the elemental silicon is bonded to the carbon-based material to form silicon carbide.
4. The anode material according to claim 1, wherein a mass ratio of the a element to the silicon element is 0.01 to 10%.
5. The anode material according to claim 1, wherein a ratio of a sum of mass of the a element and the silicon element to mass of the carbon-based material is 0.1 to 15%.
6. The anode material according to claim 1, wherein the anode material satisfies between D10, D50, and D90: D10/D50 is more than or equal to 0.03, and D90/D50 is less than or equal to 2.00; and/or
The D10 of the negative electrode material is 0.1-3 mu m, the D50 is 3-6 mu m, and the D90 is 6-12 mu m.
7. The anode material according to claim 1, wherein the carbon-based material has pores, and at least part of the a element and at least part of the silicon element are filled into the pores.
8. The anode material according to claim 7, wherein a mass ratio of the a element to the total a element located in the pores is 1/2 or more; and/or the number of the groups of groups,
the mass ratio of the silicon element to the total silicon element in the pores is greater than or equal to 1/2.
9. The anode material according to any one of claims 1 to 8, wherein the hydrophobic contact angle of the anode material is 90 to 180 °; and/or
The specific surface area of the negative electrode material is 1-35 m 2 /g; and/or the number of the groups of groups,
the tap density of the anode material is 0.74-1.50 g/cm 3 。
10. The preparation method of the anode material is characterized by comprising the following steps of:
heating a carbon source to 300-500 ℃ in a protective gas atmosphere to obtain a solid I;
mixing the solid I with a silicon source in a protective gas atmosphere, and heating to 900-1600 ℃ to obtain a solid II;
and under the atmosphere of protective gas, mixing the solid II with the source A, and heating to 300-700 ℃ to obtain the anode material.
11. A negative electrode sheet comprising the negative electrode material according to any one of claims 1 to 9, or comprising the negative electrode material produced by the method for producing a negative electrode material according to claim 10.
12. A secondary battery comprising a positive electrode tab, a separator, and the negative electrode tab of claim 11.
13. The secondary battery according to claim 12, wherein the secondary battery is a sodium ion battery having a first charge specific capacity of 250 to 480mAh/g and a first coulombic efficiency of 50 to 89%.
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