CN104600273B - A kind of phosphorous anode material for lithium-ion batteries and preparation method thereof - Google Patents
A kind of phosphorous anode material for lithium-ion batteries and preparation method thereof Download PDFInfo
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- CN104600273B CN104600273B CN201310524631.9A CN201310524631A CN104600273B CN 104600273 B CN104600273 B CN 104600273B CN 201310524631 A CN201310524631 A CN 201310524631A CN 104600273 B CN104600273 B CN 104600273B
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- positive electrode
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- cobalt
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000010405 anode material Substances 0.000 title claims abstract description 19
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 title claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 109
- 239000011572 manganese Substances 0.000 claims abstract description 58
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011651 chromium Substances 0.000 claims abstract description 21
- 239000011777 magnesium Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 18
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 15
- 239000010941 cobalt Substances 0.000 claims abstract description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011574 phosphorus Substances 0.000 claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005864 Sulphur Substances 0.000 claims abstract description 12
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 10
- 239000010936 titanium Substances 0.000 claims abstract description 10
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000002002 slurry Substances 0.000 claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 4
- 229910008690 LiaMnb Inorganic materials 0.000 claims abstract description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 17
- 238000001694 spray drying Methods 0.000 claims description 13
- 235000006748 manganese carbonate Nutrition 0.000 claims description 11
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 7
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000005751 Copper oxide Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910000431 copper oxide Inorganic materials 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910000531 Co alloy Inorganic materials 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 4
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 4
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 claims description 4
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000007767 bonding agent Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000001238 wet grinding Methods 0.000 claims description 3
- SORNWENKXWLTOD-UHFFFAOYSA-J C(C(=O)[O-])(=O)[O-].[Mn+2].[Co+2].C(C(=O)[O-])(=O)[O-] Chemical compound C(C(=O)[O-])(=O)[O-].[Mn+2].[Co+2].C(C(=O)[O-])(=O)[O-] SORNWENKXWLTOD-UHFFFAOYSA-J 0.000 claims description 2
- SYGXXQPAYVYJIN-UHFFFAOYSA-N C(O)(O)=O.[Mn].[Co].[Ni] Chemical compound C(O)(O)=O.[Mn].[Co].[Ni] SYGXXQPAYVYJIN-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- OWCMVEWJJXJEJK-UHFFFAOYSA-M O[Co]O[Ni] Chemical compound O[Co]O[Ni] OWCMVEWJJXJEJK-UHFFFAOYSA-M 0.000 claims description 2
- IFOQSAIMHJEZBZ-UHFFFAOYSA-M O[Ni+].[O-2].[Mn+2] Chemical compound O[Ni+].[O-2].[Mn+2] IFOQSAIMHJEZBZ-UHFFFAOYSA-M 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- VSERDQZIFQXCJT-UHFFFAOYSA-L [Co].[Ni].[Mn](=O)(O)O Chemical compound [Co].[Ni].[Mn](=O)(O)O VSERDQZIFQXCJT-UHFFFAOYSA-L 0.000 claims description 2
- GXYRXNQSSVKFGS-UHFFFAOYSA-N [Ni].[Co].C(C(=O)O)(=O)O Chemical compound [Ni].[Co].C(C(=O)O)(=O)O GXYRXNQSSVKFGS-UHFFFAOYSA-N 0.000 claims description 2
- DKFOQIAQSOHGNP-UHFFFAOYSA-M [OH-].[O-2].[Mn+2].[Co+2] Chemical compound [OH-].[O-2].[Mn+2].[Co+2] DKFOQIAQSOHGNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- 229910052789 astatine Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- AVOWKZBJAWDYJP-UHFFFAOYSA-N carbonic acid;cobalt;nickel Chemical compound [Co].[Ni].OC(O)=O AVOWKZBJAWDYJP-UHFFFAOYSA-N 0.000 claims description 2
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 claims description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 2
- IKAUYRPGUOKDFB-UHFFFAOYSA-N cobalt manganese nickel oxalic acid Chemical compound [Mn].[Co].[Ni].C(C(=O)O)(=O)O IKAUYRPGUOKDFB-UHFFFAOYSA-N 0.000 claims description 2
- XEUFSQHGFWJHAP-UHFFFAOYSA-N cobalt(2+) manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Co++] XEUFSQHGFWJHAP-UHFFFAOYSA-N 0.000 claims description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- HJZMCWKYJQFMPG-UHFFFAOYSA-J cobalt(2+);manganese(2+);dicarbonate Chemical compound [Mn+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O HJZMCWKYJQFMPG-UHFFFAOYSA-J 0.000 claims description 2
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 claims description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 2
- 229940116318 copper carbonate Drugs 0.000 claims description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 claims description 2
- 229940056319 ferrosoferric oxide Drugs 0.000 claims description 2
- 150000004678 hydrides Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 235000014413 iron hydroxide Nutrition 0.000 claims description 2
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical group [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- HZISTRYOBSVSHK-UHFFFAOYSA-J manganese(2+) nickel(2+) oxalate Chemical compound [Mn++].[Ni++].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O HZISTRYOBSVSHK-UHFFFAOYSA-J 0.000 claims description 2
- BLYYANNQIHKJMU-UHFFFAOYSA-N manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Ni++] BLYYANNQIHKJMU-UHFFFAOYSA-N 0.000 claims description 2
- ONZVHGFAUYGYCG-UHFFFAOYSA-L manganese(2+) oxocobalt dihydroxide Chemical compound [OH-].[Co]=O.[Mn+2].[OH-] ONZVHGFAUYGYCG-UHFFFAOYSA-L 0.000 claims description 2
- ORNCRFSGPUVBHW-UHFFFAOYSA-L manganese(2+) oxonickel dihydroxide Chemical compound [OH-].O=[Ni].[Mn+2].[OH-] ORNCRFSGPUVBHW-UHFFFAOYSA-L 0.000 claims description 2
- ZWEKKXQMUMQWRN-UHFFFAOYSA-J manganese(2+);nickel(2+);dicarbonate Chemical compound [Mn+2].[Ni+2].[O-]C([O-])=O.[O-]C([O-])=O ZWEKKXQMUMQWRN-UHFFFAOYSA-J 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 3
- 229910021529 ammonia Inorganic materials 0.000 claims 3
- 229910052739 hydrogen Inorganic materials 0.000 claims 3
- 239000001257 hydrogen Substances 0.000 claims 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical group [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 2
- 229910000990 Ni alloy Inorganic materials 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical group OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims 1
- KSHLPUIIJIOBOQ-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[Co++].[Ni++] Chemical compound [O--].[O--].[O--].[O--].[Co++].[Ni++] KSHLPUIIJIOBOQ-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims 1
- 239000011149 active material Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract 1
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- 235000019837 monoammonium phosphate Nutrition 0.000 description 13
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- 239000003792 electrolyte Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
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- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 229910013191 LiMO2 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- SDPBZSAJSUJVAT-UHFFFAOYSA-N carbonic acid;manganese Chemical compound [Mn].OC(O)=O SDPBZSAJSUJVAT-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910018428 LixBO2 Inorganic materials 0.000 description 1
- 229910018433 LixBO2−z Inorganic materials 0.000 description 1
- 229910017192 LixMn1-y Inorganic materials 0.000 description 1
- 229910017200 LixMn1−y Inorganic materials 0.000 description 1
- 229910017205 LixMn2 Inorganic materials 0.000 description 1
- 229910015160 LixMn2-y Inorganic materials 0.000 description 1
- 229910015349 LixMn2O4-z Inorganic materials 0.000 description 1
- 229910015310 LixMn2O4−z Inorganic materials 0.000 description 1
- 229910015674 LixMnO2-z Inorganic materials 0.000 description 1
- 229910015670 LixMnO2−z Inorganic materials 0.000 description 1
- 229910016205 LixNi1-y-zCoy Inorganic materials 0.000 description 1
- 229910014137 LixNiCoO2−z Inorganic materials 0.000 description 1
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical class [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- OZOAXHQNOFIFGD-UHFFFAOYSA-N manganese(2+) oxygen(2-) Chemical compound [O-2].[O-2].[Mn+2].[Mn+2] OZOAXHQNOFIFGD-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 229910000957 xLi2O Inorganic materials 0.000 description 1
- 229910006525 α-NaFeO2 Inorganic materials 0.000 description 1
- 229910006596 α−NaFeO2 Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
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- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
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Abstract
The present invention relates to a kind of phosphorous anode material for lithium-ion batteries and preparation method thereof.The group of phosphorous anode material for lithium-ion batteries becomes LiaMnbNicMdPeZfOg, wherein M is at least one of Co, Al, Ti, Fe, Cr, Cu, Zr, Mg, at least one of Z S, Si, and 0.95≤a<1.6,0≤b<1,0≤c≤0.9,0≤d≤0.5,0.001≤e<0.05,0≤f<0.2,1.95≤g<2.5.The method for preparing this positive electrode at least contains following 4 steps：1) with lithium source, phosphorus source, manganese source and nickel source, and selected from least one of cobalt source, silicon source, titanium source, source of iron, chromium source, copper source, zirconium source, magnesium source, and at least one of sulphur source and silicon source is selected from and is used as raw material, weigh corresponding raw material in molar ratio；2) liquid is added in the feed, is ground；3) ground slurry is dried；4) material after drying is roasted.This method and process process is simple, at low cost, and the positive electrode for being easy to industrialized production, and preparing in this way has high specific capacity.The invention further relates to use this material as the battery of active material.
Description
Technical field
The present invention relates to field of lithium ion battery anode, specifically a kind of phosphorous anode material for lithium-ion batteries and
Preparation method.
Background technology
The continuous development of industrial technology causes the getting worse of the present situations such as current resource, the shortage of the energy and environmental pollution,
In recent years, the exploitation that policy promotes the development and new energy of energy-conserving and emission-cutting technology was competitively put into effect in countries in the world.Lithium ion battery because
For have operating voltage it is high, it is light-weight, have extended cycle life, allow wide working range, memory-less effect, it is pollution-free the advantages that, and
Extensive concern has been obtained, has become the oversize vehicles such as bus, electric vehicle, hybrid electric vehicle, it is electric bicycle, small-sized
The major impetus source of the light electric vehicle such as platform batter car and electric tool.But lithium ion battery is as oversize vehicle
Power battery is not met by requirement than various aspects of performance such as energy, cycle life, safeties.Inhibit power battery development
Key factor be the positive electrode of battery, so develop novel positive electrode become now the most urgently solve ask
Topic.
In recent years, rich lithium solid solution cathode material became the research hotspot of anode material for lithium-ion batteries, because it has
Specific capacity height, good cycling stability, it is higher than energy the advantages that.Rich lithium solid-solution material is the Li by stratiform2MnO3And LiMO2(M=
Mn, Ni, Co) by the solid solution of different proportion formation, chemical formula can be write as xLi2MnO3·(1-x)LiMO2Or xLi2O·
yMOb(x/y>0.51).According to the literature, the method for preparing above-mentioned positive electrode have very much, as coprecipitation, sol-gal process,
High temperature solid-state method, hydrothermal synthesis method etc., wherein coprecipitation is the most commonly used.A.Manthiram etc. is prepared for using coprecipitation
Lithium-rich anode material Li[Li0.2Mn0.54Ni0.13Co0.13]O2, first discharge specific capacity reaches 250mAh/g
(J.Phys.Chem.C., 114 (2010) 9528-9533), but recycle and be short of with high rate performance, and preparation process engineering is multiple
It is miscellaneous, it is of high cost, be not suitable for the large-scale production of industrialization.Samsung uses the compound L i of general formulaxMnA2(1)、
LixMnO2-zAz(2)、LixMn1-yM′yA2(3)、LixMn2A4(4)、LixMn2O4-zAz(5)、LixMn2-yM′yA4(6)、LixBO2
(7)、LixBO2-zAz(8)、LixB1-yM″yA2(9)、LixB1-yM″yO2-zAz(10)、LixNiCoA2(11)、LixNiCoO2-zAz
(12)、LixNi1-y-zCoyM″zA2(13) (wherein 0<X≤1.5,0.01≤y≤0.1,0.01≤z≤0.5, M ' be selected from Al, Cr,
At least one of Co, Mg, La, Ce, Sr, V, M " are to be selected from selected from least one of Al, Cr, Mn, Fe, Mg, LA, Ce, Sr, V, A
O, F, S and P and B are selected from Ni or Co) and selected from semimetal, metal and its oxide composition anode active material composition
(CN1181580C), this composition easily causes component and is unevenly distributed.Samsung, which chooses, states (1)~(13) general formula statement
Compound, these compounds surface coating vanadic anhydride (CN1150645C), metal oxide (CN1209832C),
Coating there are coating thickness not grade, complex technical process, operability poor the problems such as, to influence the performance of material, and increase
Process costs.
Invention content
For above-mentioned anode material for lithium-ion batteries the problems of, the present invention provides a kind of phosphorous lithium-ion electric
Pond positive electrode and preparation method thereof, and it is fabricated to the anode and lithium ion battery of lithium ion battery.Wherein, phosphorus is with phosphatic
Form, which is added to, prepares phosphorous anode material for lithium-ion batteries in raw material, give phosphorus institute in anode material for lithium-ion batteries
The range of accounting example can improve material high rate performance and cycle performance in this way, and then meet power battery to lithium ion battery
The demand of positive electrode.
A kind of phosphorous anode material for lithium-ion batteries, chemical formula LiaMnbNicMdPeZfOg,
Wherein M is at least one of Co, Al, Ti, Fe, Cr, Cu, Zr, Mg, at least one of Z S, Si, and 0.95≤a<
1.6；0≤b≤1, preferably 0<B≤0.9, preferably 0.05≤b≤0.9；0≤c≤0.9, preferably 0.1≤c≤0.9；0≤d≤
0.5；0.001≤e<0.050, preferably 0.001≤e≤0.040, preferably 0.006≤e≤0.020；0≤f<0.2, preferably 0.01
≤ f≤0.15, preferably 0.02≤f≤0.05；1.95≤g<2.5.
It is one kind in consisting of according to positive electrode recited above：
Li0.95Mn0.21Ni0.72Co0.19P0.04S0.01O2.03、Li1.17Mn0.52Ni0.12Co0.11P0.04S0.02O2.07、
Li1.18Mn0.53Ni0.14Co0.13P0.04S0.05O2.235、Li1.21Mn0.52Ni0.13Co0.12P0.02Si0.01O2.025、
Li1.21Mn0.53Ni0.13Co0.13P0.006Si0.02O2.14、LiMn0.25Ni0.52Co0.28Al0.049P0.001S0.05O2.116、
Li1.211Mn0.534Ni0.129Co0.124P0.002S0.05O2.144、LiMn0.055Ni0.75Co0.21Al0.12Mg0.08P0.005S0.05O2.08、
LiMn0.28Ni0.58Co0.18Al0.03Zr0.03P0.02S0.08O2.305、
Li0.98Mn0.28Ni0.78Co0.16Ti0.02Al0.02Mg0.03P0.03S0.01O2.261、
Li1.04Mn0.16Ni0.76Fe0.16Al0.05Mg0.03P0.006S0.05O2.11、Li1.5Mn0.453Ni0.28Cr0.15P0.007S0.01O2.209、
Li1.2Mn0.54Ni0.13Cr0.05Al0.03Mg0.03P0.02S0.03O2.1、Li1.17Mn0.50Ni0.29P0.04S0.05O2.125、
Li1.25Mn0.40Ni0.32Co0.05Mg0.05P0.04S0.05O2.12、LiMn0.35Ni0.582Mg0.20P0.008S0.01O2.032、
LiMn0.15Ni0.75Co0.15Cr0.05P0.04S0.02O2.01、Li1.2Mn0.6Ni0.15Cu0.05P0.02Si0.01O2.07、
Li1.35Mn0.52Ni0.15Cu0.08Cr0.03P0.006Si0.01O2.025、Li1.25Mn0.62Ni0.06Co0.02Cu0.03P0.03Si0.02O2.1、
Li0.95Mn0.28Ni0.70Al0.05Cu0.05P0.04Si0.05O2.06、Li1.25Mn0.62Ni0.06Co0.04P0.015Si0.1O2.223。
The invention also provides a kind of methods for the positive electrode preparing phosphorous lithium ion battery, at least contain following 4
A step：1) with lithium source, phosphorus source, manganese source and nickel source, and selected from cobalt source, silicon source, titanium source, source of iron, chromium source, copper source, zirconium source and
At least one of magnesium source and sulphur source and/or silicon source, weigh corresponding raw material in molar ratio；2) it presses solid content and is not more than 50 weights
Measure % i.e. 0 weight %<The weight % of solid content≤50, surplus is liquid, liquid is added in the feed, carries out wet-milling, wherein liquid
Body is water, ethyl alcohol or aqueous organopolysiloxane, and the concentration of aqueous organopolysiloxane is not more than 50 weight % i.e. 0 weight %<Aqueous organopolysiloxane
The weight % of concentration≤50, remaining is water；3) ground slurry is dried；4) material after drying is roasted, is roasted
It is 750~1100 DEG C to burn temperature, and preferred calcination temperature is 800~1000 DEG C, and roasting time is 5~60h.
Lithium source is at least one of anhydrous lithium hydroxide, the water lithium hydroxide containing crystallization, lithium carbonate；Phosphorus source is phosphate, excellent
Select at least one of dihydrogen phosphate, ammonium di-hydrogen phosphate, phosphoric acid ammonia；Manganese source is manganese metal, manganese monoxide, manganese dioxide, carbonic acid
At least one of manganese；Nickel source is at least one of metallic nickel, nickel protoxide, nickel sesquioxide, nickel hydroxide, nickelous carbonate；Cobalt source
For at least one of metallic cobalt, cobaltosic oxide, cobalt sesquioxide, cobalt protoxide, cobalt hydroxide, cobalt carbonate；Silicon source is metal
At least one of aluminium, alundum (Al2O3), aluminium hydroxide；Titanium source is at least one of titanium dioxide or titanium isopropoxide；Source of iron is
At least one of metallic iron, di-iron trioxide, ferroso-ferric oxide, iron hydroxide or ferrous hydroxide；Chromium source is crome metal, three oxygen
Change at least one of two chromium, chromium hydroxide；Copper source is at least one of copper oxide, cuprous oxide, copper carbonate；Zirconium source is oxidation
At least one of zirconium, zirconium hydroxide；Magnesium source is at least one of magnesium carbonate, magnesia；Manganese source, nickel source and cobalt source are closed for manganese nickel cobalt
At least one of gold, manganous hydroxide nickel cobalt, hydroxyl oxidation manganese nickel cobalt, oxalic acid manganese nickel cobalt, carbonic acid manganese nickel cobalt, oxidation manganese nickel cobalt；Manganese
Source and nickel source are at least one in manganese-nickel, manganous hydroxide nickel, hydroxyl manganese oxide nickel, manganese oxalate nickel, manganese carbonate nickel, manganese oxide nickel
Kind；Manganese source and cobalt source are in manganese cobalt alloy, manganous hydroxide cobalt, hydroxyl manganese oxide cobalt, manganese oxalate cobalt, manganese carbonate cobalt, manganese oxide cobalt
It is at least one；Nickel source and cobalt source are nickel cobalt (alloy), hydroxide nickel cobalt, hydroxy cobalt nickel oxide, oxalic acid nickel cobalt, carbonic acid nickel cobalt, oxidation
At least one of nickel cobalt；Sulphur source is the hydride of sulfate, sulphite, sulfur oxide or sulphur, the sulphur in preferably sulfuric acid salt
At least one of sour nickel or ammonium sulfate.Silicon source is silica.The liquid used in process of lapping is deionized water, ethyl alcohol, second
At least one of the aqueous solution of alcohol, PVA aqueous solutions, aqueous sucrose solution；Dry slurry is using vacuum drying, forced air drying, spraying
At least one of dry, microwave drying；The temperature of roasting is 800~1000 DEG C.
The positive electrode prepared according to the method described above is mixed with conductive carbon and bonding agent, and obtained mixture is applied
Apply the anode that the lithium ion battery is formed on support conducting base.By the anode anode compatible with electricity, diaphragm, electrolyte
It is placed in container and forms lithium ion battery.
It is mixed with conductive agent, binder with the positive electrode prepared by the method for the present invention, dissolving in organic solvent, is formed
Anode sizing agent is coated on supporter, makes the anode of lithium ion battery.
Using this anode, and the cathode for selecting the positive electrode electricity prepared with the present invention compatible is as the negative of lithium ion battery
Diaphragm, electrolyte is added in pole, forms lithium ion battery.
It is an advantage of the invention that：
Compared with prior art, the present invention provides a kind of phosphorous anode material for lithium-ion batteries and preparation method thereof,
This positive electrode has higher chemical property, and simple for process, is readily synthesized material, to reduce cost, favorably
In industrialization continuous production.
Description of the drawings
Fig. 1 be synthetic example 1 of the present invention, 4 positive electrode of embodiment 2, embodiment 3 and embodiment X-ray diffractogram
The full spectrum [ of spectrum;Fig. 1 a][ is composed in amplification with 18~19.5 °;Fig. 1 b].
Fig. 2 be the present invention synthesize embodiment 1,4 positive electrode of embodiment 2, embodiment 3 and embodiment in 0.1C, 4.8
The first charge-discharge curve comparison figure of material under~2.0V.
Fig. 3 be the present invention synthesize embodiment 1,4 positive electrode of embodiment 2, embodiment 3 and embodiment in 0.1C, 4.8
The high rate performance curve comparison figure of material under~2.0V.
Fig. 4 be the present invention synthesize embodiment 4 and comparative example 1, comparative example 2 and comparative example 3 in 4.8~2.0V, material
First charge-discharge curve comparison figure.
Fig. 5 be the present invention synthesize embodiment 4 and comparative example 1, comparative example 2 and comparative example 3 in 4.8~2.0V, material
High rate performance curve comparison figure.
Specific implementation mode
Technical scheme of the present invention is further described with embodiment below, contributes to the preparation method to the present invention
It is further understood from, protection scope of the present invention is not limited to the examples, and protection scope of the present invention is wanted by right
Book is sought to determine.
Embodiment 1：
Prepare Li1.204Mn0.533Ni0.132Co0.131P0.001O2.02, weigh 52.052g lithium carbonates, 71.692g manganese carbonates,
12.304g cobaltosic oxides, 11.537g nickel protoxides and 0.136g ammonium dihydrogen phosphates, mixing are added 1000g deionized waters, add
It after entering into grinder grinding, is spray-dried, the powder obtained after point spray drying is through 900 DEG C of calcination 36h, with furnace cooling
But, the powder of acquisition is ground, and crosses 300 mesh sieve.
Embodiment 2：
Prepare Li1.18Mn0.53Ni0.14Co0.13P0.04S0.05O2.235, weigh 52.246g lithium carbonates, 73.010g manganese carbonates,
12.505g cobaltosic oxides, 12.531g nickel protoxides, 5.512g ammonium dihydrogen phosphates and 7.918g ammonium sulfate mix, and are added
1000g deionized waters are added to after being ground in grinder, are spray-dried, and the powder obtained after point spray drying is through 900
DEG C calcination 36h, the powder of furnace cooling, acquisition is ground, and crosses 300 mesh sieve.
Embodiment 3：
Prepare Li1.21Mn0.53Ni0.13Co0.13P0.006Si0.02O2.4, weigh 48.615g lithium carbonates, 66.252g manganese carbonates,
11.347g cobaltosic oxides, 10.559g nickel protoxides, 0.750g ammonium dihydrogen phosphates and 1.307g silica mix, and are added
1000g deionized waters are added to after being ground in grinder, are spray-dried, and the powder obtained after point spray drying is through 900
DEG C calcination 36h, the powder of furnace cooling, acquisition is ground, and crosses 300 mesh sieve.
Embodiment 4：
Prepare Li1.21Mn0.52Ni0.13Co0.12P0.02Si0.01O2.025, weigh 52.612g lithium carbonates, 70.346g manganese carbonates,
11.335g cobaltosic oxides, 11.427g nickel protoxides, 2.706g ammonium dihydrogen phosphates and 0.707g silica mix, and are added
800g deionized waters are added to after being ground in grinder, are spray-dried, and the powder obtained after point spray drying is through 900
DEG C calcination 36h, the powder of furnace cooling, acquisition is ground, and crosses 300 mesh sieve.
Embodiment 5：
Prepare Li1.211Mn0.534Ni0.129Co0.124P0.002S0.05O2.144, weigh 54.038g lithium carbonates, 74.137g carbonic acid
Manganese, 12.021g cobaltosic oxides, 11.637g nickel protoxides, 0.278g ammonium dihydrogen phosphates and 15.874g nickel sulfates, mixing, add
Enter 1000g deionized waters, is added to after being ground in grinder, is spray-dried, the powder warp obtained after point spray drying
900 DEG C of calcination 48h, the powder of furnace cooling, acquisition are ground, and cross 300 mesh sieve.
Embodiment 6：
Prepare Li1.17Mn0.50Ni0.29P0.04S0.05O2.125, weigh 48.323g lithium carbonates, 64.250g manganese carbonates,
24.214g nickel protoxides, 5.141g ammonium dihydrogen phosphates and 14.292g nickel sulfates, mixing are added 1000g deionized waters, are added to
After being ground in grinder, it is spray-dried, the powder that obtains is through 900 DEG C of calcination 48h after point spray drying, furnace cooling,
The powder of acquisition is ground, and crosses 300 mesh sieve.
Embodiment 7：
Prepare Li1.17Mn0.50Ni0.29P0.04S0.05O2.125, weigh 48.323g lithium carbonates, 48.595g manganese dioxide,
1000g deionizations are added in 26.806g11.520g nickel sesquioxides, 5.141g ammonium dihydrogen phosphates and 7.386g ammonium sulfate, mixing
Water is added to after being ground in grinder, is spray-dried, and the powder obtained after point spray drying is calcined 48h through 900 DEG C,
The powder of furnace cooling, acquisition is ground, and crosses 300 mesh sieve.
Embodiment 8：
Prepare Li1.2Mn0.54Ni0.13Cr0.05Al0.03Mg0.03P0.02S0.03O2.1, weigh 54.801g lithium carbonates, 76.725g
Manganese carbonate, 12.002g nickel protoxides, 3.214g crome metals, 2.094g alundum (Al2O3)s, 1.495g magnesia, 2.842g phosphoric acid
1000g deionized waters are added in ammonium and 4.900g ammonium sulfate, mixing, are added to after being ground in grinder, carry out microwave drying, warp
The powder obtained after drying is ground through 900 DEG C of calcination 36h, the powder of furnace cooling, acquisition, crosses 300 mesh sieve.
Embodiment 9：
Prepare Li1.35Mn0.52Ni0.15Cu0.08Cr0.03P0.006Si0.01O2.025, weigh 60.717g lithium carbonates, 55.035g bis-
Manganese oxide, 10.717g metallic nickels, 7.747g copper oxide, 1.900g crome metals, 0.840g ammonium dihydrogen phosphates and 0.732g titanium dioxides
1000g deionized waters are added in silicon, mixing, are added to after being ground in grinder, are dried in vacuo, the powder obtained after drying
Body is ground through 900 DEG C of calcination 36h, the powder of furnace cooling, acquisition, crosses 300 mesh sieve.
Embodiment 10：
Prepare Li1.25Mn0.62Ni0.06Co0.02Cu0.03P0.03Si0.02O2.1, weigh 54.694g lithium carbonates, 63.838g dioxies
Change manganese, 4.170g metallic nickels, 1.396g metallic cobalts, 2.826g copper oxide, 4.085g ammonium dihydrogen phosphates and 1.423g silica,
1000g deionized waters are added in mixing, are added to after being ground in grinder, carry out microwave drying, the powder warp obtained after drying
900 DEG C of calcination 12h, the powder of furnace cooling, acquisition are ground, and cross 300 mesh sieve.
Embodiment 11：
Prepare Li1.2Mn0.6Ni0.15Cu0.05P0.02Si0.01O2.07, weigh 50.787g lithium carbonates, 59.756g manganese dioxide,
1000g is added in 12.834g nickel protoxides, 4.556g copper oxide, 3.024g diammonium hydrogen phosphates and 0.688g silica, mixing
Deionized water is added to after being ground in grinder, carries out forced air drying, and the powder obtained after drying is calcined for 24 hours through 950 DEG C,
The powder of furnace cooling, acquisition is ground, and crosses 300 mesh sieve.
Embodiment 12：
Prepare Li1.25Mn0.62Ni0.06Co0.04P0.015Si0.1O2.223, weigh 52.834g lithium carbonates, 81.486g manganese carbonates,
5.124g nickel protoxides, 3.671g cobaltosic oxides, 1.672g ammonium dihydrogen phosphates and 6.871g silica mix, and are added
1200g deionized waters are added to after being ground in grinder, are spray-dried, and the powder obtained after point spray drying is through 950
DEG C calcination 12h, the powder of furnace cooling, acquisition is ground, and crosses 300 mesh sieve.
Embodiment 13
Prepare Li1.15Ni0.52Co0.15Al0.05Ti0.30P0.006Si0.01O2.03, weigh 44.259g lithium carbonates, 24.182g oxygen
Change sub- nickel, 12.993g cobaltosic oxides, 3.047g alundum (Al2O3)s, 43.099g titanium dioxide, 0.745g ammonium dihydrogen phosphates and
1200g deionized waters are added in 0.649g silica, mixing, are added to after being ground in grinder, are spray-dried, through dividing
The powder obtained after spray drying is ground through 950 DEG C of calcination 12h, the powder of furnace cooling, acquisition, crosses 300 mesh sieve.
Embodiment 14
Prepare Li1.2Mn0.6Co0.10Cu0.05P0.02S0.01O2.07, weigh 52.514g lithium carbonates, 81.693g manganese carbonates,
9.507g cobaltosic oxides, 2.724g ammonium dihydrogen phosphates and 1.565g ammonium sulfate, mixing are added 1200g deionized waters, are added to
After being ground in grinder, it is spray-dried, the powder that obtains is through 950 DEG C of calcination 12h after point spray drying, furnace cooling,
The powder of acquisition is ground, and crosses 300 mesh sieve.
Comparative example 1：
Prepare Li1.20Mn0.54Ni0.13Co0.13O2, weigh 37.371g lithium carbonates, 50.797g manganese carbonates, 8.539g tetra- and aoxidize
800g deionized waters are added in three cobalts, 7.946g nickel protoxides, mixing, are added to after being ground in grinder, are spray-dried,
The powder obtained after spray-dried is ground through 900 DEG C of calcination 36h, the powder of furnace cooling, acquisition, crosses 300 mesh sieve.
Comparative example 2：
Prepare Li1.19Mn0.53Ni0.15Co0.13P0.0005O2.01, weigh 51.113g lithium carbonates, 70.824g manganese carbonates,
12.131g cobaltosic oxides, 13.025g nickel protoxides and 0.403g ammonium sulfate, mixing are added 800g deionized waters, are added to
After being ground in grinder, it is spray-dried, the powder that obtains is through 900 DEG C of calcination 36h after point spray drying, furnace cooling,
The powder of acquisition is ground, and crosses 300 mesh sieve.
Comparative example 3：
Prepare Li1.132Mn0.490Ni0.123Co0.120P0.136Si0.005O2.289, weigh 46.446g lithium carbonates, 65.551g carbonic acid
Manganese, 10.202g nickel protoxides, 10.696g cobaltosic oxides, 17.366g ammonium dihydrogen phosphates and 0.334g silica, mixing,
1000g deionized waters are added, is added to after being ground in grinder, is spray-dried, the powder obtained after point spray drying
Through 900 DEG C of calcination 36h, the powder of furnace cooling, acquisition is ground, and crosses 300 mesh sieve.
Fig. 1 is the X-ray diffraction entirely [ entirely of material prepared by embodiment 1,2,3 and 4;Fig. 1 a](prepared by other specific embodiments
Material XRD spectrum it is similar, omit) and 18~19.6 ° of the X-ray diffraction of material for preparing of embodiment 1,2,3 and 4 compose [Figure
1b], it can be seen that from FIG. 1 a that the material prepared is stratiform α-NaFeO2Layer structure can be seen that the spy of material from Fig. 1 b
It is slightly moved to low-angle at sign peak.
It is prepared by anode
The material prepared using embodiment 1,2,3,4 and comparative example 1~3 is as active material, with conductive agent (SP), bonding
Agent (PVDF) is according to 8：1：1 proportioning weighs, and first by active material and the dry-mixed 4h of conductive agent, PVDF is dissolved in N-N dimethyl
In formamide, then the conductive agent of the active material mixed is added thereto, is stirred evenly, forms anode sizing agent, it will be positive
Slurry is coated on aluminium foil, is dried in drying box.
Testing of materials is prepared with half-cell
By the electrode cutting dried at 1 × 1cm, then roll-in is dried in vacuum drying chamber, as the anode of battery,
The cathode of battery uses lithium metal, and the ingredient of electrolyte is mainly the LiPF of 1M6And DMC/EC/DEC (1：1：It 1), will be positive, negative
Pole and electrolyte are placed in composition test battery in container.
The electrochemical property test of material
It is 20mA/g (0.1C), charging/discharging voltage 4.8~2V of range, test in current density by the test battery of composition
The charge-discharge property of battery.The high rate performance of battery is tested under 0.1C, 0.2C, 0.5C, 1C, 2C, 3C multiplying power.
The positive electrode prepared using embodiment 1, embodiment 2, embodiment 3 and embodiment 4, the battery of assembling are filled for the first time
The comparison diagram that discharges is as shown in Figure 2.From figure 2 it can be seen that the initial charge specific capacity of embodiment 1 is 346.8mAh/g, electric discharge
Specific capacity is 259.9mAh/g, and the initial charge specific capacity of coulombic efficiency 74.9%, embodiment 2 is 328.2mAh/g, electric discharge
Specific capacity is 263.9mAh/g, and the initial charge specific capacity of coulombic efficiency 80.2%, embodiment 3 is 353.9mAh/g, electric discharge
Specific capacity is 277.1mAh/g, and the initial charge specific capacity of coulombic efficiency 78.3%, embodiment 4 is 369.7mAh/g, electric discharge
Specific capacity is 283.6mAh/g, coulombic efficiency 76.7%.
Fig. 3 is the high rate performance comparison diagram of the lithium ion battery of positive electrode assembling prepared by embodiment 1,2,3 and 4, real
The positive electrode of the preparation of example 1 is applied, lithium ion battery is assembled, battery is 259.9mAh/g in the specific discharge capacity of 0.1C, 0.2C's
Specific discharge capacity is 235.5mAh/g, and the specific discharge capacity of 0.5C is 217.8mAh/g, and the specific discharge capacity of 1C is 197.2mAh/
The specific discharge capacity of g, 3C are 154.1mAh/g, and the specific discharge capacity for eventually passing back to 0.1C is 236.1mAh/g.It is prepared by embodiment 2
Positive electrode, assemble lithium ion battery, battery 0.1C specific discharge capacity be 263.9mAh/g, the specific discharge capacity of 0.2C
Specific discharge capacity for 249.3mAh/g, 0.5C is 225.3mAh/g, and the specific discharge capacity of 1C is 196.2mAh/g, the electric discharge of 3C
Specific capacity is 157.3mAh/g, and the specific discharge capacity for eventually passing back to 0.1C is 252.5mAh/g.Positive material prepared by embodiment 3
Material assembles lithium ion battery, and specific discharge capacity of the battery in 0.1C is 277.1mAh/g, and the specific discharge capacity of 0.2C is
The specific discharge capacity of 253.5mAh/g, 0.5C are 232.8mAh/g, and the specific discharge capacity of 1C is 210.0mAh/g, the electric discharge ratio of 3C
Capacity is 173.2mAh/g, and the specific discharge capacity for eventually passing back to 0.1C is 257.2mAh/g.Positive electrode prepared by embodiment 4,
Lithium ion battery is assembled, battery is 283.6mAh/g in the specific discharge capacity of 0.1C, and the specific discharge capacity of 0.2C is 258.0mAh/
The specific discharge capacity of g, 0.5C are 235.4mAh/g, and the specific discharge capacity of 1C is 220.9mAh/g, and the specific discharge capacity of 3C is
185.5mAh/g, the specific discharge capacity for eventually passing back to 0.1C are 262.1mAh/g.
Fig. 4 is filling for the first time for the battery of positive electrode assembling prepared by embodiment 4 and comparative example 1, comparative example 2, comparative example 3
Discharge comparison diagram, from figure 5 it can be seen that the initial charge specific capacity of embodiment 4 is 369.7mAh/g, specific discharge capacity is
283.6mAh/g, coulombic efficiency 76.7%, and the initial charge specific capacity of comparative example 1 is 319.7mAh/g, specific discharge capacity
Initial charge specific capacity for 248.8mAh/g, coulombic efficiency 77.8%, comparative example 2 is 335.7mAh/g, specific discharge capacity
Initial charge specific capacity for 231.6mAh/g, coulombic efficiency 69.0%, comparative example 3 is 252.8mAh/g, specific discharge capacity
For 195.2mAh/g, coulombic efficiency 77.2%.Comparative example 1 is to be added without phosphorus, and the phosphorus that comparative example 2 is added is relatively low, and comparative example 3 adds
High phosphorus and too low silicon, the data excessively entered are shown：It is added without or is added inappropriate phosphorus and silicon or sulphur, the ratio of electric discharge for the first time of material
Capacity can be all adversely affected.
Fig. 5 is the lithium ion battery of positive electrode assembling prepared by embodiment 4 and comparative example 1, comparative example 2, comparative example 3
The high rate performance of high rate performance comparison diagram, embodiment 4 is mentioned above, and positive electrode prepared by comparative example 1 assembles lithium-ion electric
Pond, battery are 248.8mAh/g in the specific discharge capacity of 0.1C, and the specific discharge capacity of 0.2C is 220.4mAh/g, the electric discharge of 0.5C
Specific capacity is 198.4mAh/g, and the specific discharge capacity of 1C is 179.9mAh/g, and the specific discharge capacity of 3C is 146.7mAh/g, finally
The specific discharge capacity for returning to 0.1C is 230.5mAh/g.Positive electrode prepared by comparative example 2, assembles lithium ion battery, and battery exists
The specific discharge capacity of 0.1C is 231.6mAh/g, and the specific discharge capacity of 0.2C is 193.4mAh/g, and the specific discharge capacity of 0.5C is
The specific discharge capacity of 178.1mAh/g, 1C are 169.9mAh/g, and the specific discharge capacity of 3C is 124.7mAh/g, eventually passes back to 0.1C
Specific discharge capacity be 202.1mAh/g.Positive electrode prepared by comparative example 3, assembles lithium ion battery, and battery is put 0.1C's
Electric specific capacity is 195.2mAh/g, and the specific discharge capacity of 0.2C is 184.3mAh/g, and the specific discharge capacity of 0.5C is 163.8mAh/
The specific discharge capacity of g, 1C are 146.5mAh/g, and the specific discharge capacity of 3C is 123.1mAh/g, eventually passes back to the electric discharge ratio of 0.1C
Capacity is 194.5mAh/g.Data show that the electric discharge of positive electrode prepared by embodiment 4 under high magnification is better than comparative example 1,2
With 3, silicon or sulphur are added in phosphorous rich lithium material, can not only improve the charge-discharge property of material, but also in high power
Material also shows excellent chemical property under rate.In conjunction with above-mentioned data, method provided by the invention is not only in technique
Cost is saved, and the performance of material has also reached the requirement of power battery, this method can be applied in industrial production.
Positive electrode prepared by embodiment 5~14 assembles lithium ion battery, is 4.8~2.0V in voltage range, different times
Discharge performance tables of data under rate is as shown in the table.
Claims (36)
1. a kind of phosphorous anode material for lithium-ion batteries, chemical formula LiaMnbNicMdPeZfOg, wherein M be Co, Al, Ti,
At least one of Fe, Cr, Cu, Zr, Mg, at least one of Z S, Si, and 0.95≤a<1.6,0≤b≤1,0≤c≤0.9,0
≤ d≤0.5,0.006≤e≤0.020,0.01≤f≤0.15,1.95≤g<2.5.
2. a kind of phosphorous anode material for lithium-ion batteries according to claim 1, which is characterized in that 0<b≤0.9.
3. a kind of phosphorous anode material for lithium-ion batteries according to claim 1, which is characterized in that 0.05≤b≤
0.9。
4. a kind of phosphorous anode material for lithium-ion batteries according to claim 1, which is characterized in that 0.1≤c≤0.9.
5. a kind of phosphorous anode material for lithium-ion batteries according to claim 1, which is characterized in that 0.02≤f≤
0.05。
6. a kind of phosphorous anode material for lithium-ion batteries according to claim 1, which is characterized in that the positive material
Material is one kind in consisting of：Li1.21Mn0.52Ni0.13Co0.12P0.02Si0.01O2.025、
Li1.21Mn0.53Ni0.13Co0.13P0.006Si0.02O2.14、、LiMn0.28Ni0.58Co0.18Al0.03Zr0.03P0.02S0.08O2.305、
Li1.04Mn0.16Ni0.76Fe0.16Al0.05Mg0.03P0.006S0.05O2.11、Li1.5Mn0.453Ni0.28Cr0.15P0.007S0.01O2.209、
Li1.2Mn0.54Ni0.13Cr0.05Al0.03Mg0.03P0.02S0.03O2.1、、LiMn0.35Ni0.582Mg0.20P0.008S0.01O2.032、
Li1.2Mn0.6Ni0.15Cu0.05P0.02Si0.01O2.07、Li1.35Mn0.52Ni0.15Cu0.08Cr0.03P0.006Si0.01O2.025、
Li1.25Mn0.62Ni0.06Co0.04P0.015Si0.1O2.223。
7. a kind of method preparing phosphorous anode material for lithium-ion batteries described in claim 1, which is characterized in that at least contain
There are following 4 steps：
1) with lithium source, phosphorus source, manganese source and nickel source, and in cobalt source, silicon source, titanium source, source of iron, chromium source, copper source, zirconium source and magnesium source
At least one, and it is used as raw material selected from least one of sulphur source and silicon source, weigh corresponding original by the molar ratio of the chemical formula
Material；
2) liquid is added in the feed, carries out wet-milling, is not more than 50 weight % i.e. 0 weight %< by solid content;The weight of solid content≤50
% is measured, surplus is liquid, and liquid is water, ethyl alcohol or aqueous organopolysiloxane, wherein the concentration of aqueous organopolysiloxane is no more than 50 weights
Measure % i.e. 0 weight %<The weight % of the concentration of aqueous organopolysiloxane≤50, remaining is water；
3) the good slurry of wet-milling is dried；
4) material after drying is roasted, calcination temperature is 750~1100 DEG C, and roasting time is 5~60h.
8. the preparation method of positive electrode according to claim 7, which is characterized in that the lithium source is anhydrous hydroxide
At least one of lithium, the water lithium hydroxide containing crystallization, lithium carbonate.
9. the preparation method of positive electrode according to claim 7, which is characterized in that the phosphorus source is phosphate or phosphorus
Oxide.
10. the preparation method of positive electrode according to claim 9, which is characterized in that the phosphorus source is phosphate.
11. the preparation method of positive electrode according to claim 10, which is characterized in that the phosphorus source is phosphoric acid hydrogen two
At least one of ammonia, ammonium di-hydrogen phosphate, phosphoric acid ammonia.
12. the preparation method of positive electrode according to claim 10, which is characterized in that the phosphorus source is phosphoric acid hydrogen two
Ammonia.
13. the preparation method of positive electrode according to claim 10, which is characterized in that the phosphorus source is biphosphate
Ammonia.
14. the preparation method of positive electrode according to claim 7, which is characterized in that the manganese source is manganese metal, one
At least one of manganese oxide, manganese dioxide, manganese carbonate.
15. the preparation method of positive electrode according to claim 7, which is characterized in that the nickel source is metallic nickel, oxygen
Change at least one of sub- nickel, nickel sesquioxide, nickel hydroxide, nickelous carbonate.
16. the preparation method of positive electrode according to claim 7, which is characterized in that the cobalt source is metallic cobalt, four
At least one of Co 3 O, cobalt sesquioxide, cobalt protoxide, cobalt hydroxide, cobalt carbonate.
17. the preparation method of positive electrode according to claim 7, which is characterized in that the silicon source is metallic aluminium, three
At least one of Al 2 O, aluminium hydroxide.
18. the preparation method of positive electrode according to claim 7, which is characterized in that the titanium source be titanium dioxide,
At least one of titanium isopropoxide.
19. the preparation method of positive electrode according to claim 7, which is characterized in that the source of iron is metallic iron, three
Aoxidize at least one of two iron, ferroso-ferric oxide, iron hydroxide, ferrous hydroxide.
20. the preparation method of positive electrode according to claim 7, which is characterized in that the chromium source is crome metal, three
Aoxidize at least one of two chromium, chromium hydroxide.
21. the preparation method of positive electrode according to claim 7, which is characterized in that the copper source is copper oxide, oxygen
Change at least one of cuprous, copper carbonate.
22. the preparation method of positive electrode according to claim 7, which is characterized in that the zirconium source is zirconium oxide, hydrogen
At least one of zirconium oxide.
23. the preparation method of positive electrode according to claim 7, which is characterized in that the magnesium source is magnesium carbonate, oxygen
Change at least one of magnesium.
24. the preparation method of positive electrode according to claim 7, which is characterized in that manganese source, nickel source and the cobalt source
It is aoxidized in manganese nickel cobalt, oxalic acid manganese nickel cobalt, carbonic acid manganese nickel cobalt, oxidation manganese nickel cobalt extremely for manganese nickel cobalt alloy, manganous hydroxide nickel cobalt, hydroxyl
Few one kind.
25. the preparation method of positive electrode according to claim 7, which is characterized in that the manganese source and nickel source is manganese
At least one of nickel alloy, manganous hydroxide nickel, hydroxyl manganese oxide nickel, manganese oxalate nickel, manganese carbonate nickel, manganese oxide nickel.
26. the preparation method of positive electrode according to claim 7, which is characterized in that the manganese source and cobalt source is manganese
At least one of cobalt alloy, manganous hydroxide cobalt, hydroxyl manganese oxide cobalt, manganese oxalate cobalt, manganese carbonate cobalt, manganese oxide cobalt.
27. the preparation method of positive electrode according to claim 7, which is characterized in that the nickel source and cobalt source is nickel
At least one of cobalt alloy, hydroxide nickel cobalt, hydroxy cobalt nickel oxide, oxalic acid nickel cobalt, carbonic acid nickel cobalt, cobalt nickel oxide.
28. the preparation method of positive electrode according to claim 7, which is characterized in that the sulphur source is sulfate, Asia
The hydride of sulfate, sulfur oxide or sulphur.
29. the preparation method of positive electrode according to claim 28, which is characterized in that the sulphur source is sulfate.
30. the preparation method of positive electrode according to claim 28, which is characterized in that the sulphur source be nickel sulfate or
At least one of ammonium sulfate.
31. the preparation method of positive electrode according to claim 7, which is characterized in that the silicon source is silica.
32. the preparation method of positive electrode according to claim 7, which is characterized in that the water is deionized water；Institute
The aqueous organopolysiloxane stated is at least one of aqueous solution, PVA aqueous solutions, aqueous sucrose solution of ethyl alcohol.
33. the preparation method of positive electrode according to claim 7, which is characterized in that the drying be vacuum drying,
At least one of forced air drying, spray drying, microwave drying.
34. the preparation method of positive electrode according to claim 7, which is characterized in that the temperature of roasting is 800~1000
℃。
35. a kind of anode of lithium ion battery, which is characterized in that with described in any one of claim 1-6 positive electrode or
The positive electrode prepared according to any one of claim 7-34 the methods is mixed with conductive carbon and bonding agent, and will
To mixture coated in the anode for forming the lithium ion battery on support conducting base.
36. a kind of lithium ion battery, which is characterized in that by the anode compatible with electricity of the anode described in claim 35, diaphragm, electricity
Solution matter, which is placed in container, forms lithium ion battery.
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