CN111072003A - 一种刺球状磷酸盐电极材料及其制备方法和锂离子电池 - Google Patents
一种刺球状磷酸盐电极材料及其制备方法和锂离子电池 Download PDFInfo
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- CN111072003A CN111072003A CN201911327327.9A CN201911327327A CN111072003A CN 111072003 A CN111072003 A CN 111072003A CN 201911327327 A CN201911327327 A CN 201911327327A CN 111072003 A CN111072003 A CN 111072003A
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- Prior art keywords
- phosphate
- acanthosphere
- electrode material
- salt
- lithium
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- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 81
- 239000007772 electrode material Substances 0.000 title claims abstract description 61
- 239000010452 phosphate Substances 0.000 title claims abstract description 61
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 55
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 13
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 13
- 238000002360 preparation method Methods 0.000 title description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010936 titanium Substances 0.000 claims abstract description 15
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 12
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 12
- 239000011734 sodium Substances 0.000 claims abstract description 12
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010941 cobalt Substances 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011777 magnesium Substances 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 3
- 239000011591 potassium Substances 0.000 claims abstract description 3
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 150000003624 transition metals Chemical class 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 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 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical group 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000008101 lactose Substances 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 229940080350 sodium stearate Drugs 0.000 claims description 2
- NWZBFJYXRGSRGD-UHFFFAOYSA-M sodium;octadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCOS([O-])(=O)=O NWZBFJYXRGSRGD-UHFFFAOYSA-M 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- 150000003608 titanium Chemical class 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 150000003681 vanadium Chemical class 0.000 claims description 2
- 239000011782 vitamin Substances 0.000 claims description 2
- 229940088594 vitamin Drugs 0.000 claims description 2
- 229930003231 vitamin Natural products 0.000 claims description 2
- 235000013343 vitamin Nutrition 0.000 claims description 2
- 150000003754 zirconium Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 description 15
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 229910001386 lithium phosphate Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 229910010710 LiFePO Inorganic materials 0.000 description 3
- 229910000668 LiMnPO4 Inorganic materials 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910015944 LiMn0.8Fe0.2PO4 Inorganic materials 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910004764 HSV900 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
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Abstract
本发明提出了一种刺球状磷酸盐电极材料，所述磷酸盐电极材料具有刺球状粒子形貌，其化学组成为AxMyNzPO4；其中A为碱金属元素，其为锂、钠、钾中的至少一种，M为过渡金属元素，其为铁、锰、钴、镍、钛、钒中的至少一种，N为掺杂金属元素，其为镁、钛、钒、锆、铁、锰、钴、镍、铝中的至少一种，0＜x＜3，0＜y＜1.5，0≤z≤0.05y。所述电极材料呈刺球状，通过刺球状材料的刺相互锚定，从而增强极片稳定性，提高剥离强度。
Description
技术领域
本发明涉及磷酸盐电极材料的技术领域，尤其涉及一种刺球状磷酸盐电极材料及其制备方法和锂离子电池。
背景技术
随着动力及储能领域的发展，对电池寿命的要求越来越高，而电池的寿命与极片的稳定性息息相关。在电池充放电过程中会因为体积变化、电解液浸泡、加工工艺、外力作用等，使极片发生开裂、剥离、掉粉等现象，进而导致电池寿命及安全性问题。而且极片弱的机械稳定性、黏结性会带来电池在加工过程中废品率提升，增加生产成本。
为了提高极片的稳定性，增强剥离强度。实际生产中会通过调节配方，增加粘结剂的用量来提高极片的稳定性。例如CN102306754A公开专利文献中公开了一种防止正极片脱落的锂离子电池的制作方法，通过使用两种不同分子量的粘结剂，提高了LiFePO4活性材料和集流体之间的粘结强度，但是由于粘结剂导电性差且对电池容量无贡献，因此过多的粘结剂会增大电池内阻，降低电池容量。
此外，实际生产中也会改善集流体来提高极片稳定性和加工性。例如CN108550788A公开专利文献中公开了一种正极集流体，通过使用具有垂直石墨烯层的石墨烯复合铝箔作为正极集流体，可有效增大其与活性物质的接触面积，进而增强正极极片的剥离强度，但是具有垂直石墨烯层的石墨烯复合铝箔开发难度大，增加了制作成本，不利于工业化生产。
随着对常见的电极活性材料——磷酸盐材料进行不断深入研究发现，材料形貌结构对电极材料的电化学性能具有不可忽视的影响，但是通过对磷酸盐材料形貌的控制以实现电极电学性能提高的同时，却往往伴随着极片稳定性的下降，例如CN101752564A公开专利文献中公开了一种以水热合成法合成具有一维纳米结构的磷酸铁锂，在加料速度适合的条件下，通过调节反应体系的pH值控制晶体形貌，得到具有类圆形的纳米结晶，但该一维的纳米结构不利于电极制备过程中最少量粘合剂的使用。因此，如果能实现从活性材料的形貌入手来改善极片稳定性，对本领域技术人员来说更加直接有效。
发明内容
基于背景技术存在的技术问题，本发明提出了一种刺球状磷酸盐电极材料及其制备方法和锂离子电池，所述电极材料呈刺球状，通过刺球状材料的刺相互锚定，从而增强极片稳定性，提高剥离强度。
本发明是通过如下技术方案实现的：
一种刺球状磷酸盐电极材料，所述磷酸盐电极材料具有刺球状粒子形貌，其化学组成为AxMyNzPO4；
其中A为碱金属元素，其为锂、钠、钾中的至少一种，M为过渡金属元素，其为铁、锰、钴、镍、钛、钒中的至少一种，N为掺杂金属元素，其为镁、钛、钒、锆、铁、锰、钴、镍、铝中的至少一种，0＜x＜3，0＜y＜1.5，0≤z≤0.05y。
优选地，所述电极材料为碳包覆的磷酸盐电极材料，其包括刺球状磷酸盐和包覆在所述刺球状磷酸盐外表面的碳层。
本发明还提出一种刺球状磷酸盐电极材料的制备方法，包括如下步骤：
S1、将碱金属源与磷源按照碱金属和磷元素的摩尔比为1-5:1混合溶解在水中，其中碱金属源的浓度为0.2-5mol/L，再按照磷源摩尔量的0-10mol％加入表面活性剂，在室温下反应0.5-3h，过滤，洗涤，干燥，得到化学组成为A3PO4的盐沉淀；
S2、将步骤S1得到的盐沉淀与过渡金属源按照磷和过渡金属元素的摩尔比为0.4-1.6:1混合溶解在醇水混合溶剂中，其中水占醇水混合溶剂质量的0-50％，再按照过渡金属源摩尔量的0-5mol％加入掺杂金属源，在120-220℃下反应4-20h，过滤，洗涤，干燥，得到化学组成为AxMyNzPO4的刺球状磷酸盐，即为磷酸盐电极材料。
步骤S1中，碱金属源溶液与磷源溶液之间相互反应时，通过控制反应原料和表面活性剂量来控制磷酸盐的成核及生长，从而获得具有外部稀松内部致密的球形结构的磷酸盐。
步骤S2中，将上述获得的磷酸盐与过渡金属的化合物进行水热反应，从而获得具有刺球状结构的磷酸盐。
优选地，所述碱金属源为锂盐、钠盐和/或钾盐，锂盐优选为氢氧化锂、碳酸锂、醋酸锂、硝酸锂、草酸锂、硫酸锂、氯化锂中的至少一种；所述磷源为磷酸、磷酸二氢铵、磷酸氢二铵、磷酸铵、磷酸钠、磷酸钾、磷酸二氢锂、磷酸二氢钠、磷酸二氢钾、磷酸氢二钠、磷酸氢二钾中的至少一种；所述表面活性剂为聚乙二醇、聚乙烯醇、聚乙烯吡咯烷酮、十八烷基硫酸钠、硬脂酸钠、十二烷基苯磺酸钠、抗坏血酸中的至少一种。
优选地，所述过渡金属源为铁、锰、钴、镍、钛、钒的硫酸盐、硝酸盐、草酸盐、碳酸盐、醋酸盐、氯化物、氢氧化物、氧化物中的至少一种；所述掺杂金属源为镁盐、钛盐、钒盐、锆盐、铁盐、锰盐、钴盐、镍盐、铝盐中的至少一种；所述醇溶剂为乙醇、丙醇、乙二醇、异丙醇中的至少一种。
还包括步骤S3、将步骤S2得到的刺球状磷酸盐与碳源混合后煅烧，得到碳包覆的刺球状磷酸盐电极材料；优选地，所述碳源为葡萄糖、蔗糖、乳糖、淀粉、维生素、聚乙二醇、聚丙烯酸、抗坏血酸、柠檬酸、石墨、乙炔黑、炭黑中的至少一种。
步骤S3中，将磷酸盐的粒子表面均匀包覆碳层，确保了最终获得电极材料的导电能力。
优选地，步骤S3中，将S2得到的刺球状磷酸盐与碳源混合球磨2-8h，其中有机碳源的加入量是刺球状磷酸盐质量的5-20％，再在500-1000℃下煅烧2-20h，即得碳包覆的磷酸盐电极材料。
本发明提出一种锂离子电池用电极，所述电极包括电极活性材料、导电剂和粘合剂，所述电极活性材料为上述的刺球状磷酸盐电极材料。
优选地，所述导电剂为SP导电碳黑，所述粘合剂为PVDF；所述导电剂在电极中含量为2-5wt％，所述粘合剂在电极中含量为2-5wt％。
本发明进一步提出一种锂离子电池，包括正极、负极、隔膜和电解液，所述正极或者负极为上述的锂离子电池用电极。
与现有技术相比，本发明具有如下优点：
本发明的电极材料为刺球状颗粒，颗粒之间的表面刺状结构可以相互拼插固定，从而防止掉粉，增强极片稳定性，提高电池寿命；进而也可以减少粘结剂的用量，提高正极活性物质所占比例，提高电池容量。此外刺球状电极材料有较大的比表面积，可以增加与电解液的接触，有助于锂离子的扩散，提高电池充放电性能。
附图说明
图1为本发明实施例1制备的磷酸锂的电镜扫描(SEM)图；
图2为本发明实施例1制备的磷酸亚铁锂的电镜扫描(SEM)图；
图3为为实施例1和市售的磷酸亚铁锂的1C倍率循环测试对比图。
具体实施方式
为便于理解本发明，本发明列举实施例如下。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
实施例1
一种刺球状磷酸盐电极材料，所述磷酸盐的化学组成为LiFePO4，其制备方法具体包括如下步骤：
(1)将4mol氢氧化锂与1mol磷酸加入1000ml去离子水中混合溶解，其再加入0.05mol聚乙烯吡咯烷酮，在室温下搅拌反应1h，将反应液抽滤，60℃的真空烘箱中干燥，得到Li3PO4沉淀；
(2)将步骤(1)得到的Li3PO4沉淀和1mol硫酸亚铁加入到质量比为1:1的乙醇水混合溶液中溶解完全，再置于高压反应釜中，密封后通入高纯Ar气，超声下升温至170℃，保温反应12h，再降至室温，离心分离出沉淀，乙醇洗涤3次，60℃真空烘箱中干燥，得到LiFePO4磷酸盐；
(3)将步骤(2)得到的LiFePO4磷酸盐和7.9g蔗糖(5wt％)加入到胶体磨中研磨5h，在氩气保护下，升温到700℃煅烧4h，自然冷却后，得到碳包覆的刺球状磷酸亚铁锂，即为所述刺球状磷酸盐电极材料。
图1-2给出了实施例1中步骤(1)和步骤(2)所得材料样品的电镜照片，如图1所示，可以看出所制备的Li3PO4沉淀具有外部稀松内部致密的球形结构；如图2所示，可以看出所制备的LiFePO4磷酸盐具有刺球状结构。
将实施例1所得电极材料和市售的磷酸亚铁锂电极材料(其制备方法如下所示)分别作为正极活性物质，正极极片是按照94％重量份的磷酸亚铁锂、3％重量份的SP导电碳黑和3％重量份的PVDF(HSV900)配成浆料后均匀涂敷在15um厚的铝箔上得到；铝箔事先涂布了总计2um厚的纳米碳预涂层(双面)，制成极片，极片双面敷料，双面敷料的面密度是0.02g/cm2，将极片碾压到2.3g/cm2的面密度。
市售的磷酸亚铁锂电极材料：将0.5mol碳酸锂、1mol磷酸铁及16g蔗糖分散到300mL的水中并球磨5h；研磨后的浆料通过喷雾干燥获得磷酸亚铁锂前驱体，该前驱体在氮气气氛下，升温到700℃烧结12h，获得碳包覆的磷酸亚铁锂，磷酸亚铁锂经过气流粉碎后获得成品材料。
1)极片的剥离强度测试；采用ASTM D903测试方法进行剥离强度的测试，测试3次，其结果如下表1所示：
表1实施例1所得电极材料和市售磷酸亚铁锂电极材料对应极片的剥离强度
结果可知，实施例1所得电极材料的极片剥离强度相对于市售商品化磷酸亚铁锂，剥离强度提高40％。
2)模拟电池的充放电测试；在相同的测试条件下进行测试，具体将上述极片分别与金属锂片为对电极、电解液为1M的LiPF6/EC+DMC溶液，其中EC:DMC(体积)为1∶1；隔膜采用Celgard2325型号；测试电池采用扣式电池。充放电截止电压为2.0V，电流密度为0.1C。其结果如下图3所示：
结果可知，实施例1所述电极材料和市售的电极材料在1C倍率下的放电克容量分别为147.0894mAh/g和141.0082mAh/g，循环250次容量保持分别为93.92％和93.20％，电池的大电流放电性能及循环性能也得到了改善。
实施例2
一种刺球状磷酸盐电极材料，所述磷酸盐的化学组成为K2.95Na0.03V1.98Ti0.02(PO4)3，其制备方法具体包括如下步骤：
(1)将2.95mol氢氧化钾，0.03mol氢氧化钠与1mol磷酸加入500ml去离子水中混合溶解，再加入0.03mol聚乙二醇，在室温下搅拌反应1h，将反应液抽滤，60℃的真空烘箱中干燥，得到K2.95Na0.03H0.02PO4沉淀；
(2)将步骤(1)得到的K2.95Na0.03H0.02PO4沉淀和0.66mol偏钒酸铵、0.0067mol钛酸四丁酯加入到质量比为2:1的乙二醇水混合溶液中溶解完全，再置于高压反应釜中，密封后通入高纯Ar气，超声下升温至220℃，保温反应12h，再降至室温，离心分离出沉淀，乙醇洗涤3次，60℃真空烘箱中干燥，得到K2.95Na0.03V1.98Ti0.02(PO4)3磷酸盐；
(3)将步骤(2)得到的K2.95Na0.03V1.98Ti0.02(PO4)3磷酸盐和25.1g淀粉(15wt％)加入到胶体磨中进行研磨6h，在氩气保护下，升温到850℃煅烧12h，自然冷却，得到所述刺球状磷酸盐电极材料。
参照上述方法进行试验，实施例2所得电极材料的极片剥离强度相对于常规K2.95Na0.03V1.98Ti0.02(PO4)3电极材料，剥离强度提高32％。
常规K2.95Na0.03V1.98Ti0.02(PO4)3电极材料：将0.33mol五氧化二钒、1.2mol草酸加入200ml去离子水中，70℃水浴下搅拌1h；再加入2.95mol氢氧化钾，0.03mol氢氧化钠、0.0067mol钛酸四丁酯与1mol磷酸及25g淀粉继续搅拌0.5h；然后加入500ml正丙醇搅拌0.5h，70℃下干燥，得到K2.95Na0.03V1.98Ti0.02(PO4)3前驱体；将该前驱体在400℃预热4h，再升温到750℃烧结8h，获得K2.95Na0.03V1.98Ti0.02(PO4)3电极材料。
实施例3
一种刺球状磷酸盐电极材料，所述磷酸盐的化学组成为LiMnPO4，其制备方法具体包括如下步骤：
(1)将5mol醋酸锂与1mol磷酸二氢锂加入500ml去离子水中混合溶解，在室温下搅拌反应0.5h，将反应液抽滤，60℃的真空烘箱中干燥，得到Li3PO4沉淀；
(2)将步骤(1)得到的Li3PO4沉淀和1mol硫酸锰加入到质量比为3:1的乙醇水混合溶液中溶解完全，再置于高压反应釜中，密封后通入高纯Ar气，超声下升温至150℃，保温反应4h，再降至室温，离心分离出沉淀，乙醇洗涤3次，60℃真空烘箱中干燥，得到LiMnPO4磷酸盐；
(3)将步骤(2)得到的LiMnPO4磷酸盐和7.8g葡萄糖(5wt％)加入到胶体磨中进行研磨2h，在氩气保护下，升温到1000℃煅烧2h，自然冷却，得到所述刺球状磷酸盐电极材料。
参照上述方法进行试验，实施例3所得电极材料的极片剥离强度相对于常规LiMnPO4电极材料，剥离强度提高48％。
实施例4
一种刺球状磷酸盐电极材料，所述磷酸盐的化学组成为LiMn0.8Fe0.2PO4，其制备方法具体包括如下步骤：
(1)将3mol硝酸锂与1mol磷酸铵加入500ml去离子水中混合溶解，再加入0.1mol十二烷基苯磺酸钠，在室温下搅拌反应3h，将反应液抽滤，60℃的真空烘箱中干燥，得到Li3PO4沉淀；
(2)将步骤(1)得到的Li3PO4沉淀和0.8mol硫酸锰、0.2mol硫酸亚铁加入到质量比为5:1的乙醇水混合溶液中溶解完全，再置于高压反应釜中，密封后通入高纯Ar气，超声下升温至120℃，保温反应20h，再降至室温，离心分离出沉淀，乙醇洗涤3次，60℃真空烘箱中干燥，得到LiMn0.8Fe0.2PO4磷酸盐；
(3)将步骤(2)得到的LiMn0.8Fe0.2PO4磷酸盐和31.4g葡萄糖(20wt％)加入到胶体磨中进行研磨8h，在氩气保护下，升温到500℃煅烧20h，自然冷却，得到所述刺球状磷酸盐电极材料。
参照上述方法进行试验，实施例4所得电极材料的极片剥离强度相对于常规LiMn0.8Fe0.2PO4电极材料，剥离强度提高50％。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明的技术范围内，根据本发明的技术方案及其发明加以等同替换或改变，都应涵盖在本发明的保护范围之内。
Claims (10)
1.一种刺球状磷酸盐电极材料，其特征在于，所述磷酸盐电极材料具有刺球状粒子形貌，其化学组成为AxMyNzPO4；
其中A为碱金属元素，其为锂、钠、钾中的至少一种，M为过渡金属元素，其为铁、锰、钴、镍、钛、钒中的至少一种，N为掺杂金属元素，其为镁、钛、钒、锆、铁、锰、钴、镍、铝中的至少一种，0＜x＜3，0＜y＜1.5，0≤z≤0.05y。
2.根据权利要求1所述的刺球状磷酸盐电极材料，其特征在于，所述电极材料为碳包覆的磷酸盐电极材料，其包括刺球状磷酸盐和包覆在所述刺球状磷酸盐外表面的碳层。
3.一种根据权利要求1或2所述的刺球状磷酸盐电极材料的制备方法，其特征在于，包括如下步骤：
S1、将碱金属源与磷源按照碱金属和磷元素的摩尔比为1-5:1混合溶解在水中，其中碱金属源的浓度为0.2-5mol/L，再按照磷源摩尔量的0-10mol％加入表面活性剂，在室温下反应0.5-3h，过滤，洗涤，干燥，得到化学组成为A3PO4的盐沉淀；
S2、将步骤S1得到的盐沉淀与过渡金属源按照磷和过渡金属元素的摩尔比为0.4-1.6:1混合溶解在醇水混合溶剂中，其中水占醇水混合溶剂质量的0-50％，再按照过渡金属源摩尔量的0-5mol％加入掺杂金属源，在120-220℃下反应4-20h，过滤，洗涤，干燥，得到化学组成为AxMyNzPO4的刺球状磷酸盐，即为磷酸盐电极材料。
4.根据权利要求3所述的刺球状磷酸盐电极材料的制备方法，其特征在于，所述碱金属源为锂盐、钠盐和/或钾盐，锂盐优选为氢氧化锂、碳酸锂、醋酸锂、硝酸锂、草酸锂、硫酸锂、氯化锂中的至少一种；所述磷源为磷酸、磷酸二氢铵、磷酸氢二铵、磷酸铵、磷酸钠、磷酸钾、磷酸二氢锂、磷酸二氢钠、磷酸二氢钾、磷酸氢二钠、磷酸氢二钾中的至少一种；所述表面活性剂为聚乙二醇、聚乙烯醇、聚乙烯吡咯烷酮、十八烷基硫酸钠、硬脂酸钠、十二烷基苯磺酸钠、抗坏血酸中的至少一种。
5.根据权利要求3或4所述的刺球状磷酸盐电极材料的制备方法，其特征在于，所述过渡金属源为铁、锰、钴、镍、钛、钒的硫酸盐、硝酸盐、草酸盐、碳酸盐、醋酸盐、氯化物、氢氧化物、氧化物中的至少一种；所述掺杂金属源为镁盐、钛盐、钒盐、锆盐、铁盐、锰盐、钴盐、镍盐、铝盐中的至少一种；所述醇溶剂为乙醇、丙醇、乙二醇、异丙醇中的至少一种。
6.根据权利要求3-5任一项所述的刺球状磷酸盐电极材料的制备方法，其特征在于，还包括步骤S3、将步骤S2得到的刺球状磷酸盐与碳源混合后煅烧，得到碳包覆的刺球状磷酸盐电极材料；优选地，所述碳源为葡萄糖、蔗糖、乳糖、淀粉、维生素、聚乙二醇、聚丙烯酸、抗坏血酸、柠檬酸、石墨、乙炔黑、炭黑中的至少一种。
7.根据权利要求3-6任一项所述的刺球状磷酸盐电极材料的制备方法，其特征在于，步骤S3中，将S2得到的刺球状磷酸盐与碳源混合球磨2-8h，其中碳源的加入量是刺球状磷酸盐质量的5-20％，再在500-1000℃下煅烧2-20h，即得碳包覆的磷酸盐电极材料。
8.一种锂离子电池用电极，其特征在于，所述电极包括电极活性材料、导电剂和粘合剂，所述电极活性材料为权利要求1-2任一项所述的刺球状磷酸盐电极材料。
9.根据权利要求8所述锂离子电池用电极，其特征在于，所述导电剂为SP导电碳黑，所述粘合剂为PVDF；所述导电剂在电极中含量为2-5wt％，所述粘合剂在电极中含量为1-3wt％。
10.一种锂离子电池，其特征在于，包括正极、负极、隔膜和电解液，所述正极或者负极为权利要求8或9所述的锂离子电池用电极。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101980956A (zh) * | 2008-03-31 | 2011-02-23 | 户田工业株式会社 | 磷酸铁锂颗粒粉末的制造方法、橄榄石型结构的磷酸铁锂颗粒粉末、使用该磷酸铁锂颗粒粉末的正极材料片和非水溶剂类二次电池 |
| CN102569791A (zh) * | 2010-12-16 | 2012-07-11 | 中国科学院福建物质结构研究所 | 一种具有花状结构的磷酸铁锂及其制备方法 |
| CN102629687A (zh) * | 2012-05-03 | 2012-08-08 | 哈尔滨工业大学 | 一种LiMnPO4电极材料的形貌控制合成方法 |
| CN104326467A (zh) * | 2014-10-21 | 2015-02-04 | 浙江大学 | 一种花状磷酸锰锂纳米颗粒的制备方法及产品 |
-
2019
- 2019-12-20 CN CN201911327327.9A patent/CN111072003A/zh active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101980956A (zh) * | 2008-03-31 | 2011-02-23 | 户田工业株式会社 | 磷酸铁锂颗粒粉末的制造方法、橄榄石型结构的磷酸铁锂颗粒粉末、使用该磷酸铁锂颗粒粉末的正极材料片和非水溶剂类二次电池 |
| CN102569791A (zh) * | 2010-12-16 | 2012-07-11 | 中国科学院福建物质结构研究所 | 一种具有花状结构的磷酸铁锂及其制备方法 |
| CN102629687A (zh) * | 2012-05-03 | 2012-08-08 | 哈尔滨工业大学 | 一种LiMnPO4电极材料的形貌控制合成方法 |
| CN104326467A (zh) * | 2014-10-21 | 2015-02-04 | 浙江大学 | 一种花状磷酸锰锂纳米颗粒的制备方法及产品 |
Non-Patent Citations (1)
| Title |
|---|
| XIAOLIANG PAN ET AL.: "Inheritance of spherical morphology and optimization of assembled structures during preparation of LiMnPO4 cathodes for high electrochemical properties", 《RSC ADVANCES》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112242525A (zh) * | 2020-10-19 | 2021-01-19 | 中南大学 | 一种氮掺杂碳包覆磷酸钒锰钠复合材料及其制备方法和应用 |
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