WO2023024651A1 - 磷酸锰铁锂前驱体、磷酸锰铁锂正极材料及其制备方法和电极材料、电极以及锂离子电池 - Google Patents
磷酸锰铁锂前驱体、磷酸锰铁锂正极材料及其制备方法和电极材料、电极以及锂离子电池 Download PDFInfo
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- WO2023024651A1 WO2023024651A1 PCT/CN2022/098044 CN2022098044W WO2023024651A1 WO 2023024651 A1 WO2023024651 A1 WO 2023024651A1 CN 2022098044 W CN2022098044 W CN 2022098044W WO 2023024651 A1 WO2023024651 A1 WO 2023024651A1
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- WIPO (PCT)
- Prior art keywords
- lithium
- source
- precursor
- positive electrode
- electrode material
- Prior art date
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- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 title claims abstract description 123
- 239000002243 precursor Substances 0.000 title claims abstract description 114
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 95
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 32
- 239000007772 electrode material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000011164 primary particle Substances 0.000 claims abstract description 60
- 239000011572 manganese Substances 0.000 claims abstract description 47
- 239000012798 spherical particle Substances 0.000 claims abstract description 46
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 45
- 230000014509 gene expression Effects 0.000 claims abstract description 43
- 239000013078 crystal Substances 0.000 claims abstract description 23
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 18
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims description 96
- 238000000034 method Methods 0.000 claims description 62
- 239000002002 slurry Substances 0.000 claims description 60
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 59
- 239000002245 particle Substances 0.000 claims description 39
- 239000007788 liquid Substances 0.000 claims description 37
- 239000000463 material Substances 0.000 claims description 34
- 239000010406 cathode material Substances 0.000 claims description 29
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 23
- 239000010949 copper Substances 0.000 claims description 22
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 239000010936 titanium Substances 0.000 claims description 20
- -1 polyethylene Polymers 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims description 16
- 239000011574 phosphorus Substances 0.000 claims description 16
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 15
- 239000008139 complexing agent Substances 0.000 claims description 15
- 239000002033 PVDF binder Substances 0.000 claims description 14
- 229910021529 ammonia Inorganic materials 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 14
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 14
- 229910052748 manganese Inorganic materials 0.000 claims description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 14
- 239000011149 active material Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 239000006258 conductive agent Substances 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- 229910021645 metal ion Inorganic materials 0.000 claims description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 10
- 239000004698 Polyethylene Substances 0.000 claims description 9
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 9
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 9
- 238000000975 co-precipitation Methods 0.000 claims description 9
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 9
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 9
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 9
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 9
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 9
- 229920000573 polyethylene Polymers 0.000 claims description 9
- 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 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 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 8
- 239000002041 carbon nanotube Substances 0.000 claims description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 8
- 239000008103 glucose Substances 0.000 claims description 8
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 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 7
- 229930006000 Sucrose Natural products 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 7
- 230000014759 maintenance of location Effects 0.000 claims description 7
- 229940099596 manganese sulfate Drugs 0.000 claims description 7
- 239000011702 manganese sulphate Substances 0.000 claims description 7
- 235000007079 manganese sulphate Nutrition 0.000 claims description 7
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 239000005720 sucrose Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 238000003490 calendering Methods 0.000 claims description 6
- 229940085991 phosphate ion Drugs 0.000 claims description 6
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 6
- 239000001393 triammonium citrate Substances 0.000 claims description 6
- 235000011046 triammonium citrate Nutrition 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 239000010955 niobium Substances 0.000 claims description 5
- 229920001568 phenolic resin Polymers 0.000 claims description 5
- 239000005011 phenolic resin Substances 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 4
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052789 astatine Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 3
- 235000011007 phosphoric acid Nutrition 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-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
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 235000013877 carbamide Nutrition 0.000 claims description 2
- 230000001351 cycling effect Effects 0.000 claims description 2
- REKWWOFUJAJBCL-UHFFFAOYSA-L dilithium;hydrogen phosphate Chemical compound [Li+].[Li+].OP([O-])([O-])=O REKWWOFUJAJBCL-UHFFFAOYSA-L 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
- 229960003638 dopamine Drugs 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 229940071264 lithium citrate Drugs 0.000 claims description 2
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 claims description 2
- IDNHOWMYUQKKTI-UHFFFAOYSA-M lithium nitrite Chemical compound [Li+].[O-]N=O IDNHOWMYUQKKTI-UHFFFAOYSA-M 0.000 claims description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical group [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 2
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 2
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 239000002184 metal Substances 0.000 abstract description 7
- 238000005056 compaction Methods 0.000 abstract description 6
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 229910019142 PO4 Inorganic materials 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 46
- 239000011777 magnesium Substances 0.000 description 18
- 238000004626 scanning electron microscopy Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 238000001514 detection method Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000010907 mechanical stirring Methods 0.000 description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910000358 iron sulfate Inorganic materials 0.000 description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229910000616 Ferromanganese Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
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Definitions
- the invention relates to the technical field of lithium ion batteries, in particular to a lithium manganese iron phosphate precursor, a lithium manganese iron phosphate cathode material, a preparation method thereof, an electrode material, an electrode and a lithium ion battery.
- lithium-ion batteries have continued to grow.
- cathode materials have put forward higher requirements for their safety performance and cost while focusing on high energy density.
- Lithium cobaltate is the first positive electrode material to be commercially applied, with a capacity of up to 150mAh/g, but the relative scarcity of cobalt resources, high price and toxicity severely limit its wide application and long-term development.
- nickel-cobalt-manganese ternary materials have been developed rapidly and occupy an important position in the field of power batteries, but they still face the problem of high cost and poor safety performance.
- Olivine-type cathode materials have high safety performance and cost advantages, and lithium iron phosphate has also been applied on a large scale. Due to its low voltage platform, it is difficult to meet the demand for higher energy density. Lithium manganese iron phosphate has a high voltage platform and energy density, and takes into account the characteristics of low cost, environmental friendliness and high safety performance of lithium iron phosphate, and has received widespread attention.
- the olivine-type crystal structure restricts the migration of lithium ions, resulting in lower electronic and ionic conductivity of lithium manganese iron phosphate, which affects its capacity and rate performance.
- it is usually modified by reducing the particle size and carbon coating. This will reduce the compacted density of lithium manganese iron phosphate and increase its specific surface area, thereby affecting the volumetric energy density and processing performance of the material.
- CN106328942A discloses the preparation of a lithium manganese iron phosphate positive electrode material: lithium source, manganese source, iron source, phosphorus source solution and pore-forming agent polymer solution are mixed to obtain spinning solution, which is electrospun to obtain manganese phosphate Lithium iron precursor is sintered to obtain lithium iron manganese phosphate positive electrode material.
- the lithium manganese iron phosphate cathode material obtained by the method has higher aspect ratio and porosity, and improves the rate performance of the battery.
- this process uses electrospinning technology to prepare the precursor, which is relatively complicated, high in cost, and has higher requirements for production safety, which is not conducive to large-scale industrial application.
- CN105514422A discloses a preparation method of a precursor and lithium manganese iron phosphate: mix and react a water-soluble divalent manganese source, a divalent iron source, a divalent metal M salt and a precipitant, and obtain a pre-powder after drying; then The pre-powder is dispersed in water, and soluble and decomposable ferrous salt is added, and the oxalate precursor is obtained after heat treatment; the precursor is mixed with a water-soluble lithium source, a phosphorus source and an organic carbon source, dried and roasted, Lithium manganese iron phosphate with less metal elution and excellent cycle performance can be obtained.
- this process uses ferromanganese oxalate as a precursor, which has a high gas production during the sintering process, which is not conducive to obtaining a high compaction density.
- CN105226273A discloses a lithium manganese iron phosphate and a preparation method thereof, which is characterized in that: a sol-gel method is used to prepare lithium iron phosphate sol and lithium manganese phosphate sol; Calcination to obtain lithium manganese iron phosphate.
- the method can conveniently prepare lithium iron manganese phosphate with any ratio of manganese to iron, and the production is convenient.
- this process is obtained by co-sintering lithium iron phosphate and lithium manganese phosphate. It is difficult to evenly distribute the two substances, and it is easy to enrich ferromanganese alone, resulting in phase separation, which affects the performance of electrical properties.
- the purpose of the present invention is to provide a lithium manganese iron phosphate precursor, lithium iron manganese phosphate Positive electrode material and preparation method thereof, electrode material, electrode and lithium ion battery.
- the first aspect of the present invention provides a precursor of lithium manganese iron phosphate, the expression of the precursor is (NH 4 )Mn 1-xy Fex M y PO 4 ⁇ H 2 O/C, where , 0.1 ⁇ x ⁇ 0.6, 0 ⁇ y ⁇ 0.04; M is selected from at least one of Mg, Co, Ni, Cu, Zn and Ti.
- a second aspect of the present invention provides a method for preparing a lithium manganese iron phosphate precursor, the method comprising:
- the third aspect of the present invention provides a lithium manganese iron phosphate positive electrode material
- the expression of the positive electrode material is Li i Mn 1-xyz Fe x M y M' z (PO 4 ) 1-n N n /C, where, 0.1 ⁇ x ⁇ 0.6, 0 ⁇ y ⁇ 0.04, 0 ⁇ z ⁇ 0.04, 0.9 ⁇ i ⁇ 1.2, 0 ⁇ n ⁇ 0.04, and z and n are not 0 at the same time.
- M is selected from at least one of Mg, Co, Ni, Cu, Zn and Ti; M' is selected from Mg, Ca, Sr, Ti, V, Cr, Co, Ni, Cu, Zn, Zr, Y, Mo, At least one of Nb, B, Al, W, La and Sm; N is selected from F and/or Cl.
- a fourth aspect of the present invention provides a method for preparing a lithium manganese iron phosphate positive electrode material, the method comprising:
- lithium manganese iron phosphate precursor with the expression (NH 4 )Mn 1-xy Fe x My PO 4 ⁇ H 2 O/C, where 0.1 ⁇ x ⁇ 0.6, 0 ⁇ y ⁇ 0.04; M is selected from at least one of Mg, Co, Ni, Cu, Zn and Ti;
- the fifth aspect of the present invention provides an electrode material, the electrode material contains an active material, a conductive agent and a binder, and the active material is the lithium manganese iron phosphate positive electrode material described in the third aspect or according to the fourth aspect The lithium manganese iron phosphate positive electrode material prepared by the method.
- a sixth aspect of the present invention provides an electrode, which includes a current collector and an electrode material coated and/or filled on the current collector, and the electrode material is the electrode material described in the fifth aspect.
- the seventh aspect of the present invention provides a method for preparing an electrode, the method comprising coating and/or filling a slurry containing an active material, a conductive agent, a binder and a solvent on a current collector, drying, calendering or not calendering,
- the active material is the lithium manganese iron phosphate positive electrode material described in the third aspect or the lithium manganese iron phosphate positive electrode material prepared according to the method described in the fourth aspect.
- the eighth aspect of the present invention provides a lithium-ion battery, the lithium-ion battery includes an electrode group and an electrolyte, the electrode group and the electrolyte are sealed in the battery case, the electrode group includes a positive electrode, a negative electrode and a separator, and the separator is located on the positive electrode Between the positive electrode and the negative electrode, the positive electrode is the electrode described in the sixth aspect or the electrode prepared according to the method described in the seventh aspect.
- the present invention has the following advantages:
- the lithium manganese iron phosphate precursor provided by the present invention has a secondary spherical particle structure formed by primary particles.
- the XRD spectrum shows that the precursor is a crystal structure with an orthogonal structure, and the elements in the precursor are evenly distributed. Elements enter the metal site to form nanoparticles with a stable structure, and at the same time, the surface of the nanoparticles is coated with carbon to form a dense spherical aggregate.
- the lithium manganese iron phosphate cathode material prepared by using the precursor provided by the present invention has a high compaction density;
- the lithium manganese iron phosphate positive electrode material provided by the present invention the primary particles show that it has formed a stable carbon coating, the carbon coating is uniform, and has a dense secondary spherical shape.
- the positive electrode material provided by the present invention is applied to lithium When used in lithium-ion batteries, it can improve the electrochemical performance of lithium-ion batteries, with high specific capacity and good cycle performance;
- the uniformity of element distribution in the precursor and positive electrode material can be improved, and the material structure can be improved. Stability, so as to obtain higher compaction density and electrochemical performance, and the process is simple, suitable for industrial production.
- Fig. 1 is the scanning electron micrograph of the lithium manganese iron phosphate precursor Z1 that preparation example 1 makes;
- Fig. 2 is the scanning electron micrograph of the lithium manganese iron phosphate cathode material C1 that embodiment 1 makes;
- Fig. 3 is the scanning electron micrograph of the lithium manganese iron phosphate cathode material D4 that comparative example 4 makes;
- Fig. 4 is the XRD spectrogram of the lithium manganese iron phosphate precursor Z1 that preparation example 1 makes and the lithium manganese iron phosphate cathode material C1 that embodiment 1 makes;
- the first aspect of the present invention provides a lithium manganese iron phosphate precursor, the expression of the precursor is (NH 4 )Mn 1-xy Fe x M y PO 4 ⁇ H 2 O/C, where 0.1 ⁇ x ⁇ 0.6, 0 ⁇ y ⁇ 0.04; M is at least one selected from Mg, Co, Ni, Cu, Zn and Ti.
- the purpose of the present invention can also be achieved.
- the content of carbon in the precursor is 0.05-5wt%, preferably 0.5-2wt%, more preferably 1-1.4wt%.
- M is selected from at least one of Mg, Cu and Ti.
- the precursor has a secondary spherical particle structure formed by primary particles; preferably, the average particle size of the secondary spherical particles is 1-50 ⁇ m, preferably 5-12 ⁇ m;
- the secondary spherical particles are spherical or quasi-spherical.
- the average particle size of the primary particles of the precursor is 10-500nm, preferably 40-100nm; the surface of the primary particles is coated with carbon, which can not only enhance the compactness of the primary particles agglomerated into secondary spherical particles, but also Graphite carbon is formed to build a conductive network.
- the crystal structure of the precursor can be determined by XRD characterization.
- a second aspect of the present invention provides a method for preparing a lithium manganese iron phosphate precursor, the method comprising:
- the manganese source is at least one selected from manganese sulfate, manganese nitrate, manganese acetate and manganese chloride.
- the iron source is at least one selected from ferric sulfate, ferrous sulfate, ferric nitrate, ferric acetate and ferric chloride.
- the M source is selected from at least one of M-containing sulfates, nitrates, acetates, and chlorides.
- the phosphorus source is selected from at least one of phosphoric acid, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate and triammonium phosphate, preferably phosphoric acid, monohydrogen phosphate At least one of ammonium hydrogen and ammonium dihydrogen phosphate.
- the ammonia source is selected from ammonia water, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, triammonium phosphate, ammonium bicarbonate, ammonium carbonate, ammonium sulfate and urea At least one of them, preferably at least one of ammonia water, ammonium monohydrogen phosphate and ammonium dihydrogen phosphate.
- the complexing agent is selected from citric acid and/or triammonium citrate.
- the first carbon source is selected from graphene, carbon nanotubes, phenolic resin, polyethylene, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polypropylene and toluene diisocyanate (TDI), preferably at least one of graphene, carbon nanotubes, phenolic resin, polyethylene and polyvinylidene fluoride.
- PVDF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- TDI toluene diisocyanate
- the amount of manganese source, iron source and M source satisfies: in terms of metal elements, the molar ratio of manganese source, iron source and M source is 60-80:20-40:1; Selecting the manganese source, iron source and M source with the above molar ratio range is conducive to obtaining a structurally stable lithium manganese iron phosphate precursor, which is conducive to improving the structural stability of lithium manganese iron phosphate cathode material, so that it has higher energy density.
- the amount of the phosphorus source and the ammonia source satisfies: the molar ratio of the phosphorus source in terms of phosphate ions and the ammonia source in terms of ammonium ions is 1:1-3.
- the phosphorus source and ammonia source within the molar ratio range are conducive to the uniform complexation of manganese element, iron element and optional M element to form a stable lithium manganese iron phosphate precursor.
- the concentration of total metal ions in the first mixed liquid is 0.5-3 mol/L.
- the concentration of phosphate ions in the second mixed liquid is 0.5-3 mol/L, and the concentration of ammonium ions is 0.05-15 mol/L.
- the concentration of the complexing agent in the third mixed liquid is 0.03-10 mol/L.
- step (b) the first mixed liquid and the second mixed liquid are added to the third mixed liquid in a cocurrent manner;
- the co-precipitation reaction is carried out under stirring, and the conditions of the co-precipitation reaction include: a stirring speed of 500-1000 rpm, a pH of 2-8, a temperature of 25-90° C., and a time of 1-2 h.
- the pH of the co-precipitation reaction can be controlled to be 2-8 by adjusting the adding speed of the second mixed solution (the error of the pH can be ⁇ 0.5).
- the method of solid-liquid separation is not particularly limited, and existing techniques known to those skilled in the art can be used, for example, suction filtration or pressure filtration can be used for solid-liquid separation to obtain solid materials .
- step (c) the solid-liquid separation method is obtained by pure water
- the solid material is cleaned until the conductivity of the filtrate is less than or equal to 200 ⁇ s/cm to obtain a lithium manganese iron phosphate precursor.
- the third aspect of the present invention provides a lithium manganese iron phosphate positive electrode material
- the expression of the positive electrode material is Li i Mn 1-xyz Fe x M y M' z (PO 4 ) 1-n N n /C, where, 0.1 ⁇ x ⁇ 0.6, 0 ⁇ y ⁇ 0.04, 0 ⁇ z ⁇ 0.04, 0.9 ⁇ i ⁇ 1.2, 0 ⁇ n ⁇ 0.04, and z and n are not 0 at the same time;
- M is selected from at least one of Mg, Co, Ni, Cu, Zn and Ti; M' is selected from Mg, Ca, Sr, Ti, V, Cr, Co, Ni, Cu, Zn, Zr, Y, Mo, At least one of Nb, B, Al, W, La and Sm; N is selected from F and/or Cl.
- the purpose of the present invention can be achieved.
- the content of carbon in the positive electrode material is 0.5-10wt%, preferably 1-3wt%, more preferably 1.8-3wt%.
- M is selected from at least one of Mg, Cu and Ti.
- M' is selected from at least one of Ti, Nb and B.
- N is F
- M and/or M' is distributed in a gradient on the surface of the positive electrode material.
- the positive electrode material has a secondary spherical particle structure formed by primary particles; preferably, the average particle size of the secondary spherical particles is 1-50 ⁇ m, preferably 7-15 ⁇ m; Preferably, the secondary spherical particles are spherical or quasi-spherical.
- the average particle size of the primary particles of the positive electrode material is 10-500 nm, preferably 60-100 nm; in the positive electrode material, the surface of the primary particles has a uniform carbon coating, and the agglomerated secondary spherical particles have a dense structure, And has a stable doping structure, anion doping and/or metal ion doping in a gradient distribution on the surface of the secondary spherical particles, combined with uniform carbon coating, so that the lithium iron manganese phosphate cathode material can be used with lithium When used as an ion battery, it can improve the electrochemical performance of the lithium-ion battery, with high specific capacity and good cycle performance.
- the positive electrode material has a compacted density of 1.5-2.5 g/cm 3 , a specific capacity of 145-160 mAh/g at a rate of 0.1C, and a capacity retention after 80 cycles The rate is 85-97%;
- the compacted density of the positive electrode material is 2.09-2.31g/cm 3
- the specific capacity at 0.1C rate is 152.1-157.2mAh/g
- the capacity retention rate after 80 cycles is 92.6-95.9% .
- a fourth aspect of the present invention provides a method for preparing a lithium manganese iron phosphate positive electrode material, the method comprising:
- lithium manganese iron phosphate precursor with the expression (NH 4 )Mn 1-xy Fe x My PO 4 ⁇ H 2 O/C, where 0.1 ⁇ x ⁇ 0.6, 0 ⁇ y ⁇ 0.04; M is selected from at least one of Mg, Co, Ni, Cu, Zn and Ti;
- the lithium manganese iron phosphate precursor whose expression is (NH 4 )Mn 1-xy Fex M y PO 4 ⁇ H 2 O/C can refer to the above selection, and will not be repeated here.
- the lithium source is selected from lithium oxide, lithium hydroxide, lithium chloride, lithium nitrate, lithium nitrite, lithium formate, lithium acetate, lithium oxalate, At least one of lithium carbonate, lithium phosphate, dilithium hydrogen phosphate, lithium dihydrogen phosphate and lithium citrate, preferably at least one of lithium carbonate, lithium hydroxide and lithium chloride.
- the second carbon source is selected from at least one of glucose, sucrose, fructose, cellulose, starch, citric acid, polyacrylic acid, polyethylene glycol and dopamine One, preferably at least one of glucose, sucrose, starch and cellulose.
- the source of M' is selected from oxygen-containing compounds and/or chlorides containing M', and the oxygen-containing compounds containing M' preferably contain M 'at least one of sulfate, nitrate, acetate, oxide and acid; more preferably, the source of M' is at least one of titanium dioxide, niobium pentoxide and boric acid.
- the N source is selected from at least one of ammonium fluoride, ammonium bifluoride, lithium fluoride, ammonium chloride and lithium chloride, preferably fluorine Lithium oxide.
- the molar ratio of the lithium manganese iron phosphate precursor, lithium source, M' source and/or N source to the second carbon source is 1:0.52-1.05:0.005-0.01:0.5- 1. Selecting the lithium manganese iron phosphate precursor, the lithium source, the M' source and/or the N source and the second carbon source in the above molar ratio range is conducive to improving the electronic conductivity and ion conductivity of the positive electrode material and obtaining higher electrical conductivity. performance.
- mixing and homogenizing may be performed by mechanical stirring to form a uniform second slurry.
- stirring temperature and the stirring speed are no particular limitation on the stirring temperature and the stirring speed, as long as the uniform second slurry can be formed.
- the type of the solvent is not particularly limited, subject to the ability to form a uniform second slurry
- the solvent can be water, ethanol, etc., preferably water; There is no particular limitation on the amount used, and it is also subject to the ability to form a uniform second slurry.
- the solvent in the second slurry can be removed by direct evaporation, and the temperature and process of evaporation can adopt existing techniques known to those skilled in the art, for example , static drying or spray drying may be used to remove the solvent in the second slurry.
- the calcination is carried out under the protection of an inert atmosphere, and the inert atmosphere may be a nitrogen atmosphere and/or an argon atmosphere;
- the calcination conditions include: the calcination temperature is 500-1000°C, preferably 600-800°C; the calcination time is 4-20h, preferably 6-12h.
- the method for preparing lithium manganese iron phosphate positive electrode material comprises:
- the doping element in the method for preparing lithium manganese iron phosphate positive electrode material, can effectively enter the metal site through precursor doping to form a stable structure; through the introduction of carbon source coating through the precursor, It can make the carbon coating distributed on the surface of the primary particles uniform, form a stable conductive network, and make the primary particles tightly bonded, agglomerating to form dense secondary spherical particles; and then carry out batching and sintering by secondary doping and coating carbon , can achieve gradient doping of different elements and coating of different carbon sources.
- the preparation method has a simple process, can achieve good doping and coating effects, and the prepared lithium manganese iron phosphate positive electrode material has high compaction density and electrochemical performance.
- the fifth aspect of the present invention provides an electrode material, the electrode material contains an active material, a conductive agent and a binder, and the active material is the lithium manganese iron phosphate positive electrode material described in the third aspect or according to the fourth aspect The lithium manganese iron phosphate positive electrode material prepared by the method.
- a sixth aspect of the present invention provides an electrode, which includes a current collector and an electrode material coated and/or filled on the current collector, and the electrode material is the electrode material described in the fifth aspect.
- the seventh aspect of the present invention provides a method for preparing an electrode, the method comprising coating and/or filling a slurry containing an active material, a conductive agent, a binder and a solvent on a current collector, drying, calendering or not calendering,
- the active material is the lithium manganese iron phosphate positive electrode material described in the third aspect or the lithium manganese iron phosphate positive electrode material prepared according to the method described in the fourth aspect.
- the eighth aspect of the present invention provides a lithium-ion battery, the lithium-ion battery includes an electrode group and an electrolyte, the electrode group and the electrolyte are sealed in the battery case, the electrode group includes a positive electrode, a negative electrode and a separator, and the separator is located on the positive electrode Between the positive electrode and the negative electrode, the positive electrode is the electrode described in the sixth aspect or the electrode prepared according to the method described in the seventh aspect.
- the present invention only relates to the improvement of the active material contained in the prior art electrode material, there is no special limitation on other compositions and structures of the lithium-ion battery.
- the content and the kind of the conductive agent of positive electrode material described in the present invention are known to those skilled in the art, and described conductive agent can be selected from conductive carbon black (Super-P), acetylene One or more of black, Ketjen black, graphene and carbon nanotubes, the present invention preferably uses carbon nanotubes as the conductive agent.
- conductive carbon black Super-P
- the binder of the positive electrode material in the present invention can adopt all the binders known in the art that can be used for lithium-ion batteries. It can be selected from one or more of fluorine-containing resins and/or polyolefin compounds, such as polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF) and styrene-butadiene rubber.
- PTFE polytetrafluoroethylene
- PVDF polyvinylidene fluoride
- the present invention preferably uses polyvinylidene fluoride as the adhesive Binder.
- the mass ratio of lithium manganese iron phosphate cathode material, conductive agent and binder is 80-96:10-2:10-2, preferably 90:5:5.
- the current collector in the present invention can be various current collectors known to those skilled in the art, such as aluminum foil, copper foil, nickel-plated steel strip, and the like.
- the present invention selects aluminum foil as the current collector.
- the solvent described in the present invention can be all solvents known in the art that can be used in the preparation of lithium-ion battery electrodes, such as ethanol and/or N-methylpyrrolidone (NMP), preferably N-methylpyrrolidone.
- NMP N-methylpyrrolidone
- the amount of solvent used is that which will form the desired coating slurry.
- metal lithium sheets can be used as negative electrodes of lithium ion batteries.
- the electrolyte solution of the lithium ion battery can be the electrolyte solution conventionally used in this field, and the concentration of electrolyte solution is generally 0.2-8mol/L, and the present invention selects 1mol/L LiPF 6 , ethylene carbonate ( EC) and an equal mixture of diethyl carbonate (DEC) as the electrolyte.
- the separator of the present invention has electrical insulation performance and liquid retention performance, is arranged between the positive pole and the negative pole, and is sealed in the battery casing together with the positive pole, the negative pole and the electrolyte.
- the diaphragm can be various diaphragms commonly used in the art, such as polyethylene, polypropylene, modified polyethylene felt, modified polypropylene felt, ultra-fine glass fiber Felt, vinylon felt or nylon felt and wettable polyolefin microporous membrane are welded or bonded composite membrane, the present invention uses polyethylene porous membrane as the diaphragm.
- Information such as the composition of materials, the structure or morphology of atoms or molecules inside materials can be obtained by XRD.
- the surface morphology of the materials was characterized by scanning electron microscopy (SEM).
- SEM scanning electron microscopy
- the model of the scanning electron microscope used is S-4800 (manufactured by Hitachi, Japan), and the test conditions of the scanning electron microscope are: accelerating voltage 1kV, magnification 10K.
- the average particle size of primary particles and secondary spherical particles in the material is measured by scanning electron microscope pictures.
- C element was carried out on Elementar Micro Cube Elemental Analyzer.
- the specific operation method and conditions are as follows: Weigh 1-2 mg of the sample in a tin cup, put it into the automatic sampling tray, and enter the combustion tube through the ball valve to burn at a temperature of 1000 °C (in order to remove atmospheric interference during sample injection, use helium blowing Sweep), and then use reduced copper to reduce the burned gas to form carbon dioxide, and then use TCD detector to detect carbon dioxide.
- each element and its content were obtained by testing with an inductively coupled plasma spectrometer (ICP).
- ICP inductively coupled plasma spectrometer
- the instrument was purchased from PerkinElmer Instruments Co., Ltd., and the model is PE-7000DV.
- Preparation examples 1-7 are used to illustrate the lithium manganese iron phosphate precursor and its preparation method.
- Figure 1 is a scanning electron microscope image of Z1. It can be observed from the figure that the precursor Z1 has a secondary spherical particle structure formed by primary particles. The average particle size is 8 ⁇ m.
- the precursor Z2 has a secondary spherical particle structure formed by primary particles, and the primary particles are densely bonded.
- the average particle size of the primary particles is 50 nm, and the average particle size of the secondary spherical particles is 10 ⁇ m.
- the precursor Z2 has an orthorhombic crystal structure.
- the precursor Z3 has a secondary spherical particle structure formed by primary particles, and the primary particles are densely bonded.
- the average particle size of the primary particles is 100 nm, and the average particle size of the secondary spherical particles is 12 ⁇ m.
- the precursor Z3 has an orthorhombic crystal structure.
- the precursor Z4 has a secondary spherical particle structure formed by primary particles, and the primary particles are densely bonded.
- the average particle size of the primary particles is 80 nm, and the average particle size of the secondary spherical particles is 10 ⁇ m.
- the precursor Z4 has an orthorhombic crystal structure.
- the precursor Z5 has a secondary spherical particle structure formed by primary particles, and the primary particles are densely bonded.
- the average particle size of the primary particles is 50 nm, and the average particle size of the secondary spherical particles is 6 ⁇ m.
- the precursor Z5 has an orthorhombic crystal structure.
- the precursor Z6 has a secondary spherical particle structure formed by primary particles, and the primary particles are densely bonded.
- the average particle size of the primary particles is 40 nm, and the average particle size of the secondary spherical particles is 5 ⁇ m.
- the precursor Z6 has an orthorhombic crystal structure.
- the precursor Z7 has a secondary spherical particle structure formed by primary particles, and the primary particles are densely bonded.
- the average particle size of the primary particles is 80 nm, and the average particle size of the secondary spherical particles is 8 ⁇ m.
- the precursor Z7 has an orthorhombic crystal structure.
- step (a) Prepare the lithium manganese iron phosphate precursor according to the method of Preparation Example 1, the difference is that in step (a), the third mixed solution does not contain PVDF, and the expression is (NH 4 )Mn 0.7 Fe 0.29 Mg 0.01 PO 4 ⁇ H 2 O manganese iron phosphate precursor DZ1.
- DZ1 is in the form of random flakes and no spherical aggregates are formed.
- step (a) the first mixed solution does not contain magnesium sulfate, and the third mixed solution does not contain PVDF, and the expression is (NH 4 )Mn 0.7 Fe 0.3 PO 4 ⁇ H 2 O lithium manganese iron phosphate precursor DZ2.
- DZ2 is in the form of random agglomerated blocks without forming dense spherical agglomerates.
- DZ3 is in the form of random agglomerated blocks without forming dense spherical agglomerates.
- Examples 1-7 are used to illustrate lithium manganese iron phosphate positive electrode material and its preparation method.
- the lithium manganese iron phosphate positive electrode material C1 has a secondary spherical particle structure formed by primary particles, and the primary particles are densely bonded.
- the average particle size of primary particles is 80nm
- the average particle size of secondary spherical particles is 9 ⁇ m.
- the positive electrode material C2 has a secondary spherical particle structure formed by primary particles, and the primary particles are densely bonded.
- the average particle size of the primary particles is 60 nm, and the average particle size of the secondary spherical particles is 11 ⁇ m.
- the positive electrode material C2 has an orthorhombic crystal structure.
- Precursor Z3, lithium chloride, niobium pentoxide and starch expressed as (NH 4 )Mn 0.7 Fe 0.29 Cu 0.01 PO 4 ⁇ H 2 O/C are calculated according to the molar ratio of 1:1.05:0.005:0.5 than mixed with pure water, and mixed uniformly by mechanical stirring to obtain the second slurry;
- the positive electrode material C3 has a secondary spherical particle structure formed by primary particles, and the primary particles are densely bonded.
- the average particle size of the primary particles is 100 nm, and the average particle size of the secondary spherical particles is 15 ⁇ m.
- the positive electrode material C3 has an orthorhombic crystal structure.
- the positive electrode material C4 has a secondary spherical particle structure formed by primary particles, and the primary particles are densely bonded.
- the average particle size of the primary particles is 80 nm, and the average particle size of the secondary spherical particles is 10 ⁇ m.
- the positive electrode material C4 has an orthorhombic crystal structure.
- the positive electrode material C5 has a secondary spherical particle structure formed by primary particles, and the primary particles are densely bonded.
- the average particle size of the primary particles is 70 nm, and the average particle size of the secondary spherical particles is 8 ⁇ m.
- the positive electrode material C5 has an orthorhombic crystal structure.
- the positive electrode material C6 has a secondary spherical particle structure formed by primary particles, and the primary particles are densely bonded.
- the average particle size of the primary particles is 60 nm, and the average particle size of the secondary spherical particles is 7 ⁇ m.
- the positive electrode material C6 has an orthorhombic crystal structure.
- the positive electrode material C7 has a secondary spherical particle structure formed by primary particles, and the primary particles are densely bonded.
- the average particle size of the primary particles is 90 nm, and the average particle size of the secondary spherical particles is 10 ⁇ m.
- the positive electrode material C7 has an orthorhombic crystal structure.
- the positive electrode material D1 has a secondary spherical particle structure formed by primary particles, and the primary particles are densely bonded.
- the average particle size of the primary particles is 90 nm, and the average particle size of the secondary spherical particles is 10 ⁇ m.
- the positive electrode material D2 is in the form of random agglomerated blocks, and no dense spherical agglomerates are formed.
- the difference is that the precursor DZ2 (expressed as (NH 4 )Mn 0.7 Fe 0.3 PO 4 ⁇ H 2 O) is used to prepare the lithium manganese iron phosphate cathode material, and the obtained cathode material is denoted as D3 , the expression of D3 is shown in Table 1.
- the positive electrode material D3 is in the form of random agglomerated blocks, and no dense spherical agglomerates are formed.
- the morphology of the positive electrode material D4 was observed with a scanning electron microscope, as shown in Figure 3. It can be seen from the figure that D4 is in the form of random agglomerated blocks without forming dense agglomerates.
- D5 is in the form of random agglomerated blocks without forming dense agglomerates.
- This test example is used to illustrate electrode materials, electrodes, lithium-ion batteries and their preparation methods.
- Preparation of the positive electrode sheet respectively carry out the NMP solution of the lithium iron manganese phosphate positive electrode materials C1-C7 obtained in Examples 1-7, the conductive agent carbon nanotubes, and the binder PVDF at a mass ratio of 90:5:5 mix.
- the specific method is: grind the dried positive electrode material and conductive agent in a mortar for 15 minutes, after grinding evenly, add PVDF solution (5% by mass fraction) according to the proportion, and stir on a magnetic stirrer for 6 hours;
- the slurry is uniformly coated on the aluminum foil of the current collector, and then dried in a vacuum oven at 60°C for 20 hours, and then stamped with a pressure of 100MPa to form a positive electrode sheet with a diameter of 12mm and a thickness of 120 ⁇ m, and put the positive electrode sheet at 120°C Dry in a vacuum oven for 12 h.
- Battery assembly a metal lithium sheet with a diameter of 17 mm and a thickness of 1 mm is used as the negative electrode, and a polyethylene porous film with a thickness of 25 ⁇ m coated with an alumina ceramic layer is used as the separator, and 1 mol/L LiPF 6 , An equal mixture of ethylene carbonate (EC) and diethyl carbonate (DEC) is used as the electrolyte, and the positive pole piece, separator, negative pole piece and electrolyte are placed in an Ar gas glove box with a water content and an oxygen content of less than 5ppm.
- the 2025-type button batteries were assembled inside, and the lithium-ion batteries A1-A7 were prepared respectively.
- Electrochemical performance test Use the LAND CT2001A charge and discharge instrument of Wuhan Lanbo Electronics Co., Ltd. to conduct charge and discharge tests on the battery.
- the charge and discharge voltage range is 2.5 to 4.4V.
- the assembled lithium-ion batteries A1-A7 were tested for specific capacity and cycle performance at 1C rate. The test results are shown in Table 1.
- the positive electrode sheet was prepared according to the method of the test example, except that the positive active materials used were the lithium manganese iron phosphate positive electrode materials D1-D5 obtained in Comparative Examples 1-5.
- the charge-discharge curves of the lithium manganese iron phosphate positive electrode material C1 prepared in Example 1 and the lithium manganese iron phosphate positive electrode material D1 prepared in Comparative Example 1 at a rate of 0.1C are shown in Figure 5. It can be seen from the figure that the positive electrode The button battery assembled with material C1 has a discharge specific capacity of 156.8mAh/g at 2.5-4.4V, 0.1C rate, and 149.7mAh/g at 1C rate, and the capacity retention rate after 80 cycles was 95.8%. Compared with the positive electrode material D1 of Comparative Example 1, the discharge specific capacity of the positive electrode material C1 of Example 1 at 0.1C and 1C rates and the capacity retention rate after 80 cycles of cycling are significantly improved.
- the lithium manganese iron phosphate positive electrode material provided by the present invention has a high compaction density and can be used in lithium-ion batteries to significantly increase the specific capacity of the lithium-ion battery and improve the cycle performance of the lithium-ion battery.
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Abstract
Description
Claims (20)
- 一种磷酸锰铁锂前驱体,其特征在于,所述前驱体的表达式为(NH 4)Mn 1-x-yFe xM yPO 4·H 2O/C,式中,0.1<x≤0.6,0≤y≤0.04;M选自Mg、Co、Ni、Cu、Zn和Ti中的至少一种。
- 根据权利要求1所述的磷酸锰铁锂前驱体,其中,基于所述前驱体的总重量,所述前驱体中碳元素的含量为0.05-5wt%,优选为0.5-2wt%,更优选为1-1.4wt%。
- 根据权利要求1或2所述的磷酸锰铁锂前驱体,其中,所述前驱体的表达式中,0.19≤x≤0.39,0.01≤y≤0.04;和/或,M选自Mg、Cu和Ti中的至少一种。
- 根据权利要求1-3中任意一项所述的磷酸锰铁锂前驱体,其中,所述前驱体具有由一次颗粒形成的二次球颗粒结构;和/或,所述二次球颗粒的平均粒度为1-50μm,优选为5-12μm;和/或,所述前驱体的一次颗粒的平均粒度为10-500nm,优选为40-100nm;和/或,所述前驱体具有正交晶系的晶体结构。
- 一种制备磷酸锰铁锂前驱体的方法,其特征在于,该方法包括:(a)提供含有锰源、铁源和任选的M源的第一混合液;提供含有磷源和氨源的第二混合液;提供含有络合剂和第一碳源的第三混合液;(b)将第一混合液和第二混合液加入第三混合液中进行共沉淀反应,得到第一浆料;(c)将第一浆料进行固液分离和洗涤,得到磷酸锰铁锂前驱体。
- 根据权利要求5所述的方法,其中,步骤(a)中,所述锰源选自硫酸锰、硝酸锰、乙酸锰和氯化锰中的至少一种;和/或,所述铁源选自硫酸铁、硫酸亚铁、硝酸铁、乙酸铁和氯化铁中的至少一种;和/或,所述M源选自含有M的硫酸盐、硝酸盐、乙酸盐和氯化物中的至少一种;和/或,所述磷源选自磷酸、磷酸一氢铵、磷酸二氢铵和磷酸三铵中的至少一种,优选为磷酸、磷酸一氢铵和磷酸二氢铵中的至少一种;和/或,所述氨源选自氨水、磷酸一氢铵、磷酸二氢铵、磷酸三铵、碳酸氢铵、碳酸铵、硫酸铵和尿素中的至少一种,优选为氨水、磷酸一氢铵和磷酸二氢铵中的至少一种;和/或,所述络合剂选自柠檬酸和/或柠檬酸三铵;和/或,所述第一碳源选自石墨烯、碳纳米管、酚醛树脂、聚乙烯、聚偏氟乙烯、聚四氟乙烯、聚丙烯和甲苯二异氰酸酯中的至少一种,优选为石墨烯、碳纳米管、酚醛树脂、聚乙烯和聚偏氟乙烯中的至少一种;和/或锰源、铁源和M源的用量满足:以金属元素计,锰源、铁源和M源的摩尔比为60-80:20-40:1;和/或磷源和氨源的用量满足:以磷酸根离子计的磷源和以铵根离子计的氨源的摩尔比为1:1-3。
- 根据权利要求5或6所述的方法,其中,所述第一混合液中的总金属离子的浓度为0.5-3mol/L;和/或,所述第二混合液中的磷酸根离子的浓度为0.5-3mol/L,铵根离子的浓度为0.05-15mol/L;和/或,所述第三混合液中的络合剂的浓度为0.03-10mol/L。
- 根据权利要求5-7中任意一项所述的方法,其中,步骤(b)中,第一混合液和第二混合液通过并流的方式加入第三混合液中;和/或所述共沉淀反应在搅拌下进行,所述共沉淀反应的条件包括:搅拌速度为500-1000rpm,pH为2-8,温度为25-90℃,时间为1-2h。
- 一种磷酸锰铁锂正极材料,其特征在于,所述正极材料的表达式为Li iMn 1-x-y-zFe xM yM′ z(PO 4) 1-nN n/C,式中,0.1<x≤0.6,0≤y≤0.04,0≤z≤0.04,0.9<i≤1.2,0≤n≤0.04,且z、n不同时为0;M选自Mg、Co、Ni、Cu、Zn和Ti中的至少一种;M′选自Mg、Ca、Sr、Ti、V、Cr、Co、Ni、Cu、Zn、Zr、Y、Mo、Nb、B、Al、W、La和Sm中的至少一种;N选自F和/或Cl。
- 根据权利要求9所述的磷酸锰铁锂正极材料,其中,基于所述正极材料的总重量,所述正极材料中碳元素的含量为0.5-10wt%,优选为1-3wt%,更优选为1.8-3wt%。
- 根据权利要求9或10所述的磷酸锰铁锂正极材料,其中,所述正极材料的表达式中,0.19≤x≤0.39,0.01≤y≤0.04,0.01≤z≤0.04,1≤i≤1.1,0.01≤n≤0.04;优选地,所述正极材料的表达式中,0.19≤x≤0.39,0.01≤y≤0.04,0.01≤z≤0.02,1.02≤i≤1.05,0.01≤n≤0.02;和/或M选自Mg、Cu和Ti中的至少一种;和/或,M′选自Ti、Nb和B中的至少一种;和/或,N为F。
- 根据权利要求9-11中任意一项所述的磷酸锰铁锂正极材料,其中,所述正极材料具有由一次颗粒形成的二次球颗粒结构;和/或,所述二次球颗粒的平均粒度为1-50μm,优选为7-15μm;和/或,所述正极材料的一次颗粒的平均粒度为10-500nm,优选为60-100nm;和/或所述正极材料具有正交晶系的晶体结构;和/或所述正极材料的压实密度为1.5-2.5g/cm 3,在0.1C倍率下的比容量为145-160mAh/g,循环80周后的容量保持率为85-97%;优选地,所述正极材料的压实密度为2.09-2.31g/cm 3,在0.1C倍率下的比容量为152.1-157.2mAh/g,循环80周后的容量保持率为92.6-95.9%。
- 一种制备磷酸锰铁锂正极材料的方法,其特征在于,该方法包括:(1)提供表达式为(NH 4)Mn 1-x-yFe xM yPO 4·H 2O/C的磷酸锰铁锂前驱体,式中,0.1<x≤0.6,0≤y≤0.04;M选自Mg、Co、Ni、Cu、Zn和Ti中的至少一种;(2)在溶剂的存在下,将磷酸锰铁锂前驱体、锂源、第二碳源、M′源和/或N源进行混合匀质,得到第二浆料;(3)除去第二浆料中的溶剂,得到干料,然后在惰性气氛保护下,将干料进行煅烧,得到磷酸锰铁锂正极材料。
- 根据权利要求13所述的方法,其中,步骤(2)中,所述锂源选自氧化锂、氢氧化锂、氯化锂、硝酸锂、亚硝酸锂、甲酸锂、乙酸锂、草酸锂、碳酸锂、磷酸锂、磷酸氢二锂、磷酸二氢锂和柠檬酸锂中的至少一种,优选为碳酸锂、氢氧化锂和氯化锂中的至少一种;和/或所述第二碳源选自葡萄糖、蔗糖、果糖、纤维素、淀粉、柠檬酸、聚丙烯酸、聚乙二醇和多巴胺中的至少一种,优选为葡萄糖、蔗糖、淀粉和纤维素中的至少一种;和/或所述M′源选自含有M′的含氧化合物和/或氯化物,优选为二氧化钛、五氧化二铌和硼酸中的至少一种;和/或所述N源选自氟化铵、氟化氢铵、氟化锂、氯化铵和氯化锂中的至少一种,优选为氟化锂。
- 根据权利要求13或14所述的方法,其中,磷酸锰铁锂前驱体、锂源、M′源和/或N源与第二碳源的摩尔比为1:0.52-1.05:0.005-0.01:0.5-1。
- 根据权利要求12或13所述的方法,其中,步骤(3)中,所述煅烧的条件包括:煅烧温度为500-1000℃,优选为600-800℃;煅烧时间为4-20h,优选为6-12h;和/或,所述惰性气氛为氮气气氛和/或氩气气氛。
- 一种电极材料,该电极材料含有活性物质、导电剂和粘结剂,其特征在于,所述活性物质为权利要求9-12中任意一项所述的磷酸锰铁锂正极材料或者为按照权利要求13-16中任意一项所述的方法制备得到的磷酸锰铁锂正极材料。
- 一种电极,该电极包括集流体及涂覆和/或填充于集流体上的电极材料,其特征在于,所述电极材料为权利要求17所述的电极材料。
- 一种制备电极的方法,该方法包括将含有活性物质、导电剂和粘结剂与溶剂的浆料涂覆和/或填充在集流体上,干燥,压延或不压延,其特征在于,所述活性物质为权利要求9-12中任意一项所述的磷酸锰铁锂正极材料或者为按照权利要求13-16中任意一项所述的方法制备得到的磷酸锰铁锂正极材料。
- 一种锂离子电池,该锂离子电池包括电极组和电解液,所述电极组和电解液密封在电池壳体内,所述电极组包括正极、负极和隔膜,隔膜位于正极和负 极之间,其特征在于,所述正极为权利要求18所述的电极或者为按照权利要求19所述的方法制备得到的电极。
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CN117720086B (zh) * | 2024-02-07 | 2024-05-14 | 湖南裕能新能源电池材料股份有限公司 | 磷酸锰铁锂基材、正极材料及其制备方法及锂电池 |
Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3000956A1 (fr) * | 2013-01-17 | 2014-07-18 | Commissariat Energie Atomique | Procede de synthese d'un compose lim1-x-y-znyqzfexpo4 et son utilisation comme materiau d'electrode pour accumulateur au lithium |
CN104167549A (zh) * | 2014-07-04 | 2014-11-26 | 深圳市贝特瑞新能源材料股份有限公司 | 一种微纳结构磷酸铁锰锂正极材料及其制备方法、锂离子电池 |
JPWO2013038516A1 (ja) * | 2011-09-14 | 2015-03-23 | 住友金属鉱山株式会社 | リン酸アンモニウムマンガン鉄とその製造方法、および該リン酸アンモニウムマンガン鉄を用いたリチウム二次電池用正極活物質とその製造方法、ならびに該正極活物質を用いたリチウム二次電池 |
CN105226273A (zh) | 2014-05-30 | 2016-01-06 | 比亚迪股份有限公司 | 一种磷酸锰铁锂及其制备方法及应用 |
CN105514422A (zh) | 2014-09-26 | 2016-04-20 | 比亚迪股份有限公司 | 一种前驱体和磷酸锰铁锂及其制备方法和应用 |
CN105826536A (zh) * | 2016-05-19 | 2016-08-03 | 贵州安达科技能源股份有限公司 | 一种磷酸锰铁锂及其制备方法 |
CN106328942A (zh) | 2016-11-11 | 2017-01-11 | 宁德新能源科技有限公司 | 一种磷酸铁锰锂正极材料,其制备方法和应用 |
CN106450239A (zh) * | 2016-12-08 | 2017-02-22 | 深圳市鑫永丰科技有限公司 | 一种磷酸锰铁锂复合材料及其制备方法与锂离子电池 |
CN109244391A (zh) * | 2018-08-22 | 2019-01-18 | 江苏元景锂粉工业有限公司 | 一种氮参杂碳包覆磷酸锰铁锂材料及其制备方法 |
CN111900344A (zh) * | 2020-07-02 | 2020-11-06 | 江苏海基新能源股份有限公司 | 一种碳包覆磷酸锰铁锂正极材料的制备方法 |
CN111933915A (zh) * | 2020-09-14 | 2020-11-13 | 天津斯科兰德科技有限公司 | 一种磷酸锰铁锂正极材料及其制备方法和应用 |
CN113072049A (zh) * | 2021-03-26 | 2021-07-06 | 天津斯科兰德科技有限公司 | 一种高压实密度磷酸锰铁锂/碳复合正极材料的制备方法 |
CN113942990A (zh) * | 2021-08-25 | 2022-01-18 | 北京当升材料科技股份有限公司 | 磷酸锰铁锂前驱体、磷酸锰铁锂正极材料及其制备方法和电极材料、电极以及锂离子电池 |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1305148C (zh) * | 2005-01-12 | 2007-03-14 | 清华大学 | 高密度球形磷酸铁锂及磷酸锰铁锂的制备方法 |
CN102024951A (zh) | 2010-10-30 | 2011-04-20 | 华南理工大学 | 一种氟离子掺杂的磷酸铁锂材料及其制备方法 |
JP5120523B1 (ja) | 2011-09-14 | 2013-01-16 | 住友金属鉱山株式会社 | リン酸アンモニウムマンガン鉄マグネシウムとその製造方法、および該リン酸アンモニウムマンガン鉄マグネシウムを用いたリチウム二次電池用正極活物質とその製造方法、ならびに該正極活物質を用いたリチウム二次電池 |
CN103367746A (zh) | 2013-07-16 | 2013-10-23 | 烟台卓能电池材料有限公司 | 一种多离子掺杂的碳包覆磷酸铁锂电池材料及其制备方法 |
JP5700345B2 (ja) * | 2013-07-19 | 2015-04-15 | 太平洋セメント株式会社 | リン酸マンガンリチウム正極活物質前駆体の製造方法 |
KR20160083630A (ko) * | 2014-12-31 | 2016-07-12 | 삼성에스디아이 주식회사 | 리튬이차전지용 올리빈형 양극 활물질, 그것의 제조방법 및 그것을 포함하는 리튬이차전지 |
JP5999240B1 (ja) | 2015-09-30 | 2016-09-28 | 住友大阪セメント株式会社 | リチウムイオン二次電池用電極材料およびその製造方法 |
CN105355885A (zh) * | 2015-11-26 | 2016-02-24 | 中南大学 | 一种锂离子电池复合正极材料LiMn1-xFexPO4/C的合成方法 |
CN106816582B (zh) * | 2015-11-30 | 2019-08-13 | 比亚迪股份有限公司 | 一种磷酸锰铁锂类材料及其制备方法以及电池浆料和正极与锂电池 |
CN106935851B (zh) * | 2015-12-31 | 2019-11-29 | 惠州比亚迪电池有限公司 | 一种磷酸锰铁锂类材料及其制备方法以及电池浆料和正极与锂电池 |
KR20170098728A (ko) * | 2016-02-22 | 2017-08-30 | 주식회사 엘지화학 | 리튬 전이금속 인산화물 입자를 포함하는 양극 활물질, 이의 제조 방법, 및 이를 포함하는 리튬 이차 전지 |
CN107658432A (zh) * | 2016-07-26 | 2018-02-02 | 微宏动力系统(湖州)有限公司 | 改性金属氧化物正极材料的制备方法及其正极材料 |
JP6501011B1 (ja) | 2018-02-28 | 2019-04-17 | 住友大阪セメント株式会社 | 電極材料、電極材料の製造方法、電極、及びリチウムイオン電池 |
CN109103452A (zh) * | 2018-08-28 | 2018-12-28 | 重庆大学 | 纳米磷酸锰铁锂正极复合材料的制备方法 |
CN111268664A (zh) | 2020-02-13 | 2020-06-12 | 上海华谊(集团)公司 | 磷酸锰铁中间体、磷酸锰铁锂和它们的制造方法 |
CN113078319A (zh) * | 2021-03-26 | 2021-07-06 | 天津斯科兰德科技有限公司 | 一种磷酸锰铁锂/碳复合纳米颗粒正极材料的制备方法 |
-
2021
- 2021-08-30 CN CN202111002582.3A patent/CN113942990B/zh active Active
-
2022
- 2022-06-10 EP EP22859998.1A patent/EP4245721A1/en active Pending
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-
2023
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Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPWO2013038516A1 (ja) * | 2011-09-14 | 2015-03-23 | 住友金属鉱山株式会社 | リン酸アンモニウムマンガン鉄とその製造方法、および該リン酸アンモニウムマンガン鉄を用いたリチウム二次電池用正極活物質とその製造方法、ならびに該正極活物質を用いたリチウム二次電池 |
FR3000956A1 (fr) * | 2013-01-17 | 2014-07-18 | Commissariat Energie Atomique | Procede de synthese d'un compose lim1-x-y-znyqzfexpo4 et son utilisation comme materiau d'electrode pour accumulateur au lithium |
CN105226273A (zh) | 2014-05-30 | 2016-01-06 | 比亚迪股份有限公司 | 一种磷酸锰铁锂及其制备方法及应用 |
CN104167549A (zh) * | 2014-07-04 | 2014-11-26 | 深圳市贝特瑞新能源材料股份有限公司 | 一种微纳结构磷酸铁锰锂正极材料及其制备方法、锂离子电池 |
CN105514422A (zh) | 2014-09-26 | 2016-04-20 | 比亚迪股份有限公司 | 一种前驱体和磷酸锰铁锂及其制备方法和应用 |
CN105826536A (zh) * | 2016-05-19 | 2016-08-03 | 贵州安达科技能源股份有限公司 | 一种磷酸锰铁锂及其制备方法 |
CN106328942A (zh) | 2016-11-11 | 2017-01-11 | 宁德新能源科技有限公司 | 一种磷酸铁锰锂正极材料,其制备方法和应用 |
CN106450239A (zh) * | 2016-12-08 | 2017-02-22 | 深圳市鑫永丰科技有限公司 | 一种磷酸锰铁锂复合材料及其制备方法与锂离子电池 |
CN109244391A (zh) * | 2018-08-22 | 2019-01-18 | 江苏元景锂粉工业有限公司 | 一种氮参杂碳包覆磷酸锰铁锂材料及其制备方法 |
CN111900344A (zh) * | 2020-07-02 | 2020-11-06 | 江苏海基新能源股份有限公司 | 一种碳包覆磷酸锰铁锂正极材料的制备方法 |
CN111933915A (zh) * | 2020-09-14 | 2020-11-13 | 天津斯科兰德科技有限公司 | 一种磷酸锰铁锂正极材料及其制备方法和应用 |
CN113072049A (zh) * | 2021-03-26 | 2021-07-06 | 天津斯科兰德科技有限公司 | 一种高压实密度磷酸锰铁锂/碳复合正极材料的制备方法 |
CN113942990A (zh) * | 2021-08-25 | 2022-01-18 | 北京当升材料科技股份有限公司 | 磷酸锰铁锂前驱体、磷酸锰铁锂正极材料及其制备方法和电极材料、电极以及锂离子电池 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116344791A (zh) * | 2023-05-26 | 2023-06-27 | 天津巴莫科技有限责任公司 | 正极材料及其制备方法、正极片和电池 |
CN116344791B (zh) * | 2023-05-26 | 2023-08-08 | 天津巴莫科技有限责任公司 | 正极材料及其制备方法、正极片和电池 |
CN116835560A (zh) * | 2023-08-28 | 2023-10-03 | 合肥国轩高科动力能源有限公司 | 磷酸铁锰锂复合材料和其制备方法、正极极片 |
CN116835560B (zh) * | 2023-08-28 | 2024-01-23 | 合肥国轩高科动力能源有限公司 | 磷酸铁锰锂复合材料和其制备方法、正极极片 |
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