CN116675204A - Preparation method of compact ferromanganese ammonium phosphate precursor, positive electrode material and battery - Google Patents
Preparation method of compact ferromanganese ammonium phosphate precursor, positive electrode material and battery Download PDFInfo
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- CN116675204A CN116675204A CN202310788330.0A CN202310788330A CN116675204A CN 116675204 A CN116675204 A CN 116675204A CN 202310788330 A CN202310788330 A CN 202310788330A CN 116675204 A CN116675204 A CN 116675204A
- Authority
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- China
- Prior art keywords
- phosphate
- precursor
- manganese
- ferromanganese
- ammonium
- Prior art date
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- Pending
Links
- 239000002243 precursor Substances 0.000 title claims abstract description 42
- 229910000616 Ferromanganese Inorganic materials 0.000 title claims abstract description 40
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910000148 ammonium phosphate Inorganic materials 0.000 title claims abstract description 22
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000004254 Ammonium phosphate Substances 0.000 title abstract description 20
- 235000019289 ammonium phosphates Nutrition 0.000 title abstract description 20
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 19
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 19
- 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 claims abstract description 18
- 239000010452 phosphate Substances 0.000 claims abstract description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010405 anode material Substances 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 11
- 239000011574 phosphorus Substances 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 5
- 241000257465 Echinoidea Species 0.000 claims abstract description 3
- 239000011164 primary particle Substances 0.000 claims abstract description 3
- RAFWXPDQXCSUBB-UHFFFAOYSA-K [O-]P([O-])([O-])=O.N.[Mn+2].[Fe+2] Chemical compound [O-]P([O-])([O-])=O.N.[Mn+2].[Fe+2] RAFWXPDQXCSUBB-UHFFFAOYSA-K 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 239000011572 manganese Substances 0.000 claims description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 229910052748 manganese Inorganic materials 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000002585 base Substances 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 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
- 239000011259 mixed solution Substances 0.000 claims description 9
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 9
- 239000006012 monoammonium phosphate Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229940099596 manganese sulfate Drugs 0.000 claims description 6
- 239000011702 manganese sulphate Substances 0.000 claims description 6
- 235000007079 manganese sulphate Nutrition 0.000 claims description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 239000001488 sodium phosphate Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 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
- TWHXWYVOWJCXSI-UHFFFAOYSA-N phosphoric acid;hydrate Chemical compound O.OP(O)(O)=O TWHXWYVOWJCXSI-UHFFFAOYSA-N 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 3
- 239000005696 Diammonium phosphate Substances 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 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
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 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 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 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
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 2
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- ROUPZXDBSPQFLE-UHFFFAOYSA-N triazanium;phosphate;hydrate Chemical compound [NH4+].[NH4+].[NH4+].O.[O-]P([O-])([O-])=O ROUPZXDBSPQFLE-UHFFFAOYSA-N 0.000 abstract 1
- 235000021317 phosphate Nutrition 0.000 description 15
- 239000007787 solid Substances 0.000 description 12
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 5
- -1 lithium iron ammonium manganese phosphate Chemical compound 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 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 description 1
- 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 description 1
- 239000005913 Maltodextrin Substances 0.000 description 1
- 229920002774 Maltodextrin Polymers 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 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 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 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 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 229960002737 fructose Drugs 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 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
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 229960001375 lactose Drugs 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 1
- 229940035034 maltodextrin Drugs 0.000 description 1
- 229960002160 maltose Drugs 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 229940116315 oxalic acid Drugs 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 229940032147 starch Drugs 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
- C01B25/451—Phosphates containing plural metal, or metal and ammonium containing metal and ammonium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/45—Aggregated particles or particles with an intergrown morphology
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Preparation method of compact ferromanganese ammonium phosphate precursor, positive electrode material and battery, wherein phosphorus source and ammonia water are mixed, alkali liquor is added to adjust pH to be alkaline, and then the mixture is mixed with ferromanganese metal to react, so that ferromanganese ammonium phosphate monohydrate with particle morphology of spheroid or sea urchin is obtained, primary particle size is 50-800nm, D50 is 10-30 um, and precursor tap density is 0.6g/cm 3 ＜TD＜1.8g/cm 3 ，0.6m 2 /g＜SSA＜2.5m 2 And/g. Further, the invention discloses a lithium iron manganese phosphate anode material prepared by using the ammonium iron manganese phosphate precursor prepared by the method, which is used as a lithium battery material. The precursor Na/S of the ammonium ferromanganese phosphate prepared by the invention has low impurity content, high tap density and good product crystallinity.
Description
Technical Field
The invention relates to the field of inorganic materials and lithium battery materials, in particular to a preparation method of a compact ammonium ferromanganese phosphate precursor, a positive electrode material and a battery.
Background
Along with the repair and slope-removing and technological breakthrough of new energy automobiles, the lithium iron phosphate starts to get damp again in 2020, the current air strength is still high, but the energy density of the lithium iron phosphate is close to the upper limit, the lithium manganese iron phosphate is a product of combining the lithium manganese phosphate and the lithium iron phosphate, the advantages of the two are fully combined, the high-voltage platform of the lithium manganese iron phosphate brings higher energy density, and the cycle and safety performance are superior to those of the lithium iron phosphate compared with the lithium iron phosphate and the low-temperature performance. In addition, the voltage window of the lithium iron manganese phosphate is close to that of the ternary positive electrode, the lithium iron manganese phosphate and the ternary positive electrode can be mixed in any proportion, and the safety performance can be effectively improved by adding a small amount of lithium iron manganese phosphate into the ternary positive electrode material. Currently, the manganese iron phosphate positive electrode material is successfully applied to two-wheel vehicles, the market for vehicles is opened by multiplexing with ternary materials, and the requirement of the 2025-year global manganese iron phosphate positive electrode material is estimated to be 41 ten thousand tons in the future for mainly replacing lithium iron phosphate and compounding with ternary batteries.
The lithium iron manganese phosphate and the lithium iron phosphate belong to phosphate systems, the preparation process is similar, the solid phase method is simple and suitable for industrial production, and the liquid phase method is more complex but has good product performance. However, unlike the lithium iron phosphate industry, which has mature ferric phosphate as a precursor, the development of the manganese iron phosphate industry is in an early stage, and no standard precursor exists, and since the solid phase method cannot well realize uniform solid solution and is greatly limited in performance improvement, for the lithium iron phosphate material, the precursor synthesis should be the main synthesis direction in the future, and possible precursor routes are as follows: ammonium phosphate salts, phosphates, carbonates, oxalates, and the like.
The invention takes the ammonium phosphate precursor as a research subject, and prepares the ammonium phosphate precursor with excellent performance to improve the performance of the lithium manganese iron phosphate anode material.
Disclosure of Invention
The invention aims to provide a preparation method of a compact ammonium ferromanganese phosphate precursor and a battery.
In order to achieve the above purpose, the invention adopts the following technical scheme:
compact ammonium ferromanganese phosphate precursor with NH expression 4 Mn 1-x-y Fe x M y PO 4 ·H 2 O, x is more than 0 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 0.1, and M is at least one of Mg, ni, co, cu, zn and Ti;
wherein the molar ratio of the metal element (Mn+Fe+M) of the precursor to the element P is 0.95-1.05.
According to a further technical scheme, the D50 is 10-30 um, and the primary particle size is 100-800 nm; the precursor is 0.6g/cm 3 ＜TD＜1.8g/cm 3 ，0.6m 2 /g＜SSA＜2.5m 2 /g。
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of a compact ammonium ferromanganese phosphate precursor comprises the following steps:
preparing a mixed solution of a phosphorus source and ammonia water, and then adding an alkali solution to adjust the pH value of the mixed solution to 9-11;
step two, preparing a metal mixed salt solution containing a manganese source, an iron source and an M source;
step three, preparing reaction base solution: adding pure water into the reaction kettle to serve as base solution, and then adding alkali solution to adjust the pH value of the base solution to 4-7;
step four, the mixed solution prepared in the step one and the metal mixed salt solution prepared in the step two are added into a reaction kettle in parallel flow for reaction to obtain ammonium ferromanganese phosphate monohydrate precipitate;
and fifthly, carrying out solid-liquid separation, washing and drying on the ammonium ferromanganese phosphate monohydrate precipitate prepared in the step four to obtain ammonium ferromanganese phosphate precursor powder, wherein the particle morphology of the ammonium ferromanganese phosphate precursor powder is similar to that of a sphere or a sea urchin.
In a further technical scheme, in the first step, the P element and NH are controlled 3 ·H 2 The molar ratio of O is 1 (2-5).
In a further technical scheme, in the first step, the alkali solution is at least one of ammonia water, sodium hydroxide and potassium hydroxide.
In the first step, the concentration of the phosphorus source solution is 1-4 mol/L; the phosphorus source is at least one of phosphoric acid, monoammonium phosphate, diammonium phosphate, triammonium phosphate, monosodium phosphate, disodium phosphate and trisodium phosphate.
In the second step, the concentration of the metal mixed salt solution is 0.5-3 mol/L; the manganese source is at least one of manganese sulfate, manganese nitrate, manganese acetate and manganese chloride; the iron source is at least one of ferrous sulfate, ferric nitrate, ferric acetate and ferric chloride.
In the third step, the alkaline solution is at least one of ammonia water, sodium hydroxide and potassium hydroxide.
In the fourth step, the molar ratio of the element P to the metal (Mn+Fe) is maintained as (1-3): 1.
in the fourth step, nitrogen or inert gas is continuously introduced into the reaction process kettle, the reaction temperature is 20-70 ℃, and the stirring speed is 300-900 rpm.
In a further technical scheme, in the fifth step, the drying temperature is 60-150 ℃.
Furthermore, the invention also relates to a high-capacity lithium iron manganese phosphate anode material, which is prepared by mixing the lithium source and the carbon source material with the precursor powder of the lithium iron ammonium manganese phosphate prepared in the step five, and calcining for 6-20 h in the atmosphere of nitrogen or inert gas at the calcining temperature of 400-1000 ℃.
In the scheme, the general formula of the positive electrode material is LiFe x Mn 1-x PO 4 。
According to a further technical scheme, the lithium source is at least one of lithium hydroxide and lithium carbonate. The carbon source is one or more of sucrose, glucose, polyethylene glycol, carbon black, graphene, polyvinyl alcohol, polyacrylate alcohol, citric acid, cellulose, starch, maltodextrin, fructose, lactose, maltose, oxalic acid and ascorbic acid.
Further technical proposal, the expression of the positive electrode material is Li y Mn x-z Fe 1-x M z PO 4 C; wherein x is more than or equal to 0.5<Y is more than or equal to 1.99 and less than or equal to 1.10,0.1 and z is more than or equal to 1, M is a doping element, and the doping element M is at least one of Mg, ni, co, cu, zn, ti.
The invention further provides a battery which uses the carbon-coated lithium iron manganese phosphate as a positive electrode material.
The working principle and the advantages of the invention are as follows:
the invention prepares P source and ammonia water as mixed liquid, adds alkali liquid to adjust pH to alkalinity, so as to fully dissociate phosphate radical, and PO after the reaction starts to enter liquid 4 3- After being fully dissociated, the manganese ferric ammonium phosphate is combined with metal ions to promote forward progress of reaction, the crystallinity of the synthesized manganese ferric ammonium phosphate product is high, the particles are densely accumulated, so that the lithium manganese iron phosphate anode material after lithium mixing and sintering has high capacity.
Meanwhile, the invention has the advantages of strong production operability, high productivity and the like, and is suitable for large-scale industrial production.
Drawings
FIG. 1A is a schematic diagram of NH produced in example 1 of the present invention 4 Mn 0.75 Fe 0.25 PO 4 ·H 2 SEM image one of O;
FIG. 1B is a schematic diagram of NH produced in example 1 of the present invention 4 Mn 0.75 Fe 0.25 PO 4 ·H 2 SEM image two of O;
FIG. 2 is a diagram of NH produced in example 1 of the present invention 4 Mn 0.75 Fe 0.25 PO 4 ·H 2 XRD pattern of O;
FIG. 3A is a schematic representation of NH produced in example 2 of the present invention 4 Mn 0.75 Fe 0.25 PO 4 ·H 2 SEM image one of O;
FIG. 3B is a diagram of NH produced in example 2 of the present invention 4 Mn 0.75 Fe 0.25 PO 4 ·H 2 SEM image two of O;
FIG. 4 is a diagram showing NH produced in example 2 of the present invention 4 Mn 0.75 Fe 0.25 PO 4 ·H 2 XRD pattern of O;
FIG. 5A is a NH group produced in example 3 of the present invention 4 Mn 0.75 Fe 0.25 PO 4 ·H 2 SEM image one of O;
FIG. 5B is a NH group produced in example 3 of the present invention 4 Mn 0.75 Fe 0.25 PO 4 ·H 2 SEM image two of O;
FIG. 6 is a diagram of NH produced in example 3 of the present invention 4 Mn 0.75 Fe 0.25 PO 4 ·H 2 XRD pattern of O;
FIG. 7 is an SEM image of a precursor prepared according to a comparative example of the present invention;
fig. 8 is an XRD pattern of a precursor prepared according to a comparative example of the present invention.
Detailed Description
The invention is further described below with reference to the accompanying drawings and examples:
the present invention will be described in detail with reference to the drawings, wherein modifications and variations are possible in light of the teachings of the present invention, without departing from the spirit and scope of the present invention, as will be apparent to those of skill in the art upon understanding the embodiments of the present invention.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present disclosure. As used herein, the terms "comprising," "including," "having," and the like are intended to be open-ended terms, meaning including, but not limited to.
The term (terms) as used herein generally has the ordinary meaning of each term as used in this field, in this disclosure, and in the special context, unless otherwise noted. Certain terms used to describe the present disclosure are discussed below, or elsewhere in this specification, to provide additional guidance to those skilled in the art in connection with the description herein.
Example 1:
6.8Kg of monoammonium phosphate solid with purity of 98% is weighed and dissolved in 24.7L of pure water, mixed with 15L of 20% ammonia water, and tested for pH value of 9.22; after adding the base solution into the reaction kettle, heating to 40 ℃, and introducing nitrogen.
3.85Kg of ferrous sulfate heptahydrate solid with 99% purity is weighed and dissolved in 4.8L of pure water to obtain a bivalent molten iron solution, 6.997Kg of battery-grade manganese sulfate solid is weighed and dissolved in 17.49L of pure water to obtain a bivalent manganese water solution, and the prepared ferrous manganese water solution is mixed to obtain a Mn and Fe molar ratio of 75: 25.
Adding pure water into a reaction kettle, regulating the pH value to 4.5-5.0 by using ammonia water, continuously adding a mixed solution of phosphorus and the ammonia water and the prepared ferromanganese metal aqueous solution into the reaction kettle at the speed of 55ml/min and 50ml/min respectively, continuously producing ammonium ferromanganese phosphate precipitate, continuously introducing nitrogen in the reaction process, and stirring at the reaction temperature of 50 ℃ and the stirring speed of 600rpm.
And (3) carrying out solid-liquid separation and washing on the reaction obtained ferromanganese ammonium phosphate precipitate, and drying at 90 ℃ for 12 hours to obtain ferromanganese ammonium phosphate precursor powder.
And calcining the prepared lithium iron ammonium manganese phosphate precursor with a lithium source and a carbon source to prepare the lithium iron manganese phosphate anode material.
Example 2:
6.8Kg of monoammonium phosphate solid with the purity of 98% is weighed and dissolved in 24.7L of pure water, and added into a reaction kettle together with 20L of 20% ammonia water to be used as base solution, and the pH value of the base solution is tested to be 9.86.
3.85Kg of ferrous sulfate heptahydrate solid with 99% purity is weighed and dissolved in 4.8L of pure water to obtain a bivalent molten iron solution, 6.997Kg of battery-grade manganese sulfate solid is weighed and dissolved in 17.49L of pure water to obtain a bivalent manganese water solution, and the prepared ferrous manganese water solution is mixed to obtain a Mn and Fe molar ratio of 75: 25.
Adding pure water into a reaction kettle, regulating the pH value to 5.0-5.5 by using ammonia water, continuously adding a mixed solution of phosphorus and the ammonia water and the prepared ferromanganese metal aqueous solution into the reaction kettle at the speed of 55ml/min and 50ml/min respectively, continuously producing ammonium ferromanganese phosphate precipitate, continuously introducing nitrogen in the reaction process, and stirring at the reaction temperature of 50 ℃ and the stirring speed of 600rpm.
And (3) carrying out solid-liquid separation and washing on the reaction obtained ferromanganese ammonium phosphate precipitate, and drying at 90 ℃ for 12 hours to obtain ferromanganese ammonium phosphate precursor powder.
And calcining the prepared lithium iron ammonium manganese phosphate precursor with a lithium source and a carbon source to prepare the lithium iron manganese phosphate anode material.
Example 3:
6.8Kg of monoammonium phosphate solid with purity of 98% is weighed and dissolved in 24.7L of pure water, and added into a reaction kettle together with 25L of 20% ammonia water to serve as base solution, and the pH value of the base solution is tested to be 10.27.
3.85Kg of ferrous sulfate heptahydrate solid with 99% purity is weighed and dissolved in 4.8L of pure water to obtain a bivalent molten iron solution, 6.997Kg of battery-grade manganese sulfate solid is weighed and dissolved in 17.49L of pure water to obtain a bivalent manganese water solution, and the prepared ferrous manganese water solution is mixed to obtain a Mn and Fe molar ratio of 75: 25.
Adding pure water into a reaction kettle, regulating the pH to 5.5-6.0 by using ammonia water, continuously adding a mixed solution of phosphorus and the ammonia water and the prepared ferromanganese metal aqueous solution into the reaction kettle at 55ml/min and 50ml/min respectively, continuously producing ammonium ferromanganese phosphate precipitate, continuously introducing nitrogen in the reaction process, and stirring at a reaction temperature of 50 ℃ and a stirring rotation speed of 600rpm;
and (3) carrying out solid-liquid separation and washing on the reaction obtained ferromanganese ammonium phosphate precipitate, and drying at 90 ℃ for 12 hours to obtain ferromanganese ammonium phosphate precursor powder.
And calcining the prepared lithium iron ammonium manganese phosphate precursor with a lithium source and a carbon source to prepare the lithium iron manganese phosphate anode material.
Comparative example:
6.8Kg of monoammonium phosphate solid with purity of 98% is weighed and dissolved in 24.7L of pure water to obtain monoammonium phosphate aqueous solution;
3.85Kg of ferrous sulfate heptahydrate solid with 99% purity is weighed and dissolved in 4.8L of pure water to obtain a bivalent molten iron solution, 6.997Kg of battery-grade manganese sulfate solid is weighed and dissolved in 17.49L of pure water to obtain a bivalent manganese water solution, and the prepared ferrous manganese water solution is mixed to obtain a Mn and Fe molar ratio of 75:25, an aqueous ferromanganese solution;
adding pure water into a reaction kettle, regulating the pH to 4.5-5.0 by using 20% ammonia water, continuously adding monoammonium phosphate aqueous solution, ferromanganese aqueous solution and 20% ammonia water into the reaction kettle at 55ml/min, 50ml/min and 30ml/min respectively, continuously producing ferromanganese ammonium phosphate precipitate, continuously introducing nitrogen in the reaction process, and stirring at the reaction temperature of 50 ℃ and the stirring rotation speed of 600rpm.
And (3) carrying out solid-liquid separation and washing on the reaction obtained ferromanganese ammonium phosphate precipitate, and drying at 90 ℃ for 12 hours to obtain ferromanganese ammonium phosphate precursor powder.
And calcining the prepared lithium iron ammonium manganese phosphate precursor with a lithium source and a carbon source to prepare the lithium iron manganese phosphate anode material.
Physicochemical detection is carried out on the prepared ammonium ferromanganese phosphate precursor, and the table 1 is shown below.
TABLE 1
The data from the comparison of the comparative examples with the examples in Table 1 shows that: monoammonium phosphate aqueous solution and ammonia water solution independently feed liquid, PO 4 3- The dissociation speed is low, the prepared ferromanganese ammonium phosphate has large serious agglomeration granularity and low tap, and can be found through SEM (scanning electron microscope) that after phosphorus source and ammonia are independently fed, the ferromanganese ammonium phosphate is adhered into large blocks, XRD (X-ray diffraction) shows poor crystallinity, and when the adhered large blocks are subjected to sanding after lithium source mixing, the problem of coarse particles after sanding can be caused, so that the performance of the anode material is affected. The invention prepares P source and ammonia water as mixed liquid, adds alkali liquid to adjust pH to alkalinity, so as to fully dissociate phosphate radical, and PO after the reaction starts to enter liquid 4 3- After being fully dissociated, the manganese ferric ammonium phosphate is combined with metal ions to promote forward progress of reaction, the crystallinity of the synthesized manganese ferric ammonium phosphate product is high, the particles are densely accumulated, so that the lithium manganese iron phosphate anode material after lithium mixing and sintering has high capacity.
The precursor Na/S of the ammonium ferromanganese phosphate prepared by the invention has low impurity content, high tap density and good product crystallinity.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (13)
1. A preparation method of a compact ammonium ferromanganese phosphate precursor is characterized by comprising the following steps of: comprising the following steps:
preparing a mixed solution of a phosphorus source and ammonia water, and then adding an alkali solution to adjust the pH value of the mixed solution to 9-11;
preparing a metal mixed salt solution containing a manganese source, an iron source and an M source;
preparing a reaction base solution: adding pure water into the reaction kettle to serve as base solution, and then adding alkali solution to adjust the pH value of the base solution to 4-7;
step two, the mixed solution prepared in the step one and the metal mixed salt solution are added into a reaction kettle in parallel flow for reaction to obtain ammonium ferromanganese phosphate monohydrate precipitate;
thirdly, carrying out solid-liquid separation, washing and drying on the ammonium ferromanganese phosphate monohydrate precipitate prepared in the second step to obtain ammonium ferromanganese phosphate precursor powder;
wherein the particle morphology of the ammonium ferromanganese phosphate precursor is similar to that of a sphere or sea urchin.
2. The method of manufacturing according to claim 1, characterized in that: the expression of the precursor is NH 4 Mn 1-x- y Fe x M y PO 4 ·H 2 O, x is more than 0 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 0.1, and M is at least one of Mg, ni, co, cu, zn and Ti;
wherein the molar ratio of the metal element (Mn+Fe+M) of the precursor to the element P is 0.95-1.05.
3. The preparation method according to claim 2, characterized in that: the D50 of the precursor is 10-30 um, and the primary particle size is 100-800 nm;
the precursor is 0.6g/cm 3 ＜TD＜1.8g/cm 3 ，0.6m 2 /g＜SSA＜2.5m 2 /g。
4. The method of manufacturing according to claim 1, characterized in that: in step one, control the P element and NH 3 ·H 2 The molar ratio of O is 1 (2-5).
5. The method of manufacturing according to claim 1, characterized in that: in the first step, the alkali solution is at least one of ammonia water, sodium hydroxide and potassium hydroxide.
6. The method of manufacturing according to claim 1, characterized in that: in the first step, the concentration of the phosphorus source solution is 1-4 mol/L; the phosphorus source is at least one of phosphoric acid, monoammonium phosphate, diammonium phosphate, triammonium phosphate, monosodium phosphate, disodium phosphate and trisodium phosphate.
7. The method of manufacturing according to claim 1, characterized in that: in the first step, the concentration of the metal mixed salt solution is 0.5-3 mol/L; the manganese source is at least one of manganese sulfate, manganese nitrate, manganese acetate and manganese chloride; the iron source is at least one of ferrous sulfate, ferric nitrate, ferric acetate and ferric chloride.
8. The method of manufacturing according to claim 1, characterized in that: in the first step, the alkali solution is at least one of ammonia water, sodium hydroxide and potassium hydroxide.
9. The method of manufacturing according to claim 1, characterized in that: in the second step, the molar ratio of the element P to the metal (Mn+Fe) is maintained as (1-3): 1.
10. the method of manufacturing according to claim 1, characterized in that: in the second step, nitrogen or inert gas is continuously introduced into the reaction process kettle, the reaction temperature is 20-70 ℃, and the stirring speed is 300-900 rpm.
11. The method of manufacturing according to claim 1, characterized in that: in the third step, the drying temperature is 60-150 ℃.
12. A high-capacity lithium iron manganese phosphate anode material is characterized in that: a precursor prepared according to any one of claims 3 to 11; and (3) mixing the manganese ammonium iron phosphate precursor powder prepared in the step (III) with a lithium source and a carbon source material, and calcining for 6-20 hours in the atmosphere of nitrogen or inert gas at the calcining temperature of 400-1000 ℃ to prepare the carbon-coated positive electrode material.
13. A battery, characterized in that: a lithium iron manganese phosphate positive electrode material prepared using the carbon coating of claim 12.
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