CN115072692A - Pyrolusite type manganese iron phosphate, and preparation method and application thereof - Google Patents
Pyrolusite type manganese iron phosphate, and preparation method and application thereof Download PDFInfo
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- CN115072692A CN115072692A CN202210743153.XA CN202210743153A CN115072692A CN 115072692 A CN115072692 A CN 115072692A CN 202210743153 A CN202210743153 A CN 202210743153A CN 115072692 A CN115072692 A CN 115072692A
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- Prior art keywords
- manganese
- phosphate
- iron
- source
- lithium
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- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims description 15
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000011572 manganese Substances 0.000 claims abstract description 67
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 37
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 claims abstract description 29
- 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 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052742 iron Inorganic materials 0.000 claims abstract description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 17
- 239000011574 phosphorus Substances 0.000 claims abstract description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 229910000616 Ferromanganese Inorganic materials 0.000 claims description 18
- 229910019142 PO4 Inorganic materials 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 17
- 239000010452 phosphate Substances 0.000 claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 10
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 10
- 229940077478 manganese phosphate Drugs 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-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
- 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
- COAXPURBZTUDQI-UHFFFAOYSA-H P(=O)([O-])([O-])[O-].[Mn+2].[Mn+2].[Fe+2].P(=O)([O-])([O-])[O-] Chemical compound P(=O)([O-])([O-])[O-].[Mn+2].[Mn+2].[Fe+2].P(=O)([O-])([O-])[O-] COAXPURBZTUDQI-UHFFFAOYSA-H 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 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
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 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
- 230000035484 reaction time Effects 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims 1
- 239000002243 precursor Substances 0.000 abstract description 12
- 238000005245 sintering Methods 0.000 abstract description 7
- 238000000975 co-precipitation Methods 0.000 abstract description 3
- 238000005056 compaction Methods 0.000 abstract description 3
- JEBAUTBPSKCVJM-UHFFFAOYSA-N [P].[Mn].[Fe] Chemical compound [P].[Mn].[Fe] JEBAUTBPSKCVJM-UHFFFAOYSA-N 0.000 abstract description 2
- KQFUCKFHODLIAZ-UHFFFAOYSA-N manganese Chemical compound [Mn].[Mn] KQFUCKFHODLIAZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000003801 milling Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000000463 material Substances 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 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 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 6
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 3
- 235000019838 diammonium phosphate Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000033116 oxidation-reduction process Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000005696 Diammonium phosphate Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- HQFCOGRKGVGYBB-UHFFFAOYSA-N ethanol;nitric acid Chemical compound CCO.O[N+]([O-])=O HQFCOGRKGVGYBB-UHFFFAOYSA-N 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 229940116007 ferrous phosphate Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229960001031 glucose Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- FFSSRHVDYWHLLV-UHFFFAOYSA-J iron(2+) manganese(2+) oxalate Chemical compound C(C(=O)[O-])(=O)[O-].[Fe+2].[Mn+2].C(C(=O)[O-])(=O)[O-] FFSSRHVDYWHLLV-UHFFFAOYSA-J 0.000 description 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 1
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010951 particle size reduction Methods 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- -1 sanding for 2-5H Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Classifications
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- 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
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
- C01P2006/10—Solid 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
The invention discloses a manganese-manganese x Fe 1‑x ) 5 (PO 4 ) 2 [PO 3 (OH)] 2 ·4H 2 O, x is more than or equal to 0.2 and less than 1. The manganese-iron-uniformly-doped red-phosphorus manganese ore structure is prepared by coprecipitation of a soluble divalent manganese source and a divalent iron source and controlling the manganese-iron-phosphorus ratio, the pH value and the reaction temperature in a proper range, and manganese and iron can be mixed at an atomic level. The manganese iron phosphate element content and the manganese hureaulite crystalThe conformity of the theoretical value of the model is high, and the content proportion is stable. The lithium manganese iron phosphate prepared by sand-milling and sintering the precursor with a phosphorus source, a lithium source and a carbon source shows higher battery capacity, cycle performance and compaction density.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to a manganese hurricane type manganese iron phosphate, and a preparation method and application thereof.
Background
Lithium ion batteries are currently the most promising power batteries due to their high energy density, large charging and discharging currents, long cycle life, and other characteristics. The lithium iron phosphate has the advantages of good safety, high theoretical capacity, good rate performance and the like, is one of the most widely applied lithium ion anode materials at present, and attracts more and more researchers. Meanwhile, the lithium ion battery has the disadvantages of poor electronic conductivity, small lithium ion diffusion coefficient, low working potential platform and the like, and the development and application in the field of power batteries are influenced. At present, carbon coating, particle size reduction, element doping and other modes are adopted as main improvement modes for overcoming the defects of materials. Meanwhile, the manganese phosphate lithium material (4.1eV) with the same-family structure has higher oxidation-reduction potential and has the advantages of higher output voltage and higher capacity than the lithium iron phosphate (3.4eV), but the application of the manganese phosphate lithium is greatly limited by the lower conductivity and the rate performance of the manganese phosphate lithium material. Both of them combined LiMn 1-x Fe x PO 4 the/C material can retain the advantages of high safety and high stability of the lithium iron phosphate, and simultaneously improves the working voltage of the lithium iron phosphate to different degrees according to the addition of manganese. The solid solution system is favored by researchers, and is gradually becoming a future development trend and a substitute of the lithium iron phosphate material.
In a similar manner to the preparation of lithium iron phosphate, LiMn 1-x Fe x PO 4 the/C may also be in the solid phaseDirect sintering, hydrothermal method, precipitation method and the like. The high-temperature solid phase method has the advantages of low equipment requirement, suitability for industrialization and the like, but the nucleation rate and element diffusion are difficult to control, so that the synthesized lithium iron manganese phosphate has poor consistency and inhomogeneous morphology. The hydrothermal method or the solvothermal method is to dissolve a manganese source, an iron source, a lithium source and a phosphorus source in a solvent, wherein the solvent used in the hydrothermal method is water, the solvent used in the solvothermal method is an organic solvent, the obtained mixed solution is added into a reaction kettle and stirred for reaction for a long time at about 200 ℃ to generate the lithium manganese iron phosphate, and the product of the lithium manganese iron phosphate has the advantages of small particle size, good manganese iron dispersibility, uniform phase and the like. Besides direct preparation, indirect preparation through a precursor is also a suitable method for preparing the lithium manganese iron phosphate material, and the method is mainly characterized in that the precursor of manganese and iron is precipitated through a liquid phase method, and then supplementary materials such as a lithium source and the like are added to be sintered into the lithium manganese iron phosphate. At present, two types of precursors, namely an oxalic acid system and a phosphoric acid system, and manganese and iron in manganese iron oxalate are uniformly mixed to prepare a manganese iron lithium phosphate anode material with better performance, but the defect that oxalate needs to be converted into CO in a large amount in the sintering reaction process 2 The discharge is separated, and the generation of a large amount of gas phase can influence the performances of material circulation, compaction and the like, and is not in line with the new energy environmental protection concept. The preparation method has the advantages that a large amount of gas phase is not generated in the sintering process of the ferric manganese phosphate precursor, the sintering process is easier, but the preparation is difficult at present, and the main difficulty is the disproportionation effect of trivalent manganese, so that the trivalent manganese phosphate precursor is difficult to generate trivalent manganese phosphate precipitate like ferric phosphate. In order to oxidize the trivalent substance into trivalent substance, a nitric acid-ethanol system is generally adopted, or a strong oxidant is added to oxidize the trivalent substance in a high-temperature and high-pressure environment, so that the efficiency is extremely low, the energy consumption and the pollution are high, and the industrial application is difficult. CN114057177A discloses a preparation method of manganese iron phosphate, which comprises the steps of dissolving a divalent manganese salt and a divalent ferric salt in water, and adding a phosphorus source to obtain a precursor solution; and adding alkali into the precursor solution for coprecipitation reaction, and then washing, filtering and drying to obtain the ferrous manganese phosphate, wherein the ferrous manganese phosphate comprises ferrous phosphate precipitate and ferromanganese phosphate precipitate. The method also provides a precursor of ferrous manganese iron, but the crystal thereofThe content of the type and the content of ferromanganese are not fixed, and the embodiment shows that different trace conditions have great influence on the crystal form and the content of ferromanganese, and the embodiment also has more impurity phases, which causes great inconvenience to the subsequent reaction element proportioning and the industrialized repeated preparation.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a manganese hureaulite type manganese iron phosphate, and a preparation method and application thereof.
According to one aspect of the present invention, there is provided a manganese phosphate iron of the hureaulite type having a chemical formula of (Mn) x Fe 1-x ) 5 (PO 4 ) 2 [PO 3 (OH)] 2 ·4H 2 And x is more than or equal to 0.2 and less than 1, the manganosite type ferromanganese phosphate is a monoclinic system, the space lattice structure is C2/C (15) Z-4, wherein the valence of manganese and iron is 2, the atomic levels are uniformly distributed in a unit cell, the appearance of the manganosite type ferromanganese phosphate is a columnar structure, and the granularity D50 is 8-100 mu m.
In some preferred embodiments of the invention, x is from 0.5 to 0.7.
In some preferred embodiments of the present invention, the length to diameter ratio of the particles of the manganosite type manganese iron phosphate is (1-3): 1.
The invention also provides a preparation method of the hureaulite type manganese iron phosphate, which comprises the following steps:
s1: adding a phosphorus source solution into a mixed metal solution containing a divalent manganese source and a divalent iron source to obtain a turbid solution; wherein the molar ratio of Mn to Fe in the mixed metal solution is x (1-x);
s2: and (3) reacting the turbid solution at 60-100 ℃, carrying out solid-liquid separation after the reaction is finished, and washing and drying the obtained solid to obtain the manganese-iron-manganese-phosphate.
It should be noted that the method requires certain heating conditions, and if the temperature is low and the material is difficult to crystallize to form a crystal form of the hureaulite, the temperature lower limit for forming the material by different phosphorus sources and alkali is different. In addition, the manganese-ore-type iron phosphate material finally obtained may contain a small amount of particles which do not completely grow, or a small amount of two columnar particles are combined together in an interpenetration mode, the particles have no influence on the performance of the material, and the finished product basically exists in a columnar structure.
In some embodiments of the present invention, in step S1, the molar ratio of phosphorus to manganese to iron, P (Mn + Fe), in the turbid liquid is 0.7 to 1.2. Preferably, the molar ratio of phosphorus to manganese to iron P (Mn + Fe) in the turbid liquid is 0.8-1.0.
In some embodiments of the invention, the pH of the turbid liquid is between 3 and 7 in step S1. Preferably, the pH of the turbid liquid is 4 to 5. Further, step S1 also adds an alkali solution to the mixed metal solution to adjust the pH. The alkali concentration in the reaction system is moderate, the precipitation rate is low due to the low pH value, and the heterogeneous substances with ammonium or sodium ions are generated due to the high alkali concentration or pH value. It should be noted that the alkali solution should not be added in advance, and may be added simultaneously with the phosphorus source or added subsequently, and the addition in advance may result in a higher pH at the early stage of the reaction to form an impurity phase.
In some embodiments of the present invention, in step S1, the total concentration of Mn and Fe in the turbid liquid is 0.3 to 1 mol/L.
In some embodiments of the invention, in step S1, the divalent manganese source is at least one of manganese sulfate, manganese nitrate or manganese acetate; the ferrous iron source is at least one of ferrous sulfate, ferrous nitrate or ferrous chloride.
In some embodiments of the present invention, in step S1, the phosphorus source in the phosphorus source solution is one of phosphoric acid, monoammonium phosphate, diammonium phosphate, monosodium phosphate, or disodium phosphate.
In some embodiments of the invention, in step S1, the alkali solution is at least one of NaOH or ammonia.
In some embodiments of the invention, in step S2, the reaction time is 0.5 to 8 hours.
The invention also provides lithium manganese iron phosphate which is prepared from the manganese hureaulite type manganese iron phosphate.
The invention also provides a preparation method of the lithium iron manganese phosphate, which comprises the steps of mixing the manganese ore type iron manganese phosphate with a lithium source, a phosphorus source and a carbon source, and calcining in an inert atmosphere to obtain the lithium iron manganese phosphate. Wherein the lithium source is added in an amount of Li (Mn + Fe) 1:1, and the phosphorus source having an Mn + Fe molar amount of 0.2 times is supplemented at a value of P (Mn + Fe) 1: 1.
In some embodiments of the invention, the lithium source is at least one of lithium hydroxide or lithium carbonate.
In some embodiments of the present invention, the temperature of the calcination is 600-750 ℃, and the time of the calcination is 2-10 h.
The invention also provides application of the hureaulite type ferric manganese phosphate or the ferric manganese phosphate lithium in preparation of lithium ion batteries.
According to a preferred embodiment of the present invention, at least the following advantages are provided:
1. the structure of the manganese red phosphorus ore is phosphate with stable bivalent manganese, and can be an ideal precursor of lithium iron manganese phosphate. The invention firstly adopts a soluble divalent manganese source and a divalent iron source for coprecipitation, and controls the manganese-iron-phosphorus ratio, the pH value and the reaction temperature in a proper range to prepare the manganese-iron uniformly-doped hureaulite structure, wherein the manganese and the iron can be mixed at an atomic level. Crystal form of manganese iron phosphate and manganese hureaulite structure Mn 5 (PO 4 ) 2 [PO 3 (OH)] 2 ·4H 2 And O is consistent, the crystal form is in a hexagonal prism structure, and the crystal form is pure and uniform. The special appearance is gradually unobvious when the Fe content is gradually changed into the ferromanganese solid solution, so that the manganese-iron ratio needs to be controlled in a proper range, and the reaction temperature needs to be controlled in a proper range to crystallize to form the hureaulite crystal form.
2. The process of the invention does not need to adopt organic systems such as ethanol and the like, does not need to add oxidants such as nitrate radical, hydrogen peroxide and the like, and does not produce a large amount of CO in the sintering process 2 The gas affects the material performance, and the high gas is not neededA temperature high pressure reaction kettle device. The raw materials are simple and easy to obtain, the process is easy to control, the equipment requirement is low, and the large-scale production is easy.
3. The manganese-ore-type iron manganese phosphate prepared by the method is used as a precursor of lithium manganese iron phosphate, a lithium source, a carbon source and a phosphorus source are subsequently supplemented, and the carbon-coated lithium manganese iron phosphate anode material is finally formed by calcining.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is an XRD pattern of a hureaulite type ferromanganese phosphate obtained in various examples and comparative examples of the present invention;
FIG. 2 is an SEM image of the hureaulite type ferromanganese phosphate obtained in example 1 of the present invention at different magnifications;
fig. 3 is an XRD chart of the lithium iron manganese phosphate product obtained in example 5 of the present invention;
fig. 4 is a 0.1C charge-discharge curve diagram of the lithium iron manganese phosphate product obtained in embodiment 5 of the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
The embodiment prepares the manganese-:
1. 30.42g of manganese sulfate monohydrate and 31.56g of ferrous sulfate heptahydrate are dissolved in 400ml of pure water to prepare a solution A, wherein the molar ratio (Mn: Fe) is (6: 4);
2. 40g of ammonium dihydrogen phosphate is dissolved in 100ml of pure water to prepare a solution B;
3. slowly adding the solution B into the solution A to form a mixed solution C;
4. slowly adding a small amount of ammonia water into the mixed solution C to ensure that the pH value is 5, and gradually generating precipitate to generate a turbid solution D;
5. adding the turbid solution D into a reaction container, and reacting for 4 hours at 90 ℃;
6. the reacted slurry is subjected to solid-liquid separation, the obtained solid is washed and then is placed in an oven for drying, and the manganese hureaulite type (Mn) can be obtained 0.6 Fe 0.4 ) 5 (PO 4 ) 2 [PO 3 (OH)] 2 ·4H 2 The average grain diameter of the O manganese iron phosphate is D10-4.6 μm, D50-16.4 μm and D90-46.7 μm.
Example 2
The embodiment prepares the manganese-:
1. dissolving 76g of manganese sulfate monohydrate and 10g of ferrous chloride tetrahydrate in 400ml of pure water to prepare a solution A, wherein the molar ratio (Mn: Fe) is (9: 1);
2. dissolving 55.4g of diammonium phosphate in 400ml of pure water to form a solution B;
3. slowly adding the solution B into the solution A to gradually form a turbid solution C, wherein the pH value is 4.5;
4. adding the turbid solution C into a reaction container, and reacting for 2 hours at 70 ℃;
5. the reacted slurry is subjected to solid-liquid separation, the obtained solid is washed and then is placed in an oven for drying, and the manganese hureaulite type (Mn) can be obtained 0.9 Fe 0.1 ) 5 (PO 4 ) 2 [PO 3 (OH)] 2 ·4H 2 And O manganese iron phosphate.
Example 3
The embodiment prepares the manganese-:
1. dissolving 85.9g of 50% (W/W) manganese nitrate and 16.68g of ferrous sulfate heptahydrate in 300ml of pure water to form a solution A, wherein the molar ratio (Mn: Fe) is (8: 2);
2. 34.6g of phosphoric acid (85%) was dissolved in 100ml of pure water to form a solution B, and 24g of aqueous ammonia was diluted to 100ml to form a solution C;
3. adding the solution B and the solution C into the solution A to form a turbid solution D, wherein the pH value is about 3.9;
4. adding the turbid solution D into a reaction vessel, and reacting for 4 hours at 80 ℃;
5. the reacted slurry is subjected to solid-liquid separation, washed and then placed in an oven for drying, and the manganese hureaulite type (Mn) can be obtained 0.8 Fe 0.2 ) 5 (PO 4 ) 2 [PO 3 (OH)] 2 ·4H 2 And O manganese iron phosphate.
Example 4
The embodiment prepares the manganese-:
1. dissolving 58.8g of manganese acetate tetrahydrate and 16.68g of ferrous sulfate heptahydrate in 300ml of pure water to form a solution A, wherein the molar ratio (Mn: Fe) is (8: 2);
2. 27.7g of phosphoric acid (85%) were dissolved in 100ml of pure water to form a solution B, and 24g of NaOH were dissolved in 100ml of pure water to form a solution C;
3. slowly adding the solution B and the solution C into the solution A to form a turbid solution D, wherein the pH value is 4.8;
4. adding the turbid solution D into a reaction container, and reacting for 4 hours at 80 ℃;
5. the reacted slurry is subjected to solid-liquid separation, washed and then placed in an oven for drying, and the manganese hureaulite type (Mn) can be obtained 0.8 Fe 0.2 ) 5 (PO 4 ) 2 [PO 3 (OH)] 2 ·4H 2 And O manganese iron phosphate.
Example 5
The embodiment prepares the manganese-ore-type ferric manganese phosphate and the lithium manganese iron phosphate by the following specific processes:
1. 507g of manganese sulfate monohydrate and 556g of ferrous sulfate heptahydrate are dissolved in 5L of pure water to form a solution A, wherein the molar ratio (Mn: Fe) is (6: 4);
2. 461.2g of phosphoric acid (85%) was dissolved in 2L of pure water to form solution B, and 544g of aqueous ammonia was diluted to 2L to form solution C;
3. adding the solution B and the solution C into the solution A to form a turbid solution D, wherein the pH value is 4.6;
4. adding the turbid solution D into a reaction container, and reacting for 1h at 90 ℃;
5. the reacted slurry is subjected to solid-liquid separation, washed and then placed in an oven for drying, and the manganese hureaulite type (Mn) can be obtained 0.6 Fe 0.4 ) 5 (PO 4 ) 2 [PO 3 (OH)] 2 ·4H 2 And O manganese iron phosphate.
6. Weighing 500g of prepared ferromanganese phosphate as a precursor, adding 78.2g of ammonium dihydrogen phosphate, 25.4g of lithium carbonate and 28.35g of anhydrous glucose, mixing, placing in 7L of pure water, sanding for 2-5H, finishing sanding when the granularity D50 is lower than 500nm, performing spray drying, placing the particles in a nitrogen-protected box furnace, sintering at 660 ℃ for 10H, and crushing to obtain carbon-coated lithium manganese iron phosphate (LiMn) 0.6 Fe 0.4 PO 4 and/C) material.
Example 6
The embodiment prepares the manganese-:
1. dissolving 16.9g of manganese sulfate monohydrate and 111.2g of ferrous sulfate heptahydrate in 500ml of pure water to form a solution A, wherein the molar ratio (Mn: Fe) is (2: 8);
2. dissolving 65g of diammonium hydrogen phosphate in 500ml of pure water to form a solution B;
3. slowly adding the solution B into the solution A to form a turbid solution C, wherein the pH value is 4.2;
4. adding the turbid solution C into a reaction container, and reacting for 3 hours at 90 ℃;
5. the reacted slurry is subjected to solid-liquid separation, washed and then placed in an oven for drying, and the manganese hureaulite type (Mn) can be obtained 0.2 Fe 0.8 ) 5 (PO 4 ) 2 [PO 3 (OH)] 2 ·4H 2 And O manganese iron phosphate.
Comparative example 1
The comparative example prepares a manganese iron phosphate mixed product, and the difference with the example 1 is that the reaction temperature in the step 4 is different, and the specific process is as follows:
1. 30.42g of manganese sulfate monohydrate and 31.56g of ferrous sulfate heptahydrate are dissolved in 400ml of pure water to prepare a solution A, wherein the molar ratio (Mn: Fe) is (6: 4);
2. 40g of ammonium dihydrogen phosphate is dissolved in 100ml of pure water to prepare a solution B;
3. slowly adding the solution B into the solution A to form a mixed solution C;
4. slowly adding a small amount of ammonia water into the mixed solution C to ensure that the pH value is 5, and gradually generating precipitate to generate a turbid solution D;
5. adding the turbid solution D into a reaction container, and reacting and stirring for 4 hours at 40 ℃;
6. and (3) carrying out solid-liquid separation on the reacted slurry, washing, and then placing in an oven for drying to obtain a manganese iron phosphate mixed product.
The ferromanganese phosphate obtained in examples 1 to 6 and comparative example 1 was examined for the iron (Fe) content, the manganese (Mn) content, and the phosphorus (P) content, and the examination results are shown in table 1.
TABLE 1
| Sample number | Mn％ | Fe％ | P％ | Mn:Fe | (Mn+Fe):P |
| Example 1 | 22.38 | 15.11 | 16.86 | 60:40 | 1.25 |
| Example 2 | 33.43 | 4.29 | 16.81 | 89:11 | 1.26 |
| Example 3 | 29.33 | 8.16 | 16.89 | 79:21 | 1.25 |
| Example 4 | 28.91 | 8.22 | 16.82 | 78:22 | 1.24 |
| Example 5 | 22.45 | 15.56 | 16.74 | 59:41 | 1.27 |
| Example 6 | 7.35 | 30.32 | 16.88 | 20:80 | 1.24 |
| Comparative example 1 | 12.52 | 8.27 | 7.59 | 61:39 | 1.53 |
As can be seen from Table 1, the ferromanganese proportion and the addition amount of the ferromanganese phosphate in each example are relatively close, the proportion is stable and easy to control, and the (Mn + Fe): P and the theoretical value of the crystal form 5:4 also accord with each other. The content of the main elements and (Mn + Fe) P in the comparative example 1 are obviously different because a manganite type structure cannot be generated at low temperature, but products such as ferromanganese phosphate, manganous phosphate, amorphous ferromanganese phosphate and the like are generated, the proportion is closer to 1.5, the content of crystal water and the like is higher, and the content of the main elements is lower.
As can be seen from FIG. 1, each example has high conformity with the standard card PDF #34-0146 of the hureaulite, and the product is proved to have no error and high crystallinity; comparative example 1 reduced the reaction temperature compared to example 1, and it was seen that this crystalline form was not formed.
Fig. 2 is SEM images of hureaulite type ferromanganese phosphate obtained in example 1 at different magnifications, wherein the left image is a larger SEM image and the right image is a smaller SEM image. As can be seen from figure 2, the crystal form has the appearance of a hexagonal prism structure, the appearance is relatively complete and regular, the length-diameter ratio is about 2, and in addition, a small amount of particles with other structures exist in the figure, which are particles which are not completely grown, but the material performance is not influenced.
Fig. 3 shows that the finally generated lithium manganese iron phosphate and lithium manganese phosphate standard card are in good agreement and have high crystallinity.
Test examples
The lithium manganese iron phosphate obtained in the example 5 is prepared into a battery by a method that the prepared lithium manganese iron phosphate positive electrode material, acetylene black and polyvinylidene fluoride are dissolved in N-methyl pyrrolidone according to the weight ratio of 80:10:10, and the slurry obtained after uniform stirring is coated on an aluminum foil and baked to obtain a positive electrode plate. And (3) taking the lithium sheet as a negative electrode sheet, sealing and assembling the lithium sheet into a button cell in a glove box filled with argon, and testing the charge-discharge capacity, the cycle and the like. The results are shown in Table 2.
TABLE 2
Table 2 shows the performance index of the lithium manganese iron phosphate prepared in example 5, which has high compaction density and cycle efficiency in addition to good specific capacity, due to the fact that it has good atomic-scale mixing of manganese and iron, and can suppress lattice distortion generated by manganese during the oxidation-reduction process, which is beneficial to the stability and improvement of performance.
Fig. 4 shows a charging and discharging curve of the finally generated lithium iron manganese phosphate 0.1C in example 5, two voltage platforms of the curve respectively correspond to the oxidation-reduction potentials of manganese and iron, and the specific capacity of 0.1C can reach 154mAh/g, which is equivalent to the performance of the lithium iron manganese phosphate prepared by other methods at present.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. The manganous-manganite type manganese iron phosphate is characterized in that the chemical general formula of the manganous-manganite type manganese iron phosphate is (Mn) x Fe 1-x ) 5 (PO 4 ) 2 [PO 3 (OH)] 2 ·4H 2 And x is more than or equal to 0.2 and less than 1, the manganosite type ferromanganese phosphate is a monoclinic system, the space lattice structure is C2/C (15) Z-4, wherein the valence of manganese and iron is 2, the atomic levels are uniformly distributed in a unit cell, the appearance of the manganosite type ferromanganese phosphate is a columnar structure, and the granularity D50 is 8-100 mu m.
2. The method for preparing hureaulite-type manganese iron phosphate according to claim 1, comprising the steps of:
s1: adding a phosphorus source solution into a mixed metal solution containing a divalent manganese source and a divalent iron source to obtain a turbid solution; wherein the molar ratio of Mn to Fe in the mixed metal solution is x (1-x);
s2: and (3) reacting the turbid solution at 60-100 ℃, carrying out solid-liquid separation after the reaction is finished, and washing and drying the obtained solid to obtain the manganese-iron-manganese-phosphate.
3. The method of claim 2, wherein in step S1, the molar ratio P (Mn + Fe) of phosphorus to manganese to iron in the turbid liquid is 0.7-1.2.
4. The method according to claim 2, wherein the pH of the turbid liquid in step S1 is 3 to 7.
5. The method according to claim 2, wherein in step S1, the total concentration of Mn and Fe in the turbid liquid is 0.3 to 1 mol/L.
6. The method according to claim 2, wherein in step S1, the divalent manganese source is at least one of manganese sulfate, manganese nitrate or manganese acetate; the ferrous iron source is at least one of ferrous sulfate, ferrous nitrate or ferrous chloride.
7. The method according to claim 2, wherein in step S2, the reaction time is 0.5 to 8 hours.
8. Lithium iron manganese phosphate, characterized by being produced using the hureaulite type ferromanganese phosphate according to claim 1.
9. The method for preparing lithium iron manganese phosphate according to claim 8, wherein the manganese iron hureaulite-type phosphate is mixed with a lithium source, a phosphorus source and a carbon source, and calcined in an inert atmosphere to obtain the lithium iron manganese phosphate.
10. The use of the hureaulite-type ferric manganese phosphate of claim 1 or the ferric manganese phosphate of claim 8 in the preparation of a lithium ion battery.
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| CN202210743153.XA CN115072692A (en) | 2022-06-28 | 2022-06-28 | Pyrolusite type manganese iron phosphate, and preparation method and application thereof |
| GBGB2310143.9A GB202310143D0 (en) | 2022-06-28 | 2022-09-20 | No title |
| PCT/CN2022/119983 WO2024000839A1 (en) | 2022-06-28 | 2022-09-20 | Hureaulite type manganese iron phosphate and preparation method therefor and use thereof |
| DE112022002484.4T DE112022002484T5 (en) | 2022-06-28 | 2022-09-20 | Hureaulite type manganese iron phosphate, process for its preparation and its use |
| FR2306740A FR3137078A1 (en) | 2022-06-28 | 2023-06-27 | HUREAULITE TYPE MANGANESE-IRON PHOSPHATE AND PREPARATION METHOD AND USE THEREOF |
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| CN101891177A (en) * | 2010-07-05 | 2010-11-24 | 华中农业大学 | Method for preparing manganese phosphate material |
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| CN105449207A (en) * | 2015-12-25 | 2016-03-30 | 中钢集团安徽天源科技股份有限公司 | Preparation method of manganese iron phosphate and product |
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| CN101891177A (en) * | 2010-07-05 | 2010-11-24 | 华中农业大学 | Method for preparing manganese phosphate material |
| CN107112525A (en) * | 2015-01-08 | 2017-08-29 | 台湾立凯电能科技股份有限公司 | The preparation method of battery composite material and its predecessor |
| CN114057177A (en) * | 2021-11-23 | 2022-02-18 | 湖北融通高科先进材料有限公司 | Ferrous manganese phosphate and preparation method and application thereof |
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| WO2024000839A1 (en) | 2024-01-04 |
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