GB2624735A - Hureaulite type manganese iron phosphate and preparation method therefor and use thereof - Google Patents
Hureaulite type manganese iron phosphate and preparation method therefor and use thereof Download PDFInfo
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- GB2624735A GB2624735A GB2310143.9A GB202310143A GB2624735A GB 2624735 A GB2624735 A GB 2624735A GB 202310143 A GB202310143 A GB 202310143A GB 2624735 A GB2624735 A GB 2624735A
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- GB
- United Kingdom
- Prior art keywords
- manganese
- iron phosphate
- hureaulite
- lithium
- source
- Prior art date
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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 53
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 title abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000011572 manganese Substances 0.000 claims abstract description 52
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052742 iron Inorganic materials 0.000 claims abstract description 27
- 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 27
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011574 phosphorus Substances 0.000 claims abstract description 17
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 11
- 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 abstract description 4
- 239000010452 phosphate Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 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
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 238000009826 distribution Methods 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
- 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
- 238000005056 compaction Methods 0.000 abstract description 5
- 238000000975 co-precipitation Methods 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 3
- 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 abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 3
- JEBAUTBPSKCVJM-UHFFFAOYSA-N [P].[Mn].[Fe] Chemical compound [P].[Mn].[Fe] JEBAUTBPSKCVJM-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000000463 material Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 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
- 239000002002 slurry Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 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
- 239000000047 product Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- 239000012670 alkaline solution Substances 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
- 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
- 239000003513 alkali Substances 0.000 description 3
- 230000009286 beneficial effect Effects 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
- 229940116007 ferrous phosphate Drugs 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 3
- 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 3
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 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
- 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
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 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
- 238000003801 milling Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000004576 sand 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 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
- 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
- 229910052786 argon Inorganic materials 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 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
- 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
- 150000002505 iron Chemical class 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
- 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010951 particle size reduction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 102220042174 rs141655687 Human genes 0.000 description 1
- 102220076495 rs200649587 Human genes 0.000 description 1
- 102220043159 rs587780996 Human genes 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
- 239000007790 solid phase Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
Classifications
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- 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
- 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
-
- 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
- C01P2004/60—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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Disclosed in the present invention are hureaulite type manganese iron phosphate and a preparation method therefor and a use thereof. The general chemical formula of the hureaulite type manganese iron phosphate is (MnxFe1-x)5(PO4)2[PO3(OH)]2·4H2O, wherein 0.2≤x<1. The hureaulite structure of the present invention is phosphate having relatively stable divalent manganese, and can be an ideal precursor for lithium manganese iron phosphate. The preparation method uses a soluble divalent manganese source and a soluble divalent iron source for coprecipitation, the manganese-iron uniformly doped hureaulite structure is prepared by controlling a manganese-iron-phosphorus ratio, pH, and a reaction temperature in proper ranges, and manganese and iron can be mixed at an atomic level. In the present invention, the element content of the manganese iron phosphate and the theoretical value of a crystal form of the hureaulite are high in conformity, and the content ratio is stable. The lithium manganese iron phosphate prepared by sanding and sintering the precursor of the present invention, a phosphorus source, a lithium source, and a carbon source shows relatively high battery capacity, cycle performance, and compaction density.
Description
HUREAULITE-TYPE MANGANESE IRON PHOSPHATE AND PREPARATION
METHOD AND USE THEREOF
FIELD
100011 The present disclosure belongs to the field of positive electrode materials for lithium-ion batteries, and in particular relates to a hureaul te-type manganese iron phosphate and a preparation method and use thereof.
BACKGROUND
100021 Lithium-ion batteries are currently the most promising power batteries due to their high energy density, large charge-discharge current and long cycle life. Among them, lithium iron phosphate has the advantages of good safety, high theoretical capacity and good rate capability, and becomes one of the most widely used positive electrode materials for lithium-ion batteries, attracting more and more researchers' attention. However, it also has disadvantages such as poor electronic conductivity, small lithium ion diffusion coefficient, and low working potential platform, which affects its development and application in the field of power batteries. At present, carbon coating, particle size reduction and element doping are the main improvement methods to overcome the material defects. In addition, the lithium manganese phosphate material (4.1 eV) of the same family structure has a higher redox potential than lithium iron phosphate (3.4 eV), and has the advantages of greater output voltage and higher capacity, but its lower conductivity and rate capability greatly limit the application of lithium manganese phosphate. The LiMmYexPO4/C material, which is the combination of the two, can not only retain the advantages of high safety and high stability of lithium iron phosphate, but also improve its working voltage to varying degrees according to the amount of manganese added. This solid solution system has been favored by a growing number of researchers and has gradually become the future development trend and an alternative to lithium iron phosphate materials.
[00031 Similar to the preparation method of lithium iron phosphate, LiMm_Ye"PO4/C can also be directly prepared by direct solid-phase sintering method, hydrothermal method, precipitation method, etc. The high-temperature solid-phase method has the advantages of low requirements for equipment and suitability for industrialization, but it is difficult to be control the nucleation rate and element diffusion, so the synthesized lithium manganese iron phosphate has poor uniformity and uneven morphology. The hydrothermal method or the solvothermal method comprises dissolving a manganese source, an iron source, a lithium source and a phosphorus source in a solvent, where the solvent used in the hydrothermal method is water and the solvent used in the solvothermal method is an organic solvent, adding the obtained mixed solution to a reactor, and stirring the mixture for a long time of reaction at about 200°C to produce lithium manganese iron phosphate. The product has the advantages such as small particle size, good dispersibility of manganese and iron, and uniform phase, while the disadvantages include high requirements for equipment and difficulty in achieving large-scale industrial production. In addition to direct preparation, indirect preparation from precursors is also a suitable method for preparing lithium manganese iron phosphate materials, mainly by precipitating the precursor of manganese and iron through liquid-phase method, then adding a lithium source and other supplementary materials, and sintering to obtain lithium manganese iron phosphate. At present, there are mainly two types of precursors, oxalic acid system and phosphoric acid system. In the iron manganese oxalate, manganese and iron are uniformly mixed, so that a positive electrode material of lithium manganese iron phosphate with good performance can he prepared. However, the disadvantage is that during sintering, a large amount of oxalate needs to be converted into CO2 to be released, and the generation of a large amount of gas may affect the performance of the material such as cycle and compaction, which is also inconsistent with the concept of renewable energy and environmental protection. The sintering process of the manganese iron phosphate precursor will not produce too much gas and is easier. However, it is difficult for preparation, mainly due to the disproportionation reaction of trivalent manganese, which makes it difficult to generate a precipitate of trivalent manganese phosphate similar to iron phosphate. In order to oxidize it to trivalent, it is usually necessary to use a nitric acid-ethanol system, or to add a strong oxidant for oxidization in a high temperature and high pressure environment, which causes extremely low efficiency and high energy consumption and pollution, and is difficult for industrial application. CNI I 4057177A discloses a method for producing manganese ferrous phosphate, comprising dissolving a divalent manganese salt and a divalent iron salt in water, and then adding a phosphorus source to obtain a precursor solution; and adding an alkali to the precursor solution for co-precipitation reaction, water-washing, filtering and drying to obtain
-
manganese ferrous phosphate, which contains ferrous phosphate precipitate and manganese iron phosphate precipitate. This method also provides a precursor of bivalent manganese and iron, which, nevertheless, has unfixed crystalline form and content of manganese and iron. In the Examples, it is found that different trace conditions had great influence on the crystalline form and content of manganese and iron, and there were many impurities, which cause great inconvenience to the element ratio of the subsequent reaction and industrial repeated preparation.
SUMMARY
[0004] The present disclosure aims to solve at least one of the above-mentioned technical problems existing in the prior art. For this purpose, the present disclosure provides a hureaulite-type manganese iron phosphate and a preparation method and use thereof.
[0005] According to one aspect of the present disclosure, a hureaulite-type manganese iron phosphate is provided, wherein the hureaulite-type manganese iron phosphate has a general chemical formula of (MnxFet-)5(PO4)2[1'03(011)]2-4H2O, 0.2<x<1, the hureaulite-type manganese iron phosphate belongs to the monoclinic system with a space lattice structure of C2/c(15) Z=4, where manganese and iron are divalent and are uniformly distributed in a unit cell at the atomic level, and the hureaulite-type manganese iron phosphate has morphology of a columnar structure with a particle-size distribution D50 of 8-100 urn.
[0006] In some preferred embodiments of the present disclosure, x is (15-0.7.
[0007] In some preferred embodiments of the present disclosure, the length-diameter ratio of the particles of the hureaulite-type manganese iron phosphate is (1-3):1.
[0008] The present disclosure also provides a method for producing the hureaulite-type manganese iron phosphate, comprising steps of: [0009] Si: adding a phosphorus source solution to 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:( I -x); and [0010] S2: subjecting the turbid solution to reaction at 60-100°C, performing solid-liquid separation after the reaction to obtain a solid, and washing and drying the solid to obtain the -3 -hureaulite-type manganese iron phosphate.
[00111 It should be noted that the method requires certain heating conditions. If the temperature is low, it is difficult to crystallize to form a hureaulite crystal, and there are certain differences in the lower temperature limit for formation of this substance required by different phosphorus sources and alkalis. In addition, the finally obtained hureaulite-type manganese iron phosphate material may contain a small amount of incompletely grown particles, or there may be a small amount of two-columnar particles interspersed and combined together. These particles have no effect on the performance of the material, and the finished product basically exists as particles with a columnar structure.
[00121 In some embodiments of the present disclosure, in step 51, the molar ratio of phosphorus to manganese plus iron in the turbid solution is P:(Mn+Fe)=0.7-1.2. Preferably, the molar ratio of phosphorus to manganese plus iron in the turbid solution is P:(Mn+Fe)=0.8-1.0.
[00131 In some embodiments of the present disclosure, in step Si, the pH of the turbid solution is 3-7. Preferably, the pH of the turbid solution is 4-5. Further, step Si further comprises adding an alkaline solution to the mixed metal solution to adjust the pH. The alkali concentration in the reaction system should he moderate, because too low pH causes a low precipitation rate and too high alkali concentration or pH will generate impurities with ammonium or sodium ions. It should be noted that the alkaline solution should not be added in advance, it may be added at the same time as or after the addition of the phosphorus source, because the addition of the alkaline solution in advance will lead to a high pH in the early stage of the reaction to form impurities.
[00141 In some embodiments of the present disclosure, in step 51, the total concentration of Mn and Fe in the turbid solution is 0.3-1 mol/L.
[00151 In some embodiments of the present disclosure, in step Si, the divalent manganese source is selected from the group consisting of manganese sulfate, manganese nitrate, manganese acetate and a mixture thereof; and the divalent iron source is selected from the group consisting of ferrous sulfate, ferrous nitrate, ferrous chloride and a mixture thereof [00161 In some embodiments of the present disclosure, in step Si, the phosphorus source in the phosphorus source solution is selected from the group consisting of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium dihydrogen phosphate, -4 -disodium hydrogen phosphate and a mixture thereof.
[0017] In some embodiments of the present disclosure, in step SI, the alkaline solution is selected from the group consisting of NaOH, ammonia water and a mixture thereof.
[0018] In some embodiments of the present disclosure, in step S2, the reaction is carried out for 0.5-8h.
[0019] The present disclosure also provides a lithium manganese iron phosphate, which is prepared with the hureaulite-type manganese iron phosphate.
[0020] The present disclosure also provides a method for producing the lithium manganese iron phosphate, comprising mixing the hureaulite-type manganese iron phosphate with a lithium source, a phosphorus source and a carbon source, and calcining in an inert atmosphere to obtain the lithium manganese iron phosphate. Wherein, the lithium source is added at a ratio of Li:(Mn+Fe)= I: I, and the phosphorus source is supplemented with an amount of 0.2 times the molar amount of Mn+Fe at a ratio of P:(Mn+Fe)= I: I. [0021] In some embodiments of the present disclosure, the lithium source is selected from the group consisting of lithium hydroxide, lithium carbonate and a mixture thereof [0022] In some embodiments of the present disclosure, the calcining is carried out at 600-750°C for 2-10 h. [0023] The present disclosure also provides use of the hureaulite-type manganese iron phosphate or the lithium manganese iron phosphate in the manufacture of a lithium-ion battery.
[0024] According to a preferred embodiment of the present disclosure, the present disclosure has at least the following beneficial effects: [0025] I. Hureaulite is a phosphate of more stable divalent manganese, which can be an ideal precursor of lithium manganese iron phosphate. For the first time, the present disclosure uses soluble divalent manganese source and divalent iron source for co-precipitation, and controls the manganese-iron-phosphorus ratio, pH and reaction temperature in a suitable range to prepare a hureaulite structure uniformly doped with manganese and iron, where manganese and iron can be mixed at the atomic level. The crystalline form of manganese iron phosphate is consistent with hureaulite Mn5(PO4)4P03(OH)124H20, has morphology of a hexagonal prism structure and is -5 -relatively pure and uniform. As the Fe content increases, it gradually transforms into a solid solution of manganese and iron, which will gradually make this special morphology less obvious. Therefore, it is necessary to control the manganese-iron ratio and the reaction temperature in a suitable range for crystallization to form the hureaulite crystalline form. The element content of the manganese iron phosphate of the present disclosure conforms highly to the theoretical value of the hureaulite crystalline form, and the content ratio is stable, which is suitable for industrial production.
[9026] 2. In the process of the present disclosure, the use of organic systems such as ethanol and the addition of oxidants such as nitrate and hydrogen peroxide are not required, the sintering process does not generate a large amount of CO2 and other gases to affect material properties, and the high-temperature and high-pressure reactor is not needed. The raw materials are simple and readily available, the process is easy to be controlled, and the requirements for equipment are low, which allows easy large-scale production.
[9027] 3. The hureaulite-type manganese iron phosphate prepared by the present disclosure can be used as the precursor of lithium manganese iron phosphate, and after the subsequent addition of a lithium source, carbon source and phosphorus source followed by calcination, a carbon-coated lithium manganese iron phosphate positive electrode material is obtained, which exhibits high battery capacity, cycle performance and compaction density and is beneficial for the further practical use.
BRIEF DESCRIPTION OF DRAWINGS
[00281 The present disclosure will be further described below in conjunction with the drawings and examples, wherein: [00291 FIG. 1 is an XRD pattern of the hureaulite-type manganese iron phosphate obtained in each Example and Comparative Example of the present disclosure; [90301 FIG. 2 is SEM images of the hureaulite-type manganese iron phosphate obtained in Example 1 of the present disclosure under different magnifications; [0031] FIG. 3 is an XRD pattern of the lithium manganese iron phosphate obtained in Example 5 of the present disclosure: and -6 - [00321 FIG. 4 is a 0.1C charge-discharge curve of the lithium manganese iron phosphate obtained in Example 5 of the present disclosure.
DETAILED DESCRIPTION
[9033] The concept of the present disclosure and the technical effects produced by the present disclosure will he clearly and completely described below in conjunction with the embodiments, so as to fully understand the purpose, features and effects of the present disclosure. It is apparent that the described embodiments are only a part of the embodiments of the present disclosure, rather than all of them. All the other embodiments obtained by those skilled in the art based on the embodiments of the present disclosure without any creative work fall into the scope of the present disclosure.
Example 1
[0034] In this example, a hureaulite-type manganese iron phosphate was prepared by the following steps: [0035] 1. 30.42 g of manganese sulfate monohydrate and 31.56 g of ferrous sulfate heptahydrate were dissolved in 400 ml of pure water to prepare a solution A, where the molar ratio (Mn:Fe) was (6:4).
[00361 2. 40 g of ammonium dihydrogen phosphate was dissolved in 100 ml of pure water to prepare a solution B. [0037] 3. The solution B was added slowly to the solution A to obtain a mixed solution C. [9038] 4. A small amount of ammonia water was added slowly to the mixed solution C to adjust the pH=5, and at this time, a precipitate was gradually generated to obtain a turbid solution D. [9039] 5. The turbid solution D was added into a reactor for 4 h of reaction at 90°C.
[0049] 6. The slurry obtained after the reaction was subjected to solid-liquid separation, and the obtained solid was washed and then dried in an oven to obtain a hureaulite-type manganese iron phosphate (Mn06Feo4)5(PO4)211)03(OH)12.4H20, with an average particle size D10=4.6 um, D50=16.4 pm and D90=46.7 nm. Example 2 [9041] In this example, a hureaulite-type manganese iron phosphate was prepared by the following steps: [9042] I. 76 g of manganese sulfate monohydrate and 10 g of ferrous chloride tetrahydrate were dissolved in 400 ml of pure water to prepare a solution A, where the molar ratio (Mn:Fe) was (9:1).
[9043] 2. 554 g of diammonium hydrogen phosphate was dissolved in 400 ml of pure water to prepare a solution B. [0044] 3. The solution B was added slowly to the solution A, and a turbid solution C was gradually formed, with a pH of 4.5 at this time.
[0045] 4. The turbid solution C was added into a reactor for 2 h of reaction at 70°C.
[0046] 6. The slun-y obtained after the reaction was subjected to solid-liquid separation, and the obtained solid was washed and then dried in an oven to obtain a hureaulite-type manganese iron phosphate (Mnn9Fen)5(F04211303(OH)1 2 41420.
Example 3
[0047] In this example, a hureaulite-type manganese iron phosphate was prepared by the following steps: [0048] 1. 85.9 g of 50% (W/W) manganese nitrate and 16.68 g of ferrous sulfate heptahydrate 20 were dissolved in 300 ml of pure water to prepare a solution A, where the molar ratio (Mn:Fe) was (8:2).
[9049] 2. 34.6 g of phosphoric acid (85%) was dissolved in 100 ml of pure water to prepare a solution B, and 24 g of ammonia water was diluted to 100 ml to prepare a solution C. [9059] 3. The solution B and solution C were added to the solution A, and a turbid solution D was formed, with a pH of about 3.9 at this time.
[9051] 4. The turbid solution D was added into a reactor for 4 h of reaction at 80°C.
[0052] 5. The slurry obtained after the reaction was subjected to solid-liquid separation, washed and then dried in an oven to obtain a hureaulite-type manganese iron phosphate (Muo.sFeo.2)5(Pa4)2[P03(011)]2-41120.
Example 4
[00531 In this example, a hureaulite-type manganese iron phosphate was prepared by the following steps: [0054] I. 58.8 g of manganese acetate tetrahydrate and I 6.68 g of ferrous sulfate heptahydrate were dissolved in 300 ml of pure water to prepare a solution A, where the molar ratio (Mn:Fe) was (8:2).
[0055] 2. 27.7 g of phosphoric acid (85%) was dissolved in 100 ml of pure water to prepare a 10 solution B, and 24 g of NaOH was dissolved in 100 ml of pure water to prepare a solution C. [0056] 3. The solution B and solution C were added slowly to the solution A, and a turbid solution D was formed, with a pH of 4.8 at this time.
[0057] 4. The turbid solution D was added into a reactor for 4 h of reaction at 80°C.
[0058] 5. The slurry obtained after the reaction was subjected to solid-liquid separation, 15 washed and then dried in an oven to obtain a hureaulite-type manganese iron phosphate (Mno iiFeo2)5(PO4)2I,P03(OH).12'4H20.
Example 5
[0059] In this example, a hureaulite-type manganese iron phosphate and a lithium manganese iron phosphate were prepared by the following steps: [00601 1. 507 g of manganese sulfate monohydrate and 556 g of ferrous sulfate heptahydrate were dissolved in 5 L of pure water to prepare a solution A, wherei the molar ratio (Mn:Fe) was (6:4).
[0061] 2. 461.2 g of phosphoric acid (85%) was dissolved in 2 L of pure water to prepare a solution B, and 544 g of ammonia water was diluted to 2 L to prepare a solution C. [0062] 3. The solution B and solution C were added to the solution A, and a turbid solution D was formed, with a pH of 4.6.
[9063] 4. The turbid solution D was added into a reactor for I h of reaction at 90°C.
1-00641 5. The slurry obtained after the reaction was subjected to solid-liquid separation, washed and then dried in an oven to obtain a hureaulite-type manganese iron phosphate (Mno.6Eeo.4)5(P0,02[P03(0M]2-4420.
[0065] 6. 500 g of the prepared manganese iron phosphate was used as a precursor, added with 78.2 g of ammonium dihydrogen phosphate, 25.4 g of lithium carbonate and 28.35 g of anhydrous glucose to mix, transferred to 7 L of pure water for 2-5 h of sand milling. When the particle size D50 was below 500 nm, sand milling was finished and spray drying was performed. Then, the particles were placed in a nitrogen-protected box furnace for 10 h of sintering at 660°C. After pulverization, a carbon-coated lithium manganese iron phosphate (LiMno6Ee04PO4/C) material was obtained.
Example 6
[0066] In this example, a hureaulite-type manganese iron phosphate was prepared by the following steps: [0067] 1. 16.9 g of manganese sulfate monohydrate and 111.2 g of ferrous sulfate heptahydrate were dissolved in 500 ml of pure water to prepare a solution A, where the molar ratio (Mn:Fe) was (2:8).
[0068] 2. 65 g of diammonium hydrogen phosphate was dissolved in 500 ml of pure water to prepare a solution B. [0069] 3. The solution B was added slowly to the solution A, and a turbid solution C was formed, with a pH of 4.2 at this time.
[00701 4. The turbid solution C was added into a reactor for 3 h of reaction at 90°C.
[0071] 5. The slurry obtained after the reaction was subjected to solid-liquid separation, washed and then dried in an oven to obtain a hureaulite-type manganese iron phosphate (Mno.2Eeo.$)5(Pa02W03(OH)12-4H20.
Comparative Example 1 [0072] In this comparative example, a mixed product of manganese iron phosphate was prepared by the following steps, which differ from Example I in that the temperature of the reaction in step 4 was different: -10 - [00731 1. 30.42 g of manganese sulfate monohydrate and 31.56 g of ferrous sulfate heptahydrate were dissolved in 400 ml of pure water to prepare a solution A, where the molar ratio (Mn:Fe) was (6:4).
[0074] 2. 40 g of ammonium dihydrogen phosphate was dissolved in 100 ml of pure water to prepare a solution B. [0075] 3. The solution B was added slowly to the solution A to obtain a mixed solution C. [0076] 4. A small amount of ammonia water was added slowly to the mixed solution C to adjust the pH=5, and at this time, a precipitate was gradually generated to obtain a turbid solution D. [0077] 5. The turbid solution D was added into a reactor for 4 h of reaction at 40°C.
[0078] 6. The slurry obtained after the reaction was subjected to solid-liquid separation, washed and then dried in an oven to obtain a mixed product of manganese iron phosphate.
[0079] The iron (Fe) content. manganese (Mn) content and phosphorus (P) content of the manganese iron phosphates prepared in Examples 1-6 and Comparative Example 1 were detected, and the detection results are shown in Table 1.
Table 1
Sample No. 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 I 12.52 8.27 7.59 61:39 1.53 [0080] As can be seen from Table 1, the manganese-iron ratio of the manganese iron phosphate in each example was close to the addition amount, stable and easy to be controlled, and (Mn+Fe):P also conformed highly to the theoretical value of the crystalline form, 5:4. However, in Comparative Example 1, the main element content and (Mn+Fe):P were significantly different, which was due to the failure to form a hureaulite structure at low temperature, but to form products such as manganous iron phosphate, manganous phosphate, and amorphous manganese iron phosphate, with a ratio closer to 1.5, a high content of crystal water and a low content of main elements.
[0081] It can be seen from FIG. I that each example conforms highly to the hureaulite standard 10 card PDF#34-0146, which demonstrates that the products are correct and have a high degree of crystallinity. Compared with Example I, the temperature of the reaction was lowered in Comparative Example 1, and it can be seen that this crystalline form was not formed.
[0082] FIG. 2 is SEM images of the hureaulite-type manganese iron phosphate obtained in Example I under different magnifications, where the left panel shows an SEM image of a larger magnification, and the right panel shows an SEM image of a smaller magnification. It can be seen from FIG. 2 that this crystalline form has an appearance of hexagonal prism structure, a relatively complete and regular morphology, and a length-diameter ratio of around 2. In addition, there are a small number of particles of other structures in the figure, which are not fully grown particles, but do not affect the material properties.
[0083] FIG. 3 shows that the final obtained lithium manganese iron phosphate conforms highly to the lithium manganese phosphate standard card, and has a high degree of crystallinity.
Test Example
[0084] The lithium manganese iron phosphate obtained in Example 5 was prepared into a battery according to the following method. The prepared lithium manganese iron phosphate positive electrode material, acetylene black and polyvinylidene fluoride were dissolved in N-methylpyrrolidone at a weight ratio of 80:10:10, and the slurry obtained after evenly stirring was coated on an aluminum foil and baked to obtain a positive electrode sheet. With a lithium sheet as the negative electrode, a button battery was assembled in an argon-filled glove box and tested for charge-discharge capacity, cycle and the like. The results are shown in Table 2.
-12 -
Table 2
Compaction density (g/cm3) 0.1C discharge capacity (mAh/g) 1C discharge capacity (mAh/g) Initial efficiency 1C efficiency after 300 cycles Example 5 2.37 154 146 94.8 92.3% [00851 Table 2 shows the performance indicators of the lithium manganese iron phosphate prepared in Example 5. In addition to good specific capacity, it also had high compaction density and cycle efficiency, which was attributed to its good mixing of manganese and iron at the atomic level and ability to inhibit the lattice distortion produced by manganese in the redox process, which is beneficial to the stability and improvement of performance.
[00861 FIG. 4 shows the 0.1C charge-discharge curve of the finally obtained lithium manganese iron phosphate in Example 5, and the two voltage platforms of the curve correspond to the redox potentials of manganese and iron, respectively. The specific capacity at 0.1C can reach 154 mAh/g, which is comparable to the performance of the lithium manganese iron phosphate prepared by other current methods.
[00871 The embodiments of the present disclosure have been described in detail above in conjunction with the drawings. However, the present disclosure is not limited to the above-mentioned embodiments, and various modifications can be made without departing from the purpose of the present disclosure within the scope of knowledge possessed by those of ordinary skill in the art. In addition, in the case of no conflict, the embodiments of the present disclosure and the features in the embodiments may be combined with each other.
-13 -
Claims (10)
- CLAIMS1. A hureaulite-type manganese iron phosphate, wherein the hureaulite-type manganese iron phosphate has a general chemical formula of (Mni,Fei-)s(PO4)2W03(0D)124H2O, 0.2<x<1, the hureaulite-type manganese iron phosphate belongs to the monoclinic system with a space lattice structure of C2/c(15) Z=4, where manganese and iron are divalent and are uniformly distributed in a unit cell at the atomic level, and the hureaulite-type manganese iron phosphate has morphology of a columnar structure with a particle-size distribution D50 of 8-100 ttm.
- 2. A method for producing the hureaulite-type manganese iron phosphate according to claim I, comprising steps of: Si: adding a phosphorus source solution to a mixed metal solution containing a divalent manganese source and a divalent iron source to obtain a turbid solution, wherein a molar ratio of Mn to Fe in the mixed metal solution is x:(1-x); and 52: subjecting the turbid solution to reaction at 60-100°C, performing solid-liquid separation after the reaction to obtain a solid, and washing and drying the solid to obtain the hureaulite-type manganese iron phosphate.
- 3. The method according to claim 2, wherein in step Si, a molar ratio of phosphorus to manganese plus iron in the turbid solution is P:(Mn+Fe)=0.7-1.2.
- 4. The method according to claim 2, wherein in step S I, the turbid solution has a pH of 3-7.
- 5. The method according to claim 2, wherein in step S I, a total concentration of Mn and Fe in the turbid solution is 0.3-I mol/L.
- 6. The method according to claim 2, wherein in step Si, the divalent manganese source is selected from the group consisting of manganese sulfate, manganese nitrate, manganese acetate and a mixture thereof; and the divalent iron source is selected from the group consisting of ferrous sulfate, ferrous nitrate, ferrous chloride and a mixture thereof.
- 7. The method according to claim 2, wherein in step S2, the reaction is carried out for 0.5-8 h.
- 8. A lithium manganese iron phosphate prepared with the hureaulite-type manganese iron -14 -phosphate according to claim 1.
- 9. A method for producing the lithium manganese iron phosphate according to claim 8, comprising mixing the hureaulite-type manganese iron phosphate with a lithium source, a phosphorus source and a carbon source, and calcining in an inert atmosphere to obtain the lithium 5 manganese iron phosphate.
- 10. Use of the hureaulite-type manganese iron phosphate according to claim 1 or the lithium manganese iron phosphate according to claim 8 in the manufacture of a lithium-ion battery -15 -
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| US20030104228A1 (en) * | 2001-11-07 | 2003-06-05 | Henkel Corporation | Hureaulite conversion coating as a base for the bonding of rubber to metal |
| CN102011110A (en) * | 2009-09-08 | 2011-04-13 | 日本帕卡濑精株式会社 | Iron group metal material after black surface treatment and manufacturing method thereof |
| 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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| US20030104228A1 (en) * | 2001-11-07 | 2003-06-05 | Henkel Corporation | Hureaulite conversion coating as a base for the bonding of rubber to metal |
| CN102011110A (en) * | 2009-09-08 | 2011-04-13 | 日本帕卡濑精株式会社 | Iron group metal material after black surface treatment and manufacturing method thereof |
| 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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