CN115159491A - Preparation method of high-safety high-capacity lithium iron manganese phosphate - Google Patents
Preparation method of high-safety high-capacity lithium iron manganese phosphate Download PDFInfo
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- CN115159491A CN115159491A CN202210935979.6A CN202210935979A CN115159491A CN 115159491 A CN115159491 A CN 115159491A CN 202210935979 A CN202210935979 A CN 202210935979A CN 115159491 A CN115159491 A CN 115159491A
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- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 77
- 238000005245 sintering Methods 0.000 claims abstract description 63
- 239000002002 slurry Substances 0.000 claims abstract description 48
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 46
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 46
- 239000010452 phosphate Substances 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229940116007 ferrous phosphate Drugs 0.000 claims abstract description 30
- 229910000155 iron(II) phosphate Inorganic materials 0.000 claims abstract description 30
- 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 claims abstract description 30
- 238000000498 ball milling Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 229910001386 lithium phosphate Inorganic materials 0.000 claims abstract description 18
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims abstract description 18
- 238000000975 co-precipitation Methods 0.000 claims abstract description 16
- 239000002270 dispersing agent Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000001694 spray drying Methods 0.000 claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 239000002019 doping agent Substances 0.000 claims abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 46
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 30
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 26
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 21
- 239000013078 crystal Substances 0.000 claims description 16
- 239000011572 manganese Substances 0.000 claims description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- 230000001681 protective effect Effects 0.000 claims description 14
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 13
- 229960005070 ascorbic acid Drugs 0.000 claims description 13
- 235000010323 ascorbic acid Nutrition 0.000 claims description 13
- 239000011668 ascorbic acid Substances 0.000 claims description 13
- 239000008103 glucose Substances 0.000 claims description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- 235000006708 antioxidants Nutrition 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 7
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 7
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 7
- 239000011790 ferrous sulphate Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 7
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical group [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 7
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 6
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 235000011007 phosphoric acid Nutrition 0.000 claims description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 239000007774 positive electrode material Substances 0.000 claims description 2
- 102220043159 rs587780996 Human genes 0.000 claims 2
- 239000010405 anode material Substances 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 102220053607 rs200114285 Human genes 0.000 description 21
- 238000007600 charging Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 238000007599 discharging Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000010902 jet-milling Methods 0.000 description 7
- 102220131033 rs145667920 Human genes 0.000 description 6
- 102220013698 rs397516726 Human genes 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229920000831 ionic polymer Polymers 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000007431 microscopic evaluation Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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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
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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
- 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
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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
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- 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
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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
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Abstract
The invention belongs to the technical field of lithium battery anode materials, and discloses a preparation method of high-safety high-capacity lithium iron manganese phosphate, which comprises the following steps: (1) Synthesizing a ferrous phosphate precursor by a coprecipitation method, and sintering to obtain an anhydrous ferrous phosphate precursor; (2) Synthesizing a manganous phosphate precursor by a coprecipitation method, and sintering to obtain an anhydrous manganous phosphate precursor; (3) Adding anhydrous ferrous phosphate precursor into lithium phosphate and deionized water, and performing ball milling and wet sanding to obtain slurry A; (4) Adding an anhydrous manganous phosphate precursor into lithium phosphate, an organic carbon source, a dispersing agent, a doping agent and deionized water, and performing ball milling and wet sanding to obtain slurry B; (5) And mixing the slurry A and the slurry B, and performing ball milling, spray drying, sintering and airflow crushing to obtain the high-safety high-capacity lithium manganese iron phosphate. The invention increases the stability of the slurry, relieves the agglomeration, and the prepared material has higher capacity and safety.
Description
Technical Field
The invention belongs to the technical field of lithium battery anode materials, and particularly relates to a preparation method of high-safety high-capacity lithium iron manganese phosphate.
Background
At present, a novel lithium battery anode material is developed around a high-voltage platform and a manganese-based material, and the earliest commercialization in a branch system of the novel lithium battery anode material is lithium manganese iron phosphate. Compared with lithium iron phosphate, the high-voltage manganese characteristic enables the lithium iron manganese phosphate to have a higher voltage platform, which also results in higher energy density when the specific capacity is the same, and the energy density is 13% -23% higher than that of the lithium iron phosphate under the same condition.
Lithium manganese iron phosphate also has performance defects by itself. The existing lithium iron phosphate process is mature, and the safety and stability are better; at present, the processing performance of the manganese lithium iron phosphate is poor, the reaction process is complex, the possibility of oxidation reduction exists between bivalent manganese and bivalent iron in the preparation process, and the phase uniformity of the finally generated manganese lithium iron phosphate finished product is poor; because the structure does not have a continuous common-edge octahedral network, the movement of lithium ions in a one-dimensional channel is limited, and the conductivity of the material is poor.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a high-safety high-capacity lithium manganese iron phosphate material. The high-safety high-capacity lithium iron manganese phosphate material has a more uniform phase and stronger slurry stability, and further improves the capacity and compaction of the material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of high-safety high-capacity lithium iron manganese phosphate comprises the following steps:
(1) Mixing an iron source, a phosphorus source and an antioxidant into a solution, introducing nitrogen into the solution as a protective gas to prevent oxidation, and synthesizing a ferrous phosphate precursor by a coprecipitation method; sintering the obtained ferrous phosphate precursor, and removing all crystal water to obtain an anhydrous ferrous phosphate precursor;
(2) Mixing a manganese source, a phosphorus source and an antioxidant into a solution, introducing nitrogen into the solution as a protective gas to prevent oxidation, and synthesizing a manganous phosphate precursor by a coprecipitation method; sintering the obtained manganous phosphate precursor, and removing all crystal water to obtain an anhydrous manganous phosphate precursor;
(3) Adding lithium phosphate and deionized water into the anhydrous ferrous phosphate precursor obtained in the step (1), and performing ball milling and wet sanding to obtain slurry A;
(4) Adding lithium phosphate, an organic carbon source, a dispersing agent, a doping agent and deionized water into the anhydrous manganous phosphate precursor obtained in the step (2), and performing ball milling and wet sanding to obtain slurry B;
(5) And (5) mixing the slurry A and the slurry B obtained in the steps (3) and (4), and performing ball milling, spray drying, sintering and airflow crushing to obtain the high-safety high-capacity lithium manganese iron phosphate.
Preferably, in the step (1), the iron source is ferrous sulfate; the phosphorus source is one or more selected from phosphoric acid, ammonium dihydrogen phosphate and diammonium hydrogen phosphate; the antioxidant is antiAscorbic acid; the chemical formula of the precursor of the ferrous phosphate is Fe 3 (PO 4 ) 2 ·8H 2 O; the sintering is carried out in a box type furnace, the sintering temperature is 3533333 ℃, the sintering time is 135 hours, and the sintering atmosphere is nitrogen.
Preferably, in the step (2), the manganese source is manganous sulfate; the phosphorus source is one or more selected from phosphoric acid, ammonium dihydrogen phosphate and diammonium hydrogen phosphate; the antioxidant is ascorbic acid; the chemical formula of the manganous phosphate precursor is Mn 3 (PO 4 ) 2 ·7H 2 O; the sintering is carried out in a box type furnace, the sintering temperature is 3533333 ℃, the sintering time is 135 hours, and the sintering atmosphere is nitrogen.
Preferably, in the step (3), the molar ratio of Fe/P =3.95833.998 and the molar ratio of Li/Fe =1.32531.355 in the slurry a; in the wet sanding, the granularity D53=3.3333.33um of the slurry A is controlled.
Preferably, in the step (4), the molar ratio of Mn/P =3.95833.998 and the molar ratio of Li/Mn =1.32531.355 in the slurry B; in the wet sanding, the granularity D53=3.2333.53um of the slurry B is controlled.
Preferably, in the step (4), the organic carbon source is a mixture of glucose and polyethylene glycol, the addition amount of glucose is 5313wt% of the mass of the anhydrous manganous phosphate precursor, and the addition amount of polyethylene glycol is 135wt% of the mass of the anhydrous manganous phosphate precursor; the doping agent is one or more of titanium dioxide, ammonium metavanadate and niobium pentoxide, and the addition amount of the doping agent is 332.5wt% of the mass of the anhydrous manganous phosphate precursor; the dispersant is one or more selected from anionic polyacrylate dispersant TC138, nonionic polymer TC311 and nonionic polymer TC28, and the addition amount of the dispersant is 5313wt% of the addition amount of glucose.
Preferably, in the step (5), the ball milling is carried out in a ball mill for 33333 minutes; the spray drying is carried out in the nitrogen atmosphere, the air inlet temperature is controlled to be 1833243 ℃, and the air outlet temperature is controlled to be 833123 ℃; the sintering is carried out in a box type furnace, the sintering temperature is 3333833 ℃, the sintering time is 8323h, and the sintering atmosphere is nitrogen; in the jet milling, the particle size D13 of the high-safety high-capacity lithium manganese iron phosphate obtained by final milling is more than or equal to 3.33um, D53=3.831.8um and D93 is less than or equal to 18um.
The invention also claims a high-safety high-capacity lithium iron manganese phosphate material prepared by the method.
The invention also claims application of the high-safety high-capacity lithium iron manganese phosphate in a lithium battery anode material.
Compared with the prior art, the invention has the following beneficial effects:
1. the ferrous phosphate precursor and the manganous phosphate precursor reduce the process of reducing ferric iron and ferric manganese into ferrous iron and manganous in the sintering process, and avoid the generation of phase reaction impurities; sintering and spray drying are carried out under a nitrogen atmosphere to further prevent oxidation of divalent iron and divalent manganese.
2. The dispersant is used in the production process, so that the finished product phase is pure and does not agglomerate while iron and manganese are prevented from being oxidized; in the high-temperature carbonization process, organic micromolecular substances can be generated through decomposition, and have a synergistic effect with a carbon source, so that the pore-forming of the anode material is facilitated, the appearance of crystal grains is controlled, the growth of the crystal grains is inhibited, and the agglomeration is relieved.
3. According to the invention, on the basis of taking glucose and polyethylene glycol as main carbon sources, the dispersant is added to wet the surface of the inorganic particles, so that the viscosity of the slurry is reduced, good dispersibility is obtained, and the solid content of the material and the stability of the slurry are improved.
4. According to the invention, different sanding particle sizes of the precursors are controlled, so that the ferrous phosphate precursor with large particle size and the manganous phosphate precursor with small particle size are uniformly mixed, the sanding time is reduced, the sanding efficiency is improved, the mixing of materials is ensured, and the capacity and compaction are further improved.
Drawings
FIG. 1 is an SEM photograph of a sample prepared in example 1;
FIG. 2 is an SEM photograph of a sample prepared in example 2;
FIG. 3 is an SEM photograph of a sample prepared in example 3;
FIG. 4 is an SEM photograph of a sample prepared in example 4;
FIG. 5 is an SEM photograph of a sample prepared in comparative example 1;
FIG. 6 is an SEM photograph of a sample prepared in comparative example 2;
FIG. 7 is an XRD pattern of the sample prepared in example 1;
FIG. 8 is an XRD pattern of the sample prepared in comparative example 1;
FIG. 9 is a charging and discharging curve for the charging half-cell of the sample prepared in example 1;
FIG. 10 is a charging and discharging curve for the charging half-cell of the sample prepared in example 2;
FIG. 11 is a charging and discharging curve for the charging half-cell of the sample prepared in example 3;
FIG. 12 is a plot of charging and discharging of the charging half-cell of the sample prepared in example 4;
fig. 13 is a charging and discharging curve of the charging and discharging half cell of the sample prepared in comparative example 1;
fig. 14 is a charging and discharging curve of the charging and discharging half cell of the sample prepared in comparative example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. Of course, the specific embodiments described herein are merely illustrative of the invention and are not intended to be limiting.
Although the steps in the present invention are shown and described using reference numbers, the order of the steps is not limited to any order, and the order of steps may be modified unless otherwise indicated or unless the order of steps or performance of certain steps requires otherwise. It is to be understood that the term "and/or" as used herein refers to and encompasses any and all possible combinations of one or more of the associated listed items.
Unless otherwise specified, the chemical reagents and materials of the present invention are either commercially available or synthesized from commercially available raw materials, and the dispersant anionic polyacrylate dispersant TC138, nonionic polymer TC311, and nonionic polymer TC28 are purchased from Claine manufacturers.
Example 1
A preparation method of high-safety high-capacity lithium iron manganese phosphate comprises the following steps:
(1) 778g of ferrous sulfate, 193g of ammonium dihydrogen phosphate, 13g of phosphoric acid and 13g of ascorbic acid are mixed into a solution, nitrogen is introduced into the solution to be used as protective gas to prevent oxidation, and a ferrous phosphate precursor is synthesized by a coprecipitation method; sintering the obtained manganous phosphate precursor in a box-type furnace under the nitrogen atmosphere at 433 ℃ for 5h, and removing all crystal water to obtain 433g of anhydrous ferrous phosphate precursor;
(2) Mixing 1333g of manganous sulfate, 273g of phosphoric acid and 13g of ascorbic acid into a solution, introducing nitrogen into the solution as protective gas to prevent oxidation, and synthesizing a manganous phosphate precursor by a coprecipitation method; sintering the obtained manganous phosphate precursor in a box-type furnace under the nitrogen atmosphere at the sintering temperature of 433 ℃ for 5 hours to obtain 545g of anhydrous manganous phosphate precursor after all crystal water is removed;
(3) Adding 533g of the anhydrous ferrous phosphate precursor obtained in the step (1) into 123.3g of lithium phosphate and 1133g of deionized water, and performing ball milling and wet sanding to obtain slurry A with the particle size D53=3.55 um;
(4) Adding 185.4g of lithium phosphate, 33g of glucose, 53g of polyethylene glycol, 8g of anionic polyacrylate dispersant TC138, 7.71g of ammonium metavanadate and 1133g of deionized water into 545g of the anhydrous manganous phosphate precursor obtained in the step (2), and performing ball milling and wet sanding to obtain slurry B with the particle size D53=3.35 um;
(5) Mixing the slurry A and the slurry B obtained in the steps (3) and (4), and ball-milling for 33 minutes by using a ball mill; spray drying is carried out in nitrogen atmosphere, and the air inlet temperature is controlled to be 223 ℃ and the air outlet temperature is controlled to be 133 ℃; sintering at 753 deg.C for 15 hr in a box furnace under nitrogen atmosphere, wherein the pressure in the furnace is 53Pa, introducing nitrogen for more than 3 hr before heating, the heating rate is controlled at 2 deg.C/min, and naturally cooling to 53 deg.C with the furnace after sintering; and (4) performing jet milling, and controlling the particle size D13=3.43um, D53=1.3um and D93=13um to obtain the high-safety high-capacity lithium manganese iron phosphate.
Example 2
A preparation method of high-safety high-capacity lithium iron manganese phosphate comprises the following steps:
(1) Mixing 972g of ferrous sulfate, 243g of diammonium hydrogen phosphate, 23g of phosphoric acid and 13g of ascorbic acid into a solution, introducing nitrogen into the solution as protective gas to prevent oxidation, and synthesizing a ferrous phosphate precursor by a coprecipitation method; sintering the obtained manganous phosphate precursor in a box-type furnace under the nitrogen atmosphere at 453 ℃ for 4 hours to remove all crystal water to obtain 533g of anhydrous ferrous phosphate precursor;
(2) 888g of manganous sulfate, 243g of phosphoric acid and 13g of ascorbic acid are mixed into a solution, nitrogen is introduced into the solution to be used as protective gas to prevent oxidation, and a manganous phosphate precursor is synthesized by a coprecipitation method; placing the obtained manganous phosphate precursor in a box-type furnace to be sintered under the nitrogen atmosphere, wherein the sintering temperature is 453 ℃, the sintering time is 4 hours, and 455g of anhydrous manganous phosphate precursor is obtained after all crystal water is removed;
(3) Adding 154.5g of lithium phosphate and 1133g of deionized water into 533g of the anhydrous ferrous phosphate precursor obtained in the step (1), and performing ball milling and wet sanding to obtain slurry A with the particle size D53=3.35 um;
(4) Adding 154.5g of lithium phosphate, 33g of glucose, 53g of polyethylene glycol, 3g of non-ionic polymer TC311, 3g of titanium dioxide and 1133g of deionized water into 455g of the anhydrous manganous phosphate precursor obtained in the step (2), and performing ball milling and wet sanding to obtain slurry B with the particle size D53=3.25 um;
(5) Mixing the slurry A and the slurry B obtained in the steps (3) and (4), and ball-milling for 43 minutes by using a ball mill; spray drying is carried out in nitrogen atmosphere, and the air inlet temperature is controlled to be 223 ℃ and the air outlet temperature is controlled to be 133 ℃; sintering at 733 ℃ for 12 hours in a box-type furnace under the nitrogen atmosphere, wherein the pressure in the furnace is 33Pa, nitrogen is introduced for more than 3 hours before temperature rise, the temperature rise rate is controlled to be 2 ℃/min, and the temperature is naturally reduced to 53 ℃ along with the furnace after sintering; and (3) performing jet milling, and controlling the particle size D13=3.43um, D53=1.2um and D93=13um to obtain the high-safety high-capacity lithium manganese iron phosphate.
Example 3
A preparation method of high-safety high-capacity lithium iron manganese phosphate comprises the following steps:
(1) Mixing 972g of ferrous sulfate, 223g of diammonium hydrogen phosphate, 43g of phosphoric acid and 13g of ascorbic acid into a solution, introducing nitrogen into the solution as protective gas to prevent oxidation, and synthesizing a ferrous phosphate precursor by a coprecipitation method; sintering the obtained manganous phosphate precursor in a box-type furnace under the nitrogen atmosphere at the sintering temperature of 533 ℃ for 3h, and removing all crystal water to obtain 533g of anhydrous ferrous phosphate precursor;
(2) Mixing 585g of manganous sulfate, 133g of phosphoric acid and 13g of ascorbic acid into a solution, introducing nitrogen into the solution as a protective gas to prevent oxidation, and synthesizing a manganous phosphate precursor by a coprecipitation method; sintering the obtained manganous phosphate precursor in a box-type furnace under the nitrogen atmosphere at the sintering temperature of 533 ℃ for 3h, and removing all crystal water to obtain 333g of anhydrous manganous phosphate precursor;
(3) Adding 154.2g of lithium phosphate and 1133g of deionized water into 533g of the anhydrous ferrous phosphate precursor obtained in the step (1), and performing ball milling and wet sanding to obtain slurry A with the particle size D53=3.55 um;
(4) Adding 132.8g of lithium phosphate, 33g of glucose, 53g of polyethylene glycol, 8g of non-ionic polymer TC28, 3.5g of niobium pentoxide and 1133g of deionized water into 333g of the anhydrous manganous phosphate precursor obtained in the step (2), and performing ball milling and wet sanding to obtain slurry B with the particle size D53=3.35 um;
(5) Mixing the slurry A and the slurry B obtained in the steps (3) and (4), and carrying out ball milling for 53 minutes by using a ball mill; spray drying is carried out in nitrogen atmosphere, and the air inlet temperature is controlled to be 233 ℃ and the air outlet temperature is controlled to be 133 ℃; sintering at 783 ℃ for 13 hours in a box-type furnace under the nitrogen atmosphere, wherein the pressure in the furnace is 73Pa, introducing nitrogen for more than 3 hours before heating, controlling the heating rate to be 2 ℃/min, and naturally cooling to 53 ℃ along with the furnace after sintering; and (3) carrying out jet milling, and controlling the particle size D13=3.43um, D53=3.9um and D93=13um to obtain the high-safety high-capacity lithium manganese iron phosphate.
Example 4
A preparation method of high-safety high-capacity lithium iron manganese phosphate comprises the following steps:
(1) 778g of ferrous sulfate, 183g of ammonium dihydrogen phosphate, 23g of phosphoric acid and 13g of ascorbic acid are mixed into a solution, nitrogen is introduced into the solution to be used as protective gas to prevent oxidation, and a ferrous phosphate precursor is synthesized by a coprecipitation method; sintering the obtained manganous phosphate precursor in a box-type furnace in a nitrogen atmosphere at the sintering temperature of 553 ℃ for 2h, and removing all crystal water to obtain 433g of anhydrous ferrous phosphate precursor;
(2) Mixing 1333g of manganous sulfate, 273g of phosphoric acid and 13g of ascorbic acid into a solution, introducing nitrogen into the solution as protective gas to prevent oxidation, and synthesizing a manganous phosphate precursor by a coprecipitation method; sintering the obtained manganous phosphate precursor in a box-type furnace in a nitrogen atmosphere at the sintering temperature of 553 ℃ for 2h, and removing all crystal water to obtain 545g of an anhydrous manganous phosphate precursor;
(3) Adding 123.3g of lithium phosphate and 1133g of deionized water into 433g of the anhydrous ferrous phosphate precursor obtained in the step (1), and performing ball milling and wet sanding to obtain slurry A with the particle size D53=3.33 um;
(4) Adding 185.4g of lithium phosphate, 33g of glucose, 53g of polyethylene glycol, 8g of non-ionic polymer TC28, 3g of ammonium metavanadate and 1133g of deionized water into 545g of the anhydrous manganous phosphate precursor obtained in the step (2), and performing ball milling and wet sanding to obtain slurry B with the particle size D53=3.53 um;
(5) Mixing the slurry A and the slurry B obtained in the steps (3) and (4), and ball-milling for 33 minutes by using a ball mill; spray drying is carried out in nitrogen atmosphere, and the air inlet temperature is controlled to be 223 ℃, and the air outlet temperature is controlled to be 93 ℃; sintering at 773 ℃ for 13 hours in a box type furnace under the nitrogen atmosphere, wherein the pressure in the furnace is 73Pa, introducing nitrogen for more than 3 hours before heating, controlling the heating rate to be 2 ℃/min, and naturally cooling to 83 ℃ along with the furnace after sintering; and (3) performing jet milling, and controlling the particle size D13=3.43um, D53=1.5um and D93=13um to obtain the high-safety high-capacity lithium manganese iron phosphate.
Comparative example 1
A preparation method of lithium iron manganese phosphate comprises the following steps:
(1) 313g of iron phosphate, 75g of iron oxide, 123.3g of lithium phosphate and 1133g of deionized water are mixed into a solution, and the solution is subjected to ball milling and wet sanding to obtain slurry A with the particle size D53=3.55 um;
(2) 395g of manganese dioxide B, 333g of phosphoric acid, 185.4g of lithium phosphate, 33g of glucose, 53g of polyethylene glycol, 8g of anionic polyacrylate dispersant TC138 by mass, 7.71g of ammonium metavanadate and 1133g of deionized water are mixed into a solution, and the solution is subjected to ball milling and wet sanding to obtain slurry B with the particle size D53=3.35 um;
(3) Mixing the slurry A and the slurry B obtained in the steps (1) and (2), and ball-milling for 33 minutes by using a ball mill; spray drying is carried out in nitrogen atmosphere, and the air inlet temperature is controlled to be 223 ℃ and the air outlet temperature is controlled to be 133 ℃; sintering at 753 deg.C for 15 hr in a box furnace under nitrogen atmosphere, wherein the pressure in the furnace is 53Pa, introducing nitrogen for more than 3 hr before heating, the heating rate is controlled at 2 deg.C/min, and naturally cooling to 53 deg.C with the furnace after sintering; and (3) carrying out jet milling, and controlling the particle size D13=3.43um, D53=1.3um and D93=13um to obtain the lithium iron manganese phosphate.
Comparative example 2
A preparation method of lithium iron manganese phosphate comprises the following steps:
(1) 778g of ferrous sulfate, 193g of ammonium dihydrogen phosphate, 13g of phosphoric acid and 13g of ascorbic acid are mixed into a solution, nitrogen is introduced into the solution to be used as protective gas to prevent oxidation, and a ferrous phosphate precursor is synthesized by a coprecipitation method; sintering the obtained manganous phosphate precursor in a box-type furnace under the nitrogen atmosphere at 433 ℃ for 5h, and removing all crystal water to obtain 433g of anhydrous ferrous phosphate precursor;
(2) Mixing 1333g of manganous sulfate, 273g of phosphoric acid and 13g of ascorbic acid into a solution, introducing nitrogen into the solution as protective gas to prevent oxidation, and synthesizing a manganous phosphate precursor by a coprecipitation method; sintering the obtained manganous phosphate precursor in a box-type furnace under the nitrogen atmosphere at 433 ℃ for 5h, and removing all crystal water to obtain 545g of anhydrous manganous phosphate precursor;
(3) Adding 533g of the anhydrous ferrous phosphate precursor obtained in the step (1) into 123.3g of lithium phosphate and 1133g of deionized water, and performing ball milling and wet sanding to obtain slurry A with the particle size D53=3.55 um;
(4) Adding 185.4g of lithium phosphate, 33g of glucose, 53g of polyethylene glycol, 7.71g of ammonium metavanadate and 1133g of deionized water into 545g of the anhydrous manganous phosphate precursor obtained in the step (2), and performing ball milling and wet sanding to obtain slurry B with the particle size D53=3.35 um;
(5) Mixing the slurry A and the slurry B obtained in the steps (3) and (4), and ball-milling for 33 minutes by using a ball mill; spray drying is carried out in nitrogen atmosphere, and the air inlet temperature is controlled to be 223 ℃ and the air outlet temperature is controlled to be 133 ℃; sintering at 753 ℃ for 15 hours in a box type furnace under nitrogen atmosphere, wherein the pressure in the furnace is 53Pa, nitrogen is introduced for more than 3 hours before temperature rise, the temperature rise rate is controlled to be 2 ℃/min, and the temperature is naturally reduced to 53 ℃ along with the furnace after sintering; and (3) carrying out jet milling, and controlling the particle size D13=3.43um, D53=1.3um and D93=13um to obtain the lithium iron manganese phosphate.
Dispersing the manganese iron phosphate positive electrode material prepared in the examples 1-4 and the comparative examples 1-2, super-P and PVDF in NMP according to a mass ratio of 83 3 The battery is characterized in that the volume ratio of the solvents is EC: DMC: EMC =1 (volume ratio). The test voltage range is 2.5V34.5V, the charging is carried out to 4.5V in a constant-current constant-voltage charging mode, and the cutoff current is 3.32C; the discharge was carried out to 2.5V in a constant current discharge mode. The test results are shown in table 1:
TABLE 1 basic Properties of lithium iron manganese phosphate materials
Examples 1 to 4 are high-safety high-capacity lithium manganese iron phosphate produced by the present invention, and comparative examples 1 to 2 are lithium manganese iron phosphate produced by a conventional method; the data show that the high-safety high-capacity lithium manganese iron phosphate prepared by the inventionThe first coulombic efficiency and the discharge gram capacity of the lithium iron manganese phosphate are higher than those of the lithium iron manganese phosphate prepared by the conventional method, and the conductivity and the capacity of the lithium iron manganese phosphate are higher; as can be seen from an XRD analysis chart, the lithium iron manganese phosphate prepared by the process has high purity and no impurity phase, and compared with the sample 1, the generated product contains Fe 2 P impurity phase, leading to the performance reduction of the product; scanning electron-level microscopic analysis is carried out on the products of the examples and the products of the comparative examples, and it can be seen that the high-safety high-capacity lithium manganese iron phosphate prepared by the invention has uniform particle size and better uniformity.
It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (9)
1. A preparation method of high-safety high-capacity lithium iron manganese phosphate is characterized by comprising the following steps:
(1) Mixing an iron source, a phosphorus source and an antioxidant into a solution, introducing nitrogen into the solution as a protective gas to prevent oxidation, and synthesizing a ferrous phosphate precursor by a coprecipitation method; sintering the obtained ferrous phosphate precursor, and removing all crystal water to obtain an anhydrous ferrous phosphate precursor;
(2) Mixing a manganese source, a phosphorus source and an antioxidant into a solution, introducing nitrogen into the solution as a protective gas to prevent oxidation, and synthesizing a manganous phosphate precursor by a coprecipitation method; sintering the obtained manganous phosphate precursor, and removing all crystal water to obtain an anhydrous manganous phosphate precursor;
(3) Adding lithium phosphate and deionized water into the anhydrous ferrous phosphate precursor obtained in the step (1), and performing ball milling and wet sanding to obtain slurry A;
(4) Adding lithium phosphate, an organic carbon source, a dispersing agent, a doping agent and deionized water into the anhydrous manganous phosphate precursor obtained in the step (2), and performing ball milling and wet sanding to obtain slurry B;
(5) And (4) mixing the slurry A and the slurry B obtained in the steps (3) and (4), and performing ball milling, spray drying, sintering and airflow crushing to obtain the high-safety high-capacity lithium manganese iron phosphate.
2. The method according to claim 1, wherein in the step (1), the iron source is ferrous sulfate; the phosphorus source is one or more selected from phosphoric acid, ammonium dihydrogen phosphate and diammonium hydrogen phosphate; the antioxidant is ascorbic acid; the chemical formula of the precursor of the ferrous phosphate is Fe 3 (PO 4 ) 2 ·8H 2 O; the sintering is carried out in a box type furnace, the sintering temperature is 350-600 ℃, the sintering time is 1-5 h, and the sintering atmosphere is nitrogen.
3. The production method according to claim 1, wherein in the step (2), the manganese source is manganous sulfate; the phosphorus source is one or more selected from phosphoric acid, ammonium dihydrogen phosphate and diammonium hydrogen phosphate; the antioxidant is ascorbic acid; the chemical formula of the manganous phosphate precursor is Mn 3 (PO 4 ) 2 ·7H 2 O; the sintering is carried out in a box type furnace, the sintering temperature is 350-600 ℃, the sintering time is 1-5 h, and the sintering atmosphere is nitrogen.
4. The production method according to claim 1, wherein in the step (3), the slurry a has a molar ratio of Fe/P =0.958 to 0.998, and a molar ratio of Li/Fe =1.025 to 1.055; in the wet sanding, the granularity D50= 0.30-0.60 um of the slurry A is controlled.
5. The production method according to claim 1, characterized in that, in step (4), the slurry B has a molar ratio Mn/P =0.958 to 0.998, and a molar ratio Li/Mn =1.025 to 1.055; in the wet sanding, the granularity D50= 0.20-0.50 um of the slurry B is controlled.
6. The preparation method according to claim 1, wherein in the step (4), the organic carbon source is a mixture of glucose and polyethylene glycol, the addition amount of glucose is 5 to 10wt% of the mass of the anhydrous manganous phosphate precursor, and the addition amount of polyethylene glycol is 1 to 5wt% of the mass of the anhydrous manganous phosphate precursor; the doping agent is one or more of titanium dioxide, ammonium metavanadate and niobium pentoxide, and the addition amount of the doping agent is 0-2.5 wt% of the mass of the anhydrous manganous phosphate precursor; the dispersant is one or more selected from anionic polyacrylate dispersant TC108, nonionic polymer TC311 and nonionic polymer TC28, and the addition amount of the dispersant is 5-10 wt% of the addition amount of glucose.
7. The preparation method according to claim 1, wherein in the step (5), the ball milling is carried out in a ball mill for 30 to 60 minutes; the spray drying is carried out in the nitrogen atmosphere, the air inlet temperature is controlled to be 180-240 ℃, and the air outlet temperature is controlled to be 80-120 ℃; the sintering is carried out in a box type furnace, the sintering temperature is 600-800 ℃, the sintering time is 8-20 h, and the sintering atmosphere is nitrogen; in the air flow crushing, the particle size D10 of the high-safety high-capacity lithium manganese iron phosphate obtained by final crushing is controlled to be more than or equal to 0.30um, D50 is not less than 0.8-1.8 um, and D90 is not more than 18um.
8. A high-safety high-capacity lithium iron manganese phosphate material prepared by the method of any one of claims 1 to 7.
9. The use of the high-safety high-capacity lithium iron manganese phosphate of claim 8 in a positive electrode material for a lithium battery.
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| JP2022174121A JP7513679B2 (en) | 2022-05-25 | 2022-10-31 | Manufacturing method for high-safety, high-capacity lithium manganese iron phosphate |
| EP22204965.2A EP4282827A1 (en) | 2022-05-25 | 2022-11-02 | Preparation method of high-safety high-capacity lithium manganese iron phosphate |
| US17/979,792 US20230060433A1 (en) | 2022-05-25 | 2022-11-03 | Preparation method of high-safety high-capacity lithium manganese iron phosphate |
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