CN115520846A - Preparation method and application of lithium iron manganese phosphate - Google Patents
Preparation method and application of lithium iron manganese phosphate Download PDFInfo
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- CN115520846A CN115520846A CN202211127102.0A CN202211127102A CN115520846A CN 115520846 A CN115520846 A CN 115520846A CN 202211127102 A CN202211127102 A CN 202211127102A CN 115520846 A CN115520846 A CN 115520846A
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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 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 126
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 65
- 230000002378 acidificating effect Effects 0.000 claims abstract description 51
- 238000002156 mixing Methods 0.000 claims abstract description 36
- 239000011343 solid material Substances 0.000 claims abstract description 36
- 239000011572 manganese Substances 0.000 claims abstract description 32
- 229910052742 iron Inorganic materials 0.000 claims abstract description 27
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011574 phosphorus Substances 0.000 claims abstract description 20
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 20
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- MQMHJMFHCMWGNS-UHFFFAOYSA-N phosphanylidynemanganese Chemical compound [Mn]#P MQMHJMFHCMWGNS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002585 base Substances 0.000 claims abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 235000019820 disodium diphosphate Nutrition 0.000 claims abstract description 11
- GYQBBRRVRKFJRG-UHFFFAOYSA-L disodium pyrophosphate Chemical compound [Na+].[Na+].OP([O-])(=O)OP(O)([O-])=O GYQBBRRVRKFJRG-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- 150000002696 manganese Chemical class 0.000 claims abstract description 9
- 238000001694 spray drying Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 30
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims description 16
- -1 iron ions Chemical class 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 8
- 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
- 239000002253 acid Substances 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000010405 anode material Substances 0.000 abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 57
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 37
- 229910000398 iron phosphate Inorganic materials 0.000 description 21
- 238000003756 stirring Methods 0.000 description 18
- 239000005955 Ferric phosphate Substances 0.000 description 16
- 229940032958 ferric phosphate Drugs 0.000 description 16
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 16
- 239000002244 precipitate Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 12
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 12
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 12
- 235000019799 monosodium phosphate Nutrition 0.000 description 12
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000010406 cathode material Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 8
- 238000000975 co-precipitation Methods 0.000 description 7
- 229940099596 manganese sulfate Drugs 0.000 description 7
- 239000011702 manganese sulphate Substances 0.000 description 7
- 235000007079 manganese sulphate Nutrition 0.000 description 7
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 7
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 6
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 6
- 239000011565 manganese chloride Substances 0.000 description 6
- 235000002867 manganese chloride Nutrition 0.000 description 6
- 229940099607 manganese chloride Drugs 0.000 description 6
- 229910000616 Ferromanganese Inorganic materials 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- UBYFFBZTJYKVKP-UHFFFAOYSA-J [Mn+4].[O-]P([O-])(=O)OP([O-])([O-])=O Chemical compound [Mn+4].[O-]P([O-])(=O)OP([O-])([O-])=O UBYFFBZTJYKVKP-UHFFFAOYSA-J 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 229930091371 Fructose Natural products 0.000 description 4
- 239000005715 Fructose Substances 0.000 description 4
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 229910000160 potassium phosphate Inorganic materials 0.000 description 4
- 235000011009 potassium phosphates Nutrition 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 3
- 229930006000 Sucrose Natural products 0.000 description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 3
- 235000011180 diphosphates Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- 235000011008 sodium phosphates Nutrition 0.000 description 3
- 239000005720 sucrose Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 3
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 2
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910011990 LiFe0.5Mn0.5PO4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000006258 conductive agent Substances 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
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
-
- 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
-
- 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
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A preparation method of lithium iron manganese phosphate and application thereof are disclosed, wherein an acidic ferrophosphorus solution is used as a base solution, and the acidic ferrophosphorus solution, a premixed phosphorus-manganese solution and an alkali solution are flowed to react, wherein the premixed phosphorus-manganese solution is prepared by mixing a disodium dihydrogen pyrophosphate solution and a manganese salt solution in a pipeline mixer in advance and then entering a reaction system, washing and dehydrating the obtained solid to obtain a first solid material, mixing the first solid material with a lithium source and water to perform hydrothermal reaction, adding a carbon source to perform spray drying, and calcining to obtain the lithium iron manganese phosphate. The invention can prepare phosphorus: (iron + manganese) =1:1, and the iron and manganese are uniformly mixed, and the lithium iron manganese phosphate anode material has high specific capacity and cycle performance.
Description
Technical Field
The invention belongs to the technical field of lithium battery anode materials, and particularly relates to a preparation method and application of lithium iron manganese phosphate.
Background
The types of the anode materials of the lithium ion battery are many, and the main types of the anode materials include lithium cobaltate, lithium manganate, nickel manganese cobalt ternary materials, lithium iron phosphate and the like. Lithium cobaltate is a variety with the highest industrialization degree, the most mature technology and the largest output in the existing anode materials, is mainly used in the field of small batteries of mobile phones, digital products and the like, but has high price and heavy pollution due to the cobalt and nickel raw materials, and has the danger of overheating and firing or explosion after the batteries are large-sized. Therefore, relatively speaking, the lithium ion battery with the positive electrode material of lithium manganate, ternary material and lithium iron phosphate has better safety performance and lower cost, so the investment of the industry at present is mainly focused on the materials. Among them, lithium iron phosphate is generally seen well in the industry due to its potential advantages in cycle life and material cost that other two materials do not have, and represents the future development direction of the positive electrode material of the power battery.
Lithium iron phosphate has a relatively regular olivine structure, so that the lithium iron phosphate has the advantages of large discharge capacity, low price, no toxicity and difficulty in causing environmental pollution, and the research on the lithium iron phosphate is popular in recent years.
Although lithium iron phosphate has many advantages, due to the structural limitation, when the lithium iron phosphate is applied to a battery, the lithium iron phosphate has the defects of low electronic conductivity, small lithium ion diffusion coefficient and low tap density of a material, so that the application of the lithium iron phosphate is greatly limited. In order to widen the application of lithium iron phosphate, a manganese compound is introduced into lithium iron phosphate to form a lithium iron manganese phosphate solid solution, and the lithium iron manganese phosphate solid solution has high electrochemical reaction voltage and good electrolyte compatibility, so that the lithium iron manganese phosphate solid solution has good capacitance and cycle effect.
Existing synthesis of LiMn x Fe 1-x PO 4 Methods for producing solid solution materials generally include high-temperature solid-phase reaction, liquid-phase coprecipitation, hydrothermal methods, sol-gel methods, redox methods, solid-phase microwave methods, and mechanical ball milling methods. High temperature solid phase reaction and hydrothermal methods are currently used.
The patent with publication number CN102769131A discloses a method for preparing a lithium iron manganese phosphate/carbon composite material, which takes ammonium dihydrogen phosphate, a lithium source, a manganese source, an iron source, a carbon source and metal doping elements as raw materials, and after mixing and drying, the raw materials are heated to 450-700 ℃ under the atmosphere condition, dried for 1-12 hours at constant temperature, and cooled to obtain the lithium iron manganese phosphate/carbon composite material. The method has the following disadvantages: 1. the solid phase method is difficult to uniformly coat the carbon source on the surface of the cathode material; 2. because the manganese and iron transition metal elements exist in the lithium manganese iron phosphate, the problem of how to mix the two elements uniformly needs to be fully considered in the process of preparing the material, if the uniform mixing is not achieved, the electrochemical performance of the prepared material cannot meet the requirement of commercial application, and the purpose of uniformly mixing the two elements cannot be achieved by adopting a solid phase method in the patent.
Therefore, a method for preparing a high-capacity and high-cycle-performance lithium iron manganese phosphate cathode material by uniformly mixing iron and manganese on an atomic layer is needed.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a preparation method and application of lithium iron manganese phosphate, wherein the method can prepare phosphorus: (iron + manganese) =1:1, and the iron and manganese are uniformly mixed, and the lithium iron manganese phosphate anode material has high specific capacity and cycle performance.
According to one aspect of the invention, the preparation method of the lithium iron manganese phosphate comprises the following steps:
s1: mixing ferric iron salt, phosphate and acid to prepare an acidic ferrophosphorus solution;
s2: taking part of the acidic ferrophosphorus solution as a base solution, adding alkali to adjust the pH value of the base solution, and then adding the rest of the acidic ferrophosphorus solution, a phosphorus-manganese premixed solution and an alkali solution in a concurrent flow manner to perform reaction, wherein the phosphorus-manganese premixed solution is prepared by mixing a disodium dihydrogen pyrophosphate solution and a manganese salt solution in a pipeline mixer in advance and then entering a reaction system;
s3: step S2, after the reaction is finished, carrying out solid-liquid separation, and washing and dehydrating the obtained solid to obtain a first solid material;
s4: mixing the first solid material with a lithium source and water, carrying out hydrothermal reaction under an acidic condition, adding a carbon source after the reaction is finished, mixing, and carrying out spray drying to obtain a second solid material;
s5: and calcining the second solid material in an inert atmosphere to obtain the lithium iron manganese phosphate.
In some embodiments of the invention, in step S1, the ferric salt is at least one of ferric sulfate, ferric chloride, or ferric nitrate.
In some embodiments of the invention, in step S1, the phosphate is at least one of sodium phosphate, ammonium phosphate or potassium phosphate.
In some embodiments of the invention, in step S1, the acid is at least one of sulfuric acid, hydrochloric acid, or nitric acid.
In some embodiments of the present invention, in step S1, the molar ratio of iron to phosphorus in the acidic ferrophosphorus solution is 1: (1.02-1.05).
In some embodiments of the invention, in step S1, the pH of the acidic ferrophosphorus solution is in the range of-1.0 to 0.5.
In some embodiments of the invention, in step S2, the pH of the base solution is 1.8 to 2.0; in the reaction process, the pH of the reaction system is controlled to be 1.8-2.0.
In some embodiments of the invention, in step S2, the manganese salt is at least one of manganese sulfate, manganese chloride or manganese nitrate.
In some embodiments of the invention, in step S2, the alkali solution is a sodium hydroxide solution. Further, the concentration of the alkali solution is 1.0-2.0mol/L.
In some embodiments of the invention, in step S2, the concentration of the disodium dihydrogen pyrophosphate solution is 0.5-1.0mol/L; the concentration of the manganese salt solution is 0.5-1.0mol/L.
In some embodiments of the present invention, in step S2, the feeding flow rate of the acidic ferrophosphorus solution is 100 to 200ml/h, the iron ion concentration in the acidic ferrophosphorus solution is 0.1 to 2.0mol/L, and the acidic ferrophosphorus solution and the premixed solution of phosphorus and manganese have an iron-manganese ratio of (0.25 to 4): 1 feeding.
In some embodiments of the invention, in step S2, the reaction is carried out at a rotational speed of 200 to 350 r/min.
In some embodiments of the invention, the temperature of the dehydration in step S3 is 550 to 700 ℃. Further, the dehydration time is 2-4h. The dehydration process is beneficial to the transformation of the crystal form into a hexagonal crystal system, so that lithium ions are better inserted.
In some embodiments of the present invention, in step S4, after the first solid material is mixed with the lithium source and water, an acid is added to adjust the pH to 2.5 to 4.0, and then the hydrothermal reaction is performed.
In some embodiments of the present invention, in step S4, the ratio of the first solid material to the lithium source is in a molar ratio (Fe + Mn): li =1: (1.0-1.2).
In some embodiments of the present invention, in step S4, the amount of water is 100% to 200% of the total mass of the first solid material and the lithium source solid.
In some embodiments of the present invention, the temperature of the hydrothermal reaction in step S4 is 100 to 120 ℃. Further, the time of the hydrothermal reaction is 2-4h.
In some embodiments of the invention, in step S4, the lithium source is at least one of lithium nitrate, lithium acetate, lithium hydroxide or lithium carbonate.
In some embodiments of the present invention, in step S4, the amount of the carbon source is 0.3 to 0.5 times the molar amount of the iron element in the first solid material.
In some embodiments of the invention, in step S4, the carbon source is at least one of glucose, sucrose or fructose.
In some embodiments of the invention, the temperature of the calcination in step S5 is 600 to 850 ℃. Further, the calcining time is 6-20h.
The invention also provides application of the method in preparation of the lithium ion battery.
According to a preferred embodiment of the invention, at least the following advantages are achieved:
1. according to the invention, in the coprecipitation process, pH is controlled to enable different precipitates to be generated under the action of iron and manganese and different precipitants, so as to obtain a mixed precipitate of ferric phosphate and manganese pyrophosphate, the hydrothermal reaction is carried out under an acidic condition, the manganese pyrophosphate in the mixed precipitate is further subjected to hydrothermal hydrolysis, the manganese pyrophosphate in the precipitate is formed into lithium manganese phosphate in advance, then a carbon source is added, and the lithium manganese phosphate is prepared by spraying, drying and sintering. The reaction equation is as follows:
coprecipitation reaction:
2Mn 2+ +P 2 O 7 4- →Mn 2 P 2 O 7 ；
Fe 3+ +PO 4 3- →FePO 4 ；
hydrothermal reaction:
H 2 O+2Li + +Mn 2 P 2 O 7 →2LiMnPO 4 +2H + ；
sintering reaction:
C+Li 2 O+2FePO 4 →2LiFePO 4 +CO。
2. because ferric ions can be combined with phosphate radicals to form precipitates and can also be combined with pyrophosphate, ferric phosphate seed crystals are firstly pre-synthesized in a base solution in the coprecipitation process, pyrophosphate and manganese are mixed in a pipeline mixer for pre-crystallization during feeding, so that pyrophosphate robbing by ferric iron and manganese is avoided, generated manganese pyrophosphate crystal grains enter a reaction system of ferric phosphate and are agglomerated with the ferric phosphate, ferric manganese coprecipitation is carried out under the induction of the ferric phosphate seed crystals, the final precipitate is a mixture of the ferric phosphate and the manganese pyrophosphate, and the ferric phosphate and the manganese are mixed more uniformly by a coprecipitation method, so that the subsequent preparation of the lithium iron manganese phosphate is facilitated, and the specific capacity and the cycle performance of the material are improved. And in the whole process, P =1:1 in the precipitate (Fe + Mn) is ensured, so that sufficient phosphorus content is ensured for the next step of synthesizing the lithium manganese iron phosphate, and the problem of supplementing a phosphorus source is avoided.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is an SEM photograph of a ferromanganese precipitate prepared in example 1 of the present invention;
fig. 2 is an SEM image of lithium manganese iron phosphate prepared in example 1 of the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
The embodiment prepares the lithium manganese iron phosphate, and the specific process comprises the following steps:
step 1, mixing ferric sulfate and sodium phosphate according to the molar ratio of iron to phosphorus being 1.02, and adding sulfuric acid to prepare an acidic ferric phosphate solution with the iron ion concentration of 0.1mol/L, pH of 0.5;
step 2, preparing a disodium dihydrogen pyrophosphate solution with the concentration of 0.5 mol/L;
step 3, preparing a manganese sulfate solution with the concentration of 0.5 mol/L;
step 4, preparing a sodium hydroxide solution with the concentration of 1.0mol/L;
step 5, adding the acidic iron phosphate solution serving as a base solution into a reaction kettle until the acidic iron phosphate solution overflows a bottom stirring paddle, adding the sodium hydroxide solution prepared in the step 4 into the reaction kettle, adjusting the pH value in the kettle to be 1.8-2.0, and controlling the stirring speed in the kettle to be 200r/min;
step 6, adding the acidic iron phosphate solution prepared in the step 1, a phosphorus-manganese premixed solution and the sodium hydroxide solution prepared in the step 4 into a reaction kettle in a parallel flow manner, wherein the phosphorus-manganese premixed solution is prepared by mixing the disodium dihydrogen pyrophosphate solution prepared in the step 2 and the manganese salt solution prepared in the step 3 in a manganese-phosphorus ratio of 1:1 through a pipeline mixer before entering the reaction kettle and then flowing into the reaction kettle; controlling the flow of the acidic ferric phosphate solution in the reaction kettle to be 100ml/h, the feeding iron-manganese ratio of the reaction kettle to be 1:1, the pH value in the kettle to be 1.8-2.0 and the stirring speed in the kettle to be 200r/min;
step 7, stopping feeding after the reaction kettle is full, performing solid-liquid separation, washing the obtained solid material with pure water, and dehydrating at 550 ℃ for 4 hours to obtain iron-manganese precipitate;
step 8, mixing the ferro-manganese precipitate obtained in the step 7 with lithium nitrate according to a molar ratio (Fe + Mn) that Li =1 (1.0-1.2), adding deionized water accounting for 100% of the total mass of solids, adjusting the pH to 2.5 by using nitric acid, and carrying out hydrothermal reaction in a closed reaction kettle for 4 hours at the reaction temperature of 120 ℃;
step 9, after the hydrothermal reaction is finished, adding glucose with the molar weight of 0.3 time that of the iron element into the reaction kettle, uniformly mixing, and then carrying out spray drying to obtain a solid material;
and step 10, calcining the solid material obtained in the step 9 for 14 hours at 750 ℃ under the protection of inert gas, and naturally cooling to room temperature to obtain a finished product of the lithium iron manganese phosphate cathode material.
Example 2
The embodiment prepares the lithium manganese iron phosphate, and the specific process comprises the following steps:
step 1, mixing ferric nitrate and ammonium phosphate according to the molar ratio of iron to phosphorus elements of 1.04, and adding nitric acid to prepare an acidic ferric phosphate solution with the iron ion concentration of 1.0mol/L, pH of 0;
step 2, preparing a disodium dihydrogen pyrophosphate solution with the concentration of 0.8 mol/L;
step 3, preparing a manganese nitrate solution with the concentration of 0.8 mol/L;
step 4, preparing a sodium hydroxide solution with the concentration of 1.5 mol/L;
step 5, adding the acidic iron phosphate solution serving as a base solution into a reaction kettle until the acidic iron phosphate solution overflows a bottom stirring paddle, adding the sodium hydroxide solution prepared in the step 4 into the reaction kettle, adjusting the pH value in the kettle to be 1.8-2.0, and controlling the stirring speed in the kettle to be 300r/min;
step 6, adding the acidic iron phosphate solution prepared in the step 1, a phosphorus-manganese premixed solution and the sodium hydroxide solution prepared in the step 4 into a reaction kettle in a parallel flow manner, wherein the phosphorus-manganese premixed solution is prepared by mixing the disodium dihydrogen pyrophosphate solution prepared in the step 2 and the manganese salt solution prepared in the step 3 in a manganese-phosphorus ratio of 1:1 through a pipeline mixer before entering the reaction kettle, and then flowing into the reaction kettle; controlling the flow of the acidic ferric phosphate solution in the reaction kettle to be 150ml/h, the feeding iron-manganese ratio of the reaction kettle to be 2:1, the pH value in the kettle to be 1.8-2.0 and the stirring speed in the kettle to be 300r/min;
step 7, stopping feeding when the reaction kettle is full, performing solid-liquid separation, washing the obtained solid material with pure water, and dehydrating at the temperature of 600 ℃ for 3 hours to obtain iron-manganese precipitate;
step 8, mixing the ferro-manganese precipitate obtained in the step 7 with lithium acetate according to a molar ratio (Fe + Mn) that Li =1 (1.0-1.2), adding deionized water accounting for 150% of the total mass of solids, adjusting the pH to 3.0 by using nitric acid, and carrying out hydrothermal reaction in a closed reaction kettle for 3 hours at the reaction temperature of 110 ℃;
step 9, after the hydrothermal reaction is finished, adding sucrose with the molar weight of the iron element being 0.4 times that of the sucrose into the reaction kettle, uniformly mixing, and then carrying out spray drying to obtain a solid material;
and step 10, calcining the solid material obtained in the step 9 at 600 ℃ for 20 hours under the protection of inert gas, and naturally cooling to room temperature to obtain a finished product of the lithium iron manganese phosphate cathode material.
Example 3
The embodiment prepares the lithium manganese iron phosphate, and the specific process comprises the following steps:
step 1, mixing ferric chloride and potassium phosphate according to the molar ratio of iron to phosphorus being 1.05, and adding hydrochloric acid to prepare an acidic ferric phosphate solution with the iron ion concentration of 2.0mol/L, pH of-1.0;
step 2, preparing 1.0mol/L disodium dihydrogen pyrophosphate solution;
step 3, preparing a manganese chloride solution with the concentration of 1.0mol/L;
step 4, preparing a sodium hydroxide solution with the concentration of 2.0 mol/L;
step 5, adding the acidic iron phosphate solution serving as a base solution into a reaction kettle until the acidic iron phosphate solution overflows a bottom stirring paddle, adding the sodium hydroxide solution prepared in the step 4 into the reaction kettle, adjusting the pH value in the kettle to be 1.8-2.0, and controlling the stirring speed in the kettle to be 350r/min;
step 6, adding the acidic iron phosphate solution prepared in the step 1, a phosphorus-manganese premixed solution and the sodium hydroxide solution prepared in the step 4 into a reaction kettle in a parallel flow manner, wherein the phosphorus-manganese premixed solution is prepared by mixing the disodium dihydrogen pyrophosphate solution prepared in the step 2 and the manganese salt solution prepared in the step 3 in a manganese-phosphorus ratio of 1:1 through a pipeline mixer before entering the reaction kettle and then flowing into the reaction kettle; controlling the flow of the acidic ferric phosphate solution in the reaction kettle to be 200ml/h, the feeding iron-manganese ratio of the reaction kettle to be 4:1, the pH value in the kettle to be 1.8-2.0 and the stirring speed in the kettle to be 350r/min;
step 7, stopping feeding after the reaction kettle is full, performing solid-liquid separation, washing the obtained solid material with pure water, and dehydrating at the temperature of 700 ℃ for 2 hours to obtain iron-manganese precipitate;
step 8, mixing the ferro-manganese precipitate obtained in the step 7 with lithium hydroxide according to a molar ratio (Fe + Mn) that Li =1 (1.0-1.2), adding deionized water accounting for 200% of the total mass of solids, adjusting the pH to 4.0 by using nitric acid, and carrying out hydrothermal reaction in a closed reaction kettle for 2 hours at the reaction temperature of 120 ℃;
step 9, after the hydrothermal reaction is finished, adding fructose with the molar weight of 0.5 time that of the iron element into the reaction kettle, uniformly mixing, and then carrying out spray drying to obtain a solid material;
and step 10, calcining the solid material obtained in the step 9 for 6 hours at 850 ℃ under the protection of inert gas, and naturally cooling to room temperature to obtain a finished product of the lithium iron manganese phosphate cathode material.
Comparative example 1
This comparative example prepared a lithium manganese iron phosphate, which is mainly different from example 1 in that the phosphorus source was sodium dihydrogen phosphate, and the phosphorus source, the manganese source, and the iron source were directly co-flowed and co-precipitated, and the specific process was:
step 1, mixing ferric sulfate and sodium phosphate according to the molar ratio of iron to phosphorus being 1.02, and adding sulfuric acid to prepare an acidic ferric phosphate solution with the iron ion concentration of 0.1mol/L, pH of 0.5;
step 2, preparing a sodium dihydrogen phosphate solution with the concentration of 0.5 mol/L;
step 3, preparing a manganese sulfate solution with the concentration of 0.5 mol/L;
step 4, preparing a sodium hydroxide solution with the concentration of 1.0mol/L;
step 5, adding the acidic iron phosphate solution serving as a base solution into a reaction kettle until the acidic iron phosphate solution overflows a bottom stirring paddle, adding the sodium hydroxide solution prepared in the step 4 into the reaction kettle, adjusting the pH value in the kettle to be 1.8-2.0, and controlling the stirring speed in the kettle to be 200r/min;
step 6, adding the acidic iron phosphate solution prepared in the step 1, the sodium dihydrogen phosphate solution prepared in the step 2, the manganese sulfate solution prepared in the step 3 and the sodium hydroxide solution prepared in the step 4 into a reaction kettle in a parallel flow manner; controlling the flow of the acidic iron phosphate solution in the reaction kettle to be 100ml/h, the feeding iron-manganese ratio of the reaction kettle to be 1:1, the feeding molar ratio of sodium dihydrogen phosphate to manganese sulfate to be 1:1, controlling the pH value in the reaction kettle to be 1.8-2.0 and the stirring speed in the reaction kettle to be 200r/min;
step 7, stopping feeding when the reaction kettle is full, performing solid-liquid separation, washing the obtained solid material with pure water, and dehydrating at the temperature of 550 ℃ for 4 hours;
step 8, mixing the solid material obtained in the step 7 with lithium nitrate according to a molar ratio (Fe + Mn) Li =1 (1.0-1.2), adding deionized water accounting for 100% of the total mass of the solid, adding glucose accounting for 0.3 time of the molar weight of the iron element into the reaction kettle, uniformly mixing, and performing spray drying to obtain a solid material;
and 9, calcining the solid material obtained in the step 8 for 14 hours at 750 ℃ under the protection of inert gas, and naturally cooling to room temperature to obtain a finished product of the lithium iron manganese phosphate cathode material.
Comparative example 2
The lithium iron manganese phosphate prepared by the comparative example is different from the lithium iron manganese phosphate prepared by the example 2 in that the phosphorus source is sodium dihydrogen phosphate, the phosphorus source, the manganese source and the iron source are directly co-flowed and co-precipitated, and the specific process is as follows:
step 1, mixing ferric chloride and potassium phosphate according to the molar ratio of iron to phosphorus being 1.05, and adding hydrochloric acid to prepare an acidic ferric phosphate solution with the iron ion concentration of 2.0mol/L, pH of-1.0;
step 2, preparing a sodium dihydrogen phosphate solution with the concentration of 1.0mol/L;
step 3, preparing a manganese chloride solution with the concentration of 1.0mol/L;
step 4, preparing a sodium hydroxide solution with the concentration of 2.0 mol/L;
step 5, adding an acidic iron phosphate solution serving as a base solution into a reaction kettle until the acidic iron phosphate solution overflows a bottom stirring paddle, adding the sodium hydroxide solution prepared in the step 4 into the reaction kettle, adjusting the pH value in the kettle to be 1.8-2.0, and controlling the stirring speed in the kettle to be 350r/min;
step 6, adding the acidic iron phosphate solution prepared in the step 1, the sodium dihydrogen phosphate solution prepared in the step 2, the manganese chloride solution prepared in the step 3 and the sodium hydroxide solution prepared in the step 4 into a reaction kettle in a parallel flow manner; controlling the flow of the acidic iron phosphate solution in the reaction kettle to be 200ml/h, the feeding iron-manganese ratio of the reaction kettle to be 4:1, the feeding molar ratio of sodium dihydrogen phosphate to manganese sulfate to be 1:1, controlling the pH value in the kettle to be 1.8-2.0, and the stirring speed in the kettle to be 350r/min;
step 7, stopping feeding when the reaction kettle is full, performing solid-liquid separation, washing the obtained solid material with pure water, and dehydrating for 2 hours at the temperature of 700 ℃;
step 8, mixing the solid material obtained in the step 7 with lithium hydroxide according to a molar ratio (Fe + Mn) that Li =1 (1.0-1.2), adding deionized water accounting for 150% of the total mass of the solid, adding fructose with the molar weight 0.5 times that of the iron element into the reaction kettle, uniformly mixing, and performing spray drying to obtain a solid material;
and 9, calcining the solid material obtained in the step 8 for 6 hours at 850 ℃ under the protection of inert gas, and naturally cooling to room temperature to obtain a finished product of the lithium iron manganese phosphate cathode material.
Comparative example 3
The lithium iron manganese phosphate prepared by the comparative example is different from the lithium iron manganese phosphate prepared by the example 3 in that the phosphorus source is sodium dihydrogen phosphate, the phosphorus source, the manganese source and the iron source are directly co-flowed and co-precipitated, and the specific process is as follows:
step 1, mixing ferric chloride and potassium phosphate according to the molar ratio of iron to phosphorus being 1.05, and adding hydrochloric acid to prepare an acidic ferric phosphate solution with the iron ion concentration of 2.0mol/L, pH of-1.0;
step 2, preparing a sodium dihydrogen phosphate solution with the concentration of 1.0mol/L;
step 3, preparing a manganese chloride solution with the concentration of 1.0mol/L;
step 4, preparing a sodium hydroxide solution with the concentration of 2.0 mol/L;
step 5, adding the acidic iron phosphate solution serving as a base solution into a reaction kettle until the acidic iron phosphate solution overflows a bottom stirring paddle, adding the sodium hydroxide solution prepared in the step 4 into the reaction kettle, adjusting the pH value in the kettle to be 1.8-2.0, and controlling the stirring speed in the kettle to be 350r/min;
step 6, adding the acidic iron phosphate solution prepared in the step 1, the sodium dihydrogen phosphate solution prepared in the step 2, the manganese chloride solution prepared in the step 3 and the sodium hydroxide solution prepared in the step 4 into a reaction kettle in a parallel flow manner; controlling the flow of the acidic iron phosphate solution in the reaction kettle to be 200ml/h, the feeding iron-manganese ratio of the reaction kettle to be 4:1, the feeding molar ratio of sodium dihydrogen phosphate to manganese sulfate to be 1:1, controlling the pH value in the reaction kettle to be 1.8-2.0 and the stirring speed in the reaction kettle to be 350r/min;
step 7, stopping feeding when the reaction kettle is full, performing solid-liquid separation, washing the obtained solid material with pure water, and dehydrating for 2 hours at the temperature of 700 ℃;
step 8, mixing the solid material obtained in the step 7 with lithium hydroxide according to a molar ratio (Fe + Mn) that Li =1 (1.0-1.2), adding deionized water accounting for 200% of the total mass of the solid, adding fructose with the molar weight 0.5 times that of the iron element into the reaction kettle, uniformly mixing, and performing spray drying to obtain a solid material;
and 9, calcining the solid material obtained in the step 8 for 6 hours at 850 ℃ under the protection of inert gas, and naturally cooling to room temperature to obtain a finished product of the lithium iron manganese phosphate cathode material.
ICP measurement of the percentage of the main content element was performed on the lithium iron manganese phosphate products obtained in examples 1 to 3 and comparative examples 1 to 3, and the results are shown in table 1.
TABLE 1
| Li/％ | Fe/％ | Mn/％ | P/％ | Li:Fe:Mn:P | Chemical formula of calculation | |
| Example 1 | 4.43 | 17.78 | 17.41 | 19.71 | 1:0.5:0.5:1 | LiFe 0.5 Mn 0.5 PO 4 |
| Example 2 | 4.42 | 23.66 | 11.61 | 19.68 | 1:0.66:0.33:1 | LiFe 0.66 Mn 0.33 PO 4 |
| Example 3 | 4.41 | 28.36 | 6.96 | 19.66 | 1:0.8:0.2:1 | LiFe 0.8 Mn 0.2 PO 4 |
| Comparative example 1 | 4.40 | 35.26 | 0.12 | 19.64 | 1:1:0:1 | LiFePO 4 |
| Comparative example 2 | 4.41 | 35.33 | 0.07 | 19.63 | 1:1:0:1 | LiFePO 4 |
| Comparative example 3 | 4.40 | 35.35 | 0.042 | 19.63 | 1:1:0:1 | LiFePO 4 |
As can be seen from the detection results in table 1, the manganese content in the comparative example is extremely low, and ideal lithium iron manganese phosphate cannot be obtained. It is shown that the conventional coprecipitation method is difficult to precipitate ferromanganese at the same time.
Test examples
Mixing the lithium iron manganese phosphate positive electrode materials obtained in the examples and the comparative examples, acetylene black as a conductive agent and PVDF as a binder according to a mass ratio of 8; the diaphragm is Celgard2400 polypropylene porous membrane; the solvent in the electrolyte is a solution composed of EC, DMC and EMC according to a mass ratio of 1 6 ，LiPF 6 The concentration of (A) is 1.0mol/L; a 2023 button cell battery was assembled in a glove box. Carrying out charge-discharge cycle performance test on the battery, and testing the discharge specific capacity of 0.1C and 1C within the range of cut-off voltage of 2.2-4.3V; the results of testing electrochemical properties are shown in table 2.
TABLE 2
It can be seen from table 2 that the electrochemical performance of the embodiment is significantly better than that of the comparative example, which indicates that the lithium manganese iron phosphate obtained by sintering the prepared ferric manganese phosphate has higher specific capacity and cycle performance.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. The preparation method of the lithium iron manganese phosphate is characterized by comprising the following steps of:
s1: mixing trivalent ferric salt, phosphate and acid to prepare an acidic ferrophosphorus solution;
s2: taking part of the acidic ferrophosphorus solution as a base solution, adding alkali to adjust the pH value of the base solution, and then adding the rest of the acidic ferrophosphorus solution, a phosphorus-manganese premixed solution and an alkali solution in a concurrent flow manner to perform reaction, wherein the phosphorus-manganese premixed solution is prepared by mixing a disodium dihydrogen pyrophosphate solution and a manganese salt solution in a pipeline mixer in advance and then entering a reaction system;
s3: after the reaction in the step S2 is finished, carrying out solid-liquid separation, and washing and dehydrating the obtained solid to obtain a first solid material;
s4: mixing the first solid material with a lithium source and water, carrying out hydrothermal reaction under an acidic condition, adding a carbon source after the reaction is finished, mixing, and carrying out spray drying to obtain a second solid material;
s5: and calcining the second solid material in an inert atmosphere to obtain the lithium iron manganese phosphate.
2. The method according to claim 1, wherein in step S1, the molar ratio of iron to phosphorus in the acidic ferrophosphorus solution is 1: (1.02-1.05).
3. The method according to claim 1, wherein the pH of the acidic ferrophosphorus solution in step S1 is in the range of-1.0 to 0.5.
4. The method according to claim 1, wherein in step S2, the pH of the base solution is 1.8 to 2.0; in the reaction process, the pH of the reaction system is controlled to be 1.8-2.0.
5. The method according to claim 1, wherein in step S2, the concentration of the disodium dihydrogen pyrophosphate solution is 0.5 to 1.0mol/L; the concentration of the manganese salt solution is 0.5-1.0mol/L.
6. The preparation method according to claim 5, wherein in step S2, the feed flow rate of the acidic ferrophosphorus solution is 100-200ml/h, the concentration of iron ions in the acidic ferrophosphorus solution is 0.1-2.0mol/L, and the iron-manganese ratio of the acidic ferrophosphorus solution to the premixed liquid of phosphorus and manganese is (0.25-4): 1 feeding.
7. The method according to claim 1, wherein the temperature of the dehydration in step S3 is 550 to 700 ℃.
8. The method according to claim 1, wherein in step S4, the first solid material is mixed with a lithium source and water, and then the hydrothermal reaction is performed after adding acid to adjust the pH to 2.5-4.0.
9. The method according to claim 1, wherein the temperature of the hydrothermal reaction in step S4 is 100-120 ℃.
10. Use of the method according to any one of claims 1 to 9 for the preparation of a lithium ion battery.
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| WO2024055519A1 (en) * | 2022-09-16 | 2024-03-21 | 广东邦普循环科技有限公司 | Preparation method and use of lithium manganese iron phosphate |
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| JP2011100592A (en) * | 2009-11-05 | 2011-05-19 | Tayca Corp | Method of manufacturing carbon-olivine type lithium ferromanganese phosphate complex, and positive electrode material for lithium ion battery |
| CN105702954A (en) * | 2014-11-26 | 2016-06-22 | 比亚迪股份有限公司 | Positive electrode material LiMn1-xFexPO4 / C and preparation method thereof |
| CN112125292A (en) * | 2020-08-14 | 2020-12-25 | 中国科学院金属研究所 | Hydrothermal synthesis method of lithium manganese iron phosphate |
| CN113659134A (en) * | 2021-07-09 | 2021-11-16 | 江苏乐能电池股份有限公司 | Method for preparing nanoscale lithium manganese iron phosphate material by using co-crystallization method |
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- 2023-02-22 WO PCT/CN2023/077687 patent/WO2024055519A1/en unknown
- 2023-06-27 FR FR2306737A patent/FR3139952A1/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011100592A (en) * | 2009-11-05 | 2011-05-19 | Tayca Corp | Method of manufacturing carbon-olivine type lithium ferromanganese phosphate complex, and positive electrode material for lithium ion battery |
| CN105702954A (en) * | 2014-11-26 | 2016-06-22 | 比亚迪股份有限公司 | Positive electrode material LiMn1-xFexPO4 / C and preparation method thereof |
| CN112125292A (en) * | 2020-08-14 | 2020-12-25 | 中国科学院金属研究所 | Hydrothermal synthesis method of lithium manganese iron phosphate |
| CN113659134A (en) * | 2021-07-09 | 2021-11-16 | 江苏乐能电池股份有限公司 | Method for preparing nanoscale lithium manganese iron phosphate material by using co-crystallization method |
| CN114940485A (en) * | 2022-07-25 | 2022-08-26 | 蜂巢能源科技股份有限公司 | Lithium iron manganese phosphate precursor and preparation method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024055519A1 (en) * | 2022-09-16 | 2024-03-21 | 广东邦普循环科技有限公司 | Preparation method and use of lithium manganese iron phosphate |
| CN115676794A (en) * | 2022-10-24 | 2023-02-03 | 广东邦普循环科技有限公司 | Method for preparing lithium iron manganese phosphate cathode material by coprecipitation and application thereof |
| CN115676794B (en) * | 2022-10-24 | 2024-01-09 | 广东邦普循环科技有限公司 | Method for preparing lithium iron manganese phosphate positive electrode material by coprecipitation and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2024055519A1 (en) | 2024-03-21 |
| CN115520846B (en) | 2023-11-03 |
| FR3139952A1 (en) | 2024-03-22 |
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