CN114988386B - Lithium iron manganese phosphate positive electrode material, and preparation method and application thereof - Google Patents
Lithium iron manganese phosphate positive electrode material, and preparation method and application thereof Download PDFInfo
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- CN114988386B CN114988386B CN202210688198.1A CN202210688198A CN114988386B CN 114988386 B CN114988386 B CN 114988386B CN 202210688198 A CN202210688198 A CN 202210688198A CN 114988386 B CN114988386 B CN 114988386B
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- lithium
- phosphoric acid
- salt
- positive electrode
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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 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000007774 positive electrode material Substances 0.000 title claims description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 96
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 82
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 78
- 238000000034 method Methods 0.000 claims abstract description 60
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 48
- 238000000975 co-precipitation Methods 0.000 claims abstract description 41
- 238000005245 sintering Methods 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 239000002002 slurry Substances 0.000 claims abstract description 25
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims abstract description 23
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002244 precipitate Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000002019 doping agent Substances 0.000 claims abstract description 15
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims abstract description 14
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims abstract description 14
- 239000000174 gluconic acid Substances 0.000 claims abstract description 14
- 235000012208 gluconic acid Nutrition 0.000 claims abstract description 14
- 239000010405 anode material Substances 0.000 claims abstract description 13
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 11
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 11
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 11
- 239000011572 manganese Substances 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 238000004821 distillation Methods 0.000 claims abstract description 7
- 239000011268 mixed slurry Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 229940099596 manganese sulfate Drugs 0.000 claims description 8
- 235000007079 manganese sulphate Nutrition 0.000 claims description 8
- 239000011702 manganese sulphate Substances 0.000 claims description 8
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 5
- 239000011790 ferrous sulphate Substances 0.000 claims description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- 150000001844 chromium Chemical class 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 150000002751 molybdenum Chemical class 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 150000002821 niobium Chemical class 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 150000003481 tantalum Chemical class 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 150000003608 titanium Chemical class 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 150000003657 tungsten Chemical class 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 150000003681 vanadium Chemical class 0.000 claims description 2
- 150000003754 zirconium Chemical class 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 52
- 238000006243 chemical reaction Methods 0.000 description 48
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 28
- 229910052744 lithium Inorganic materials 0.000 description 28
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 24
- 229910052698 phosphorus Inorganic materials 0.000 description 24
- 239000011574 phosphorus Substances 0.000 description 24
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 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 11
- 239000008103 glucose Substances 0.000 description 11
- 238000001354 calcination Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000007788 liquid Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 5
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 5
- 239000013589 supplement Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 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
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 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 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000005550 wet granulation Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a lithium iron manganese phosphate anode material, and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Mixing ammonium bicarbonate, a manganese source and an iron source to obtain a mixed carbonate precipitate, mixing the mixed carbonate precipitate with concentrated phosphoric acid, and adding gluconic acid to obtain first slurry; (2) Mixing and stirring the first slurry, lithium bicarbonate, lithium hydroxide, a phosphoric acid source, a doping agent and an aqueous alcohol solution to obtain mixed slurry, and performing reduced pressure distillation to obtain coprecipitation balls; (3) The lithium iron manganese phosphate anode material is obtained by sintering the coprecipitation balls, and the invention adopts a simple wet coprecipitation method to granulate once, so that the defects of high process cost and relatively complex process in the traditional process are avoided, the energy consumption is greatly reduced, the synthesis cost is lowered, and the manufacturing process is simplified.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a lithium iron manganese phosphate anode material, a preparation method and application thereof.
Background
The ferric phosphate has the advantages of rich resources, good safety performance, good cycle life, environmental friendliness and the like, is one of the preferred positive electrode materials of the power battery, and the lithium manganese phosphate has higher working potential (4.1V) and is in the stable electrochemical window of the existing general electrolyte system, so that the energy density of the lithium manganese phosphate is 21% higher than that of LFP in theory, and the lithium manganese phosphate is considered as an LFP upgrade. However, due to poor conductivity, the lithium iron manganese phosphate has high conductivity and cycle performance of the lithium iron phosphate and a high voltage platform of the lithium iron manganese phosphate, and is difficult to have practical application value at present, and is considered to be a new energy anode material of the next generation which is better to be selected for replacing the lithium iron phosphate.
CN107128892a discloses a preparation method of a lithium iron manganese phosphate anode material, which uses an iron source, a phosphorus source, a manganese source, a lithium source and a carbon source to sinter and prepare lithium iron manganese phosphate, and the phosphorus source, the iron source, the manganese source and the lithium source are put into a reaction kettle, and are put into pure water according to the solid content of 5-60% to be stirred and mixed; adding a carbon source according to the solid content mass ratio of 50-200%; stirring and mixing the mixture in a reaction kettle at the temperature of 120-150 ℃ for reaction; spray drying the material; calcining the material in a nitrogen atmosphere; and (5) tunnel drying the materials.
CN113929073a discloses a method for preparing lithium manganese iron phosphate by a solid phase method. The preparation method comprises the following steps: weighing a certain amount of manganese source and iron source according to a molar ratio of 7:3, weighing a lithium source, a phosphorus source, a carbon source and a doping agent according to a certain stoichiometric ratio, adding pure water, ball milling and sanding, controlling the sanding particle size D50 to be less than or equal to 300nm, and spray drying to obtain brown precursor powder. And sintering the precursor under the protection of nitrogen atmosphere, controlling the sintering temperature to be 600-700 ℃, and then crushing, screening and removing iron to obtain the lithium manganese iron phosphate anode material.
The preparation method of the lithium manganese iron phosphate positive electrode material adopts a grinding spray method, and the method has the problems of high energy consumption and high cost, so that the wide application of the lithium manganese iron phosphate positive electrode material is greatly limited.
Disclosure of Invention
The invention aims to provide a lithium manganese iron phosphate positive electrode material, a preparation method and application thereof, and the invention avoids the defects of high process cost and relatively complex process flow existing in the traditional process by adopting simple wet coprecipitation one-time granulation, thereby greatly reducing energy consumption, reducing synthesis cost and simplifying manufacturing process.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a lithium iron manganese phosphate positive electrode material, the method comprising the steps of:
(1) Mixing ammonium bicarbonate, a manganese source and an iron source to obtain a mixed carbonate precipitate, mixing the mixed carbonate precipitate with concentrated phosphoric acid, and adding gluconic acid to obtain first slurry;
(2) Mixing and stirring the first slurry, lithium bicarbonate, lithium hydroxide, a phosphoric acid source, a doping agent and an aqueous alcohol solution to obtain mixed slurry, and performing reduced pressure distillation to obtain coprecipitation balls;
(3) And sintering the coprecipitation balls to obtain the lithium iron manganese phosphate anode material.
According to the preparation method of the lithium iron manganese phosphate material, a spray drying process is omitted, wet coprecipitation one-time granulation is adopted, any single solid phase precursor is not required to be prepared, a proper amount of insufficient elements are supplemented after wet granulation, and then the lithium iron manganese phosphate material is directly sintered and synthesized after uniform mixing. Can greatly reduce energy consumption, reduce synthesis cost and simplify manufacturing process.
The first slurry is gradually added into a reaction kettle to carry out coprecipitation, then the first slurry, the prepared lithium bicarbonate, lithium hydroxide, phosphoric acid, doping agent and the like are added into the reaction kettle to carry out reaction, 80 percent aqueous alcohol solution is put into the reaction kettle in advance, as enough phosphoric acid and glucose are added into the first slurry, the undissolved solid content is less than 5 percent, suspension is formed after ball milling, slow stirring is assisted, the first slurry can ensure the uniformity of feeding into the reaction kettle at each moment, the temperature of the reaction kettle is controlled before the reaction starts, the operation at a lower temperature can ensure that the volatility of ethanol is reduced to a lower level, meanwhile, the bicarbonate of the system can not be rapidly decomposed in a large amount to cause excessive bubble content, through high-speed stirring, various solutions which are continuously added can be fully mixed and uniformly dispersed in a reaction kettle in the shortest time, and a coprecipitation reaction occurs in a specific environment in the kettle, after preparation, a first slurry, a lithium bicarbonate solution, a lithium hydroxide solution, a phosphoric acid solution and a doping solution are synchronously and slowly added into the reaction kettle at the same time to start the coprecipitation reaction, the pH value of the system is controlled, the lithium hydroxide solution or the dilute phosphoric acid solution is alternately added, lithium which is deleted in the process is coordinated and supplemented by the lithium bicarbonate solution, the proportion of lithium, metal and phosphorus in the process and the final process is ensured, the concentration is continuously carried out in the process of carrying out, the liquid discharged after the concentration is added into a certain amount of ethanol again, and the mixed solution of ethanol and water which are prepared again is continuously added into the reaction kettle, so that the concentration of ethanol and water in the reaction kettle is ensured to be basically balanced. And (3) respectively recovering and treating the water and the ethanol by a reduced pressure distillation mode after the coprecipitation reaction is finished, so as to finally obtain the spheroid coprecipitation ball.
Preferably, the mass concentration of the ammonium bicarbonate in the step (1) is 180-150 g/L, for example: 80g/L, 100g/L, 110g/L, 130g/L, 150g/L, etc.
Preferably, the manganese source comprises a manganese sulfate solution having a mass concentration of 80 to 150g/L (e.g., 80g/L, 100g/L, 110g/L, 130g/L, 150g/L, etc.).
Preferably, the iron source comprises a ferrous sulfate solution having a mass concentration of 80-150 g/L (e.g., 80g/L, 100g/L, 110g/L, 130g/L, 150g/L, etc.).
The mass ratio of phosphoric acid in the concentrated phosphoric acid in the step (1) is 80-90%, for example: 80%, 82%, 85%, 88%, 90%, etc.
Preferably, the process of mixing the mixed carbonate precipitate and concentrated phosphoric acid is diluted with water.
Preferably, the mass ratio of the gluconic acid to the phosphoric acid in the concentrated phosphoric acid is 0.2-0.3:1, for example: 0.2:1, 0.22:1, 0.25:1, 0.28:1, or 0.3:1, etc.
The invention can adjust the content of glucose in the final coprecipitation sample through the addition amount change of the gluconic acid and the phosphoric acid, the concentration of the glucose and the like, thereby indirectly controlling the carbon content and the distribution in the final sintered sample.
Preferably, in the first slurry of step (1), the molar ratio of the total molar amount of metal ions to phosphate ions is 1 (1.01 to 1.05), for example: 1:1.01, 1:1.02, 1:1.03, 1:1.04, or 1:1.05, etc.
Preferably, the mass concentration of the lithium bicarbonate in the step (2) is 50-70 g/L, for example: 50g/L, 55g/L, 60g/L, 65g/L, 70g/L, etc.
Preferably, the mass concentration of the lithium hydroxide is 40-60 g/L, for example: 40g/L, 45g/L, 50g/L, 55g/L, 60g/L, etc.
Preferably, the phosphoric acid source comprises dilute phosphoric acid.
Preferably, the mass ratio of phosphoric acid in the diluted phosphoric acid is 3-8%, for example: 3%, 4%, 5%, 6%, 7% or 8%, etc.
Preferably, the dopant comprises any one or a combination of at least two of nickel salt, cobalt salt, manganese salt, calcium salt, magnesium salt, tungsten salt, molybdenum salt, zirconium salt, titanium salt, vanadium salt, niobium salt, tantalum salt, or chromium salt.
Preferably, the doping amount of the dopant is 1 to 3% of the mass of the positive electrode material, for example: 1%, 1.5%, 2%, 2.5% or 3%, etc.
Preferably, the volume ratio of water to ethanol in the hydroalcoholic solution is 1 (0.8-1.2), for example: 1:0.8, 1:0.9, 1:1, 1:1.1, or 1:1.2, etc.
Preferably, the temperature of the mixing and stirring in the step (2) is 20-40 ℃, for example: 20 ℃, 25 ℃, 30 ℃, 35 ℃ or 40 ℃ and the like.
Preferably, the pH of the mixing and stirring is 3 to 5, for example: 3. 3.5, 4, 4.5 or 5, etc.
Preferably, the speed of the mixing and stirring is 1200-2000 rpm, for example: 1200rpm, 1400rpm, 1600rpm, 1800rpm, 2000rpm, etc.
Preferably, the particle size of the coprecipitation spheres is 2 to 4 μm, for example: 2 μm, 2.5 μm, 3 μm, 3.5 μm or 4 μm, etc.
The granularity and morphology of the final coprecipitation sample can be controlled by adjusting the addition amount of ethanol, the reaction temperature and the rotating speed in the reaction stage of the method. The liquid which is continuously concentrated and discharged in the process is added with enough ethanol again and then is added into the system again, so that the proportion balance of water and ethanol in the reaction system is ensured.
The method comprises the steps of analyzing and detecting the content mole ratio and percentage content of lithium, metal and phosphorus in the coprecipitation balls before sintering, if the deviation from a set value is greater than 0.01, adding equivalent lithium hydroxide, manganese carbonate, ferric oxide or phosphorus pentoxide by calculation, supplementing 0.5% glucose, then mixing at a high speed for 5-10min, sampling, analyzing and mixing uniformly. If the uniformity is insufficient, the mixing time is prolonged for 5min.
Preferably, the sintering treatment of step (3) includes one-step sintering and two-step sintering.
Preferably, the temperature of the one-step sintering is 450 to 480 ℃, for example: 450 ℃, 455 ℃, 460 ℃, 470 ℃ or 480 ℃ and the like.
Preferably, the one-step sintering time is 3 to 6 hours, for example: 3h, 3.5h, 4h, 5h or 6h, etc.
Preferably, the temperature of the two-step sintering is 680 to 700 ℃, for example: 680 ℃, 685 ℃, 690 ℃, 695 ℃ or 700 ℃ and the like.
Preferably, the two-step sintering time is 12-16 hours, for example: 12h, 13h, 14h, 15h or 16h, etc.
In a second aspect, the invention provides a lithium iron manganese phosphate positive electrode material prepared by the method according to the first aspect, wherein the lithium iron manganese phosphate positive electrode material has a chemical formula of Li a Mn b Fe c X d PO 4 Wherein a is 1 to 1.02, b is 0.1 to 0.9, c is 1 to 0.05, d is 0.001 to 0.05, X is any one or a combination of at least two of nickel, cobalt, manganese, calcium, magnesium, tungsten, molybdenum, zirconium, titanium, vanadium, niobium, tantalum or chromium.
In a third aspect, the invention provides a positive electrode sheet comprising a lithium iron manganese phosphate positive electrode material according to the second aspect.
In a fourth aspect, the present invention provides a lithium ion battery comprising the positive electrode sheet according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the preparation method of the lithium iron manganese phosphate material, a spray drying process is omitted, wet coprecipitation one-time granulation is adopted, any single solid phase precursor is not required to be prepared, a proper amount of insufficient elements are supplemented after wet granulation, and then the lithium iron manganese phosphate material is directly sintered and synthesized after uniform mixing.
(2) The particle size and morphology of the final coprecipitation sample can be controlled by adjusting the addition amount of ethanol, the reaction temperature and the rotating speed in the reaction stage. The liquid which is continuously concentrated and discharged in the process is added with enough ethanol again and then is added into the system again, so that the proportion balance of water and ethanol in the reaction system is ensured.
(3) According to the invention, the lithium content in the lithium bicarbonate or lithium hydroxide is ensured to be slightly fluctuated within the range of the theoretical proportioning in the process of adding the lithium bicarbonate or lithium hydroxide and the final sample, and the normal set lithium proportioning value can be realized only by a small amount of supplement or no supplement of a lithium source in the subsequent sintering process, so that the subsequent calcination is convenient and direct.
(4) The invention ensures that the phosphorus raw material fluctuates slightly within a set range by adding the phosphoric acid, and the normal set phosphorus proportioning value can be realized by only supplementing a small amount of phosphorus source or not supplementing the phosphorus source in the subsequent sintering process, thereby being convenient for directly carrying out subsequent calcination.
Drawings
FIG. 1 is an SEM image of co-precipitation spheres according to example 1.
Fig. 2 is an SEM image of the positive electrode material described in example 1.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a lithium iron manganese phosphate positive electrode material, which is prepared by the following steps:
(1) Preparing 200g/L ammonium bicarbonate solution, preparing 50g/L lithium hydroxide solution, preparing 60g/L lithium bicarbonate solution, preparing manganese sulfate into 100g/L solution, preparing ferrous sulfate into 100g/L solution, preparing 5% dilute phosphoric acid solution, preparing 1g/L nickel chloride solution as doping agent, firstly precipitating manganese sulfate and ferric sulfate solution by using ammonium bicarbonate, forming carbonate precipitate, washing and dehydrating for standby, quantitatively adding 85% concentrated phosphoric acid solution into the carbonate precipitate, adding a proper amount of water to dilute and ensure that the carbonate precipitate can be dissolved by phosphoric acid, then adding gluconic acid with the total phosphate mass of 25% to continuously stir and dissolve carbonate slag, continuously stirring for 0.5h after no bubble is generated in the system, then placing the slurry into a ball mill for ball milling for 3h, and obtaining first slurry for gradually adding into a reaction kettle for coprecipitation after the operation is completed, wherein the granularity is smaller than 600 nm; the molar ratio of total metal to phosphorus in the first slurry is 1:1.03;
(2) Synchronously and slowly adding the first slurry and the prepared lithium bicarbonate, lithium hydroxide, phosphoric acid and nickel chloride solution into a reaction kettle to start coprecipitation reaction, controlling the pH=4 of the system, alternately adding the lithium hydroxide solution or the dilute phosphoric acid solution, then using the lithium bicarbonate solution to coordinate and supplement lithium which is missing in the process, ensuring that the molar ratio and percentage of lithium to metal to phosphorus in the process and the final ratio of lithium to metal to phosphorus are 1.01:1.03, continuously concentrating in the process of the reaction, continuously adding a certain amount of ethanol into the liquid discharged after concentration, continuously adding the mixed solution of ethanol and water which is prepared again into the reaction kettle, ensuring that the concentration of ethanol and water in the reaction kettle is basically balanced, respectively recovering the water and the ethanol in a mode of reduced pressure distillation after the coprecipitation reaction is finished, finally obtaining 3 mu m type spherical coprecipitation balls, dehydrating and drying the coprecipitation balls, then analyzing and detecting the content mole ratio and percentage of lithium, metal and phosphorus, if the content of lithium hydroxide, the manganese oxide and the phosphorus deviate from the set value by more than 0.01, continuously adding a certain amount of ethanol, manganese hydroxide, ferric oxide or phosphorus oxide, mixing the lithium hydroxide and phosphorus for 5-5% glucose, continuously mixing the mixture for 5-5 min, and continuously analyzing the glucose concentration for 10min if the concentration is not uniform;
an SEM image of the coprecipitation spheres is shown in fig. 1;
(3) Sintering the coprecipitation balls, wherein the sintering is divided into two sections, the temperature of one section reaches 450 ℃ at a heating rate of 2 ℃/min, the constant temperature is kept for 5 hours, the temperature is then increased to 680 ℃ and kept for 15 hours, the whole process is protected by nitrogen, and the lithium iron manganese phosphate anode material with the nickel doping amount of 1% is obtained after the calcination is completed;
an SEM image of the positive electrode material is shown in fig. 2.
Example 2
The embodiment provides a lithium iron manganese phosphate positive electrode material, which is prepared by the following steps:
(1) Preparing 200g/L ammonium bicarbonate solution, preparing 50g/L lithium hydroxide solution, preparing 60g/L lithium bicarbonate solution, preparing manganese sulfate into 100g/L solution, preparing ferrous sulfate into 100g/L solution, preparing 5% dilute phosphoric acid solution, preparing 1g/L cobalt nitrate solution as doping agent, firstly precipitating manganese sulfate and ferric sulfate solution by using ammonium bicarbonate, forming carbonate precipitate, washing and dehydrating for standby, quantitatively adding 85% concentrated phosphoric acid solution into the carbonate precipitate, adding a proper amount of water to dilute and ensure that the carbonate precipitate can be dissolved by phosphoric acid, then adding gluconic acid with the total phosphate mass of 25% to continuously stir and dissolve carbonate slag, continuously stirring for 0.5h after no bubble is generated in the system, then placing the slurry into a ball mill for ball milling for 3h, and obtaining first slurry for gradually adding into a reaction kettle for coprecipitation after the operation is completed, wherein the granularity is smaller than 600 nm; the molar ratio of total metal to phosphorus in the first slurry is 1:1.02;
(2) Synchronously and slowly adding the first slurry and the prepared lithium bicarbonate, lithium hydroxide, phosphoric acid and cobalt nitrate solution into a reaction kettle to start coprecipitation reaction, controlling the pH=4 of the system, alternately adding the lithium hydroxide solution or the dilute phosphoric acid solution, then using the lithium bicarbonate solution to coordinate and supplement lithium which is missing in the process, ensuring that the molar ratio and percentage of lithium to metal to phosphorus in the process and the final ratio of lithium to metal to phosphorus are 1.01:1.03, continuously concentrating in the process of the reaction, continuously adding a certain amount of ethanol into the liquid discharged after concentration, continuously adding the mixed solution of ethanol and water which is prepared again into the reaction kettle, ensuring that the concentration of ethanol and water in the reaction kettle is basically balanced, respectively recovering the water and the ethanol in a mode of reduced pressure distillation after the coprecipitation reaction is finished, finally obtaining 3 mu m type spherical coprecipitation balls, dehydrating and drying the coprecipitation balls, then analyzing and detecting the content mole ratio and percentage of lithium, metal and phosphorus, if the content of lithium hydroxide, manganese oxide and phosphorus deviate from the set value by more than 0.01, continuously adding a certain amount of ethanol, manganese hydroxide, ferric oxide or phosphorus oxide, mixing the mixture for 5-5% glucose, continuously and continuously sampling for 5-5 min, and continuously mixing the glucose, and continuously sampling for 10-5% glucose concentration;
(3) And (3) carrying out sintering treatment on the coprecipitation balls, wherein the sintering treatment is divided into two sections, the temperature of one section reaches 450 ℃ at a heating rate of 2 ℃/min, the constant temperature is kept for 5 hours, the temperature is then increased to 680 ℃ and kept for 15 hours, the calcination is continued, nitrogen is introduced for protection in the whole process, and the cobalt doping amount of the lithium iron manganese phosphate anode material with the cobalt doping amount of 2% is obtained after the calcination is completed.
Example 3
The embodiment provides a lithium iron manganese phosphate positive electrode material, which is prepared by the following steps:
(1) Preparing 200g/L ammonium bicarbonate solution, preparing 50g/L lithium hydroxide solution, preparing 60g/L lithium bicarbonate solution, preparing manganese sulfate into 100g/L solution, preparing ferrous sulfate into 100g/L solution, preparing 5% dilute phosphoric acid solution, preparing 1g/L alum sulfate solution serving as a doping agent, firstly precipitating manganese sulfate and ferric sulfate solution by using ammonium bicarbonate, forming carbonate precipitate, washing and dehydrating for standby, quantitatively adding 85% concentrated phosphoric acid solution into the carbonate precipitate, adding a proper amount of water to dilute and ensure that the carbonate precipitate can be dissolved by phosphoric acid, then adding gluconic acid with the total phosphate mass of 25% to continuously stir and dissolve carbonate slag, continuously stirring for 0.5h after no bubble is generated in the system, then placing the slurry into a ball mill for ball milling for 3h, and obtaining a first slurry for gradually adding into a reaction kettle for coprecipitation after the operation is completed; the molar ratio of total metal to phosphorus in the first slurry is 1:1.03;
(2) Synchronously and slowly adding the first slurry and the prepared lithium bicarbonate, lithium hydroxide, phosphoric acid and vitriol solution into a reaction kettle to start coprecipitation reaction, controlling the pH=4 of the system, alternately adding the lithium hydroxide solution or the diluted phosphoric acid solution, then using the lithium bicarbonate solution to coordinate and supplement lithium which is missing in the process, ensuring that the molar ratio of lithium to metal to phosphorus is 1.01:1.03 in the process and finally, continuously concentrating in the process of the reaction, continuously adding a certain amount of ethanol into the liquid discharged after concentration, continuously adding the mixed solution of ethanol and water which is prepared again into the reaction kettle, ensuring that the concentration of the ethanol and the water in the reaction kettle is basically balanced, respectively recovering the water and the ethanol in a mode of reduced pressure distillation after the coprecipitation reaction is finished, finally obtaining 3 mu m type spherical coprecipitation balls, dehydrating and drying the coprecipitation balls, then analyzing and detecting the content mole ratio and percentage content of lithium, metal to phosphorus, and glucose, if the content of lithium hydroxide, the manganese oxide and the phosphorus deviate from the set value by more than 0.01, continuously adding a certain amount of ethanol, continuously adding ethanol to the mixed solution of ethanol and water to the mixed solution, continuously adding ethanol and mixing the ethanol and the mixed solution into the reaction kettle for 5-5 min, and continuously analyzing the mixture until the concentration of glucose is not uniform for 5min;
(3) And (3) carrying out sintering treatment on the coprecipitation balls, wherein the sintering treatment is divided into two sections, the temperature of one section reaches 450 ℃ at a heating rate of 2 ℃/min, the constant temperature is kept for 5 hours, the temperature is then increased to 680 ℃ and kept for 15 hours, the calcination is continued, nitrogen is introduced for protection in the whole process, and the vanadium doping amount of the lithium iron manganese phosphate anode material with the vanadium doping amount of 1% is obtained after the calcination is completed.
Example 4
This example differs from example 1 only in that the amount of gluconic acid added in step (2) is 20% of that of phosphoric acid, and other conditions and parameters are exactly the same as in example 1.
Example 5
This example differs from example 1 only in that the amount of gluconic acid added in step (2) is 30% of that of phosphoric acid, and other conditions and parameters are exactly the same as in example 1.
Example 6
This example differs from example 1 only in that the temperature of the coprecipitation in step (2) is 45℃and other conditions and parameters are exactly the same as in example 1.
Example 7
This example differs from example 1 only in that the stirring speed in step (2) is 1000rpm, and other conditions and parameters are exactly the same as in example 1.
Example 8
The difference between this example and example 1 is that the volume ratio of ethanol to water in the mixture of ethanol and water in step (2) is 1:2, and the other conditions and parameters are exactly the same as in example 1.
Example 9
The difference between this example and example 1 is that the volume ratio of ethanol to water in the mixture of ethanol and water in step (2) is 2:1, and the other conditions and parameters are exactly the same as in example 1.
Example 10
This example differs from example 1 only in that the temperature of the one-step sintering in step (3) is 500 ℃, and other conditions and parameters are exactly the same as in example 1.
Example 11
This example differs from example 1 only in that the temperature of the two-step sintering in step (3) is 750 ℃, and other conditions and parameters are exactly the same as in example 1.
Example 12
This example differs from example 1 only in that the temperature of the two-step sintering in step (3) is 650 ℃, and other conditions and parameters are exactly the same as in example 1.
Example 13
This example differs from example 1 only in that the nickel doping amount is 5%, and other conditions and parameters are exactly the same as those of example 1.
Example 14
This example differs from example 1 only in that the nickel doping amount is 0.5%, and other conditions and parameters are exactly the same as those of example 1.
Comparative example 1
This comparative example differs from example 1 only in that no nickel source was added, and other conditions and parameters were exactly the same as example 1.
Comparative example 2
This comparative example differs from example 1 only in that lithium bicarbonate was not added in step (2), and other conditions and parameters were exactly the same as in example 1. As a result, it was found that the system would collapse without adding lithium bicarbonate, since the total amount of lithium in the system could not be balanced, and the balance of acid and base could be achieved with lithium hydroxide and phosphoric acid, but the total amount of lithium could not meet the design requirements, and lithium bicarbonate needs to be added to balance the lithium amount ratio, and the lithium amount is insufficient or causes a significant decrease in capacity.
Performance test:
the positive electrode materials obtained in examples 1 to 14 and comparative examples 1 to 2 were used to prepare positive electrode sheets, lithium sheets were used as negative electrodes, and batteries were prepared, and the battery tests were conducted in the same mode as the lithium iron phosphate system, with a charge cut-off voltage of 4.3V, and the test results are shown in table 1:
TABLE 1
| 0.1 g capacity (mAh/g) | 1C gram Capacity (mAh/g) | |
| Example 1 | 148 | 137 |
| Example 2 | 146 | 135.5 |
| Example 3 | 141 | 130.5 |
| Example 4 | 146 | 135 |
| Example 5 | 147.2 | 137.3 |
| Example 6 | 144.5 | 132.5 |
| Example 7 | 146.5 | 135.1 |
| Example 8 | 144 | 132 |
| Example 9 | 149 | 138 |
| Example 10 | 146 | 133 |
| Example 11 | 142 | 128 |
| Example 12 | 145.5 | 132 |
| Example 13 | 141.5 | 130.1 |
| Example 14 | 145 | 133.9 |
| Comparative example1 | 144 | 131 |
| Comparative example 2 | / | / |
As can be seen from Table 1, the lithium iron manganese phosphate anode material prepared by the method disclosed by the invention can achieve a capacity of more than 141mAh/g at 0.1C and a capacity of more than 130.5mAh/g at 1C.
As can be seen from comparison of examples 1 and examples 4 to 5, the addition amount of the gluconic acid according to the present invention affects the performance of the positive electrode material, and if the addition amount of the gluconic acid is too large, the carbon content in the final-fired lithium manganese iron phosphate is too high, resulting in a decrease in capacity, and if the addition amount of the gluconic acid is too small, the carbon content in the final-fired lithium manganese iron phosphate is too low, resulting in a decrease in capacity.
As can be seen from the comparison of examples 1 and examples 6-9, the particle size and morphology of the final coprecipitated sample can be controlled by adjusting the amount of ethanol added, the reaction temperature and the rotational speed in the reaction stage of the present invention. The liquid which is continuously concentrated and discharged in the process is added with enough ethanol again and then is added into the system again, so that the proportion balance of water and ethanol in the reaction system is ensured.
As can be seen from the comparison between the embodiment 1 and the embodiments 10-12, the two-stage sintering temperature of the invention can affect the performance of the positive electrode material, and the positive electrode material with better appearance and stable performance can be prepared by controlling the two-stage sintering temperature.
As can be seen from a comparison of example 1 and examples 13 to 14, the doping amount of the dopant affects the performance of the resulting positive electrode material, and the present application can obtain a positive electrode material excellent in performance by controlling the doping amount of the dopant.
As can be seen from the comparison of example 1 and comparative example 1, doping with a small amount of dopant can significantly improve the performance of the positive electrode material.
By comparing the embodiment 1 with the comparative example 2, the invention ensures that the lithium content in the process and the final sample is slightly fluctuated within the range of the theoretical proportioning by adding lithium bicarbonate or lithium hydroxide, and the normal set lithium proportioning value can be realized by only a small amount of supplementary or non-supplementary lithium source in the subsequent sintering process, thereby facilitating the subsequent calcination directly.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (24)
1. The preparation method of the lithium iron manganese phosphate anode material is characterized by comprising the following steps of:
(1) Mixing ammonium bicarbonate, a manganese source and an iron source to obtain a mixed carbonate precipitate, mixing the mixed carbonate precipitate with concentrated phosphoric acid, and adding gluconic acid to obtain first slurry;
(2) Mixing and stirring the first slurry, lithium bicarbonate, lithium hydroxide, a phosphoric acid source, a doping agent and an aqueous alcohol solution to obtain mixed slurry, and performing reduced pressure distillation to obtain coprecipitation balls; the doping amount of the doping agent is 1-3% of the mass of the positive electrode material;
the volume ratio of water to ethanol in the hydroalcoholic solution is 1 (0.8-1.2);
the pH of the mixed and stirred solution is 3-5;
(3) And sintering the coprecipitation balls to obtain the lithium iron manganese phosphate anode material.
2. The preparation method of claim 1, wherein the mass concentration of the ammonium bicarbonate in the step (1) is 180-150 g/L.
3. The method of claim 1, wherein the manganese source in step (1) comprises a manganese sulfate solution having a mass concentration of 80-150 g/L.
4. The method of claim 1, wherein the iron source in step (1) comprises a ferrous sulfate solution having a mass concentration of 80-150 g/L.
5. The preparation method of claim 1, wherein the mass ratio of phosphoric acid in the concentrated phosphoric acid in the step (1) is 80-90%.
6. The method of claim 1, wherein the step (1) is performed by adding water to dilute the mixed carbonate precipitate and concentrated phosphoric acid during the mixing.
7. The method according to claim 1, wherein the mass ratio of the gluconic acid in the step (1) to the phosphoric acid in the concentrated phosphoric acid is 0.2 to 0.3:1.
8. The method of claim 1, wherein the first slurry in step (1) has a molar ratio of total metal ions to phosphate ions of 1 (1.01 to 1.05).
9. The preparation method of claim 1, wherein the mass concentration of lithium bicarbonate in the step (2) is 50-70 g/L.
10. The preparation method of claim 1, wherein the mass concentration of lithium hydroxide in the step (2) is 40-60 g/L.
11. The method of claim 1, wherein in step (2), the phosphoric acid source comprises dilute phosphoric acid.
12. The method according to claim 11, wherein the mass ratio of phosphoric acid in the diluted phosphoric acid is 3-8%.
13. The method of claim 1, wherein the dopant of step (2) comprises any one or a combination of at least two of a nickel salt, a cobalt salt, a manganese salt, a calcium salt, a magnesium salt, a tungsten salt, a molybdenum salt, a zirconium salt, a titanium salt, a vanadium salt, a niobium salt, a tantalum salt, and a chromium salt.
14. The method according to claim 1, wherein the temperature of the mixing and stirring in the step (2) is 20-40 ℃.
15. The method according to claim 1, wherein the speed of mixing and stirring in the step (2) is 1200 to 2000rpm.
16. The method according to claim 1, wherein the particle size of the coprecipitated balls in the step (2) is 2 to 4 μm.
17. The method of claim 1, wherein the sintering treatment of step (3) comprises a one-step sintering and a two-step sintering.
18. The method of claim 17, wherein the one-step sintering is performed at a temperature of 450-480 ℃.
19. The method of claim 17, wherein the one-step sintering is performed for 3 to 6 hours.
20. The method of claim 17, wherein the two-step sintering is performed at a temperature of 680-700 ℃.
21. The method of claim 17, wherein the two-step sintering is performed for 12 to 16 hours.
22. A lithium iron manganese phosphate positive electrode material, characterized in that the lithium iron manganese phosphate positive electrode material is prepared by the method according to any one of claims 1 to 21, and the lithium iron manganese phosphate positive electrode material has a chemical formula of Li a Mn b Fe c X d PO 4 Wherein a is 1-1.02, b is 0.1-0.9, c is 1-b, d is 0.001-0.05, X is any one or a combination of at least two of nickel, cobalt, manganese, calcium, magnesium, tungsten, molybdenum, zirconium, titanium, vanadium, niobium, tantalum or chromium.
23. A positive electrode sheet comprising the lithium iron manganese phosphate positive electrode material according to claim 22.
24. A lithium ion battery comprising the positive electrode sheet of claim 23.
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