CN114988386A - 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
- Publication number
- CN114988386A CN114988386A CN202210688198.1A CN202210688198A CN114988386A CN 114988386 A CN114988386 A CN 114988386A CN 202210688198 A CN202210688198 A CN 202210688198A CN 114988386 A CN114988386 A CN 114988386A
- Authority
- CN
- China
- Prior art keywords
- lithium
- phosphoric acid
- salt
- mixing
- coprecipitation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 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 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 94
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 75
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 47
- 238000000975 co-precipitation Methods 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 40
- 238000005245 sintering Methods 0.000 claims abstract description 37
- 238000002156 mixing Methods 0.000 claims abstract description 31
- 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 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000002244 precipitate Substances 0.000 claims abstract description 16
- 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
- 239000010406 cathode material Substances 0.000 claims abstract description 14
- 239000002019 doping agent Substances 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
- 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
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 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
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 239000011268 mixed slurry Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 64
- 239000000243 solution Substances 0.000 claims description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000010405 anode material Substances 0.000 claims description 11
- 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 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
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 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 3
- 238000005469 granulation Methods 0.000 abstract description 3
- 230000003179 granulation Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 57
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 26
- 229910052744 lithium Inorganic materials 0.000 description 26
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 17
- 229910052698 phosphorus Inorganic materials 0.000 description 17
- 239000011574 phosphorus Substances 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 238000001354 calcination Methods 0.000 description 10
- 230000001502 supplementing effect Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000498 ball milling Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 8
- 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 7
- 239000008103 glucose Substances 0.000 description 7
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 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
- 239000011259 mixed solution Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 235000006748 manganese carbonate Nutrition 0.000 description 4
- 239000011656 manganese carbonate Substances 0.000 description 4
- 229940093474 manganese carbonate Drugs 0.000 description 4
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 4
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 238000001035 drying Methods 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
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000013589 supplement Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 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
- 238000007865 diluting Methods 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 238000003801 milling Methods 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
- 239000004576 sand Substances 0.000 description 2
- 239000007790 solid phase Substances 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
- 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
- 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
- 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
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Images
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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a lithium iron manganese phosphate positive electrode 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 a first slurry; (2) mixing and stirring the first slurry, lithium bicarbonate, lithium hydroxide, a phosphoric acid source, a doping agent and a water-alcohol solution to obtain a mixed slurry, and carrying out reduced pressure distillation to obtain a coprecipitation ball; (3) the lithium iron manganese phosphate cathode material is obtained by sintering the coprecipitation ball, and the invention avoids the defects of high process cost and relatively complex process in the traditional process by simple wet coprecipitation one-time granulation, thereby greatly reducing energy consumption, reducing synthesis cost and simplifying the manufacturing process.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a lithium iron manganese phosphate positive electrode material, and a preparation method and application thereof.
Background
The ferric phosphate has the advantages of rich resources, good safety performance, long cycle life, environmental friendliness and the like, is one of the preferred anode materials of the power battery, and the lithium manganese phosphate has a higher working potential (4.1V) and is within a stable electrochemical window of the conventional general electrolyte system, so that the energy density of the lithium manganese phosphate is 21% higher than that of LFP theoretically, and the lithium manganese phosphate is considered to be an LFP upgraded plate. However, the lithium manganese phosphate has poor conductivity and is difficult to have practical application value at present, and the lithium manganese phosphate not only has high conductivity and cycle performance of the lithium manganese phosphate, but also has a high-voltage platform of the lithium manganese phosphate, and is considered to be a next-generation new energy positive electrode material which is better selected for replacing the lithium iron phosphate.
CN107128892A discloses a preparation method of a lithium iron manganese phosphate anode material, which comprises the steps of sintering an iron source, a phosphorus source, a manganese source, a lithium source and a carbon source to prepare lithium iron manganese phosphate, putting the phosphorus source, the iron source, the manganese source and the lithium source into a reaction kettle, and adding pure water according to the solid content of 5-60% to stir and mix; adding a carbon source according to the solid content mass ratio of 50-200%; the mixture is stirred and mixed for reaction at the temperature of 120-150 ℃ in a reaction kettle; spray drying the material; calcining the material in nitrogen atmosphere; the material was tunnel dried.
CN113929073A discloses a method for preparing lithium iron manganese 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, then weighing lithium source, phosphorus source, carbon source and dopant according to a certain stoichiometric ratio, adding pure water, performing ball milling and sand milling, controlling the sand milling particle size D50 to be less than or equal to 300nm, and performing spray drying to obtain brown precursor powder. And sintering the precursor under the protection of a nitrogen atmosphere, controlling the sintering temperature to be 600-700 ℃, and then crushing, screening and deironing to obtain the lithium iron manganese phosphate anode material.
The preparation method of the lithium iron manganese phosphate cathode material adopts a grinding and spraying method, and the method has the problems of high energy consumption and high cost, so that the wide application of the lithium iron manganese phosphate cathode material is greatly limited.
Disclosure of Invention
The invention aims to provide a lithium iron manganese phosphate positive electrode material and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of a lithium iron manganese phosphate positive electrode material, which 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 a first slurry;
(2) mixing and stirring the first slurry, lithium bicarbonate, lithium hydroxide, a phosphoric acid source, a doping agent and a water-alcohol solution to obtain a mixed slurry, and carrying out reduced pressure distillation to obtain a coprecipitation ball;
(3) and sintering the coprecipitation ball to obtain the lithium iron manganese phosphate anode material.
According to the preparation method of the lithium iron manganese phosphate material, the spray drying process is omitted, wet coprecipitation one-time granulation is adopted, any single solid phase precursor does not need to be prepared, the insufficient elements are supplemented in a proper amount after wet granulation, and then the lithium iron manganese phosphate material is directly synthesized by sintering after uniform mixing. Can greatly reduce energy consumption, reduce synthesis cost and simplify the manufacturing process.
The first slurry is gradually added into a reaction kettle for coprecipitation, then the first slurry and prepared lithium bicarbonate, lithium hydroxide, phosphoric acid, doping agent and the like are added into the reaction kettle for reaction, 80 percent of hydroalcoholic solution is put into the reaction kettle in advance, because sufficient phosphoric acid and glucose are added into the first slurry, the amount of insoluble solids is less than 5 percent, suspension is formed after ball milling, and then the mixture is stirred at a low speed, the first slurry can ensure the uniformity of feeding the materials into the reaction kettle at every moment, the temperature of the reaction kettle is controlled before the reaction starts, the volatility of ethanol can be reduced to a lower level when the reaction kettle is operated at a lower temperature, simultaneously, the bicarbonate of the system can not be rapidly decomposed in a large quantity to cause excessive bubble amount, various solutions continuously added next can be fully mixed and uniformly dispersed into the reaction kettle in the shortest time through high-speed stirring, and carrying out coprecipitation reaction in a specific environment in the reaction kettle, after the preparation work is finished, synchronously and slowly adding the first slurry, a lithium bicarbonate solution, a lithium hydroxide solution, a phosphoric acid solution and a doping solution into the reaction kettle to start the coprecipitation reaction, controlling the pH of the system, alternately adding the lithium hydroxide solution or a dilute phosphoric acid solution, then coordinately supplementing missing lithium in the process by using the lithium bicarbonate solution, ensuring the proportion of lithium to metal and phosphorus in the process and finally, continuously concentrating in the reaction process, adding a certain amount of ethanol into the liquid discharged after concentration again, continuously adding the prepared mixed solution of ethanol and water into the reaction kettle, and ensuring the basic balance of the concentrations of the ethanol and the water in the reaction kettle. And respectively recycling water and ethanol by using reduced pressure distillation after the coprecipitation reaction of the waste water which is produced in the whole reaction process is finished, and finally obtaining the sphere-like coprecipitation ball.
Preferably, the mass concentration of the ammonium bicarbonate in the step (1) is 180-150 g/L, such as: 80g/L, 100g/L, 110g/L, 130g/L, 150g/L, etc.
Preferably, the manganese source comprises a manganese sulfate solution with a mass concentration of 80-150 g/L (such as 80g/L, 100g/L, 110g/L, 130g/L or 150 g/L).
Preferably, the iron source comprises a ferrous sulfate solution with a mass concentration of 80-150 g/L (for example, 80g/L, 100g/L, 110g/L, 130g/L or 150 g/L).
The mass ratio of phosphoric acid in the concentrated phosphoric acid obtained in the step (1) is 80-90%, for example: 80%, 82%, 85%, 88%, 90%, etc.
Preferably, water is added for dilution during the process of mixing the mixed carbonate precipitate and concentrated phosphoric acid.
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 method can adjust the content of glucose in the final coprecipitation sample through the change of the adding amount of the gluconic acid and the phosphoric acid, the concentration of the glucose and the like, thereby indirectly controlling the content and the distribution of carbon in the final sintered sample.
Preferably, in the first slurry in the step (1), the molar ratio of the total molar amount of the metal ions to the molar amount of the phosphate ions is 1 (1.01-1.05), such as: 1:1.01, 1:1.02, 1:1.03, 1:1.04, 1:1.05 and the like.
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, or the like.
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 source of phosphoric acid comprises dilute phosphoric acid.
Preferably, the mass ratio of phosphoric acid in the dilute phosphoric acid is 3-8%, for example: 3%, 4%, 5%, 6%, 7%, 8%, etc.
Preferably, the dopant includes any one 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, or a combination of at least two thereof.
Preferably, the doping amount of the dopant is 1-3% of the mass of the positive electrode material, such as: 1%, 1.5%, 2%, 2.5%, 3%, etc.
Preferably, the volume ratio of water to ethanol in the hydroalcoholic solution is 1 (0.8-1.2), such as: 1:0.8, 1:0.9, 1:1, 1:1.1 or 1:1.2, etc.
Preferably, the temperature of mixing and stirring in the step (2) is 20-40 ℃, for example: 20 ℃, 25 ℃, 30 ℃, 35 ℃ or 40 ℃ and the like.
Preferably, the pH value of the mixing stirring is 3-5, such as: 3. 3.5, 4, 4.5 or 5, etc.
Preferably, the mixing and stirring speed is 1200-2000 rpm, such as: 1200rpm, 1400rpm, 1600rpm, 1800rpm, 2000rpm, or the like.
Preferably, the particle size of the coprecipitation ball is 2 to 4 μm, for example: 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, or the like.
The reaction stage of the method can control the granularity and the appearance of the final coprecipitation sample by adjusting the adding amount of ethanol, the reaction temperature and the rotating speed. In the process, the liquid discharged by continuous concentration is added with sufficient ethanol again and then added into the system again, so that the reaction system is ensured to be in the proportion balance of water and ethanol.
The method comprises the steps of analyzing and detecting the content molar ratio and percentage content of lithium, metal and phosphorus in the coprecipitation ball before sintering, adding equal amount of lithium hydroxide, manganese carbonate, ferric oxide or phosphorus pentoxide and supplementing 0.5% of glucose by calculation if the deviation of the content molar ratio and percentage content deviates from a set value to be more than 0.01, then mixing at high speed for 5-10min, sampling, analyzing and mixing uniformly. And if the uniformity is not enough, continuing to prolong the mixing time for 5 min.
Preferably, the sintering treatment in step (3) comprises one-step sintering and two-step sintering.
Preferably, the temperature of the one-step sintering is 450-480 ℃, for example: 450 ℃, 455 ℃, 460 ℃, 470 ℃ or 480 ℃ and the like.
Preferably, the time of the one-step sintering is 3-6 h, for example: 3h, 3.5h, 4h, 5h or 6h and the like.
Preferably, the temperature of the two-step sintering is 680-700 ℃, for example: 680 deg.C, 685 deg.C, 690 deg.C, 695 deg.C or 700 deg.C, etc.
Preferably, the time of the two-step sintering is 12-16 h, for example: 12h, 13h, 14h, 15h or 16h and the like.
In a second aspect, the invention provides a lithium iron manganese phosphate positive electrode material, which is prepared by the method in the first aspect, and 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, and X is any one or 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 plate, which includes the lithium iron manganese phosphate positive electrode material according to the second aspect.
In a fourth aspect, the invention provides a lithium ion battery, which comprises the positive electrode plate 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 is adopted for one-time granulation, no single solid phase precursor is required to be prepared, the insufficient elements are supplemented in a proper amount after wet granulation, and then the lithium iron manganese phosphate material is directly synthesized by sintering after uniform mixing.
(2) The granularity and the morphology of a final coprecipitation sample can be controlled by adjusting the adding amount of ethanol, the reaction temperature and the rotating speed in the reaction stage. In the process, the liquid discharged by continuous concentration is added with sufficient ethanol again and then added into the system again, so that the reaction system is ensured to be in the proportion balance of water and ethanol.
(3) According to the invention, the lithium content in the process and the final sample is ensured to fluctuate within the range of the theoretical ratio by adding the lithium bicarbonate or the lithium hydroxide, and the normally set lithium ratio value can be realized by only needing a little supplement or not supplementing a lithium source in the subsequent sintering process, so that the subsequent calcination can be conveniently and directly carried out.
(4) The invention ensures that the phosphorus raw material fluctuates slightly within a set range by adding the phosphoric acid, and the normally set phosphorus proportioning value can be realized only by supplementing a small amount or not supplementing a phosphorus source in the subsequent sintering process, thereby facilitating the direct subsequent calcination.
Drawings
FIG. 1 is an SEM image of the co-precipitated spheres of example 1.
Fig. 2 is an SEM image of the cathode material described in example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a lithium iron manganese phosphate anode material, and a preparation method of the lithium iron manganese phosphate anode material comprises the following steps:
(1) preparing 200g/L ammonium bicarbonate solution, 50g/L lithium hydroxide solution, 60g/L lithium bicarbonate solution, preparing 100g/L manganese sulfate solution, preparing 100g/L ferrous sulfate solution, preparing 5% diluted phosphoric acid solution, preparing 1g/L nickel chloride solution as dopant, firstly precipitating manganese sulfate and ferric sulfate solution with ammonium bicarbonate to form carbonate precipitate, washing with water and dewatering for later use, quantitatively adding 85% concentrated phosphoric acid solution into the carbonate precipitate, diluting with appropriate amount of water to ensure that the solution can be dissolved by phosphoric acid, then adding gluconic acid with the mass of 25 percent of the total phosphate, continuously stirring and dissolving the carbonate slag, continuously stirring for 0.5h after no bubbles are generated in the system, then, the slurry is put into a ball mill for ball milling for 3 hours, the granularity after the ball milling is less than 600nm, and first slurry can be obtained after the operation is finished and is gradually added into a reaction kettle for coprecipitation; 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 prepared lithium bicarbonate, lithium hydroxide, phosphoric acid and nickel chloride solution into a reaction kettle to start coprecipitation reaction, controlling the pH of the system to be 4, alternately adding the lithium hydroxide solution or dilute phosphoric acid solution, then using the lithium bicarbonate solution to coordinate and supplement the lithium which is lost in the process, ensuring the ratio of the lithium to metal and phosphorus to be 1.01:1:1.03 in the process of reaction, continuously concentrating continuously in the process of reaction, adding a certain amount of ethanol into the liquid discharged after concentration, continuously adding the prepared ethanol and water mixed solution into the reaction kettle, ensuring the concentration of the ethanol and the water in the reaction kettle to be basically balanced, respectively recovering the water and the ethanol in a reduced pressure distillation mode after the coprecipitation reaction is finished by the waste water which is excessive in the whole reaction process, and finally obtaining a 3 mu m spherical coprecipitation ball, dehydrating and drying the coprecipitation ball, analyzing and detecting the content molar ratio and percentage content of lithium, metal and phosphorus, if the deviation of the content molar ratio and percentage content is more than 0.01, adding equal amount of lithium hydroxide, manganese carbonate, ferric oxide or phosphorus pentoxide by calculation, supplementing 0.5% of glucose, then mixing at high speed for 5-10min, sampling, analyzing the mixing uniformity, and if the uniformity is not enough, continuing to prolong the mixing time for 5 min;
the SEM image of the coprecipitation ball is shown in figure 1;
(3) sintering the coprecipitation ball, wherein the sintering treatment is divided into two sections, the temperature rise rate of one section is 2 ℃/min, the temperature is kept for 5h at a constant temperature after reaching 450 ℃, then the temperature is raised to 680 ℃, the constant temperature is kept for 15h, the calcination is carried out, nitrogen protection is introduced in the whole process, and the lithium manganese iron phosphate cathode material with the nickel doping amount of 1% is obtained after the calcination is completed;
the SEM image of the cathode material is shown in fig. 2.
Example 2
The embodiment provides a lithium iron manganese phosphate cathode material, and a preparation method of the lithium iron manganese phosphate cathode material comprises the following steps:
(1) preparing 200g/L ammonium bicarbonate solution, 50g/L lithium hydroxide solution, 60g/L lithium bicarbonate solution, preparing 100g/L manganese sulfate solution, preparing 100g/L ferrous sulfate solution, preparing 5% diluted phosphoric acid solution, preparing 1g/L cobalt nitrate solution as dopant, firstly precipitating manganese sulfate and ferric sulfate solution with ammonium bicarbonate to form carbonate precipitate, washing with water and dehydrating for later use, adding 85% concentrated phosphoric acid solution into the carbonate precipitate, adding appropriate amount of water to dilute and ensure that the carbonate precipitate can be dissolved by phosphoric acid, then adding gluconic acid with the mass of 25 percent of the total phosphate, continuously stirring and dissolving the carbonate slag, continuously stirring for 0.5h after no bubbles are generated in the system, then, the slurry is put into a ball mill for ball milling for 3 hours, the granularity after the ball milling is less than 600nm, and first slurry can be obtained after the operation is finished and is gradually added into a reaction kettle for coprecipitation; the molar ratio of total metal and phosphorus in the first slurry was 1: 1.02;
(2) synchronously and slowly adding the first slurry and prepared lithium bicarbonate, lithium hydroxide, phosphoric acid and cobalt nitrate solution into a reaction kettle to start coprecipitation reaction, controlling the pH of the system to be 4, alternately adding the lithium hydroxide solution or dilute phosphoric acid solution, then using the lithium bicarbonate solution to coordinate and supplement the lost lithium in the process, ensuring the ratio of the lithium to metal and phosphorus to be 1.01:1:1.03 in the process of reaction, continuously concentrating continuously in the process of reaction, adding a certain amount of ethanol into the liquid discharged after concentration, continuously adding the mixed liquid of ethanol and water which is prepared again into the reaction kettle, ensuring the concentration of the ethanol and the water in the reaction kettle to be basically balanced, respectively recovering the water and the ethanol in a reduced pressure distillation mode after the coprecipitation reaction is finished by the waste water which is excessive in the whole reaction process, and finally obtaining the 3 mu m spherical coprecipitation ball, dehydrating and drying the coprecipitation ball, analyzing and detecting the content molar ratio and percentage content of lithium, metal and phosphorus, if the deviation of the content molar ratio and percentage content is more than 0.01, adding equal amount of lithium hydroxide, manganese carbonate, ferric oxide or phosphorus pentoxide by calculation, supplementing 0.5% of glucose, then mixing at high speed for 5-10min, sampling, analyzing the mixing uniformity, and if the uniformity is not enough, continuing to prolong the mixing time for 5 min;
(3) and sintering the coprecipitation ball, wherein the sintering treatment is divided into two sections, the temperature rise rate of one section is 2 ℃/min, the temperature is kept at a constant temperature for 5h after reaching 450 ℃, then the temperature is raised to 680 ℃, the constant temperature is kept for 15h, the calcination is carried out, the nitrogen protection is introduced in the whole process, and the lithium manganese iron phosphate cathode 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 anode material, and a preparation method of the lithium iron manganese phosphate anode material comprises the following steps:
(1) preparing 200g/L ammonium bicarbonate solution, 50g/L lithium hydroxide solution, 60g/L lithium bicarbonate solution, preparing 100g/L manganese sulfate solution, preparing 100g/L ferrous sulfate solution, preparing 5% diluted phosphoric acid solution, preparing 1g/L vitriol solution, precipitating manganese sulfate and ferric sulfate solution with ammonium bicarbonate to form carbonate precipitate, washing with water, dewatering, adding 85% concentrated phosphoric acid solution into the carbonate precipitate, diluting with appropriate amount of water to dissolve the carbonate precipitate, then adding gluconic acid with the mass of 25 percent of the total phosphate, continuously stirring and dissolving the carbonate slag, continuously stirring for 0.5h after no bubbles are generated in the system, then, the slurry is put into a ball mill for ball milling for 3 hours, the granularity after the ball milling is less than 600nm, and first slurry can be obtained after the operation is finished and is gradually added into a reaction kettle for coprecipitation; the molar ratio of total metal and phosphorus in the first slurry is 1: 1.03;
(2) synchronously and slowly adding the first slurry and prepared lithium bicarbonate, lithium hydroxide, phosphoric acid and vitriol solution into a reaction kettle to start coprecipitation reaction, controlling the pH of the system to be 4, alternately adding lithium hydroxide solution or dilute phosphoric acid solution, then coordinately supplementing missing lithium in the process by using the lithium bicarbonate solution, ensuring the ratio of lithium to metal to phosphorus to be 1.01:1:1.03 in the process of reaction, continuously and continuously concentrating the solution in the process of reaction, adding a certain amount of ethanol into the liquid discharged after concentration, continuously adding the prepared mixed solution of ethanol and water into the reaction kettle, ensuring the concentration of ethanol and water in the reaction kettle to be basically balanced, respectively recovering water and ethanol by a reduced pressure distillation mode after the coprecipitation reaction is finished by using waste water generated in the whole reaction process, and finally obtaining a 3 mu m-like spherical coprecipitation ball, dehydrating and drying the coprecipitation ball, analyzing and detecting the content molar ratio and percentage content of lithium, metal and phosphorus, if the deviation of the content molar ratio and percentage content is more than 0.01, adding equal amount of lithium hydroxide, manganese carbonate, ferric oxide or phosphorus pentoxide by calculation, supplementing 0.5% of glucose, then mixing at high speed for 5-10min, sampling, analyzing the mixing uniformity, and if the uniformity is not enough, continuing to prolong the mixing time for 5 min;
(3) and sintering the coprecipitation ball, wherein the sintering treatment is divided into two sections, the temperature rise rate of one section is 2 ℃/min, the constant temperature is kept for 5h after the temperature reaches 450 ℃, then the temperature is raised to 680 ℃, the constant temperature is kept for 15h, the calcination is carried out, the nitrogen protection is introduced in the whole process, and the lithium manganese iron phosphate cathode material with the vanadium doping amount of 1% is obtained after the calcination is completed.
Example 4
The present example is different from example 1 only in that the added amount of gluconic acid in step (2) is 20% of phosphoric acid, and other conditions and parameters are exactly the same as those of example 1.
Example 5
The present example is different from example 1 only in that the amount of gluconic acid added in step (2) is 30% of phosphoric acid, and other conditions and parameters are exactly the same as those 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 the other conditions and parameters are exactly the same as those in example 1.
Example 7
This example is different from example 1 only in that the stirring speed in step (2) is 1000rpm, and other conditions and parameters are completely the same as those in example 1.
Example 8
The present example is different from example 1 only in that the volume ratio of ethanol to water in the mixed solution of ethanol and water in step (2) is 1:2, and the other conditions and parameters are completely the same as those in example 1.
Example 9
The present example is different from example 1 only in that the volume ratio of ethanol to water in the mixed solution of ethanol and water in step (2) is 2:1, and the other conditions and parameters are completely the same as those in example 1.
Example 10
The present example is different from example 1 only in that the temperature of the one-step sintering in step (3) is 500 ℃, and other conditions and parameters are completely the same as those in example 1.
Example 11
This example is different from example 1 only in that the temperature of the two-step sintering in step (3) is 750 ℃, and other conditions and parameters are completely the same as those in example 1.
Example 12
This example is different 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 those in example 1.
Example 13
This example is different from example 1 only in that the amount of doped nickel is 5%, and other conditions and parameters are exactly the same as those of example 1.
Example 14
This example is different from example 1 only in that the amount of nickel doped 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 the other conditions and parameters were exactly the same as in example 1.
Comparative example 2
This comparative example differs from example 1 only in that lithium hydrogencarbonate was not added in step (2), and the other conditions and parameters were exactly the same as those in example 1. The result shows that the system is broken down without adding lithium bicarbonate, because the total lithium amount of the system can not realize balance, lithium hydroxide and phosphoric acid can realize acid-base balance, but the total lithium amount can not reach the design requirement, lithium bicarbonate needs to be supplemented to balance the lithium amount proportion, and the lithium amount is insufficient or the capacity is greatly reduced.
And (3) performance testing:
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 to prepare batteries, the battery test was performed in the same mode as that of a lithium iron phosphate system, the charge cut-off voltage was 4.3V, and the test results are shown in table 1:
TABLE 1
| 0.1C gram 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 example 1 | 144 | 131 |
| Comparative example 2 | / | / |
As can be seen from the table 1, the lithium iron manganese phosphate positive electrode material prepared in the embodiments 1 to 3 has a capacity of more than 141mAh/g at 0.1 gram and more than 130.5mAh/g at 1 gram.
As can be seen from comparison between example 1 and examples 4 to 5, the addition amount of gluconic acid according to the present invention affects the performance of the obtained positive electrode material, and if the addition amount of gluconic acid is too large, the carbon content in the finally-fired lithium manganese iron phosphate is too high, which results in a decrease in capacity, and if the addition amount of gluconic acid is too small, the carbon content in the finally-fired lithium manganese iron phosphate is too low, which results in a decrease in capacity.
As can be seen from comparison between example 1 and examples 6-9, the reaction stage of the present invention can control the particle size and morphology of the final co-precipitated sample by adjusting the amount of ethanol added, the reaction temperature and the rotation speed. In the process, the liquid discharged by continuous concentration is added with sufficient ethanol again and then added into the system again, so that the reaction system is ensured to be in proportion balance of water and ethanol.
Compared with the examples 10 to 12, the temperature of the two-stage sintering of the invention can affect the performance of the anode material, and the anode material with good appearance and stable performance can be prepared by controlling the temperature of the two-stage sintering.
As can be seen from comparison between example 1 and examples 13 to 14, the doping amount of the dopant affects the performance of the obtained positive electrode material, and the positive electrode material with excellent performance can be obtained by controlling the doping amount of the dopant.
Compared with the embodiment 1 and the comparative example 1, the performance of the cathode material can be obviously improved by doping a small amount of the dopant.
Compared with the comparative example 2, the method has the advantages that the lithium bicarbonate or lithium hydroxide is added to ensure that the lithium content in the process and the final sample fluctuates within the range of the theoretical ratio in a small way, the normally set lithium ratio value can be realized only by supplementing a small amount of lithium source or not in the subsequent sintering process, so that the subsequent calcination is conveniently and directly performed, the pH value of the system can be adjusted by adding the lithium bicarbonate, and if only the lithium hydroxide or the lithium carbonate is added, the pH value of the system can be obviously increased, and the cathode material cannot be obtained when the pH value exceeds the range.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The preparation method of the lithium iron manganese phosphate cathode 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 a first slurry;
(2) mixing and stirring the first slurry, lithium bicarbonate, lithium hydroxide, a phosphoric acid source, a doping agent and a water-alcohol solution to obtain a mixed slurry, and carrying out reduced pressure distillation to obtain a coprecipitation ball;
(3) and sintering the coprecipitation ball to obtain the lithium iron manganese phosphate anode material.
2. The preparation method according to claim 1, wherein the mass concentration of the ammonium bicarbonate in the step (1) is 180-150 g/L;
preferably, the manganese source comprises a manganese sulfate solution with the mass concentration of 80-150 g/L;
preferably, the iron source comprises a ferrous sulfate solution with the mass concentration of 80-150 g/L.
3. The preparation method according to claim 1 or 2, wherein the mass ratio of phosphoric acid in the concentrated phosphoric acid in the step (1) is 80-90%;
preferably, water is added for dilution during the process of mixing the mixed carbonate precipitate and concentrated phosphoric acid;
preferably, the mass ratio of the gluconic acid to the phosphoric acid in the concentrated phosphoric acid is 0.2-0.3: 1.
4. The method according to any one of claims 1 to 3, wherein in the first slurry in the step (1), the total molar amount of the metal ions and the molar ratio of the phosphate ions are 1 (1.01) to 1.05.
5. The method according to any one of claims 1 to 4, wherein the mass concentration of the lithium bicarbonate in the step (2) is 50 to 70 g/L;
preferably, the mass concentration of the lithium hydroxide is 40-60 g/L;
preferably, the phosphoric acid source comprises dilute phosphoric acid;
preferably, the mass ratio of phosphoric acid in the dilute phosphoric acid is 3-8%;
preferably, the dopant comprises any one 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 or a combination of at least two of the above;
preferably, the doping amount of the dopant is 1-3% of the mass of the positive electrode material;
preferably, the volume ratio of water to ethanol in the hydroalcoholic solution is 1 (0.8-1.2).
6. The method according to any one of claims 1 to 5, wherein the temperature of the mixing and stirring in the step (2) is 20 to 40 ℃;
preferably, the pH value of the mixing and stirring is 3-5;
preferably, the mixing and stirring speed is 1200-2000 rpm;
preferably, the particle size of the coprecipitation ball is 2-4 μm.
7. The production method according to any one of claims 1 to 6, wherein the sintering treatment in the step (3) includes one-step sintering and two-step sintering;
preferably, the temperature of the one-step sintering is 450-480 ℃;
preferably, the one-step sintering time is 3-6 h;
preferably, the temperature of the two-step sintering is 680-700 ℃;
preferably, the time of the two-step sintering is 12-16 h.
8. The lithium iron manganese phosphate cathode material is characterized by being prepared by the method of any one of claims 1 to 7, and having 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, and X is any one or combination of at least two of nickel, cobalt, manganese, calcium, magnesium, tungsten, molybdenum, zirconium, titanium, vanadium, niobium, tantalum or chromium.
9. A positive electrode tab, characterized in that the positive electrode tab comprises the lithium iron manganese phosphate positive electrode material according to claim 8.
10. A lithium ion battery comprising the positive electrode sheet of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210688198.1A CN114988386B (en) | 2022-06-16 | 2022-06-16 | Lithium iron manganese phosphate positive electrode material, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210688198.1A CN114988386B (en) | 2022-06-16 | 2022-06-16 | Lithium iron manganese phosphate positive electrode material, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114988386A true CN114988386A (en) | 2022-09-02 |
| CN114988386B CN114988386B (en) | 2024-02-02 |
Family
ID=83035974
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210688198.1A Active CN114988386B (en) | 2022-06-16 | 2022-06-16 | Lithium iron manganese phosphate positive electrode material, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114988386B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN115893361A (en) * | 2022-11-26 | 2023-04-04 | 浙江新安化工集团股份有限公司 | Carbon-coated metal-doped lithium iron phosphate material and preparation method and application thereof |
| CN117509596A (en) * | 2023-11-23 | 2024-02-06 | 新洋丰农业科技股份有限公司 | Preparation method of ferric manganese phosphate solid solution and ferric manganese lithium phosphate |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101980956A (en) * | 2008-03-31 | 2011-02-23 | 户田工业株式会社 | Lithium iron phosphate powder manufacturing method, olivine structured lithium iron phosphate powder, cathode sheet using said lithium iron phosphate powder, and non-aqueous solvent secondary battery |
| WO2013038516A1 (en) * | 2011-09-14 | 2013-03-21 | 住友金属鉱山株式会社 | Manganese iron ammonium phosphate, method for producing same, positive electrode active material for lithium secondary batteries using manganese iron ammonium phosphate, method for producing positive electrode active material for lithium secondary batteries using manganese iron ammonium phosphate, and lithium secondary battery using positive electrode active material for lithium secondary batteries using manganese iron ammonium phosphate |
| CN104681795A (en) * | 2015-01-29 | 2015-06-03 | 北大先行科技产业有限公司 | Preparation method for lithium ferric manganese phosphate/carbon composite material |
| US20150372303A1 (en) * | 2012-12-21 | 2015-12-24 | Dow Global Technologies Llc | Method for Making Lithium Transition Metal Olivines Using Water/Cosolvent Mixtures |
| CN107069030A (en) * | 2017-04-18 | 2017-08-18 | 湘潭大学 | A kind of preparation method of pattern and the double controllable lithium-rich manganese-based anode materials of size |
| CN107658451A (en) * | 2017-09-18 | 2018-02-02 | 北京理工大学 | A kind of 622NCM tertiary cathode materials and preparation method thereof |
| CN107768613A (en) * | 2017-09-01 | 2018-03-06 | 上海交通大学 | A kind of preparation method of the iron manganese phosphate for lithium of carbon coated |
| CN111933915A (en) * | 2020-09-14 | 2020-11-13 | 天津斯科兰德科技有限公司 | Lithium iron manganese phosphate positive electrode material and preparation method and application thereof |
| CN112978704A (en) * | 2021-05-08 | 2021-06-18 | 蜂巢能源科技有限公司 | Modified lithium iron phosphate material and preparation method thereof |
| CN113942990A (en) * | 2021-08-25 | 2022-01-18 | 北京当升材料科技股份有限公司 | Lithium manganese iron phosphate precursor, lithium manganese iron phosphate positive electrode material, preparation method of lithium manganese iron phosphate positive electrode material, electrode and lithium ion battery |
| CN114380280A (en) * | 2021-12-08 | 2022-04-22 | 上海兰钧新能源科技有限公司 | Preparation method of lithium iron manganese phosphate cathode material |
-
2022
- 2022-06-16 CN CN202210688198.1A patent/CN114988386B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101980956A (en) * | 2008-03-31 | 2011-02-23 | 户田工业株式会社 | Lithium iron phosphate powder manufacturing method, olivine structured lithium iron phosphate powder, cathode sheet using said lithium iron phosphate powder, and non-aqueous solvent secondary battery |
| WO2013038516A1 (en) * | 2011-09-14 | 2013-03-21 | 住友金属鉱山株式会社 | Manganese iron ammonium phosphate, method for producing same, positive electrode active material for lithium secondary batteries using manganese iron ammonium phosphate, method for producing positive electrode active material for lithium secondary batteries using manganese iron ammonium phosphate, and lithium secondary battery using positive electrode active material for lithium secondary batteries using manganese iron ammonium phosphate |
| US20150372303A1 (en) * | 2012-12-21 | 2015-12-24 | Dow Global Technologies Llc | Method for Making Lithium Transition Metal Olivines Using Water/Cosolvent Mixtures |
| CN104681795A (en) * | 2015-01-29 | 2015-06-03 | 北大先行科技产业有限公司 | Preparation method for lithium ferric manganese phosphate/carbon composite material |
| CN107069030A (en) * | 2017-04-18 | 2017-08-18 | 湘潭大学 | A kind of preparation method of pattern and the double controllable lithium-rich manganese-based anode materials of size |
| CN107768613A (en) * | 2017-09-01 | 2018-03-06 | 上海交通大学 | A kind of preparation method of the iron manganese phosphate for lithium of carbon coated |
| CN107658451A (en) * | 2017-09-18 | 2018-02-02 | 北京理工大学 | A kind of 622NCM tertiary cathode materials and preparation method thereof |
| CN111933915A (en) * | 2020-09-14 | 2020-11-13 | 天津斯科兰德科技有限公司 | Lithium iron manganese phosphate positive electrode material and preparation method and application thereof |
| CN112978704A (en) * | 2021-05-08 | 2021-06-18 | 蜂巢能源科技有限公司 | Modified lithium iron phosphate material and preparation method thereof |
| CN113942990A (en) * | 2021-08-25 | 2022-01-18 | 北京当升材料科技股份有限公司 | Lithium manganese iron phosphate precursor, lithium manganese iron phosphate positive electrode material, preparation method of lithium manganese iron phosphate positive electrode material, electrode and lithium ion battery |
| CN114380280A (en) * | 2021-12-08 | 2022-04-22 | 上海兰钧新能源科技有限公司 | Preparation method of lithium iron manganese phosphate cathode material |
Non-Patent Citations (2)
| Title |
|---|
| ARNOLD, G: "《Fine-particle lithium iron phosphate LiFePO4 synthesized by a new low-cost aqueous precipitation technique》", 《JOURNAL OF POWER SOURCES》 * |
| 刘龙: "《 贫锰矿和废铁屑制备磷酸锰铁锂前驱体的研究》", 《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN115893361A (en) * | 2022-11-26 | 2023-04-04 | 浙江新安化工集团股份有限公司 | Carbon-coated metal-doped lithium iron phosphate material and preparation method and application thereof |
| CN117509596A (en) * | 2023-11-23 | 2024-02-06 | 新洋丰农业科技股份有限公司 | Preparation method of ferric manganese phosphate solid solution and ferric manganese lithium phosphate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114988386B (en) | 2024-02-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114988386B (en) | Lithium iron manganese phosphate positive electrode material, and preparation method and application thereof | |
| CN101327922B (en) | Preparation of LiFePO4 | |
| CN102569780B (en) | Method for preparing lithium ion battery cathode material with layered structure | |
| US20200328406A1 (en) | Layered lithium-rich manganese-based cathode material with olivine structured limpo4 surface modification and preparation method thereof | |
| CN107359318B (en) | Method for synthesizing iron phosphate precursor with spherical-like porous structure and lithium iron phosphate cathode material | |
| CN106920934A (en) | The preparation method of the codoping modified ternary precursor of cobalt magnesium and positive electrode based on high-nickel material | |
| WO2023155539A1 (en) | Preparation method for sodium ferrovanadium phosphate material and application thereof | |
| CN114940485B (en) | Lithium manganese iron phosphate precursor and preparation method and application thereof | |
| CN112390292A (en) | Bulk phase doped manganous-manganic oxide and preparation method and application thereof | |
| WO2023155544A1 (en) | Preparation method for polyanionic positive electrode material | |
| CN103715422B (en) | Electrolysis prepares the method for the nickelic system positive electrode of lithium ion battery | |
| CN115676797A (en) | Lithium manganese iron phosphate material, preparation method and application thereof | |
| CN110911652B (en) | Nano spherical alpha-MnO 2 /Bi 2 O 3 Material, preparation method and application thereof | |
| CN104993142B (en) | Sulfonated graphene lithium battery positive electrode additive and application thereof | |
| CN106848227A (en) | A kind of preparation method of the modified lithium-rich manganese-based anode material in surface | |
| CN106129383A (en) | A kind of ball-shaped lithium-ion battery anode material with nanoscale biphase Gradient distribution structure and synthetic method thereof | |
| CN116216682A (en) | Preparation method and application of ferric manganese phosphate precursor | |
| CN114784270B (en) | Preparation method of sodium ion battery material | |
| CN115974036A (en) | Spherical lithium ferric manganese phosphate nano-particles and preparation method thereof | |
| CN102556999B (en) | Reduction processing method for synthesizing lithium iron phosphate materials | |
| CN109437333A (en) | A kind of nickel galaxite presoma and preparation method thereof and anode material for lithium-ion batteries | |
| CN114864932A (en) | Preparation method of sodium ion battery positive electrode material | |
| CN114014292A (en) | Preparation method of lithium iron manganese phosphate | |
| CN115557543B (en) | Surface in-situ coating type positive electrode lithium supplementing material and preparation method thereof | |
| CN112164798B (en) | Surface stability enhanced positive electrode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |