CN116730310A - Method for preparing lithium ion battery anode material lithium iron manganese phosphate - Google Patents
Method for preparing lithium ion battery anode material lithium iron manganese phosphate Download PDFInfo
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- CN116730310A CN116730310A CN202310621222.4A CN202310621222A CN116730310A CN 116730310 A CN116730310 A CN 116730310A CN 202310621222 A CN202310621222 A CN 202310621222A CN 116730310 A CN116730310 A CN 116730310A
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- manganese phosphate
- lithium
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- lithium iron
- iron manganese
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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 66
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000010405 anode material Substances 0.000 title claims abstract description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 100
- 229910052742 iron Inorganic materials 0.000 claims abstract description 57
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 46
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 34
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 23
- 238000001694 spray drying Methods 0.000 claims abstract description 21
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 20
- 239000011572 manganese Substances 0.000 claims abstract description 20
- 239000011268 mixed slurry Substances 0.000 claims abstract description 18
- 239000012046 mixed solvent Substances 0.000 claims abstract description 18
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 18
- 239000000654 additive Substances 0.000 claims abstract description 15
- 230000000996 additive effect Effects 0.000 claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000010439 graphite Substances 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 8
- 239000008103 glucose Substances 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 4
- 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 claims description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 241001330002 Bambuseae Species 0.000 claims description 2
- 229920000858 Cyclodextrin Polymers 0.000 claims description 2
- 239000005639 Lauric acid Substances 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 12
- 239000002245 particle Substances 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000011164 primary particle Substances 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 description 14
- 238000005303 weighing Methods 0.000 description 10
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010902 jet-milling Methods 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical class [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a method for preparing lithium ion battery anode material lithium iron manganese phosphate, which comprises the following steps: dispersing phosphoric acid in water, and then adding oxalic acid to obtain a mixed solvent; dispersing an iron source, a manganese source, a lithium source, a carbon source and an additive in a mixed solvent to obtain mixed slurry; spray drying and continuously stirring the mixed slurry at an air inlet temperature of 280-320 ℃ to obtain a uniform and compact lithium iron manganese phosphate precursor coated with a surface carbon source; sintering the precursor of the lithium iron manganese phosphate in an inert gas environment, and cooling and crushing to obtain the carbon-coated lithium iron manganese phosphate. The method provided by the invention has the advantages of simple synthesis process, easily controlled process, low energy consumption, environmental protection, no pollution, high efficiency and low cost, and is suitable for industrial production, and the prepared material has small primary particles and uniform particle distribution. The lithium iron manganese phosphate prepared by the invention has the discharge specific capacity of more than 148mAh/g and the discharge efficiency of more than 90 percent at 0.1C.
Description
Technical Field
The invention belongs to the technical field of lithium iron manganese phosphate synthesis, and particularly relates to a method for preparing lithium iron manganese phosphate serving as a positive electrode material of a lithium ion battery.
Background
With the market development of new energy electric vehicles, in the long-term planning of the automobile industry, it is pointed out that the specific energy density of a power battery monomer reaches 300Wh/kg in 2020, the specific energy density of a system reaches 260Wh/kg, the cost is reduced to below 1 yuan/Wh, and the specific energy of a power battery system reaches 350Wh/kg in 2025. The energy density of the battery is mainly determined by the positive electrode material. At present, three main technical means for improving the energy density of a lithium ion battery are as follows: the compaction density, gram capacity and voltage platform of the lithium ion battery anode material are improved, and the lithium iron phosphate anode material is limited by the lower compaction density (2.4 g/cm), gram capacity (145 mAh/g) and voltage platform (3.2V) of the lithium iron phosphate anode material, so that the energy density of the lithium iron phosphate battery is a main barrier for limiting the further large-scale application of the lithium iron phosphate anode material in the new energy electric vehicle market.
Compared with the lithium iron phosphate anode material, the lithium iron manganese phosphate anode material has the theoretical capacity of 170mAh/g, has the advantages of stable structure, high safety, long circulation, low cost, environmental protection and the like, and is provided with a higher voltage platform (4.1V) and is positioned in a stable electrochemical window of an organic electrolyte system. The energy density of the lithium iron manganese phosphate battery is improved by more than 30 percent compared with the current lithium iron phosphate battery, and is basically the same as that of the current ternary battery. However, the main defects of the existing lithium iron manganese phosphate materials are small actual capacity and poor rate capability, and the problems limit the practical application of the lithium iron manganese phosphate materials.
Disclosure of Invention
The invention aims to provide a method for preparing lithium iron manganese phosphate serving as a positive electrode material of a lithium ion battery, so as to solve the problem that the preparation of the lithium iron manganese phosphate is difficult in the prior art.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for preparing a lithium ion battery anode material lithium iron manganese phosphate comprises the following steps:
(1) Firstly dispersing phosphoric acid in a proper amount of pure water to prepare a phosphoric acid aqueous solution, then weighing 50% -100% of oxalic acid, adding the oxalic acid into the phosphoric acid aqueous solution, fully and uniformly stirring the oxalic acid aqueous solution by a stirrer to obtain a mixed solvent, sequentially weighing an iron source, a manganese source, a lithium source, a carbon source and an additive, uniformly dispersing the iron source, the manganese source, the carbon source and the additive in the mixed solvent, continuously stirring the materials in the adding process, fully reacting the iron source, the manganese source and the phosphoric acid under the action of the oxalic acid, and then reacting the iron source, the manganese source and the phosphoric acid with the lithium source, the carbon source and the additive to obtain mixed slurry; preferably, the molar ratio of oxalic acid/(Fe, mn) in the mixed slurry is 1-1.05, the molar ratio of P/(Fe, mn) is 1-1.05, the molar ratio of Li/(Fe, mn) is 1.01-1.15, the mass of the carbon source is 4-14% of the mass of the iron source, and the mass of the additive is 0.1-2% of the mass of the iron source; further preferably, the iron source is iron powder or iron block, the manganese source is manganese powder or manganese block, the lithium source is lithium hydroxide, lithium carbonate or lithium acetate, and the carbon source is at least one of glucose, sucrose, starch, cyclodextrin, citric acid, lauric acid, bamboo fiber, polyethylene glycol, polyacrylic acid, polyvinyl alcohol, polyaniline, pyromellitic acid, polyvinylpyrrolidone and expandable graphite; the additive is titanium dioxide, aluminum hydroxide, ammonium metavanadate or magnesium hydroxide.
(2) Spray drying the mixed slurry at an air inlet temperature of 280-320 ℃, and continuously stirring in the spray drying process to obtain a uniform and compact lithium iron manganese phosphate precursor coated with a surface carbon source; preferably, the D50 of the lithium iron manganese phosphate precursor is 10-30 mu m.
(3) Sintering the lithium iron manganese phosphate precursor in an inert gas environment, wherein the sintering temperature is 600-850 ℃, the sintering time is 6-15h, and cooling and crushing to obtain a finished product of the carbon-coated lithium iron manganese phosphate with the D50 of 1-3 mu m.
Compared with the prior art, the invention has the beneficial effects that:
the method provided by the invention has the advantages of simple synthesis process, easily controlled process, low energy consumption, environmental protection, no pollution, high efficiency and low cost, and is suitable for industrial production, and the prepared material has small primary particles and uniform particle distribution. In the spray drying process, the slurry is quickly dried in time by controlling the air inlet temperature of 280-320 ℃ to obtain the carbon-coated uniform lithium iron manganese phosphate precursor particles, so that the product with excellent performance is prepared. The invention improves the conductivity of the battery by doping the additive, is beneficial to improving the discharge capacity of the battery and has stable cycle performance. The lithium iron manganese phosphate prepared by the invention has the discharge specific capacity of more than 148mAh/g and the discharge efficiency of more than 90 percent at 0.1C.
Drawings
FIG. 1 is an SEM image of a lithium iron manganese phosphate precursor obtained after spray drying of example 1;
FIG. 2 is an XRD pattern of the lithium iron manganese phosphate product prepared in example 1;
FIG. 3 is an SEM image of a lithium iron manganese phosphate precursor obtained after spray drying of a comparative example;
Detailed Description
The present invention will be further described with reference to examples, which are not intended to be limiting, so that those skilled in the art will better understand the present invention and practice it.
In addition, the preparation processes in the following examples are conventional means in the art unless specifically described, and therefore, will not be described in detail; the raw materials used in the following embodiments are all commercially available products, and are commercially available.
Example 1
A method for preparing a lithium ion battery anode material lithium iron manganese phosphate comprises the following steps:
(1) Iron powder is selected as an iron source, manganese powder is selected as a manganese source, lithium carbonate is selected as a lithium source, glucose, polyethylene glycol and expandable graphite are selected as carbon sources, titanium dioxide is selected as an additive, phosphoric acid is firstly dispersed in a proper amount of pure water to prepare a phosphoric acid aqueous solution, then 85% oxalic acid is weighed and added into the phosphoric acid aqueous solution, and the mixture is fully and uniformly stirred by a stirrer to obtain a mixed solvent. Taking an iron source as a reference amount, weighing 1kg of the iron source and 1kg of the manganese source, and respectively weighing the rest raw materials according to the following dosage: oxalic acid/(Fe, mn) molar ratio is 1.01, P/(Fe, mn) molar ratio is 1.01, li/(Fe, mn) molar ratio is 1.035, glucose addition is 10% of iron source mass, polyethylene glycol addition is 3% of iron source mass, expandable graphite addition is 1% of iron source mass, titanium dioxide addition is 1% of iron source mass, and the weighed materials are sequentially added into a mixed solvent, and fully stirred and uniformly mixed to prepare mixed slurry.
(2) And (3) carrying out spray drying on the uniformly mixed slurry at the air inlet temperature of 300 ℃, and continuously stirring the slurry in the spray drying process to obtain the lithium iron manganese phosphate precursor with the granularity of 19.8 mu m.
In this embodiment, scanning electron microscope analysis is performed on the precursor after spray drying, as shown in fig. 1, it can be seen that the particle surface of the precursor of lithium iron manganese phosphate obtained by spraying at a higher air inlet temperature is smooth, the stacking is compact, the particle size distribution is uniform, the melting, wrapping, decomposition and carbonization of the carbon source in the sintering process are facilitated, and the precursor of lithium iron manganese phosphate can be coated more uniformly.
(3) Sintering and preserving heat of the precursor in the step 2 for 10 hours at 780 ℃ under the protection of inert atmosphere, wherein the heat is preserved for 1 hour at 300 ℃, 350 ℃ and 420 ℃ respectively, and then cooling is carried out to obtain carbon-coated lithium iron manganese phosphate; and (3) carrying out jet milling on the sintered carbon-coated lithium iron manganese phosphate to obtain a finished product with the granularity D50 of 2.58 mu m.
Fig. 2 is an XRD pattern of the lithium iron manganese phosphate product prepared in example 1, it can be seen from fig. 2 that the sample has sharp and distinct diffraction peaks, and no diffraction peaks of other impurities such as iron phosphorus compounds, manganese oxides, etc. are observed, and the XRD pattern of the lithium iron manganese phosphate product prepared in example 1 is substantially identical to that of the lithium iron phosphate XRD standard pattern, indicating that manganese has entered into the lithium iron phosphate structure under the synthesis method herein, indicating that the lithium iron manganese phosphate product synthesized by the method has a single olivine structure.
Example 2
A method for preparing a lithium ion battery anode material lithium iron manganese phosphate comprises the following steps:
(1) Iron powder is selected as an iron source, manganese powder is selected as a manganese source, lithium carbonate is selected as a lithium source, sucrose, polyvinyl alcohol and expandable graphite are selected as carbon sources, aluminum hydroxide is selected as an additive, phosphoric acid is firstly dispersed in a proper amount of pure water to prepare a phosphoric acid aqueous solution, then 65% oxalic acid is weighed and added into the phosphoric acid aqueous solution, and the mixture is fully and uniformly stirred by a stirrer to obtain a mixed solvent. Taking an iron source as a reference amount, weighing 1kg of the iron source and 1kg of the manganese source, and respectively weighing the rest raw materials according to the following dosage: the formula with oxalic acid/(Fe, mn) mole ratio of 1.02, P/(Fe, mn) mole ratio of 1.02, li/(Fe, mn) mole ratio of 1.025, sucrose addition of 8%, polyvinyl alcohol addition of 4%, expandable graphite addition of 2% and aluminum hydroxide addition of 1.6% is weighed, and the weighed materials are sequentially added into a mixed solvent and fully stirred and uniformly mixed to prepare mixed slurry.
(2) And (3) carrying out spray drying on the uniformly mixed slurry at the air inlet temperature of 300 ℃, and continuously stirring the slurry in the spray drying process to obtain the lithium iron manganese phosphate precursor with the granularity of 19.2 mu m.
(3) Sintering and preserving heat for 8 hours at 800 ℃ under the protection of inert atmosphere, wherein the heat is preserved for 1 hour at 300 ℃, 350 ℃ and 420 ℃ respectively, and then cooling is carried out to obtain the carbon-coated lithium iron manganese phosphate. And (3) carrying out jet milling on the sintered carbon-coated lithium iron manganese phosphate to obtain a finished product with the granularity D50 of 2.64 mu m.
Example 3
A method for preparing a lithium ion battery anode material lithium iron manganese phosphate comprises the following steps:
(1) Iron powder is selected as an iron source, manganese powder is selected as a manganese source, lithium carbonate is selected as a lithium source, starch, polyacrylic acid and expandable graphite are selected as carbon sources, ammonium metavanadate is selected as an additive, phosphoric acid is firstly dispersed in a proper amount of pure water to prepare a phosphoric acid aqueous solution, then 75% oxalic acid is weighed and added into the phosphoric acid aqueous solution, and the mixture is fully and uniformly stirred by a stirrer to obtain a mixed solvent. Taking an iron source as a reference amount, weighing 1kg of the iron source and 1kg of the manganese source, and respectively weighing the rest raw materials according to the following dosage: the molar ratio of oxalic acid/(Fe, mn) is 1.03, the molar ratio of P/(Fe, mn) is 1.03, the molar ratio of Li/(Fe, mn) is 1.15, the starch addition amount is 6%, the polyacrylic acid addition amount is 6%, the expandable graphite addition amount is 2%, the ammonium metavanadate addition amount is 0.8%, the materials are weighed, the weighed materials are sequentially added into a mixed solvent, and the mixed solvent is fully stirred and uniformly mixed to prepare mixed slurry.
(2) And (3) carrying out spray drying on the uniformly mixed slurry at the air inlet temperature of 300 ℃, and continuously stirring the slurry in the spray drying process to obtain the lithium iron manganese phosphate precursor with the granularity of 17.8 mu m.
(3) Sintering and preserving heat of the precursor for 12 hours at 760 ℃ under the protection of inert atmosphere, wherein the heat is preserved for 1 hour at 300 ℃, 350 ℃ and 420 ℃ respectively, and then cooling is carried out to obtain the carbon-coated lithium iron manganese phosphate. And carrying out jet milling on the sintered carbon-coated lithium iron manganese phosphate to obtain a finished product with the granularity D50 of 2.71 mu m.
Example 4
A method for preparing a lithium ion battery anode material lithium iron manganese phosphate comprises the following steps:
(1) Iron powder is selected as an iron source, manganese powder is selected as a manganese source, lithium carbonate is selected as a lithium source, glucose, citric acid and polyethylene glycol are selected as carbon sources, magnesium hydroxide is selected as an additive, phosphoric acid is firstly dispersed in a proper amount of pure water to prepare a phosphoric acid aqueous solution, then 95% oxalic acid is weighed and added into the phosphoric acid aqueous solution, the phosphoric acid aqueous solution is fully and uniformly stirred by a stirrer to obtain a mixed solvent, 1kg of the iron source and 1kg of the manganese source are weighed by taking the iron source as reference amounts, and the rest raw materials are respectively weighed according to the following amounts: the molar ratio of oxalic acid/(Fe, mn) is 1.04, the molar ratio of P/(Fe, mn) is 1.04, the molar ratio of Li/(Fe, mn) is 1.01, the addition of glucose, citric acid and expandable graphite is 6%, 4% and 3%, respectively, the addition of magnesium hydroxide is 1.5% of the formula, the materials are weighed, the weighed materials are sequentially added into a mixed solvent, and the mixed solvent is fully stirred and uniformly mixed to prepare mixed slurry.
(2) And (3) carrying out spray drying on the uniformly mixed slurry at the air inlet temperature of 280 ℃, and continuously stirring the slurry in the spray drying process to obtain the lithium iron manganese phosphate precursor with the granularity of 21.5 mu m.
(3) Sintering and preserving heat of the precursor for 10 hours at 790 ℃ under the protection of inert atmosphere, wherein the heat is preserved for 1 hour at 300 ℃, 350 ℃ and 420 ℃ respectively, and then cooling is carried out to obtain the carbon-coated lithium iron manganese phosphate. And (3) carrying out jet milling on the sintered carbon-coated lithium iron manganese phosphate to obtain a finished product with the granularity D50 of 2.66 mu m.
Comparative example
The comparative example differs from example 1 in that the inlet air temperature of the spray drying in step (2) is different.
A method for preparing a lithium ion battery anode material lithium iron manganese phosphate comprises the following steps:
(1) Iron powder is selected as an iron source, manganese powder is selected as a manganese source, lithium carbonate is selected as a lithium source, glucose, polyethylene glycol and expandable graphite are selected as carbon sources, titanium dioxide is selected as an additive, phosphoric acid is firstly dispersed in a proper amount of pure water to prepare a phosphoric acid aqueous solution, then 85% oxalic acid is weighed and added into the phosphoric acid aqueous solution, and the mixture is fully and uniformly stirred by a stirrer to obtain a mixed solvent. Taking an iron source as a reference amount, weighing 1kg of the iron source and 1kg of the manganese source, and respectively weighing the rest raw materials according to the following dosage: oxalic acid/(Fe, mn) molar ratio is 1.01, P/(Fe, mn) molar ratio is 1.01, li/(Fe, mn) molar ratio is 1.035, glucose addition is 10% of iron source mass, polyethylene glycol addition is 3% of iron source mass, expandable graphite addition is 1% of iron source mass, titanium dioxide addition is 1% of iron source mass, and the weighed materials are sequentially added into a mixed solvent, and fully stirred and uniformly mixed to prepare mixed slurry.
(2) And (3) carrying out spray drying on the uniformly mixed slurry at the air inlet temperature of 245 ℃, and continuously stirring the slurry in the spray drying process to obtain the lithium iron manganese phosphate precursor with the granularity of 25.8 mu m.
As a result of scanning electron microscope analysis on the precursor after spray drying of the comparative example, as shown in FIG. 3, because the air inlet temperature is not high enough, the sprayed droplets are possibly not dried in time, and the droplets are accumulated together and dried to form larger particles or collide with the inner wall of a spray tower after drying to cause cracking, so that the precursor of the lithium iron manganese phosphate is loose porous spheres, the D50 is larger, the particle size distribution range is relatively wider, and the melting, wrapping, decomposition and carbonization processes of a carbon source in sintering are not facilitated.
(3) Sintering and preserving heat for 10 hours at 780 ℃ under the protection of inert atmosphere, wherein the heat is preserved for 1 hour at 300 ℃, 350 ℃ and 420 ℃ respectively, and then cooling is carried out to obtain the carbon-coated lithium iron manganese phosphate. And (3) carrying out jet milling on the sintered carbon-coated lithium iron manganese phosphate to obtain a finished product with the granularity D50 of 2.86 mu m.
Performance testing
The lithium iron manganese phosphate prepared in each of the above examples and comparative examples is used as a positive electrode active material, and the positive electrode active material is prepared by the following mass ratio: conductive agent (acetylene black): the binder (polytetrafluoroethylene) =96:2:2 is prepared into positive electrode slurry, then the positive electrode slurry is coated on a positive electrode current collector to form a positive electrode, and metal lithium is used as a negative electrode to prepare a button cell for performance test. The charge-discharge cutoff voltage was 2 to 4V, the charge-discharge magnification was 0.1C, and the test results are shown in table 1.
TABLE 1
As can be seen from table 1, the battery made of lithium iron manganese phosphate prepared in the examples has a high specific charge-discharge capacity and charge-discharge efficiency.
It will be apparent that the described embodiments are some, but not all, embodiments of the invention. Based on the examples herein, one of ordinary skill in the art would obtain this without undue burden. All other embodiments of (2) fall within the scope of the present invention.
Claims (8)
1. The method for preparing the lithium ion battery anode material lithium iron manganese phosphate is characterized by comprising the following steps of:
(1) Dispersing phosphoric acid in water, and then adding oxalic acid to obtain a mixed solvent; uniformly dispersing an iron source, a manganese source, a lithium source, a carbon source and an additive in a mixed solvent to obtain mixed slurry;
(2) Spray drying the mixed slurry at an air inlet temperature of 280-320 ℃, and continuously stirring in the spray drying process to obtain a uniform and compact lithium iron manganese phosphate precursor coated with a surface carbon source;
(3) Sintering the precursor of the lithium iron manganese phosphate in an inert gas environment, and cooling and crushing to obtain the carbon-coated lithium iron manganese phosphate.
2. The method for preparing the lithium ion battery anode material lithium iron manganese phosphate according to claim 1, which is characterized in that: in the step (1), the iron source is iron powder; the manganese source is manganese powder; the lithium source is lithium hydroxide, lithium carbonate or lithium acetate; the carbon source is at least one of glucose, sucrose, starch, cyclodextrin, citric acid, lauric acid, bamboo fiber, polyethylene glycol, polyacrylic acid, polyvinyl alcohol, polyaniline, pyromellitic acid, polyvinylpyrrolidone and expandable graphite.
3. The method for preparing the lithium ion battery anode material lithium iron manganese phosphate according to claim 2, which is characterized in that: the molar ratio of oxalic acid/(Fe, mn) in the mixed slurry is 1-1.05, the molar ratio of P/(Fe, mn) is 1-1.05, and the molar ratio of Li/(Fe, mn) is 1.01-1.15; the mass of the carbon source is 4-14% of that of the iron source.
4. The method for preparing the lithium ion battery anode material lithium iron manganese phosphate according to claim 2, which is characterized in that: in the step (1), the additive is titanium dioxide, aluminum hydroxide, ammonium metavanadate or magnesium hydroxide.
5. The method for preparing the lithium ion battery anode material lithium iron manganese phosphate according to claim 4, which is characterized in that: the mass of the additive is 0.1-2% of the mass of the iron source.
6. The method for preparing the lithium ion battery anode material lithium iron manganese phosphate according to claim 1, which is characterized in that: in the step (2), the D50 of the lithium iron manganese phosphate precursor is 10-30 mu m.
7. The method for preparing the lithium ion battery anode material lithium iron manganese phosphate according to claim 1, which is characterized in that: in the step (3), the sintering temperature is 600-850 ℃ and the sintering time is 6-15h.
8. The method for preparing the lithium ion battery anode material lithium iron manganese phosphate according to claim 1, which is characterized in that: in the step (3), the D50 of the carbon-coated lithium iron manganese phosphate is 1-3 mu m.
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