CN117303337A - Doping preparation method of lithium iron manganese phosphate composite anode material - Google Patents
Doping preparation method of lithium iron manganese phosphate composite anode material Download PDFInfo
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- CN117303337A CN117303337A CN202311187803.8A CN202311187803A CN117303337A CN 117303337 A CN117303337 A CN 117303337A CN 202311187803 A CN202311187803 A CN 202311187803A CN 117303337 A CN117303337 A CN 117303337A
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- lithium iron
- doping
- lithium
- manganese phosphate
- phosphate composite
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- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000010405 anode material Substances 0.000 title claims abstract description 25
- 239000002019 doping agent Substances 0.000 claims abstract description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 17
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011268 mixed slurry Substances 0.000 claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 239000011572 manganese Substances 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
- 238000001694 spray drying Methods 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 6
- 238000000975 co-precipitation Methods 0.000 claims abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011574 phosphorus Substances 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 11
- 239000007774 positive electrode material Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 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 7
- 229960001031 glucose Drugs 0.000 claims description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000616 Ferromanganese Inorganic materials 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 7
- 238000009792 diffusion process Methods 0.000 abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 5
- 238000000227 grinding Methods 0.000 abstract description 3
- 239000011164 primary particle Substances 0.000 abstract description 3
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 abstract 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 4
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 description 4
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010902 jet-milling Methods 0.000 description 2
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000007709 nanocrystallization Methods 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- FTXWZTQWJZKPTB-UHFFFAOYSA-H [Li+].P(=O)([O-])([O-])[O-].[Mn+2].[Li+].P(=O)([O-])([O-])[O-].[Fe+2] Chemical compound [Li+].P(=O)([O-])([O-])[O-].[Mn+2].[Li+].P(=O)([O-])([O-])[O-].[Fe+2] FTXWZTQWJZKPTB-UHFFFAOYSA-H 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of lithium battery anode materials, and particularly relates to a preparation method for doping a lithium manganese iron phosphate anode material. The invention discloses a doping preparation method of a lithium iron manganese phosphate composite anode material, which comprises the steps of 1) preparing a lattice doped type manganese iron phosphate precursor by coprecipitation of soluble manganese sources, iron sources, phosphorus sources and first doping agents with different contents. 2) And (3) dehydrating the precursor prepared in the step (1), and grinding the dehydrated precursor, the lithium source, the composite carbon source and the second doping agent to prepare mixed slurry. 3) And (3) spray-drying, sintering and air-powder the mixed slurry to prepare the lithium iron manganese phosphate composite anode material. According to the preparation method, the doping element quantity of the first doping agent is determined according to the manganese element content, the original lattice parameter is changed through element doping, a lithium ion diffusion channel is increased, and the ion conductivity is improved. The second doping agent has good high temperature resistance, ensures good doping property, can inhibit the growth of primary particle size in the material sintering process, ensures the preparation of small-particle-size materials, and shortens the diffusion path of lithium ions.
Description
Technical Field
The invention belongs to the technical field of lithium battery anode materials, and particularly relates to a preparation method for doping a lithium manganese iron phosphate anode material.
Technical Field
The lithium iron manganese phosphate belongs to a product obtained by mixing and doping lithium iron phosphate and lithium manganese phosphate, and is the same as the lithium iron phosphate in structure and has an ordered and regular olivine structure in crystal form, so that the lithium iron phosphate has higher structural stability as the lithium iron phosphate. Compared with noble metals cobalt and nickel, the manganese element has low price and lower raw material preparation cost. The advantages of high safety performance, high thermal stability and the like similar to that of the lithium iron phosphate are combined, so that the lithium iron phosphate has the advantages of the lithium iron phosphate and the lithium manganese phosphate, and meanwhile, the short plate with low energy density of the lithium iron phosphate can be made up, so that the lithium iron phosphate is also known as an 'upgrading edition of the lithium iron phosphate'.
The theoretical capacity of the lithium iron manganese phosphate is 170mAh/g which is the same as that of the lithium iron phosphate; but the voltage platform of the lithium iron manganese phosphate material is 4.1V, which is far higher than 3.4V of the lithium iron phosphate, and the voltage of the platform is improved by 20%, so that the same battery capacity density is promoted by 20% compared with the lithium iron phosphate material.
The conductivity of the lithium iron manganese phosphate is lower than that of the lithium iron phosphate, and the charge-discharge rate performance is also poorer. And the content of manganese element in the lithium iron manganese phosphate is higher, and a large amount of manganese can be dissolved out in the high-temperature process, so that the high-temperature cycle life is shortened. Current routine practice is to improve the material conductivity and cycling problems through doping, cladding, nanocrystallization, like lithium iron. However, it is difficult to significantly improve such problems by conventional modification methods such as doping and nanocrystallization.
Disclosure of Invention
The invention aims to improve the defects in the prior art and provides a doping preparation method of a lithium iron manganese phosphate composite anode material.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the invention relates to a preparation method of a lithium iron manganese phosphate composite anode material, which comprises the following steps:
(1) And co-precipitating soluble manganese sources, iron sources, phosphorus sources and first dopants with different contents to prepare the lattice doped ferromanganese phosphate precursor.
(2) And (3) dehydrating the precursor prepared in the step (1), and grinding the dehydrated precursor, the lithium source, the composite carbon source and the second doping agent to prepare mixed slurry.
(3) And (3) spray-drying, sintering and air-powder the mixed slurry to prepare the lithium iron manganese phosphate composite anode material.
According to the preparation method, in the step (1), the mole ratio of manganese element, iron element and doping element in the soluble manganese source, iron source and first doping agent is (0.6-0.9): (0.4-0.1): (0.006-0.009).
According to the preparation method in the step (1), the first doping agent is one or a mixture of more of magnesium sulfate, aluminum nitrate and sodium sulfate.
According to the preparation method, in the step (1), the coprecipitation reaction temperature is 90-120 ℃ and the reaction pH is 1-4.
According to the preparation method, in the step (2), the second dopant is one or a mixture of two of nano titanium oxide and nano aluminum oxide.
According to the preparation method, in the step (2), the particle size D50-N of the second dopant is 30-60nm.
According to the preparation method, in the step (2), the particle size D50 of the mixed slurry is 120-300nm.
According to the preparation method, in the step (2), the carbon source is a combination of two or more of anhydrous glucose, soluble starch, PEG, citric acid, phenolic resin and the like.
The preparation method is characterized in that the sintering temperature is 750-850 ℃.
According to the preparation method, in the step (3), the particle size D50 of the gas is 0.5-1.0um.
The technical scheme of the invention has the beneficial effects that:
according to the preparation method, the doping element quantity of the first doping agent is determined according to the manganese element content, the original lattice parameter is changed through element doping, a lithium ion diffusion channel is increased, and the ion conductivity is improved. The second doping agent has good high temperature resistance, the sanding granularity is determined according to the second doping agent granularity, the growth of primary particle size in the sintering process of the material can be inhibited while the good doping property is ensured, the preparation of small-particle-size material is ensured, and the lithium ion diffusion path is shortened. The ion conductivity and the electron conductivity of the material are further improved by combining the coating of the composite carbon source, and the multiplying power performance of the material is greatly improved.
The invention can be realized by slightly modifying the original lithium iron phosphate production line, has low equipment cost and is easy to industrialize.
Drawings
Fig. 1 is a discharge graph of the lithium iron manganese phosphate cathode material prepared in example 1.
Fig. 2 is a graph showing the rate performance of the lithium manganese iron lithium phosphate positive electrode material prepared in example 2.
Fig. 3 is an EIS comparison graph of the lithium manganese iron phosphate positive electrode material prepared in example 3 and the material prepared in comparative example.
Description of the embodiments
The present invention will be further described with reference to specific embodiments, and various substitutions and alterations are made according to the ordinary skill and familiar means of the art without departing from the above technical idea of the present invention, and are included in the scope of the present invention.
The invention relates to a preparation method of a lithium iron manganese phosphate composite anode material, which comprises the following steps:
(1) Mixing a soluble manganese source, an iron source, a phosphorus source and a first doping agent, wherein the atomic mole ratio of manganese element, iron element and doping element in the soluble manganese source, the iron source and the first doping agent is (0.6-0.9): (0.4-0.1): (0.006-0.009), preparing lattice doped ferromanganese phosphate precursor by coprecipitation, wherein the coprecipitation reaction temperature is 90-120 ℃ and the reaction pH is 1-4; wherein the first doping agent is one or a mixture of more of magnesium sulfate, aluminum nitrate and sodium sulfate;
(2) Dehydrating the prepared precursor in the step (1), adding a lithium source, a composite carbon source and a second doping agent, wherein the second doping agent is one or two of nano titanium oxide and nano aluminum oxide, the particle size D50-N of the second doping agent is 30-60nm, the carbon source is the combination of two or more of anhydrous glucose, soluble starch, PEG, citric acid, phenolic resin and the like, and then grinding to prepare mixed slurry, and the particle size D50 of the mixed slurry is 120-300nm;
(3) And (3) spray drying the mixed slurry, sintering, wherein the sintering temperature is 750-850 ℃, and finally carrying out jet milling, wherein the particle size D50 of particles after jet milling is 0.5-1.0um, so as to finally obtain the lithium manganese iron phosphate composite anode material.
The invention will be further illustrated by three examples
Examples
A preparation method of lithium iron manganese phosphate composite anode material comprises the following steps:
(1) 1014g of manganese sulfate monohydrate, 1112g of ferrous sulfate heptahydrate, 1150g of ammonium dihydrogen phosphate and 1.3g of aluminum nitrate are subjected to pH adjustment to 2.1 by phosphoric acid, and a reaction temperature is 100 ℃ to prepare a lattice doped precursor.
(2) 1000g of dehydrated precursor obtained in the step (1), 250g of lithium carbonate, 1.5g of nano titanium dioxide (D50-N=50nm), 60g of anhydrous glucose and 30g of PEG-1000 are sanded to prepare mixed slurry with the D50 of 200 nm.
(3) Spray drying the slurry obtained in the step (2), sintering for 780-10 h, and obtaining the final lithium iron manganese phosphate composite anode material from gas powder until D50 is 0.7um
And (3) detecting the product performance: material 1C discharge capacity 140mAh/g
Examples
A preparation method of lithium iron manganese phosphate composite anode material comprises the following steps:
(1) 1183g of manganese sulfate monohydrate, 834g of ferrous sulfate heptahydrate, 1150g of ammonium dihydrogen phosphate and 0.89g of magnesium nitrate are subjected to phosphoric acid adjustment to pH 1.5, and the reaction temperature is 100 ℃ to prepare the lattice doped precursor.
(2) 1000g of dehydrated precursor obtained in the step (1), 250g of lithium carbonate, 1.5g of nano titanium dioxide (D50-N=30nm), 60g of anhydrous glucose and 30g of PEG-1000 are sanded to prepare mixed slurry with the D50 of 150 nm.
(3) Spray drying the slurry obtained in the step (2), sintering for 780-10 h, and obtaining the final lithium iron manganese phosphate composite anode material from gas powder until D50 is 0.8um
And (3) detecting the product performance: the discharge capacity of the material 5C is 113.2mAh/g, and a positive electrode material multiplying power performance curve chart of the lithium iron manganese phosphate positive electrode material shown in figure 2 is obtained.
Examples
A preparation method of lithium iron manganese phosphate composite anode material comprises the following steps:
(1) 1014g of manganese sulfate monohydrate, 1112g of ferrous sulfate heptahydrate, 1150g of ammonium dihydrogen phosphate and 1.0g of aluminum nitrate are subjected to pH adjustment to 2.1 by phosphoric acid, and a reaction temperature is 100 ℃ to prepare a lattice doped precursor.
(2) 1000g of dehydrated precursor obtained in the step (1), 250g of lithium carbonate, 1.8g of nano aluminum oxide (D50-N=50 nm), 60g of anhydrous glucose and 30g of soluble starch are sanded to prepare a mixed slurry with the D50 of 200 nm.
(3) Spray drying the slurry obtained in the step (2), sintering for 800-10 h, and obtaining the final lithium iron manganese phosphate composite anode material from gas powder until D50 is 0.7um
And (3) detecting the product performance: the prepared material has low battery resistance and high lithium ion diffusion coefficient.
Comparative example
The preparation method of the lithium iron manganese phosphate anode material comprises the following steps:
(1) 1014g of manganese sulfate monohydrate, 1112g of ferrous sulfate heptahydrate and 1150g of ammonium dihydrogen phosphate are prepared, the pH is regulated to 2.1 by phosphoric acid, and the reaction temperature is 100 ℃.
(2) 1000g of dehydrated precursor obtained in the step (1), 250g of lithium carbonate, 60g of anhydrous glucose and 30g of PEG-1000 are sanded to prepare mixed slurry with the D50 of 200 nm.
(3) And (3) spray drying the slurry obtained in the step (2), sintering for 780-10 h, and obtaining the final lithium iron manganese phosphate composite anode material from gas powder until the D50 is 0.7 um.
The finished product obtained in example 3 was tested with the finished product obtained in comparative example to obtain an EIS comparison of the materials shown in fig. 3.
According to the preparation method, the doping element quantity of the first doping agent is determined according to the manganese element content, the original lattice parameter is changed through element doping, a lithium ion diffusion channel is increased, and the ion conductivity is improved. The second doping agent has good high temperature resistance, the sanding granularity is determined according to the second doping agent granularity, the growth of primary particle size in the sintering process of the material can be inhibited while the good doping property is ensured, the preparation of small-particle-size material is ensured, and the lithium ion diffusion path is shortened. The ion conductivity and the electron conductivity of the material are further improved by combining the coating of the composite carbon source, and the multiplying power performance of the material is greatly improved.
The invention can be realized by slightly modifying the original lithium iron phosphate production line, has low equipment cost and is easy to industrialize.
Claims (10)
1. The doping preparation method of the lithium iron manganese phosphate composite anode material is characterized by comprising the following steps of:
(1) Mixing a soluble manganese source, an iron source, a phosphorus source and a first doping agent, and coprecipitating to prepare a lattice doped ferromanganese phosphate precursor;
(2) Dehydrating the precursor prepared in the step (1), adding a lithium source, a composite carbon source and a second doping agent, and sanding to prepare mixed slurry;
(3) And (3) spray-drying, sintering and air-powder the mixed slurry to prepare the lithium iron manganese phosphate composite anode material.
2. The method for preparing the lithium iron manganese phosphate composite positive electrode material according to claim 1, which is characterized in that: in the step (1), the atomic mole ratio of the manganese element, the iron element and the doping element in the soluble manganese source, the iron source and the first doping agent is (0.6-0.9): (0.4-0.1): (0.006-0.009).
3. The method for preparing the lithium iron manganese phosphate composite positive electrode material according to claim 1, which is characterized in that: in the step (1), the first dopant is one or a mixture of more of magnesium sulfate, aluminum nitrate and sodium sulfate.
4. The method for preparing the lithium iron manganese phosphate composite positive electrode material according to claim 1, which is characterized in that: in the step (1), the coprecipitation reaction temperature is 90-120 ℃ and the reaction pH is 1-4.
5. The method for preparing the lithium iron manganese phosphate composite positive electrode material according to claim 1, which is characterized in that: in the step (2), the second dopant is one or a mixture of two of nano titanium oxide and nano aluminum oxide.
6. The method for preparing the lithium iron manganese phosphate composite positive electrode material according to claim 1, which is characterized in that: in the step (2), the second dopant particle size D50-N is 30-60nm.
7. The method for preparing the lithium iron manganese phosphate composite positive electrode material according to claim 1, which is characterized in that: in the step (2), the particle size D50 of the mixed slurry is 120-300nm.
8. The method for preparing a lithium iron manganese phosphate composite anode material according to claim 1, wherein in the step (2), the carbon source is a combination of two or more of anhydrous glucose, soluble starch, PEG, citric acid, phenolic resin and the like.
9. The method for preparing a lithium iron manganese phosphate composite positive electrode material according to claim 1, wherein in the step (3), the sintering temperature is 750-850 ℃.
10. The method for preparing lithium iron manganese phosphate composite anode material according to claim 1, wherein in the step (3), the particle size D50 of the gas-powder particles is 0.5-1.0um.
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