WO2023124574A1 - 钛、锆共掺杂碳包覆磷酸铁锂材料及其制备方法与应用 - Google Patents
钛、锆共掺杂碳包覆磷酸铁锂材料及其制备方法与应用 Download PDFInfo
- Publication number
- WO2023124574A1 WO2023124574A1 PCT/CN2022/131291 CN2022131291W WO2023124574A1 WO 2023124574 A1 WO2023124574 A1 WO 2023124574A1 CN 2022131291 W CN2022131291 W CN 2022131291W WO 2023124574 A1 WO2023124574 A1 WO 2023124574A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- zirconium
- titanium
- iron phosphate
- carbon
- lithium iron
- Prior art date
Links
- 239000000463 material Substances 0.000 title claims abstract description 95
- 239000010936 titanium Substances 0.000 title claims abstract description 84
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 80
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 70
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 70
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 62
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 62
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002002 slurry Substances 0.000 claims abstract description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007921 spray Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 14
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 14
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 14
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000000498 ball milling Methods 0.000 claims abstract description 8
- 238000003801 milling Methods 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 8
- 238000005469 granulation Methods 0.000 claims abstract description 4
- 230000003179 granulation Effects 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000007774 positive electrode material Substances 0.000 claims abstract description 4
- 238000001694 spray drying Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000007791 liquid phase Substances 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 238000000889 atomisation Methods 0.000 claims description 12
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000004576 sand Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 7
- 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 7
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 7
- 239000008103 glucose Substances 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 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 6
- 229930006000 Sucrose Natural products 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 5
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 5
- 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
- 239000012467 final product Substances 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 238000005056 compaction Methods 0.000 abstract description 10
- 150000002500 ions Chemical class 0.000 abstract description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 20
- -1 titanium ions Chemical class 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000010406 cathode material Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000001354 calcination Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940098458 powder spray Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 238000001228 spectrum Methods 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
-
- 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
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- 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
Definitions
- the invention belongs to the technical field of new energy materials and their preparation, and in particular relates to a carbon-coated lithium iron phosphate material co-doped with titanium and zirconium and a preparation method thereof.
- the material can be used as a high-performance cathode material in lithium-ion power batteries.
- LiFePO 4 lithium iron phosphate
- LiFePO 4 lithium iron phosphate
- Lithium-ion batteries using this material as the cathode material have been widely used in portable fields including electronic devices, automobiles, ships and energy storage.
- the demand for lithium-ion power batteries has continued to increase.
- the installed capacity of power batteries with LiFePO 4 as the cathode material has gradually increased, which has led to the market for LiFePO 4 cathode materials. Showing a momentum of rapid growth.
- doping titanium ions on the Fe site of the material can effectively enhance its lithium ion and electron transport capabilities [J.Power Sources, 189 (2009) 440; J.Electrochem .Soc., 160(2013) A3148; CN108598383A; CN111498825A].
- the effect of titanium ion doping on the compaction density of LiFePO 4 materials is not very significant.
- zirconium ions can be doped into Li sites of LiFePO 4 materials [J.Alloys Compd., 739(2018)529; J.Electrochem.Soc., 166(2019)A410;
- the particle size and shape of the LiFePO 4 material can be adjusted, and the coating effect of carbon can be optimized to make the interaction between the carbon material and LiFePO 4 closer. Therefore, zirconium ion doping can achieve the purpose of improving the compaction density of LiFePO 4 materials.
- the present invention aims at the defects and improvement needs of the above-mentioned prior art, and proposes a method by doping metal titanium ions and zirconium ions respectively into the Fe site and Li site of LiFePO 4 material, through the synergistic doping energy of titanium ions and zirconium ions Effectively improve the electrochemical performance and compaction density of the LiFePO 4 material to obtain a titanium and zirconium co-doped carbon-coated lithium iron phosphate material with high energy density and high power density, its preparation method and its application.
- the above-mentioned titanium and zirconium co-doped carbon-coated lithium iron phosphate material the chemical expression of the material is Li 1-y Zry Fe 1-x Ti x PO 4 /C, wherein titanium is doped to the Fe site, zirconium Doped to the Li site, and 0.001 ⁇ x ⁇ 0.05, 0.001 ⁇ y ⁇ 0.02.
- the carbon content of the material is 0.5-5.0wt%
- the preparation method of the titanium and zirconium co-doped carbon-coated lithium iron phosphate material is to mix iron phosphate, lithium carbonate, carbon source, titanium source and zirconium source in a liquid medium, and the mixture is ball milled and sanded After grinding to a certain slurry particle size, spray drying technology is used for granulation. Finally, the dried spray material is sintered in an atmosphere furnace and then pulverized to obtain titanium and zirconium co-doped carbon-coated lithium iron phosphate material.
- the preparation method of the titanium and zirconium co-doped carbon-coated lithium iron phosphate material comprises the following steps:
- the atomization frequency is 20-80 Hz
- the temperature of the air inlet of the heating air is 100-300° C.
- the temperature of the air outlet is 50-200° C.
- step (3) Pre-sinter the dried spray material obtained in step (3) in an atmosphere furnace with protective gas at 300-500°C for 2-5h, and then sinter at 500-900°C for 5-15h to prepare Titanium, zirconium co-doped carbon-coated lithium iron phosphate material.
- the titanium source is one or more of titanium dioxide, titanyl sulfate, titanium tetrachloride and tetrabutyl titanate .
- the zirconium source is one or more of zirconium oxide, zirconium hydroxide, zirconium nitrate and zirconium phosphate.
- the liquid medium is one or more of deionized water and absolute ethanol.
- the carbon source is one or more of glucose, sucrose, citric acid and polyethylene glycol, and the added amount of the carbon source should ensure that the carbon content in the final product is 0.5-5.0 wt%.
- the atomization frequency is 60Hz, the air inlet temperature is 200°C, and the air outlet temperature is 100°C; the pre-sintering temperature is 400°C, and the time is 3h; the sintering temperature is 800°C, and the time is 10h.
- the material is used as a positive electrode material in a lithium-ion battery, and the material is as described in claim 1 and any one of claims 1-9
- Preparation method The prepared titanium and zirconium co-doped carbon-coated lithium iron phosphate material.
- the titanium and zirconium co-doped carbon-coated lithium iron phosphate material and the preparation method thereof of the present invention have cheap and wide range of raw materials, simple process, can be industrialized batch production, can add titanium source and zirconium source to the reaction system at the same time, realize Titanium ions dope the Fe site of LiFePO 4 material, and zirconium ions dope the Li site. Titanium ion doping can improve the intrinsic conductivity of LiFePO 4 material, and zirconium ion doping can adjust the shape size and optimize the carbon density. Coating effect to increase compaction density;
- the co-doping of titanium ions and zirconium ions can produce a synergistic effect. On the one hand, it can enhance the lithium ion and electron transport capabilities of LiFePO 4 materials, and on the other hand, it can effectively improve the compaction density of the material.
- the resulting titanium and zirconium co-doped carbon-coated The discharge capacity of lithium iron phosphate material at 0.1C is greater than 158.0mAh g –1 , the first coulombic efficiency is higher than 96.0%, the discharge capacity of 1C is greater than 145.0mAh g –1 , and the compacted density reaches 2.50g mL –1 , which is very suitable as High energy and high power density lithium ion power battery cathode material.
- Figure 1 is the XRD spectrum of carbon-coated lithium iron phosphate and zirconium and titanium co-doped carbon-coated lithium iron phosphate;
- Fig. 2 is the SEM picture of zirconium, titanium co-doped carbon-coated lithium iron phosphate of the present invention
- Figure 3 is the first charge and discharge diagram of carbon-coated lithium iron phosphate and zirconium and titanium co-doped carbon-coated lithium iron phosphate.
- the titanium and zirconium co-doped carbon-coated lithium iron phosphate material of the present invention is prepared by doping metal titanium ions and zirconium ions respectively into the Fe site and Li site of LiFePO4 material through a specific process.
- the specific chemical expression is Li 1-y Zry Fe 1-x Ti x PO 4 /C, where titanium is doped to the Fe site, zirconium is doped to the Li site, and 0.001 ⁇ x ⁇ 0.05, 0.001 ⁇ y ⁇ 0.02, the carbon in the product The content is 0.5-5.0wt%.
- the preparation method of the titanium and zirconium co-doped carbon-coated lithium iron phosphate material of the present invention is to mix iron phosphate, lithium carbonate, carbon source, titanium source and zirconium source in a liquid medium, and the mixture is ball milled and sand milled After reaching a certain slurry particle size, spray drying technology is used for granulation, and finally the dried spray material is sintered in an atmosphere furnace and then pulverized to finally obtain titanium and zirconium co-doped carbon-coated lithium iron phosphate material; the specific steps are as follows :
- the product is pulverized to obtain a black powder product.
- the titanium source is one or more of titanium dioxide, titanyl sulfate, titanium tetrachloride and tetrabutyl titanate;
- the zirconium source is one or more of zirconium oxide, zirconium hydroxide, zirconium nitrate and zirconium phosphate;
- the liquid medium is one or more of deionized water and absolute ethanol.
- the carbon source is one or more of glucose, sucrose, citric acid and polyethylene glycol, and the amount of carbon source added should make the carbon content in the final product controlled at 0.5-5.0wt%.
- the protective gas is argon or nitrogen.
- the titanium source is tetrabutyl titanate
- the zirconium source is zirconium hydroxide
- the liquid phase medium is deionized water.
- the carbon source in step (2) is glucose and polyethylene glycol
- the carbon content in the final product is 1.5 wt%
- the particle size of the slurry is 0.4 ⁇ m.
- the atomization frequency is 60 Hz
- the temperature of the heated air inlet is 200°C
- the temperature of the air outlet is 100°C.
- the shielding gas in step (4) is Ar
- the pre-sintering temperature and time are 350°C and 3h, respectively
- the sintering temperature and time are 800°C and 10h, respectively.
- the tuyere temperature is 100°C; finally, the dry spray material is pre-sintered at 350°C for 3 hours in an atmosphere furnace filled with argon, and then sintered at 800°C for 10 hours; after the calcination is completed, it can be pulverized to obtain a black powder of titanium and zirconium co-doped Carbon-coated lithium iron phosphate material, the carbon content of the material is 0.5wt%, the discharge capacity at 0.1C is 158.3mAh g –1 , the first Coulombic efficiency is 98.4%, the discharge capacity at 1C is 145.5mAh g –1 , and the compacted density is 2.52 g mL –1 .
- the temperature at the air outlet is 120°C; finally, the dry spray material is pre-sintered at 430°C for 3 hours in an atmosphere furnace filled with nitrogen, and then sintered at 800°C for 9 hours; after the calcination is completed, it can be pulverized to obtain a black powder of titanium and zirconium co-doped Carbon-coated lithium iron phosphate material, the carbon content of the material is 1.5wt%, the discharge capacity at 0.1C is 159.2mAh g –1 , the first Coulombic efficiency is 96.5%, the discharge capacity at 1C is 139.0mAh g –1 , and the compacted density is 2.39 g mL –1 .
- the carbon content of this material is 5.0wt%, the discharge capacity at 0.1C is 157.0mAh g –1 , and the first Coulombic efficiency is 96.2%.
- the discharge capacity of 1C is 140.5mAh g –1 , and the compacted density is 2.35g mL –1 .
- the present invention also adopts undoped carbon-coated lithium iron phosphate material, that is, no titanium source and zirconium source are added in the preparation process as a comparative example.
- undoped carbon-coated lithium iron phosphate material that is, no titanium source and zirconium source are added in the preparation process as a comparative example.
- the present invention can effectively improve the electrochemical performance and compaction density of the lithium iron phosphate material due to the addition of titanium ions and zirconium ions to the Fe site and the Li site of the carbon-coated lithium iron phosphate material, and is very suitable for use as a high-energy And high power density lithium ion power battery cathode material. It is easy for those skilled in the art to understand that the above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention, All should be included within the protection scope of the present invention.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明涉及一种钛、锆共掺杂碳包覆磷酸铁锂材料及其制备方法及应用,该材料的化学表达式为Li 1-yZr yFe 1-xTi xPO 4/C,其中钛掺杂到Fe位,锆掺杂到Li位,且0.001≤x≤0.05,0.001≤y≤0.02;其制备方法是将磷酸铁、碳酸锂、碳源、钛源和锆源在液相介质中进行混合,混合料经过球磨和砂磨至一定浆料粒径之后采用喷雾干燥技术进行造粒,最后将干燥的喷雾料在气氛炉中烧结制得。该材料作为正极材料应用于锂离子电池。本发明通过向碳包覆的磷酸铁锂中掺入钛和锆元素,有效地增强了磷酸铁锂的离子和电子传输能力,提高了该材料的压实密度,非常适用于作为高能量和高功率密度锂离子动力电池正极材料。
Description
本申请要求于2021年12月29日提交中国专利局、申请号为202111629862.7、发明名称为“钛、锆共掺杂碳包覆磷酸铁锂材料及其制备方法与应用”的中国专利申请的优先权,其全部内容通过引用结合在本申请中。
本发明属于新能源材料及其制备技术领域,具体涉及一种钛、锆共掺杂碳包覆磷酸铁锂材料及其制备方法,该材料可作为高性能正极材料在锂离子动力电池中应用。
1997年,J.Goodenough等人报道了磷酸铁锂(LiFePO
4)可用作锂离子电池正极材料,该项研究在学术界引起了极大的轰动,同时开启了LiFePO
4的产业化发展历程。由于其具有循环寿命长、安全性高和低成本等优势,LiFePO
4已经迅速发展成为一种十分重要的锂离子电池正极材料,以该材料为正极材料的锂离子电池已经被广泛应用到包括便携式电子设备、汽车、船舶和储能在内的领域。近年来,随着我国新能源汽车产业的快速发展,锂离子动力电池的需求量不断增加,其中以LiFePO
4为正极材料的动力电池的装机量占比逐步增加,由此导致LiFePO
4正极材料市场呈现出快速增长的势头。
然而,和其它正极材料尤其是三元正极材料相比,LiFePO
4的比容量和压实密度仍然偏低,同时较低的离子和电子导电率致使该材料的大电流充放电能力较差。以上这些缺陷严重限制了LiFePO
4能量密度和功率密度的提升。为了提高LiFePO
4的电化学性能和压实密度,研究者多采用形貌尺寸控制、碳包覆和离子掺杂等技术手段来克服该材料固有的缺陷。金属离子掺杂是提高LiFePO
4电化学性能的重要方法,如在该材料Fe位掺杂钛离子可以有效增强其锂离子和电子传输能力[J.Power Sources,189(2009)440;J.Electrochem.Soc.,160(2013)A3148;CN108598383A;CN111498825A]。然而,钛离子掺杂对LiFePO
4材料压实密度的提升效果不是太显著。近年来,相关研究表明锆离子可以掺入LiFePO
4材料的Li位[J.Alloys Compd.,739(2018)529;J.Electrochem.Soc.,166(2019)A410;CN108682833B],该掺杂不仅能够调节LiFePO
4材料 的粒径和形貌,而且可以优化碳的包覆效果、使碳材料和LiFePO
4之间的作用更加紧密。因此,锆离子掺杂可以实现提升LiFePO
4材料压实密度的目的。
综上所述,若能实现钛离子和锆离子对LiFePO
4材料进行协同掺杂,则有可能克服该材料的固有缺陷,有效提升其本征电导率和压实密度,实现其能量密度和功率密度的显著提升。
因此,研发出一种具有钛、锆共掺杂碳包覆磷酸铁锂材料是需要解决的技术问题。
发明内容
本发明针对上述现有技术存在的缺陷和改进需求,而提出一种通过向LiFePO
4材料的Fe位和Li位分别掺入金属钛离子和锆离子,通过钛离子和锆离子的协同掺杂能有效地提高LiFePO
4材料的电化学性能和压实密度而得到具有高能量密度和高功率密度的钛、锆共掺杂碳包覆磷酸铁锂材料及其制备方法及其应用。
本发明是通过以下技术方案实现的:
上述的钛、锆共掺杂碳包覆磷酸铁锂材料,所述材料的化学表达式为Li
1-yZr
yFe
1-xTi
xPO
4/C,其中钛掺杂到Fe位,锆掺杂到Li位,且0.001≤x≤0.05,0.001≤y≤0.02。所述材料的碳含量为0.5-5.0wt%
所述的钛、锆共掺杂碳包覆磷酸铁锂材料的制备方法,是将磷酸铁、碳酸锂、碳源、钛源和锆源在液相介质中进行混合,混合料经过球磨和砂磨至一定浆料粒径之后采用喷雾干燥技术进行造粒,最后将干燥的喷雾料在气氛炉中烧结后进行粉碎,最终得到钛、锆共掺杂碳包覆磷酸铁锂材料。
所述的钛、锆共掺杂碳包覆磷酸铁锂材料的制备方法,其包括以下步骤:
(1)将磷酸铁、碳酸锂、钛源和锆源按元素摩尔比Li:Zr:Fe:Ti:P=1-y:y:1-x:x:1进行称量并在液相介质中进行混合,其中0.001≤x≤0.05,0.001≤y≤0.02;
(2)向所述步骤(1)得到的混合料中加入碳源之后进行球磨和砂磨,使浆料粒径控制在0.1-0.8μm;
(3)将所述步骤(2)得到的浆料进行喷雾干燥,雾化频率为20-80Hz,加热空气进风口温度为100-300℃,出风口温度为50-200℃;
(4)将所述步骤(3)所得干燥的喷雾料在通有保护气的气氛炉中于300-500℃预烧结2-5h,随后在500-900℃烧结5-15h,即可制备出钛、锆共掺杂碳包覆磷酸铁锂材料。
所述的钛、锆共掺杂碳包覆磷酸铁锂材料的制备方法,其中:所述钛源为二氧化钛、硫酸氧钛、四氯化钛和钛酸四丁脂中的一种或几种。所述锆源为氧化锆、氢氧化锆、硝酸锆和磷酸锆中的一种或几种。所述液相介质为去离子水和无水乙醇中的一种或几种。所述碳源为葡萄糖、蔗糖、柠檬酸和聚乙二醇中的一种或几种,碳源的加入量应保证最终产物中的碳含量在0.5-5.0wt%。所述的雾化频率为60Hz,进风口温度为200℃,出风口温度为100℃;所述预烧结温度为400℃,时间为3h;所述烧结温度为800℃,时间为10h。
上述的钛、锆共掺杂碳包覆磷酸铁锂材料的应用,所述材料作为正极材料应用于锂离子电池中,所述材料为如权利要求1及权利要求1-9任意一项所述制备方法制备得到的钛、锆共掺杂碳包覆磷酸铁锂材料。
本发明的钛、锆共掺杂碳包覆磷酸铁锂材料及其制备方法,所用原料廉价而广泛、工艺简单,可进行工业化批量生产,可向反应体系中同时加入钛源和锆源,实现钛离子对LiFePO
4材料Fe位进行掺杂、锆离子对Li位进行掺杂,钛离子掺杂能够提升LiFePO
4材料的本征电导率,锆离子掺杂则能够通过调节形貌尺寸和优化碳包覆效果来提高压实密度;
钛离子和锆离子共掺杂能够产生协同效应,一方面增强LiFePO
4材料的锂离子和电子传输能力,另一方面有效提升该材料的压实密度,所得的钛、锆共掺杂碳包覆磷酸铁锂材料在0.1C的放电容量大于158.0mAh g
–1,首次库伦效率高于96.0%,1C的放电容量大于145.0mAh g
–1,压实密度达到2.50g mL
–1,非常适用于作为高能量和高功率密度锂离子动力电池正极材料。
图1为碳包覆磷酸铁锂与锆、钛共掺杂碳包覆磷酸铁锂的XRD谱线图;
图2为本发明的锆、钛共掺杂碳包覆磷酸铁锂的SEM图;
图3为碳包覆磷酸铁锂与锆、钛共掺杂碳包覆磷酸铁锂的首次充放电图。
本发明的钛、锆共掺杂碳包覆磷酸铁锂材料,是通过向LiFePO
4材料的Fe位和Li位分别掺入金属钛离子和锆离子通过特定工艺制备而成,具体的化学表达式为Li
1-yZr
yFe
1-xTi
xPO
4/C,其中钛掺杂到Fe位,锆掺杂到Li位,且0.001≤x≤0.05,0.001≤y≤0.02,产物中的碳含量为0.5-5.0wt%。
本发明的钛、锆共掺杂碳包覆磷酸铁锂材料的制备方法是将磷酸铁、碳酸锂、碳源、钛源和锆源在液相介质中进行混合,混合料经过球磨和砂磨至一定浆料粒径之后采用喷雾干燥技术进行造粒,最后将干燥的喷雾料在气氛炉中烧结后进行粉碎,最终得到钛、锆共掺杂碳包覆磷酸铁锂材料;其具体步骤如下:
(1)将磷酸铁、碳酸锂、钛源和锆源按元素摩尔比Li:Zr:Fe:Ti:P=1-y:y:1-x:x:1进行称量并在液相介质中进行混合,其中0.001≤x≤0.05,0.001≤y≤0.02;
(2)向所述步骤(1)得到的混合料中加入碳源之后进行球磨和砂磨,使浆料粒径控制在0.1-0.8μm;
(3)将所述步骤(2)得到的浆料进行喷雾干燥,得到黄色的粉末喷雾料;雾化频率为20-80Hz,加热空气进风口温度为100-300℃,出风口温度为50-200℃;
(4)将所述步骤(3)所得干燥的喷雾料在通有保护气的气氛炉中于300-500℃预烧结2-5h,随后在500-900℃烧结5-15h,即可制备出钛、锆共掺杂碳包覆磷酸铁锂材料;
(5)烧结过程结束后将产物进行粉碎,得到黑色粉末产物。
上述步骤(1)中:钛源为二氧化钛、硫酸氧钛、四氯化钛和钛酸四丁脂中的一种或几种;
锆源为氧化锆、氢氧化锆、硝酸锆和磷酸锆中的一种或几种;
液相介质为去离子水和无水乙醇中的一种或几种。
上述步骤(2)中:碳源为葡萄糖、蔗糖、柠檬酸和聚乙二醇中的一种或几种,碳源的加入量应使最终产物中的碳含量控制在0.5-5.0wt%。
上述步骤(4)中:保护气为氩气或氮气。
优先地,步骤(1)中钛源为钛酸四丁脂,锆源为氢氧化锆,液相介质为去离子水。
优先地,步骤(2)中碳源为葡萄糖和聚乙二醇,最终产物中的碳含量为1.5wt%,浆料的粒径为0.4μm。
优先地,步骤(3)中雾化频率为60Hz,加热空气进风口温度为200℃,出风口温度为100℃。
优先地,步骤(4)中保护气为Ar,预烧结温度和时间分别为350℃和3h,烧结温度和时间分别为800℃和10h。
下面根据具体的实施例进一步说明本发明:
实施例1
将磷酸铁、碳酸锂、钛酸四丁酯和氢氧化锆按元素摩尔比Li:Zr:Fe:Ti:P=0.985:0.015:0.99:0.01:1进行称量并在去离子水中进行混合;随后向混合料中加入葡萄糖之后对其进行球磨和砂磨处理,使浆料粒径控制在0.4μm;将浆料进行喷雾干燥,雾化频率为50Hz,加热空气进风口温度为200℃,出风口温度为100℃;最后将干燥喷雾料在充满氩气的气氛炉中于350℃预烧结3h后继续在800℃烧结10h;煅烧完成后进行粉碎即可得黑色粉末的钛、锆共掺杂碳包覆磷酸铁锂材料,该材料的碳含量为0.5wt%,0.1C的放电容量为158.3mAh g
–1,首次库伦效率98.4%,1C的放电容量145.5mAh g
–1,压实密度2.52g mL
–1。
实施例2
将磷酸铁、碳酸锂、二氧化钛和氧化锆按元素摩尔比Li:Zr:Fe:Ti:P=0.98:0.02:0.96:0.04:1进行称量并在去离子水中进行混合;随后向混合料中加入蔗糖之后对其进行球磨和砂磨处理,使浆料粒径控制在0.2μm;将浆料进行喷雾干燥,雾化频率为60Hz,加热空气进风口温度为150℃,出风口温度为70℃;最后将干燥喷雾料在充满氮气的气氛炉中于300℃预烧结5h后继续在750℃烧结12h;煅烧完成后进行粉碎即可得黑色粉末的钛、锆共掺杂碳包覆磷酸铁锂材料,该材料的碳含量为1.1wt%,0.1C的放电容量为159.1mAh g
–1,首次库伦效率97.3%,1C的放电容量148.0mAh g
–1,压实密度2.38g mL
–1。
实施例3
将磷酸铁、碳酸锂、硫酸氧钛和硝酸锆按元素摩尔比Li:Zr:Fe:Ti:P=0.985:0.015:0.99:0.02:1进行称量并在无水乙醇中进行混合;随后向混合料中加 入柠檬酸和聚乙二醇之后对其进行球磨和砂磨处理,使浆料粒径控制在0.1μm;将浆料进行喷雾干燥,雾化频率为80Hz,加热空气进风口温度为100℃,出风口温度为50℃;最后将干燥喷雾料在充满氩气的气氛炉中于380℃预烧结4h后继续在600℃烧结12h;煅烧完成后进行粉碎即可得黑色粉末的钛、锆共掺杂碳包覆磷酸铁锂材料,该材料的碳含量为2.0wt%,0.1C的放电容量为156.5mAh g
–1,首次库伦效率95.3%,1C的放电容量140.2mAh g
–1,压实密度2.25g mL
–1。
实施例4
将磷酸铁、碳酸锂、四氯化钛和钛酸四丁酯、硝酸锆和磷酸锆按元素摩尔比Li:Zr:Fe:Ti:P=0.995:0.005:0.95:0.05:1进行称量并在去离子水中进行混合;随后向混合料中加入葡萄糖之后对其进行球磨和砂磨处理,使浆料粒径控制在0.5μm;将浆料进行喷雾干燥,雾化频率为50Hz,加热空气进风口温度为180℃,出风口温度为90℃;最后将干燥喷雾料在充满氩气的气氛炉中于320℃预烧结4h后继续在500℃烧结12h;煅烧完成后进行粉碎即可得黑色粉末的钛、锆共掺杂碳包覆磷酸铁锂材料,该材料的碳含量为3.5wt%,0.1C的放电容量为153.3mAh g
–1,首次库伦效率94.1%,1C的放电容量135.3mAh g
–1,压实密度2.15g mL
–1。
实施例5
将磷酸铁、碳酸锂、四氯化钛和磷酸锆按元素摩尔比Li:Zr:Fe:Ti:P=0.999:0.001:0.98:0.02:1进行称量并在去离子水中进行混合;随后向混合料中加入蔗糖和柠檬酸之后对其进行球磨和砂磨处理,使浆料粒径控制在0.6μm;将浆料进行喷雾干燥,雾化频率为40Hz,加热空气进风口温度为220℃,出风口温度为120℃;最后将干燥喷雾料在充满氮气的气氛炉中于430℃预烧结3h后继续在800℃烧结9h;煅烧完成后进行粉碎即可得黑色粉末的钛、锆共掺杂碳包覆磷酸铁锂材料,该材料的碳含量为1.5wt%,0.1C的放电容量为159.2mAh g
–1,首次库伦效率96.5%,1C的放电容量139.0mAh g
–1,压实密度2.39g mL
–1。
实施例6
将磷酸铁、碳酸锂、二氧化钛、硫酸氧钛、四氯化钛、氢氧化锆按元素摩尔比Li:Zr:Fe:Ti:P=0.98:0.02:0.999:0.001:1进行称量并在去离子水中进行混合;随后向混合料中加入葡萄糖和柠檬酸之后对其进行球磨和砂磨处理,使浆料粒径控制在0.8μm;将浆料进行喷雾干燥,雾化频率为20Hz,加热空气进风口温 度为300℃,出风口温度为200℃;最后将干燥喷雾料在充满氩气的气氛炉中于500℃预烧结2h后继续在900℃烧结5h;煅烧完成后进行粉碎即可得黑色粉末的钛、锆共掺杂碳包覆磷酸铁锂材料,该材料的碳含量为1.0wt%,0.1C的放电容量为155.5mAh g
–1,首次库伦效率94.4%,1C的放电容量136.2mAh g
–1,压实密度2.55g mL
–1。
实施例7
将磷酸铁、碳酸锂、钛酸四丁脂、氧化锆、氢氧化锆和硝酸锆按元素摩尔比Li:Zr:Fe:Ti:P=0.99:0.01:0.97:0.03:1进行称量并在无水乙醇中进行混合;随后向混合料中加入蔗糖、柠檬酸和聚乙二醇之后对其进行球磨和砂磨处理,使浆料粒径控制在0.7μm;将浆料进行喷雾干燥,雾化频率为30Hz,加热空气进风口温度为280℃,出风口温度为150℃;最后将干燥喷雾料在充满氮气的气氛炉中于400℃预烧结2h后继续在850℃烧结7h;煅烧完成后进行粉碎即可得黑色粉末的钛、锆共掺杂碳包覆磷酸铁锂材料,该材料的碳含量为5.0wt%,0.1C的放电容量为157.0mAh g
–1,首次库伦效率96.2%,1C的放电容量140.5mAh g
–1,压实密度2.35g mL
–1。
本发明还采用未掺杂的碳包覆磷酸铁锂材料,即在制备过程中未加入钛源和锆源作为对比例,参考图1、图2、图3,通过这些图不难发现,钛、锆共掺杂能有效地提高碳包覆磷酸铁锂的电化学性能,可得到一种具有高能量和高功率密度的锂离子电池正极材料。
本发明由于向碳包覆的磷酸铁锂材料中Fe位和Li位分别掺入钛离子和锆离子,能有效地提高磷酸铁锂材料的电化学性能和压实密度,非常适用于作为高能量和高功率密度锂离子动力电池正极材料。本领域的技术人员容易理解,以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (10)
- 一种钛、锆共掺杂碳包覆磷酸铁锂材料,其特征在于:所述材料的化学表达式为Li 1-yZr yFe 1-xTi xPO 4/C,其中钛掺杂到Fe位,锆掺杂到Li位,且0.001≤x≤0.05,0.001≤y≤0.02。
- 如权利要求1所述钛、锆共掺杂碳包覆磷酸铁锂材料,其特征在于:所述材料的碳含量为0.5-5.0wt%
- 如权利要求1所述的钛、锆共掺杂碳包覆磷酸铁锂材料的制备方法,是将磷酸铁、碳酸锂、碳源、钛源和锆源在液相介质中进行混合,混合料经过球磨和砂磨至一定浆料粒径之后采用喷雾干燥技术进行造粒,最后将干燥的喷雾料在气氛炉中烧结后进行粉碎,最终得到钛、锆共掺杂碳包覆磷酸铁锂材料。
- 如权利要求3所述的钛、锆共掺杂碳包覆磷酸铁锂材料的制备方法,其包括以下步骤:(1)将磷酸铁、碳酸锂、钛源和锆源按元素摩尔比Li:Zr:Fe:Ti:P=1-y:y:1-x:x:1进行称量并在液相介质中进行混合,其中0.001≤x≤0.05,0.001≤y≤0.02;(2)向所述步骤(1)得到的混合料中加入碳源之后进行球磨和砂磨,使浆料粒径控制在0.1-0.8μm;(3)将所述步骤(2)得到的浆料进行喷雾干燥,雾化频率为20-80Hz,加热空气进风口温度为100-300℃,出风口温度为50-200℃;(4)将所述步骤(3)所得干燥的喷雾料在通有保护气的气氛炉中于300-500℃预烧结2-5h,随后在500-900℃烧结5-15h,即可制备出钛、锆共掺杂碳包覆磷酸铁锂材料。
- 如权利要求4所述的钛、锆共掺杂碳包覆磷酸铁锂材料的制备方法,其特征在于:所述钛源为二氧化钛、硫酸氧钛、四氯化钛和钛酸四丁脂中的一种或几种。
- 如权利要求4所述的钛、锆共掺杂碳包覆磷酸铁锂材料的制备方法,其特征在于:所述锆源为氧化锆、氢氧化锆、硝酸锆和磷酸锆中的一种或几种。
- 如权利要求4所述的钛、锆共掺杂碳包覆磷酸铁锂材料的制备方法,其特征在于:所述液相介质为去离子水和无水乙醇中的一种或几种。
- 如权利要求4所述的钛、锆共掺杂碳包覆磷酸铁锂材料的制备方法,其特征在于:所述碳源为葡萄糖、蔗糖、柠檬酸和聚乙二醇中的一种或几种,碳源的加入量应保证最终产物中的碳含量在0.5-5.0wt%。
- 如权利要求4所述的钛、锆共掺杂碳包覆磷酸铁锂材料的制备方法,其特征在于:所述的雾化频率为60Hz,进风口温度为200℃,出风口温度为100℃;所述预烧结温度为400℃,时间为3h;所述烧结温度为800℃,时间为10h。
- 一种钛、锆共掺杂碳包覆磷酸铁锂材料的应用,其特征在于:所述材料作为正极材料应用于锂离子电池中,所述材料为如权利要求1及权利要求1-9任意一项所述制备方法制备得到的钛、锆共掺杂碳包覆磷酸铁锂材料。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020237020861A KR20230109731A (ko) | 2021-12-29 | 2022-11-11 | 티타늄-지르코늄 공동 도핑된 탄소-코팅된 리튬인산철 물질 및 이의 제조 방법 및 용도 |
JP2023529058A JP2024510061A (ja) | 2021-12-29 | 2022-11-11 | チタンとジルコニウムを共ドープした炭素被覆リン酸鉄リチウム材料及びその製造方法と応用 |
US18/037,811 US20240166517A1 (en) | 2021-12-29 | 2022-11-11 | Titanium-zirconium co-doped carbon-coated lithium iron phosphate material and production method and use thereof |
EP22891174.9A EP4230580A1 (en) | 2021-12-29 | 2022-11-11 | Titanium and zirconium co-doped, carbon-coated lithium iron phosphate material, preparation method therefor and use thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111629862.7 | 2021-12-29 | ||
CN202111629862.7A CN114314548B (zh) | 2021-12-29 | 2021-12-29 | 钛、锆共掺杂碳包覆磷酸铁锂材料及其制备方法与应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2023124574A1 true WO2023124574A1 (zh) | 2023-07-06 |
Family
ID=81014749
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2022/131291 WO2023124574A1 (zh) | 2021-12-29 | 2022-11-11 | 钛、锆共掺杂碳包覆磷酸铁锂材料及其制备方法与应用 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20240166517A1 (zh) |
EP (1) | EP4230580A1 (zh) |
JP (1) | JP2024510061A (zh) |
KR (1) | KR20230109731A (zh) |
CN (1) | CN114314548B (zh) |
WO (1) | WO2023124574A1 (zh) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114314548B (zh) * | 2021-12-29 | 2022-11-25 | 湖北万润新能源科技股份有限公司 | 钛、锆共掺杂碳包覆磷酸铁锂材料及其制备方法与应用 |
CN115528296B (zh) * | 2022-09-29 | 2023-12-29 | 欣旺达动力科技股份有限公司 | 一种二次电池 |
CN116845235B (zh) * | 2023-08-29 | 2024-04-02 | 深圳海辰储能控制技术有限公司 | 正极材料、正极极片及电池 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101200289A (zh) * | 2006-12-15 | 2008-06-18 | 中国电子科技集团公司第十八研究所 | 一种磷酸铁锂材料及其制备方法 |
JP2012012262A (ja) * | 2010-07-02 | 2012-01-19 | Nichia Corp | オリビン型リチウム遷移金属複合酸化物及びその製造方法 |
CN102468489A (zh) * | 2010-11-18 | 2012-05-23 | 芯和能源股份有限公司 | 磷酸锂铁材料的制造方法及由其制得的磷酸锂铁粉末 |
CN103078113A (zh) * | 2013-01-15 | 2013-05-01 | 浙江南都电源动力股份有限公司 | 钒、钛离子共掺杂磷酸铁锂材料及其制备方法 |
CN108598383A (zh) | 2018-03-15 | 2018-09-28 | 桑顿新能源科技有限公司 | 一种Ti、N共掺杂的球形磷酸铁锂复合材料的制备方法 |
CN108682833A (zh) | 2018-06-12 | 2018-10-19 | 四会市恒星智能科技有限公司 | 一种磷酸铁锂基改性正极材料制备方法 |
CN111498825A (zh) | 2020-04-18 | 2020-08-07 | 蒋央芳 | 一种掺杂钛的磷酸铁锂的制备方法 |
CN112978704A (zh) * | 2021-05-08 | 2021-06-18 | 蜂巢能源科技有限公司 | 改性磷酸铁锂材料及其制备方法 |
CN114314548A (zh) * | 2021-12-29 | 2022-04-12 | 湖北万润新能源科技股份有限公司 | 钛、锆共掺杂碳包覆磷酸铁锂材料及其制备方法与应用 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090220858A1 (en) * | 2008-02-29 | 2009-09-03 | Byd Company Limited | Composite Compound With Mixed Crystalline Structure |
JP2010086658A (ja) * | 2008-09-29 | 2010-04-15 | Fdk Corp | 非水電解液二次電池 |
CN102044667A (zh) * | 2010-11-26 | 2011-05-04 | 兰州金川新材料科技股份有限公司 | 一种球形掺杂磷酸铁锂/炭复合粉体的制备方法 |
US9884765B2 (en) * | 2011-06-17 | 2018-02-06 | National Tsing Hua University | Ferrous phosphate powders, lithium iron phosphate powders for li-ion battery, and methods for manufacturing the same |
US11476462B2 (en) * | 2011-06-22 | 2022-10-18 | National Tsing Hua University | LiFePO4 precursor for manufacturing electrode material of Li-ion battery and method for manufacturing the same |
CN106784828A (zh) * | 2016-12-30 | 2017-05-31 | 尹宗杰 | 一种层铸成型石墨烯‑金属复合材料及制备方法 |
CN107611413B (zh) * | 2017-10-18 | 2021-04-06 | 威远县大禾陶瓷原料有限公司 | 一种掺杂钛的磷酸铁锂正极材料的制备方法 |
CN108011104A (zh) * | 2017-12-12 | 2018-05-08 | 桑顿新能源科技有限公司 | 一种高压实密度磷酸铁锂正极材料及其制备方法 |
-
2021
- 2021-12-29 CN CN202111629862.7A patent/CN114314548B/zh active Active
-
2022
- 2022-11-11 KR KR1020237020861A patent/KR20230109731A/ko unknown
- 2022-11-11 JP JP2023529058A patent/JP2024510061A/ja active Pending
- 2022-11-11 US US18/037,811 patent/US20240166517A1/en active Pending
- 2022-11-11 EP EP22891174.9A patent/EP4230580A1/en active Pending
- 2022-11-11 WO PCT/CN2022/131291 patent/WO2023124574A1/zh active Application Filing
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101200289A (zh) * | 2006-12-15 | 2008-06-18 | 中国电子科技集团公司第十八研究所 | 一种磷酸铁锂材料及其制备方法 |
JP2012012262A (ja) * | 2010-07-02 | 2012-01-19 | Nichia Corp | オリビン型リチウム遷移金属複合酸化物及びその製造方法 |
CN102468489A (zh) * | 2010-11-18 | 2012-05-23 | 芯和能源股份有限公司 | 磷酸锂铁材料的制造方法及由其制得的磷酸锂铁粉末 |
CN103078113A (zh) * | 2013-01-15 | 2013-05-01 | 浙江南都电源动力股份有限公司 | 钒、钛离子共掺杂磷酸铁锂材料及其制备方法 |
CN108598383A (zh) | 2018-03-15 | 2018-09-28 | 桑顿新能源科技有限公司 | 一种Ti、N共掺杂的球形磷酸铁锂复合材料的制备方法 |
CN108682833A (zh) | 2018-06-12 | 2018-10-19 | 四会市恒星智能科技有限公司 | 一种磷酸铁锂基改性正极材料制备方法 |
CN111498825A (zh) | 2020-04-18 | 2020-08-07 | 蒋央芳 | 一种掺杂钛的磷酸铁锂的制备方法 |
CN112978704A (zh) * | 2021-05-08 | 2021-06-18 | 蜂巢能源科技有限公司 | 改性磷酸铁锂材料及其制备方法 |
CN114314548A (zh) * | 2021-12-29 | 2022-04-12 | 湖北万润新能源科技股份有限公司 | 钛、锆共掺杂碳包覆磷酸铁锂材料及其制备方法与应用 |
Non-Patent Citations (4)
Title |
---|
J. ALLOYS COMPD., vol. 739, 2018, pages 529 |
J. ELECTROCHEM. SOC, vol. 166, 2019, pages A410 |
J. ELECTROCHEM. SOC., vol. 160, 2013, pages A3148 |
J. POWER SOURCES, vol. 189, 2009, pages 440 |
Also Published As
Publication number | Publication date |
---|---|
JP2024510061A (ja) | 2024-03-06 |
KR20230109731A (ko) | 2023-07-20 |
US20240166517A1 (en) | 2024-05-23 |
CN114314548B (zh) | 2022-11-25 |
EP4230580A1 (en) | 2023-08-23 |
CN114314548A (zh) | 2022-04-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2023124574A1 (zh) | 钛、锆共掺杂碳包覆磷酸铁锂材料及其制备方法与应用 | |
CN102088074B (zh) | 一种复合硅酸盐正极材料的制备方法 | |
CN111217347A (zh) | 一种高压实磷酸铁锂材料及其制备方法 | |
CN101164870B (zh) | 一种高性能复合相磷酸铁锂材料的制造方法 | |
CN101955175A (zh) | 一种磷酸亚铁锂的工业制备方法 | |
CN101944591A (zh) | 一种锂离子电池用钛酸锂负极材料及其制备方法 | |
CN101964415A (zh) | 一种锂离子电池负极材料的制备方法 | |
US20240105937A1 (en) | Preparation method of high-rate lithium iron phosphate positive electrode material | |
CN102723494A (zh) | 一种掺杂改性高温锰酸锂正极材料及其制备方法 | |
WO2023174152A1 (zh) | 正极材料的制备方法、正极材料、正极片和钠离子电池 | |
CN106602059A (zh) | 一种水系锂离子电池材料的制备方法 | |
CN113725418A (zh) | 一种稀土氧化物包覆改性的锂离子电池用三元正极材料及其制备方法 | |
CN110957478B (zh) | 一种磷酸钛钇锂修饰的高镍正极复合材料及其制备方法 | |
CN108923032A (zh) | 以金属氧化物修饰的锂离子电池三元正极材料及制备方法 | |
CN111342024A (zh) | 一种长循环锰酸锂正极材料及其制备方法 | |
CN108682853B (zh) | 磷酸铁锂的制备方法及由其制得的磷酸铁锂正极材料 | |
CN110620217A (zh) | 一种锌掺杂磷酸铁锂/碳复合材料及制备方法 | |
CN111740101B (zh) | 磷酸铁锂材料及其制备方法 | |
CN115621460B (zh) | 一种正极材料及其制备方法 | |
CN107324379A (zh) | 一种高容量钛酸锂材料制备方法 | |
CN116936767A (zh) | 一种高容量水系加工磷酸铁锂正极制备方法 | |
CN115353085B (zh) | 一种含补锂剂的磷酸铁锂复合材料及其制备方法、应用和含其的电池 | |
CN101527354B (zh) | 一种磷酸亚铁锂正极复合材料的制备方法 | |
CN108023079B (zh) | 一种混合过渡金属硼酸盐负极材料及其制备方法 | |
CN111969189A (zh) | 一种锂离子电池复合负极材料及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 2023529058 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 18037811 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 2022891174 Country of ref document: EP Effective date: 20230516 |
|
ENP | Entry into the national phase |
Ref document number: 20237020861 Country of ref document: KR Kind code of ref document: A |