CN116730313A - Preparation method of ultralow-temperature lithium iron phosphate positive electrode material - Google Patents
Preparation method of ultralow-temperature lithium iron phosphate positive electrode material Download PDFInfo
- Publication number
- CN116730313A CN116730313A CN202310751994.XA CN202310751994A CN116730313A CN 116730313 A CN116730313 A CN 116730313A CN 202310751994 A CN202310751994 A CN 202310751994A CN 116730313 A CN116730313 A CN 116730313A
- Authority
- CN
- China
- Prior art keywords
- source
- iron phosphate
- lithium iron
- temperature
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 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 40
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 20
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000005751 Copper oxide Substances 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- -1 lithium iron phosphate-copper Chemical compound 0.000 claims abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 239000011574 phosphorus Substances 0.000 claims abstract description 10
- 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
- 239000002131 composite material Substances 0.000 claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 7
- 239000010405 anode material Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000007670 refining Methods 0.000 claims abstract description 4
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 17
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 15
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 15
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 9
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000011268 mixed slurry Substances 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 229910007857 Li-Al Inorganic materials 0.000 description 1
- 229910008447 Li—Al Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HNCXPJFPCAYUGJ-UHFFFAOYSA-N dilithium bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].[Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F HNCXPJFPCAYUGJ-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 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
- H01M4/58—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
- 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
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- 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
-
- 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
Abstract
The invention provides a preparation method of an ultralow-temperature lithium iron phosphate positive electrode material. The method comprises the following steps of step 1, mixing a carbon source, an iron source, a lithium source, a phosphorus source and a copper source according to a certain proportion, fully grinding in a grinder, and refining to obtain slurry a; step 2, placing the slurry a obtained in the step 1 in a microwave oven for drying for a period of time, cooling to room temperature, and taking out to obtain a precursor b; and 3, adding the precursor b obtained in the step 2 into an atmosphere sintering furnace, sintering for a certain time at high temperature, and cooling to room temperature to obtain the lithium iron phosphate-copper composite anode material. According to the preparation method, the low-cost copper oxide is added into the raw material system to modify the lithium iron phosphate, so that the conductivity and low-temperature performance of the lithium iron phosphate are greatly improved, a carbothermic reduction method is used for preparing the lithium iron phosphate-copper complex-phase substance, the operation is simple, the process is easy to control, and the performance of the prepared material is remarkably improved.
Description
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to a preparation method of an ultralow-temperature lithium iron phosphate anode material.
Background
The lithium iron phosphate electrode material has the advantages of high specific capacity, stable working voltage, quick charge, environment friendliness, low cost and the like, and is widely applied to the field of electric automobiles. However, the lithium iron phosphate has poor performance in a low-temperature environment, and the main reason is that the diffusion coefficient of lithium ions in the lithium iron phosphate is smaller and the diffusion distance is shorter. Based on this, a method for improving the low-temperature performance of lithium iron phosphate is generally used for shortening a lithium ion transmission path by reducing the particle size of the material, improving the overall performance of the material by increasing crystal defects through element doping, and improving the electron conductivity and the lithium ion diffusion migration rate of the lithium iron phosphate through carbon coating.
For example, chinese patent publication No. CN102623701a discloses a low temperature type nano lithium iron phosphate preparation method by doping metal ion oxide (MnO) 2 、TiO 2 、MgO、Nb 2 O 5 ) And the capacity of lithium iron phosphate prepared by the carbon source is 80% of the normal temperature at-20 ℃ and 55% of the normal temperature at-40 ℃. Chinese patent No. CN114583159a discloses a method for preparing low-temperature lithium iron phosphate, which uses cellular ferric phosphate as raw material, and forms a special interlayer structure in the preparation process of lithium iron phosphate positive electrode material by using layered double hydroxide (Li-Al LDH), thereby greatly improving the low-temperature performance of lithium iron phosphate positive electrode material, and the 1C charge-discharge capacity retention rate can reach more than 80% at-10 ℃. Chinese patent No. CN109980195B discloses a preparation method of ultralow temperature lithium ion battery capable of working normally at-60 ℃, which uses lithium iron phosphate coated mesoporous carbon as positive electrode material and uses electrostatic spinning technology to prepare mesoporous-knot-rich materialThe structured hard carbon material is used as a negative electrode material, and the lithium ion battery is assembled by electrolyte prepared by bis (trifluoro methanesulfonimide) lithium salt and DIOX (1, 3 dioxane) +EC (ethylene carbonate) +VC (vinylene carbonate) solvent, and can still work normally at the temperature of minus 60 ℃. A common problem with all of the above examples is that carbon coating of lithium iron phosphate is required to improve battery performance, which results in a lower volumetric specific capacity of the battery.
Disclosure of Invention
Based on the above, a preparation method of an ultralow-temperature lithium iron phosphate positive electrode material is provided, and the lithium iron phosphate prepared by the method has excellent ultralow-temperature performance.
The technical scheme of the invention is as follows: the invention provides a preparation method of an ultralow-temperature lithium iron phosphate positive electrode material, which comprises the following steps:
step 1, mixing a carbon source, an iron source, a lithium source, a phosphorus source and a copper source according to a certain proportion, fully grinding in a grinder, and refining to obtain slurry a;
step 2, placing the slurry a obtained in the step 1 in a microwave oven for drying for a period of time, cooling to room temperature, and taking out to obtain a precursor b;
and 3, adding the precursor b obtained in the step 2 into an atmosphere sintering furnace, sintering for a certain time at high temperature, and cooling to room temperature to obtain the lithium iron phosphate-copper composite anode material.
Further, in the step 1, the molar ratio of the lithium source to the iron source to the copper source to the phosphorus source is (1-1.05): 0.6-0.8: (0.2-0.4): 1, grinding time is 2-5h.
Further, in the step 2, the microwave power during microwave drying is 3000-6000W/m 2 The microwave time is 2-5 hours, and the temperature is controlled at 300-350 ℃.
Further, in the step 3, the sintering temperature is 700-750 ℃ and the sintering time is 4-7h.
Further, the iron source is ferric oxide (Fe 2 O 3 ) Or ferroferric oxide (Fe) 3 O 4 ) At least one of them.
Further, the phosphorus source is lithium dihydrogen phosphate (LiH) 2 PO 4 ) Lithium phosphate (Li) 3 PO 4 ) And (3) a mixture.
Further, the Cu source is copper oxide (CuO) whiskers.
Compared with the prior art, the invention has the following advantages:
according to the preparation method of the ultralow-temperature lithium iron phosphate positive electrode material, the structure of the carbon removal layer coated lithium iron phosphate is changed, a complex-phase network structure is formed by adopting a conductive material dispersion distribution mode, conductive particles in one crystal grain are uniformly distributed in a network shape, and the conduction distance of lithium ions is short, so that the low-temperature performance is improved. The preparation method of the invention greatly improves the volume specific capacity, improves the low-temperature performance of the lithium iron phosphate, has very low cost, and has simple and easy operation.
In addition, the preparation method of the invention modifies the lithium iron phosphate by adding the low-cost copper oxide into the raw material system, thereby greatly improving the conductivity and the low-temperature performance of the lithium iron phosphate. The carbothermal reduction method is used for preparing the lithium iron phosphate-copper complex phase substance, the operation is simple, the process is easy to control, and the performance of the prepared material is obviously improved.
Description of the embodiments
The following will make clear the technical solutions in the examples of the present invention, which are described as merely an example of an aspect of the present invention, not all the examples. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of an ultralow-temperature lithium iron phosphate positive electrode material, which comprises the following steps:
step 1, mixing a carbon source, an iron source, a lithium source, a phosphorus source and a copper source according to a certain proportion, fully grinding in a grinder, and refining to obtain slurry a;
step 2, placing the slurry a obtained in the step 1 in a microwave oven for drying for a period of time, cooling to room temperature, and taking out to obtain a precursor b;
and 3, adding the precursor b obtained in the step 2 into an atmosphere sintering furnace, sintering for a certain time at high temperature, and cooling to room temperature to obtain the lithium iron phosphate-copper composite anode material.
Further, in the step 1, the molar ratio of the lithium source to the iron source to the copper source to the phosphorus source is (1-1.05): 0.6-0.8: (0.2-0.4): 1, grinding time is 2-5h.
Further, in the step 2, the microwave power during microwave drying is 3000-6000W/m 2 The microwave time is 2-5 hours, and the temperature is controlled at 300-350 ℃.
Further, in the step 3, the sintering temperature is 700-750 ℃ and the sintering time is 4-7h.
Further, the iron source is ferric oxide (Fe 2 O 3 ) Or ferroferric oxide (Fe) 3 O 4 ）。
Further, the phosphorus source is lithium dihydrogen phosphate (LiH) 2 PO 4 ) Lithium phosphate (Li) 3 PO 4 ) And (3) a mixture.
Further, the Cu source is copper oxide (CuO) whiskers.
Compared with the prior art, the invention has the following advantages:
according to the preparation method of the ultralow-temperature lithium iron phosphate positive electrode material, the structure of the carbon removal layer coated lithium iron phosphate is changed, a complex-phase network structure is formed by adopting a conductive material dispersion distribution mode, conductive particles in one crystal grain are uniformly distributed in a network shape, and the conduction distance of lithium ions is short, so that the low-temperature performance is improved. The preparation method of the invention greatly improves the volume specific capacity, improves the low-temperature performance of the lithium iron phosphate, has very low cost, and has simple and easy operation.
In addition, the preparation method of the invention modifies the lithium iron phosphate by adding the low-cost copper oxide into the raw material system, thereby greatly improving the conductivity and the low-temperature performance of the lithium iron phosphate. The carbothermal reduction method is used for preparing the lithium iron phosphate-copper complex phase substance, the operation is simple, the process is easy to control, and the performance of the prepared material is obviously improved.
Examples
31.94g (0.2 mol) of ferric oxide, 39.00g (0.39 mol) of lithium dihydrogen phosphate, 1.04g (0.01 mol) of lithium phosphate and 7.68g (0.08 mol) of copper oxide are weighed, the weighed lithium dihydrogen phosphate and lithium phosphate are added into 500ml of deionized water, and after uniform stirring until no bubbles are generated, other raw materials of ferric oxide and copper oxide are added, and then the mixture is poured into a grinder to be ground for 2 hours. Sieving to obtain mixed slurry L1, and drying the slurry L1 in a microwave oven at 300 ℃ for 3h to obtain a precursor q1. And sintering the precursor in a sintering furnace at 750 ℃ for 5 hours, and cooling to room temperature to obtain the lithium iron phosphate-copper composite material.
Examples
31.94g (0.2 mol) of ferric oxide, 39.00g (0.39 mol) of lithium dihydrogen phosphate, 1.04g (0.01 mol) of lithium phosphate and 8.64g (0.09 mol) of copper oxide are weighed, the weighed lithium dihydrogen phosphate and lithium phosphate are added into 500ml of deionized water, and after uniform stirring until no bubbles are generated, other raw materials of ferric oxide and copper oxide are added, and then the mixture is poured into a grinder to be ground for 2 hours. Sieving to obtain mixed slurry L1, and drying the slurry L1 in a microwave oven at 300 ℃ for 3h to obtain a precursor q1. And sintering the precursor in a sintering furnace at 750 ℃ for 5 hours, and cooling to room temperature to obtain the lithium iron phosphate-copper composite material.
Examples
31.938g (0.2 mol) of ferric oxide, 39 (0.39 mol) of lithium dihydrogen phosphate, 1.04g (0.01 mol) of lithium phosphate and 9.60g (0.10 mol) of copper oxide are weighed, the weighed lithium dihydrogen phosphate and lithium phosphate are added into 500ml of deionized water, and after uniform stirring until no bubbles are generated, other raw materials of ferric oxide and copper oxide are added, and then the mixture is poured into a grinder to be ground for 2 hours. Sieving to obtain mixed slurry L1, and drying the slurry L1 in a microwave oven at 300 ℃ for 3h to obtain a precursor q1. And sintering the precursor in a sintering furnace at 750 ℃ for 5 hours, and cooling to room temperature to obtain the lithium iron phosphate-copper composite material.
Examples
31.94g (0.2 mol) of ferric oxide, 39.00g (0.39 mol) of lithium dihydrogen phosphate, 1.04g (0.01 mol) of lithium phosphate and 10.56g (0.11 mol) of copper oxide are weighed, the weighed lithium dihydrogen phosphate and lithium phosphate are added into 500ml of deionized water, and after uniform stirring until no bubbles are generated, other raw materials of ferric oxide and copper oxide are added, and then the mixture is poured into a grinder to be ground for 2 hours. Sieving to obtain mixed slurry L1, and drying the slurry L1 in a microwave oven at 300 ℃ for 3h to obtain a precursor q1. And sintering the precursor in a sintering furnace at 750 ℃ for 5 hours, and cooling to room temperature to obtain the lithium iron phosphate-copper composite material.
Examples
31.94g (0.2 mol) of ferric oxide, 39.00g (0.39 mol) of lithium dihydrogen phosphate, 1.04g (0.01 mol) of lithium phosphate and 11.52g (0.12 mol) of copper oxide are weighed, the weighed lithium dihydrogen phosphate and lithium phosphate are added into 500ml of deionized water, and after uniform stirring until no bubbles are generated, other raw materials of ferric oxide and copper oxide are added, and then the mixture is poured into a grinder to be ground for 2 hours. Sieving to obtain mixed slurry L1, and drying the slurry L1 in a microwave oven at 300 ℃ for 3h to obtain a precursor q1. And sintering the precursor in a sintering furnace at 750 ℃ for 5 hours, and cooling to room temperature to obtain the lithium iron phosphate-copper composite material.
Comparative example
31.94g (0.2 mol) of ferric oxide, 39.00g (0.39 mol) of lithium dihydrogen phosphate and 1.04g (0.01 mol) of lithium phosphate are weighed, the weighed lithium dihydrogen phosphate and lithium phosphate are added into 500ml of deionized water, after uniform stirring until no bubbles are generated, other raw materials of ferric oxide are added, and then the mixture is poured into a grinder to be ground for 2 hours. Sieving to obtain mixed slurry L1, and drying the slurry L1 in a microwave oven at 300 ℃ for 3h to obtain a precursor q1. And sintering the precursor in a sintering furnace at 750 ℃ for 5 hours, and cooling to room temperature to obtain the lithium iron phosphate material.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and although the present invention has been described in detail with reference to the foregoing embodiment, it will be apparent to those skilled in the art that modifications, equivalent substitutions, improvements and other technical features can be made within the spirit and principle of the present invention, and any modifications, equivalent substitutions, improvements and the like are included in the scope of the present invention.
Claims (7)
1. The preparation method of the ultralow-temperature lithium iron phosphate positive electrode material is characterized by comprising the following steps of:
step 1, mixing a carbon source, an iron source, a lithium source, a phosphorus source and a copper source according to a certain proportion, fully grinding in a grinder, and refining to obtain slurry a;
step 2, placing the slurry a obtained in the step 1 in a microwave oven for drying for a period of time, cooling to room temperature, and taking out to obtain a precursor b;
and 3, adding the precursor b obtained in the step 2 into an atmosphere sintering furnace, sintering for a certain time at high temperature, and cooling to room temperature to obtain the lithium iron phosphate-copper composite anode material.
2. The method for preparing the ultralow-temperature lithium iron phosphate positive electrode material according to claim 1, wherein in the step 1, the molar ratio of the lithium source to the iron source to the copper source to the phosphorus source is (1-1.05): (0.6-0.8): (0.2-0.4): 1, grinding time is 2-5h.
3. The method for preparing ultralow temperature lithium iron phosphate positive electrode material according to claim 1, wherein in the step 2, the microwave power is 3000-6000W/m during microwave drying 2 The microwave time is 2-5 hours, and the temperature is controlled at 300-350 ℃.
4. The method for preparing ultralow temperature lithium iron phosphate positive electrode material according to claim 1, wherein in the step 3, the sintering temperature is 700-750 ℃ and the sintering time is 4-7h.
5. The method for preparing an ultralow-temperature lithium iron phosphate positive electrode material according to claim 1, wherein the iron source is at least one of ferric oxide or ferroferric oxide.
6. The method for preparing ultralow-temperature lithium iron phosphate positive electrode material according to claim 1, wherein the phosphorus source is a mixture of lithium dihydrogen phosphate and lithium phosphate.
7. The method for preparing an ultralow temperature lithium iron phosphate positive electrode material according to claim 1, wherein the Cu source is copper oxide whisker.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310751994.XA CN116730313A (en) | 2023-06-25 | 2023-06-25 | Preparation method of ultralow-temperature lithium iron phosphate positive electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310751994.XA CN116730313A (en) | 2023-06-25 | 2023-06-25 | Preparation method of ultralow-temperature lithium iron phosphate positive electrode material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116730313A true CN116730313A (en) | 2023-09-12 |
Family
ID=87911269
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310751994.XA Pending CN116730313A (en) | 2023-06-25 | 2023-06-25 | Preparation method of ultralow-temperature lithium iron phosphate positive electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116730313A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081695A (en) * | 2007-06-27 | 2007-12-05 | 上海电力学院 | Preparation method of doped modified ferric phosphate lithium |
| CN101746742A (en) * | 2008-12-11 | 2010-06-23 | 中国电子科技集团公司第十八研究所 | Method for preparing lithium ion battery anode material spherical LiFePO4 |
| CN103779563A (en) * | 2014-01-20 | 2014-05-07 | 重庆特瑞电池材料股份有限公司 | Method for preparing copper/carbon-coated lithium iron phosphate |
| CN104577112A (en) * | 2013-10-21 | 2015-04-29 | 大连市沙河口区中小微企业服务中心 | Preparation method of lithium iron phosphate and lithium iron phosphate |
| CN109795998A (en) * | 2018-12-29 | 2019-05-24 | 合肥融捷能源材料有限公司 | A kind of preparation method and lithium iron phosphate positive material promoting lithium iron phosphate positive material compacted density |
| CN113078323A (en) * | 2021-03-26 | 2021-07-06 | 天津斯科兰德科技有限公司 | Preparation method of composite multi-element iron phosphate manganese vanadium lithium cathode material |
-
2023
- 2023-06-25 CN CN202310751994.XA patent/CN116730313A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081695A (en) * | 2007-06-27 | 2007-12-05 | 上海电力学院 | Preparation method of doped modified ferric phosphate lithium |
| CN101746742A (en) * | 2008-12-11 | 2010-06-23 | 中国电子科技集团公司第十八研究所 | Method for preparing lithium ion battery anode material spherical LiFePO4 |
| CN104577112A (en) * | 2013-10-21 | 2015-04-29 | 大连市沙河口区中小微企业服务中心 | Preparation method of lithium iron phosphate and lithium iron phosphate |
| CN103779563A (en) * | 2014-01-20 | 2014-05-07 | 重庆特瑞电池材料股份有限公司 | Method for preparing copper/carbon-coated lithium iron phosphate |
| CN109795998A (en) * | 2018-12-29 | 2019-05-24 | 合肥融捷能源材料有限公司 | A kind of preparation method and lithium iron phosphate positive material promoting lithium iron phosphate positive material compacted density |
| CN113078323A (en) * | 2021-03-26 | 2021-07-06 | 天津斯科兰德科技有限公司 | Preparation method of composite multi-element iron phosphate manganese vanadium lithium cathode material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hou et al. | Solid electrolytes and interfaces in all-solid-state sodium batteries: Progress and perspective | |
| Lyu et al. | 3D-printed electrodes for lithium metal batteries with high areal capacity and high-rate capability | |
| CN1754275A (en) | High energy and power density electrochemical cells | |
| CN110085805B (en) | Composite anode and application thereof in solid polymer lithium ion battery | |
| WO2015050031A1 (en) | Covered cathode active material and lithium battery | |
| Huo et al. | Challenges of Stable Ion Pathways in Cathode Electrode for All‐Solid‐State Lithium Batteries: A Review | |
| JP2011238594A (en) | Cathode material for lithium ion secondary battery and method for manufacturing the same | |
| CN114789993B (en) | Modified sulfur silver germanium mineral solid electrolyte and preparation method and application thereof | |
| CN111009659A (en) | Preparation method and application of biomass carbon/poly-sodium manganese fluorophosphate composite material | |
| CN102315440A (en) | Spinel composite material, preparation method and application thereof | |
| CN113161523B (en) | Non-stoichiometric lithium iron manganese phosphate positive electrode material, and preparation method and application thereof | |
| CN102339999B (en) | Polyanion composite material, its preparation method and application | |
| Hou et al. | Progress on high voltage PEO-based polymer solid electrolytes in lithium batteries | |
| CN114702013B (en) | Sodium ion battery metal selenide anode material and preparation method and application thereof | |
| Peng et al. | Halogen‐Rich Lithium Argyrodite Solid‐State Electrolytes: A Review | |
| CN112349955A (en) | Preparation method of sulfide-based solid electrolyte and sulfide-based solid electrolyte | |
| CN115189014A (en) | Preparation and application of composite electrolyte membrane based on sodium ion sulfide solid electrolyte | |
| CN111430787B (en) | Composite film solid electrolyte and preparation method and application thereof | |
| CN116534917A (en) | Coated sodium ion layered oxide positive electrode material and preparation method thereof | |
| CN116730313A (en) | Preparation method of ultralow-temperature lithium iron phosphate positive electrode material | |
| CN112510254B (en) | Novel sulfide solid electrolyte and preparation method and application thereof | |
| CN114843592A (en) | Mixed conductor sulfide solid electrolyte, preparation method and all-solid-state battery | |
| CN114421004A (en) | Sulfide solid electrolyte and preparation method and application thereof | |
| CN107623117A (en) | A kind of preparation method of high power capacity, high-tap-density lithium iron phosphate material | |
| Du et al. | Research Progress of All-Solid-State Lithium-Sulfur Batteries with Sulfide Solid Electrolytes: Materials, Interfaces, Challenges, and Prospects |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |