CN114368735A - Method for producing high-compaction high-capacity lithium iron phosphate - Google Patents
Method for producing high-compaction high-capacity lithium iron phosphate Download PDFInfo
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- CN114368735A CN114368735A CN202210082832.7A CN202210082832A CN114368735A CN 114368735 A CN114368735 A CN 114368735A CN 202210082832 A CN202210082832 A CN 202210082832A CN 114368735 A CN114368735 A CN 114368735A
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- 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 143
- 238000005056 compaction Methods 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 98
- 239000002002 slurry Substances 0.000 claims abstract description 78
- 239000002243 precursor Substances 0.000 claims abstract description 51
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 238000000227 grinding Methods 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims abstract description 35
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000654 additive Substances 0.000 claims abstract description 32
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 32
- 230000000996 additive effect Effects 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000001694 spray drying Methods 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 12
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 47
- 239000002994 raw material Substances 0.000 claims description 23
- 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052742 iron Inorganic materials 0.000 claims description 20
- 229910052698 phosphorus Inorganic materials 0.000 claims description 20
- 239000011574 phosphorus Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 9
- 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
- 229920002472 Starch Polymers 0.000 claims description 7
- 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 7
- 229930006000 Sucrose Natural products 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 7
- 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
- 239000008103 glucose Substances 0.000 claims description 7
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 7
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 7
- 239000001095 magnesium carbonate Substances 0.000 claims description 7
- 239000008107 starch Substances 0.000 claims description 7
- 235000019698 starch Nutrition 0.000 claims description 7
- 239000005720 sucrose Substances 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 description 19
- 239000000463 material Substances 0.000 description 17
- 238000011056 performance test Methods 0.000 description 13
- 238000005245 sintering Methods 0.000 description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 238000007599 discharging Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010344 co-firing Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
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- 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
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- 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
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- 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
- C01P2006/11—Powder tap density
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a method for producing high-compaction high-capacity lithium iron phosphate, which comprises the following steps: step 1, mixing and grinding pure water, iron phosphate, a lithium source, a carbon source and an additive according to a proportion to obtain a mixture with the particle size of 0.8-1.2 mu m to obtain large-particle slurry A; step 2, grinding the large-particle slurry A into a mixture with the particle size of 0.1-0.5 mu m to obtain small-particle slurry B; step 3, carrying out spray drying on the small-particle slurry B to obtain a lithium iron phosphate precursor dried substance C; step 4, performing heat treatment on the dried lithium iron phosphate precursor C to obtain a lithium iron phosphate sinter D; and 5, uniformly mixing the lithium iron phosphate precursor dry matter C and the lithium iron phosphate sintered matter D, and then performing secondary heat treatment and airflow grading treatment to obtain a lithium iron phosphate finished product E.
Description
Technical Field
The invention belongs to the technical field of energy storage materials, and particularly relates to a method for producing high-compaction high-capacity lithium iron phosphate.
Background
The increasingly severe energy crisis is one of the major challenges facing the 21 st century, and development of novel energy sources with environmental protection and sustainable development is crucial to meet the increasing energy demand of human beings; the lithium ion battery has the advantages of high working voltage, high energy density and the like, is the most potential secondary battery, and has the advantages of high capacity, long cycle life, high thermal stability, environmental friendliness, low cost and the like by taking the lithium iron phosphate as the anode material of the lithium ion battery.
The compaction density has a great influence on the performance of the lithium ion battery and has a close relation with the specific capacity, efficiency, internal resistance and cycle performance of a pole piece, generally, the greater the compaction density is, the higher the energy density of the battery can be, therefore, the compaction density is also taken as one of the reference indexes of the energy density of the material, under a certain process condition, the greater the compaction density is, the higher the energy density of the battery is, most of the available compaction density of the lithium iron phosphate in the current market is 2.2-2.5g/cm3, and the lower the compaction density restricts the energy density of the battery.
In view of the phenomenon that the compaction density and gram volume of the lithium iron phosphate synthesized by the high-temperature solid phase method are incompatible (the compaction density is high and the gram volume is low or the gram volume is high and the compaction density is low), the problems of compaction density and gram volume of the material can be simultaneously improved by the mixed doping sintering process of the lithium iron phosphate precursor dry matter and the lithium iron phosphate sinter matter according to the proportion.
Disclosure of Invention
Based on the technical problems, the invention aims to provide a method for producing high-compaction high-capacity lithium iron phosphate, which overcomes the defects of the prior art, and can simultaneously improve the compaction density and the gram volume of materials by a lithium iron phosphate precursor dry product and a lithium iron phosphate sinter according to a proportional mixed sintering process, and the specific technical scheme is as follows:
a method for producing high-compaction high-capacity lithium iron phosphate comprises the following steps:
step 1, preparing large-particle slurry A: mixing pure water, iron phosphate, a lithium source, a carbon source and an additive in proportion and grinding the mixture into a mixture with the particle size of 0.8-1.2 mu m to obtain large-particle slurry A;
step 2, preparing small particle slurry B: grinding the large-particle slurry A prepared in the step one into a mixture with the particle size of 0.1-0.5 mu m to obtain small-particle slurry B;
step 3, preparing a lithium iron phosphate precursor dried product C: spray drying the small particle slurry B prepared in the step two to obtain a lithium iron phosphate precursor dried substance C;
step 4, preparing a lithium iron phosphate sinter D: placing the dried lithium iron phosphate precursor C prepared in the third step into an atmosphere furnace for first heat treatment to obtain a lithium iron phosphate sinter D;
step 5, preparing a lithium iron phosphate finished product E: and D, uniformly mixing the lithium iron phosphate precursor dried substance C obtained in the third step and the lithium iron phosphate sintered substance D obtained in the fourth step, placing the mixture in an atmosphere furnace for secondary heat treatment, and performing airflow classification treatment to obtain a lithium iron phosphate finished product E.
In the reaction raw material containing lithium, iron and phosphorus, the molar ratio of Li to Fe to P is (1-1.1): (0.95-1.0): 1-1.05).
The carbon source comprises any one or a combination of at least two of sucrose, glucose, starch, citric acid and PEG, and the mass of the carbon source is 5-15 wt% of that of the reaction raw materials containing lithium, iron and phosphorus.
The additive comprises any one or a combination of at least two of alumina, magnesium carbonate, titanium oxide, zirconia and ammonium vanadate, and the mass of the additive is 0.1-1 wt% of that of the reaction raw material containing lithium, iron and phosphorus.
Further, in step 1: mixing and grinding pure water, iron phosphate, a lithium source, a carbon source and an additive according to a proportion to obtain a mixture with the particle size of 0.8-1.2 mu m, and obtaining large-particle slurry A, wherein the grinding time is 1-3 h.
Further, in the step 2: and (3) grinding the large-particle slurry A prepared in the step (1) into a mixture with the particle size of 0.1-0.5 mu m to obtain small-particle slurry B, wherein the grinding time is 4-8 h.
Further, in the step 3: and drying the small-particle slurry B by using a spray drying tower, wherein the inlet temperature of the small-particle slurry B passing through the spray drying tower is 200-300 ℃, the outlet temperature of the small-particle slurry B is 50-100 ℃, and the feeding frequency of the small-particle slurry B is 10-45 Hz.
Further, in the step 4: and placing the lithium iron phosphate precursor dried substance C in an atmosphere furnace for primary heat treatment at the temperature of 400-700 ℃, wherein the reducing gas in the atmosphere furnace is nitrogen, and the sintering time is 5-10 h.
Further, in the step 5: the mass ratio of the lithium iron phosphate precursor dry matter C to the lithium iron phosphate sintered matter D is (1-5): 1, the heat treatment temperature is 600-.
The invention has the beneficial effects that:
(1) according to the invention, the mixed sintering is introduced in the sintering stage (after the lithium iron phosphate precursor dry matter C and the lithium iron phosphate sintered matter D are uniformly mixed, the mixture is placed in an atmosphere furnace for secondary heat treatment, and then the air flow grading treatment is carried out, so that the lithium iron phosphate finished product is obtained), the compaction density of the lithium iron phosphate finished product can be greatly improved, and the compaction density of the lithium iron phosphate finished product can be controlled to be 2.65-2.75g/cm3And meanwhile, the electrochemical performance of the product can be improved.
(2) The magnetic foreign matter is less than 0.5ppm, the 0.1C capacity reaches more than 159mAh/g, and the 2000 th cycle discharge specific capacity reaches more than 142 mAh/g.
(3) In the invention, additives such as alumina, magnesium carbonate, titanium oxide, zirconia, ammonium vanadate and the like are added in the sintering process, the compacted density of the lithium iron phosphate prepared by the method, the first discharge specific capacity of 0.1C and the 2000 th cycle discharge specific capacity are obviously improved, and the magnetic foreign matters are greatly reduced.
(4) The method has the advantages of simple process, effective improvement of the morphology of the lithium iron phosphate anode material, low cost and wide application prospect.
Drawings
Fig. 1 is a flow chart of a method of producing highly compacted high capacity lithium iron phosphate according to the present invention.
Fig. 2 is an SEM image of lithium iron phosphate obtained in example 1 of the present invention.
Fig. 3 is an SEM image of lithium iron phosphate obtained in example 2 of the present invention.
Fig. 4 is an SEM magnified view of lithium iron phosphate obtained in example 1 of the present invention.
Fig. 5 is an SEM image of lithium iron phosphate obtained in example 3 of the present invention.
Fig. 6 is an SEM image of lithium iron phosphate obtained in example 4 of the present invention.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the following embodiments are merely simple examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which this invention belongs, and test reagents used in the following examples are conventional biochemical reagents unless otherwise specified, and the experimental procedures are conventional procedures unless otherwise specified.
The following are typical, but non-limiting, examples of the invention.
Example 1
A method for producing high-compaction high-capacity lithium iron phosphate is characterized by comprising the following steps:
step 1, preparing large-particle slurry A: mixing pure water, iron phosphate, a lithium source, a carbon source and an additive in proportion and grinding the mixture into a mixture with the particle size of 0.8 mu m to obtain large-particle slurry A;
step 2, preparing small particle slurry B: grinding the large-particle slurry A prepared in the step one into a mixture with the particle size of 0.1 mu m to obtain small-particle slurry B;
step 3, preparing a lithium iron phosphate precursor dried product C: spray drying the small particle slurry B prepared in the step two to obtain a lithium iron phosphate precursor dried substance C;
step 4, preparing a lithium iron phosphate sinter D: placing the dried lithium iron phosphate precursor C prepared in the third step into an atmosphere furnace for first heat treatment to obtain a lithium iron phosphate sinter D;
step 5, preparing a lithium iron phosphate finished product E: and D, uniformly mixing the lithium iron phosphate precursor dried substance C obtained in the third step and the lithium iron phosphate sintered substance D obtained in the fourth step, placing the mixture in an atmosphere furnace for secondary heat treatment, and performing airflow classification treatment to obtain a lithium iron phosphate finished product E.
In the reaction raw material containing lithium, iron and phosphorus, the molar ratio of Li to Fe to P is 1:0.95: 1.
Preferably, the carbon source comprises any one or a combination of at least two of sucrose, glucose, starch, citric acid or PEG, and the mass of the carbon source is 5wt% of the mass of the reaction raw material containing lithium, iron and phosphorus.
Preferably, the additive comprises alumina, and the mass of the additive is 0.1wt% of the mass of the reaction raw material containing lithium, iron and phosphorus.
Preferably, in step 1: mixing pure water, iron phosphate, a lithium source, a carbon source and an additive in proportion, and grinding the mixture into a mixture with the particle size of 0.8 mu m to obtain large-particle slurry A, wherein the grinding time is 1 h.
Preferably, in the step 2: and (3) grinding the large-particle slurry A prepared in the step (1) into a mixture with the particle size of 0.1 mu m to obtain small-particle slurry B, wherein the grinding time is 4-8 h.
Preferably, in the step 3: and drying the small-particle slurry B by using a spray drying tower, wherein the inlet temperature of the small-particle slurry B passing through the spray drying tower is 200 ℃, the outlet temperature of the small-particle slurry B passing through the spray drying tower is 50 ℃, and the feeding frequency of the small-particle slurry B is 10 Hz.
Preferably, in the step 4: and placing the lithium iron phosphate precursor dried product C in an atmosphere furnace for first heat treatment at the temperature of 400 ℃, wherein the reducing gas in the atmosphere furnace is nitrogen, and the sintering time is 5 h.
Preferably, in the step 5: the mass ratio of the lithium iron phosphate precursor dry matter C to the lithium iron phosphate sintered matter D is 1:1, the heat treatment temperature is 600 ℃, the reducing gas in the atmosphere furnace is nitrogen, and the heat treatment time is 8 hours.
The performance test results of the lithium iron phosphate material prepared in this example are shown in table 1.
Example 2
A method for producing high-compaction high-capacity lithium iron phosphate is characterized by comprising the following steps:
step 1, preparing large-particle slurry A: mixing pure water, iron phosphate, a lithium source, a carbon source and an additive in proportion and grinding the mixture into a mixture with the particle size of 1.2 mu m to obtain large-particle slurry A;
step 2, preparing small particle slurry B: grinding the large-particle slurry A prepared in the step one into a mixture with the particle size of 0.5 mu m to obtain small-particle slurry B;
step 3, preparing a lithium iron phosphate precursor dried product C: spray drying the small particle slurry B prepared in the step two to obtain a lithium iron phosphate precursor dried substance C;
step 4, preparing a lithium iron phosphate sinter D: placing the dried lithium iron phosphate precursor C prepared in the third step into an atmosphere furnace for first heat treatment to obtain a lithium iron phosphate sinter D;
step 5, preparing a lithium iron phosphate finished product E: and D, uniformly mixing the lithium iron phosphate precursor dried substance C obtained in the third step and the lithium iron phosphate sintered substance D obtained in the fourth step, placing the mixture in an atmosphere furnace for secondary heat treatment, and performing airflow classification treatment to obtain a lithium iron phosphate finished product E.
In the reaction raw material containing lithium, iron and phosphorus, the molar ratio of Li to Fe to P is 1.1: 1.0: 1.05.
Preferably, the carbon source comprises any one or a combination of at least two of sucrose, glucose, starch, citric acid or PEG, and the mass of the carbon source is 15 wt% of the mass of the reaction raw material containing lithium, iron and phosphorus.
Preferably, the additive comprises magnesium carbonate, and the mass of the additive is 1wt% of the mass of the reaction raw material containing lithium, iron and phosphorus.
Preferably, in step 1: mixing and grinding pure water, iron phosphate, a lithium source, a carbon source and an additive according to a proportion to obtain a mixture with the particle size of 1.2 mu m to obtain large-particle slurry A, wherein the grinding time is 3 hours.
Preferably, in the step 2: and (3) grinding the large-particle slurry A prepared in the step (1) into a mixture with the particle size of 0.5 mu m to obtain small-particle slurry B, wherein the grinding time is 8 h.
Further, in the step 3: and drying the small particle slurry B by using a spray drying tower, wherein the inlet temperature of the small particle slurry B passing through the spray drying tower is 300 ℃, the outlet temperature of the small particle slurry B passing through the spray drying tower is 100 ℃, and the feeding frequency of the small particle slurry B is 45 Hz.
Preferably, in the step 4: and placing the lithium iron phosphate precursor dried product C in an atmosphere furnace for first heat treatment at the temperature of 700 ℃, wherein the reducing gas in the atmosphere furnace is nitrogen, and the sintering time is 10 h.
Preferably, in the step 5: the mass ratio of the lithium iron phosphate precursor dry matter C to the lithium iron phosphate sintered matter D is 5:1, the heat treatment temperature is 800 ℃, the reducing gas in the atmosphere furnace is nitrogen, and the heat treatment time is 10 hours.
The performance test results of the lithium iron phosphate material prepared in this example are shown in table 1.
Example 3
A method for producing high-compaction high-capacity lithium iron phosphate is characterized by comprising the following steps:
step 1, preparing large-particle slurry A: mixing pure water, iron phosphate, a lithium source, a carbon source and an additive in proportion and grinding the mixture into a mixture with the particle size of 1 mu m to obtain large-particle slurry A;
step 2, preparing small particle slurry B: grinding the large-particle slurry A prepared in the step one into a mixture with the particle size of 0.3 mu m to obtain small-particle slurry B;
step 3, preparing a lithium iron phosphate precursor dried product C: spray drying the small particle slurry B prepared in the step two to obtain a lithium iron phosphate precursor dried substance C;
step 4, preparing a lithium iron phosphate sinter D: placing the dried lithium iron phosphate precursor C prepared in the third step into an atmosphere furnace for first heat treatment to obtain a lithium iron phosphate sinter D;
step 5, preparing a lithium iron phosphate finished product E: and D, uniformly mixing the lithium iron phosphate precursor dried substance C obtained in the third step and the lithium iron phosphate sintered substance D obtained in the fourth step, placing the mixture in an atmosphere furnace for secondary heat treatment, and performing airflow classification treatment to obtain a lithium iron phosphate finished product E.
Preferably, in the reaction raw material containing lithium, iron and phosphorus, the element molar ratio of Li to Fe to P is 1.05:0.98: 1.02.
Preferably, the carbon source comprises any one or a combination of at least two of sucrose, glucose, starch, citric acid and PEG, and the mass of the carbon source is 5-15 wt% of that of the reaction raw material containing lithium, iron and phosphorus.
Preferably, the additive comprises titanium oxide, and the mass of the additive is 0.5 wt% of the mass of the reaction raw material containing lithium, iron and phosphorus.
Preferably, in step 1: mixing and grinding pure water, iron phosphate, a lithium source, a carbon source and an additive in proportion into a mixture with the particle size of 1 mu m to obtain large-particle slurry A, wherein the grinding time is 2 hours.
Preferably, in the step 2: and (3) grinding the large-particle slurry A prepared in the step (1) into a mixture with the particle size of 0.3 mu m to obtain small-particle slurry B, wherein the grinding time is 6 h.
Further, in the step 3: and drying the small particle slurry B by using a spray drying tower, wherein the inlet temperature of the small particle slurry B passing through the spray drying tower is 250 ℃, the outlet temperature of the small particle slurry B passing through the spray drying tower is 80 ℃, and the feeding frequency of the small particle slurry B is 28 Hz.
Further, in the step 4: the temperature of the lithium iron phosphate precursor dried product C in an atmosphere furnace for carrying out the first heat treatment is 550 ℃, the reducing gas in the atmosphere furnace is nitrogen, and the sintering time is 8 h.
Preferably, in the step 5: the mass ratio of the lithium iron phosphate precursor dry matter C to the lithium iron phosphate sintered matter D is 2:1, the heat treatment temperature is 700 ℃, the reducing gas in the atmosphere furnace is nitrogen, and the heat treatment time is 9 hours.
The performance test results of the lithium iron phosphate material prepared in this example are shown in table 1.
Example 4
In this example, the raw materials and operations were the same as in example 1 except that the mass ratio of the lithium iron phosphate precursor dried product C to the lithium iron phosphate sintered product D was changed to 3:1 and the additive was changed to zirconia.
The performance test results of the lithium iron phosphate material prepared in this example are shown in table 1.
Example 5
In this example, the raw materials and operations were the same as those in example 1 except that the mass ratio of the dried lithium iron phosphate precursor C to the sintered lithium iron phosphate D was changed to 4:1 and the additive was changed to ammonium vanadate.
The performance test results of the lithium iron phosphate material prepared in this example are shown in table 1.
Comparative example 1
Mixing and grinding pure water, iron phosphate, a lithium source, a carbon source and an additive in proportion for 1h, grinding the mixture into a mixture with the particle size of 0.8 mu m, and obtaining large-particle slurry A, wherein the additive comprises any one or a combination of at least two of alumina, magnesium carbonate, titanium oxide, zirconium oxide and ammonium vanadate, the mass of the additive is 0.1t% of the mass of a reaction raw material containing lithium, iron and phosphorus, the element molar ratio of the lithium, the iron and the phosphorus is Li: Fe: P =1:0.95:1, the carbon source comprises any one or a combination of at least two of sucrose, glucose, starch, citric acid or PEG, and the mass of the carbon source is 5wt% of the mass of the reaction raw material containing the lithium, the iron and the phosphorus.
Grinding the large-particle slurry A for 4 hours to obtain a mixture with the particle size of 0.1 mu m, thus obtaining small-particle slurry B;
and (3) carrying out spray drying on the small-particle slurry B by using a spray drying tower to obtain a lithium iron phosphate precursor dried product C, wherein the inlet temperature of the lithium iron phosphate precursor dried product C passing through the spray drying tower is 200 ℃, the outlet temperature of the lithium iron phosphate precursor dried product C passing through the spray drying tower is 50 ℃, and the feeding frequency of the lithium iron phosphate precursor dried product C is 10 Hz.
And (3) placing the dried lithium iron phosphate precursor C in an atmosphere furnace for carrying out primary heat treatment for 5 hours to obtain a lithium iron phosphate sinter D, wherein the heat treatment temperature is 400 ℃, and the reducing gas is nitrogen.
The performance test results of the lithium iron phosphate material prepared in the comparative example are shown in table 1.
Comparative example 2
Mixing and grinding pure water, iron phosphate, a lithium source, a carbon source and an additive in proportion for 1h, grinding the mixture into a mixture with the particle size of 0.8 mu m, and obtaining large-particle slurry A, wherein the additive comprises any one or a combination of at least two of alumina, magnesium carbonate, titanium oxide, zirconium oxide and ammonium vanadate, the mass of the additive is 0.1t% of the mass of a reaction raw material containing lithium, iron and phosphorus, the element molar ratio of the lithium, the iron and the phosphorus is Li: Fe: P =1:0.95:1, the carbon source comprises any one or a combination of at least two of sucrose, glucose, starch, citric acid or PEG, and the mass of the carbon source is 5wt% of the mass of the reaction raw material containing the lithium, the iron and the phosphorus.
Grinding the large-particle slurry A for 4 hours to obtain a mixture with the particle size of 0.1 mu m, thus obtaining small-particle slurry B;
and (3) carrying out spray drying on the small-particle slurry B by using a spray drying tower to obtain a lithium iron phosphate precursor dried product C, wherein the inlet temperature of the lithium iron phosphate precursor dried product C passing through the spray drying tower is 200 ℃, the outlet temperature of the lithium iron phosphate precursor dried product C passing through the spray drying tower is 50 ℃, and the feeding frequency of the lithium iron phosphate precursor dried product C is 10 Hz.
And (3) placing the dried lithium iron phosphate precursor C in an atmosphere furnace for carrying out primary heat treatment for 5 hours to obtain a lithium iron phosphate sinter D, wherein the heat treatment temperature is 400 ℃, and the reducing gas is nitrogen.
And (3) placing the lithium iron phosphate sinter D in an atmosphere furnace for heat treatment, and then performing airflow classification treatment to obtain a lithium iron phosphate finished product E, wherein the heat treatment temperature is 600 ℃, the reducing atmosphere in the atmosphere furnace is nitrogen, and the heat treatment time is 8 h.
The performance test results of the lithium iron phosphate material prepared in the comparative example are shown in table 1.
Comparative example 3
In this comparative example, the raw materials and operations were the same as in example 1 except that the mass ratio of the lithium iron phosphate precursor dried product C to the lithium iron phosphate sintered product D was changed to 6: 1.
The performance test results of the lithium iron phosphate material prepared in the comparative example are shown in table 1.
Comparative example 4
In this comparative example, the raw materials and operations were the same as in example 1 except that the mass ratio of the lithium iron phosphate precursor dried product C to the lithium iron phosphate sintered product D was changed to 0.5: 1.
The performance test results of the lithium iron phosphate material prepared in the comparative example are shown in table 1.
Comparative example 5
This comparative example was conducted in the same manner as in example 1 except that the additive components were replaced with "any one or a combination of at least two of alumina, magnesium carbonate, zirconia and ammonium vanadate".
The performance test results of the lithium iron phosphate material prepared in the comparative example are shown in table 1.
Comparative example 6
In this comparative example, the raw materials and operations were the same as in example 1 except that the treatment temperature of the lithium iron phosphate precursor dried product C and the lithium iron phosphate sintered product D were changed to 810 ℃.
The performance test results of the lithium iron phosphate material prepared in the comparative example are shown in table 1.
The performance test method comprises the following steps:
the lithium iron phosphate materials prepared in the examples and the comparative examples were subjected to the following performance tests:
(1) testing of compacted density: the three-principle longitudinal and transverse compacted density tester is used for measuring the compacted density. And placing a powder sample with a certain mass in a metal sleeve, and keeping the ratio of the mass of the sample to the volume of the sample after compaction under a certain pressure for a certain time, wherein the unit is g/cm 3. The calculation formula is as follows: ρ =10 m/(S × H1), where m represents the sample mass, S represents the cross-sectional area of the inner bore of the metal sleeve, and H1 represents the height of the sample after pressing.
(2) Electrochemical testing: the lithium iron phosphate material prepared by the invention is prepared into a positive pole piece, the negative pole is a graphite negative pole, the diaphragm is Celgard2400, the electrolyte is 1mol/L LiPF6, dimethyl carbonate and ethyl methyl carbonate mixed solution (volume ratio is 1:1: 1), and the 18650 cylindrical single cell is assembled. The preparation process of the positive pole piece comprises the following steps: mixing a positive electrode material, a conductive agent acetylene black and a binder PVDF according to the mass percentage of 94:3:3, taking N-methyl pyrrolidone as a solvent, preparing slurry, coating the slurry on an aluminum foil, and drying in vacuum to obtain the positive electrode piece. The preparation process of the negative pole piece comprises the steps of carrying out negative pole batching on graphite, a thickening agent CMC, a binder SBR and conductive carbon powder according to the weight ratio of 95:1:2:2 in a water system to obtain uniform negative pole slurry, and uniformly coating the prepared negative pole slurry on a negative pole current collector Cu foil and cooling to obtain the negative pole piece. Under the condition of normal temperature, the prepared cylindrical battery is tested on a LAND battery test system of Wuhan Jinnuo electronic Limited company, the charging and discharging voltage interval is 2.0-3.65V, the first discharging specific capacity and the 2000 th cyclic discharging specific capacity of the battery are tested under the current density of 1C, the 2000 th cyclic capacity retention ratio is calculated, and the 2000 th cyclic capacity retention ratio = 2000 th cyclic discharging specific capacity/first discharging specific capacity.
(3) Detecting the element content: in an adequate absolute ethyl alcohol environment, a magnetic rod is used for adsorbing magnetic substances in the positive lithium iron phosphate powder material, then the magnetic rod is transferred into a conical flask, the substances without magnetism on the magnetic rod are cleaned, a certain amount of aqua regia is added, the substances are dissolved under the heating condition, and after cooling and constant volume, the element content is detected by an inductively coupled plasma emission spectrometer (ICP-OES).
The test results are shown in table 1 below:
table 1 shows that the compacted density and the electrochemical performance of examples 1 to 5 are significantly improved and the magnetic foreign matter is significantly reduced compared to those of comparative examples 1 to 6, because the preparation method of the above example improves the compacted density and the electrochemical performance of the lithium iron phosphate finished product by introducing the co-firing at the sintering stage.
As can be seen from table 1, in comparative example 5, since no additive is added, the measured compaction density, 0.1C first discharge specific capacity and 2000 th cycle discharge specific capacity are all reduced as compared with example 1, and the magnetic foreign matter is significantly increased, so that the compaction density and electrochemical performance of the finished lithium iron phosphate product with the additive are also significantly enhanced, and the magnetic foreign matter is also reduced.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. A method for producing high-compaction high-capacity lithium iron phosphate is characterized by comprising the following steps:
step 1, preparing large-particle slurry A: mixing pure water, iron phosphate, a lithium source, a carbon source and an additive in proportion and grinding the mixture into a mixture with the particle size of 0.8-1.2 mu m to obtain large-particle slurry A;
step 2, preparing small particle slurry B: grinding the large-particle slurry A prepared in the step one into a mixture with the particle size of 0.1-0.5 mu m to obtain small-particle slurry B;
step 3, preparing a lithium iron phosphate precursor dried product C: spray drying the small particle slurry B prepared in the step two to obtain a lithium iron phosphate precursor dried substance C;
step 4, preparing a lithium iron phosphate sinter D: placing the dried lithium iron phosphate precursor C prepared in the third step into an atmosphere furnace for first heat treatment to obtain a lithium iron phosphate sinter D;
step 5, preparing a lithium iron phosphate finished product E: and D, uniformly mixing the lithium iron phosphate precursor dried substance C obtained in the third step and the lithium iron phosphate sintered substance D obtained in the fourth step, placing the mixture in an atmosphere furnace for secondary heat treatment, and performing airflow classification treatment to obtain a lithium iron phosphate finished product E.
2. The method of claim 1, wherein the molar ratio of Li to Fe to P is (1-1.1) to (0.95-1.0) to (1-1.05).
3. The method for producing high-compaction high-capacity lithium iron phosphate according to claim 1, wherein the carbon source comprises one or a combination of at least two of sucrose, glucose, starch, citric acid and PEG, and the mass of the carbon source is 5-15 wt% of the mass of the reaction raw material containing lithium, iron and phosphorus.
4. The method for producing high-compaction high-capacity lithium iron phosphate according to claim 1, wherein the additive comprises any one or a combination of at least two of alumina, magnesium carbonate, titanium oxide, zirconium oxide and ammonium vanadate, and the mass of the additive is 0.1-1 wt% of that of a reaction raw material containing lithium, iron and phosphorus.
5. The method for producing highly compacted high-capacity lithium iron phosphate according to claim 1, wherein in the step 1: the grinding time is 1-3 h.
6. The method for producing highly compacted high-capacity lithium iron phosphate according to claim 1, wherein in the step 2: the grinding time is 4-8 h.
7. The method for producing highly compacted high-capacity lithium iron phosphate according to claim 1, wherein in the step 3: and drying the small-particle slurry B by using a spray drying tower, wherein the inlet temperature of the small-particle slurry B passing through the spray drying tower is 200-300 ℃, the outlet temperature of the small-particle slurry B is 50-100 ℃, and the feeding frequency of the small-particle slurry B is 10-45 Hz.
8. The method for producing highly compacted high-capacity lithium iron phosphate according to claim 1, wherein in the step 4: and placing the lithium iron phosphate precursor dried substance C in an atmosphere furnace for carrying out primary heat treatment at the temperature of 400-700 ℃, wherein the reducing gas in the atmosphere furnace is nitrogen, and the heat treatment time is 5-10 h.
9. The method for producing highly compacted high-capacity lithium iron phosphate according to claim 1, wherein in the step 5: the mass ratio of the lithium iron phosphate precursor dry matter C to the lithium iron phosphate sintered matter D is (1-5): 1, the heat treatment temperature is 600-.
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