CN113659132A - Preparation method of high-performance nanoscale lithium iron phosphate cathode material - Google Patents
Preparation method of high-performance nanoscale lithium iron phosphate cathode material Download PDFInfo
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- CN113659132A CN113659132A CN202110779070.1A CN202110779070A CN113659132A CN 113659132 A CN113659132 A CN 113659132A CN 202110779070 A CN202110779070 A CN 202110779070A CN 113659132 A CN113659132 A CN 113659132A
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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 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000010406 cathode material Substances 0.000 title claims abstract description 6
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 30
- 238000005056 compaction Methods 0.000 claims abstract description 28
- 239000010405 anode material Substances 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 7
- 238000009826 distribution Methods 0.000 claims abstract description 7
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 7
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000007774 positive electrode material Substances 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 6
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 239000004576 sand Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 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 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 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 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 239000012256 powdered iron Substances 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000012798 spherical particle Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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
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Abstract
The invention discloses a preparation method of a high-performance nanoscale lithium iron phosphate cathode material, which is characterized by preparing a high-compaction-density ferric phosphate intermediate with a certain particle size distribution by controlling the concentration of a reactant, the stirring speed, the reaction time and the reaction temperature, and then preparing the high-compaction-density lithium iron phosphate cathode material by using the intermediate as a raw material through carbon doping; the ferric phosphate intermediate prepared by the invention is spherical or spheroidal particles with nano-to micron-sized particles, has good particle size distribution, and the highest compaction density can be 2.6g/cm3The material is a good material for preparing high-compaction-density lithium iron phosphate; the lithium iron phosphate anode material prepared by the invention can simultaneously meet the conductivity and high compaction density,is an excellent anode material for preparing a high-power and energy-density lithium iron phosphate battery.
Description
Technical Field
The invention belongs to the technical field of new energy materials, and relates to a preparation method of a high-compaction-density lithium iron phosphate positive electrode material.
Background
The lithium iron phosphate battery has the characteristics of high theoretical capacity, high working voltage, proper energy density, small self-discharge, long cycle life, no memory effect, low price, good thermal stability, environmental friendliness and the like, and is expected to replace a LiCoO2 battery with higher cost to become a new generation of lithium ion battery.
Compared with the ternary anode material, the lithium iron phosphate has low tap density, so that the prepared battery core pole piece has low compaction density, the energy density is limited, and the lithium iron phosphate industry is pressed by the ternary anode material once. However, because of low cost, more environmental protection and high safety performance, the lithium iron phosphate is an ideal material for the anode material of the lithium ion battery, the safety performance of the current passenger vehicle is gradually emphasized, the market occupation ratio of the lithium iron phosphate is higher and higher, and if the problem of low compaction of the lithium iron phosphate can be solved, the energy density of the lithium iron phosphate anode material can be further improved.
At present, a solid-phase synthesis method is mostly adopted for preparing a lithium iron phosphate positive electrode material, a precursor is synthesized firstly, then sintering is carried out, and finally crushing is carried out to obtain the lithium iron phosphate positive electrode material with a certain particle size, and the compaction density of the lithium iron phosphate material is influenced by the mass of the precursor, the sintering temperature and the particle size after crushing, so the improvement can be carried out from the three aspects, wherein the improvement space of the compaction density by the temperature and the crushing particle size during sintering is limited, the requirement for preparing the high-compaction-density lithium iron phosphate material cannot be met, and particularly, the method for improving the compaction of the lithium iron phosphate material by improving the compaction density of the precursor is the most effective and the most obvious method.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a preparation method of a high-performance nanoscale lithium iron phosphate positive electrode material, which is to prepare a ferric phosphate intermediate with a certain particle size distribution, and then prepare, calcine and crush the ferric phosphate intermediate with a lithium source and a carbon source according to a certain proportion to finally obtain the high-compaction-density lithium iron phosphate positive electrode material.
The technical scheme of the invention is realized by the following modes: a preparation method of a high-performance nanoscale lithium iron phosphate cathode material comprises the following steps:
A) preparing precursor iron phosphate:
respectively preparing a ferrous salt aqueous solution, a phosphorus source aqueous solution and a hydrogen peroxide solution in a mol ratio, adding the ferrous salt aqueous solution and the phosphate aqueous solution in a reaction kettle according to a certain stoichiometric ratio, controlling the concentration of the added hydrogen peroxide solution, reacting at the stirring speed of 100-1000 rpm for 0.5-6 h at the reaction temperature of 20-80 ℃ to generate an iron phosphate (III) mixed solution with a certain particle size distribution, and performing filter pressing, washing, drying and crushingObtaining spherical or spheroidal particles with a compacted density of 2.35-2.65g/cm3-2.6g/cm3Powdered iron phosphate powder intermediate;
B) weighing the powder ferric phosphate powder intermediate obtained in the step A), adding a lithium source and a carbon source according to the proportion of 1:1.01-0.02:0.1-0.2, dissolving in pure water, sanding for 2h in a sand mill, spray-drying the slurry, and then N2Calcining at 700 ℃ for 12h under the protection of atmosphere, raising the temperature at the rate of 5 ℃/min, naturally cooling to room temperature, crushing by using a crusher to obtain a spherical or spheroidal lithium iron phosphate anode material with the particle size D50 of 3.8-8.34 mu m, and measuring the compaction density of 2.42-2.6g/cm3。
Preferably, the concentration of the ferrous salt solution in the A) is 0.5-2mol/L, and the ferrous salt solution is one or more of ferric sulfate, ferric nitrate and ferric chloride; the concentration of the phosphorus source solution is 0.5-2mol/L, and the phosphorus source solution is one or more of phosphoric acid, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, potassium monohydrogen phosphate, potassium dihydrogen phosphate, potassium phosphate, sodium monohydrogen phosphate, sodium dihydrogen phosphate and sodium phosphate; the hydrogen peroxide solution is industrial grade or analytically pure hydrogen peroxide solution, and the concentration is 27.5% -50%.
Preferably, the drying temperature in the step A) is 200-800 ℃, and the drying time is 0.5-3 h.
Preferably, the iron phosphate powder after the pulverization in the above A) has a particle size of 7.38 to 17.85 μm.
Preferably, the iron phosphate intermediate with a certain particle size distribution in the B) is determined according to the particle size of D50; the lithium source is one or more of lithium carbonate, lithium oxalate, lithium acetate and lithium hydroxide; the carbon source is one or more of glucose, sucrose, PEG, acetylene black, graphene and carbon black.
Preferably, the inert gas in B) is one or more of nitrogen, argon, carbon dioxide, and the like.
Preferably, the calcining temperature in the step B) is 400-800 ℃, and the calcining time is 4-24 h; the particle size of the crushed D50 is 1-20 μm.
The invention can simultaneously meet the conductivity and high compaction density, and is an excellent anode material for preparing the lithium iron phosphate battery with high power and energy density.
Drawings
FIG. 1 is an SEM image of nanoscale spherical iron phosphate.
FIG. 2 shows LiFePO4SEM image of/C.
Detailed Description
Example 1
The preparation method of the high-compaction iron phosphate particles comprises the steps of slowly dropwise adding 500ml of 1mol/L phosphoric acid solution into a three-neck flask filled with 500ml of 1mol/L ferric sulfate solution through a dropping funnel, heating the flask in a water bath at 60 ℃ to maintain the reaction temperature, then slowly adding 35g of 27.5% industrial grade hydrogen peroxide solution, adjusting the mechanical stirring speed to be 100rpm, reacting for 1 hour, generating mixed liquid containing nano iron phosphate after the system becomes white, filtering, washing, dehydrating and drying at 300 ℃ for 10 hours, crushing by airflow to obtain iron phosphate powder with D50 of 13.52 mu m, and measuring the compaction density to be 2.43g/cm3. The appearance is shown in figure 1.
Feeding the iron phosphate, lithium carbonate and sucrose according to the proportion of 1:1.01:0.1, dissolving in pure water, sanding for 2h in a sand mill, spray-drying the slurry, calcining for 12h at 700 ℃ under the protection of N2 atmosphere, raising the temperature at a rate of 5 ℃/min, naturally cooling to room temperature, crushing by using a crusher to obtain the lithium iron phosphate anode material with the particle size D50 of 3.8 mu m, and measuring the compacted density of 2.42g/cm3. The appearance is shown in figure 2.
Example 2
The preparation method of the high-compaction iron phosphate particles comprises the steps of slowly dripping 500ml of 1mol/L ammonium dihydrogen phosphate solution into a three-neck flask filled with 250ml of 2mol/L ferric sulfate solution through a dropping funnel, heating the flask in a water bath at 50 ℃ to maintain the reaction temperature, then slowly adding 15g of 50% industrial grade hydrogen peroxide solution, adjusting the mechanical stirring speed to 300rpm, reacting for 30min, generating mixed liquid containing nano iron phosphate after the system turns white in color, filtering, washing, dehydrating and drying at 300 ℃ for 10h, crushing by airflow to obtain iron phosphate powder with D50 of 17.85 mu m, and measuring the compaction density to be 2.35g/cm3。
Mixing the iron phosphate with lithium carbonate and sucroseFeeding materials according to the ratio of 1:1.02:0.2, dissolving in pure water, sanding for 3h in a sand mill, spray-drying the slurry, calcining at 650 ℃ for 13h under the protection of N2 atmosphere, heating at the rate of 5 ℃/min, naturally cooling to room temperature, crushing by using a crusher to obtain a lithium iron phosphate anode material with the particle size D50 of 4.83 mu m, and measuring the compaction density of 2.48g/cm3。
Example 3
The preparation method of high-compaction iron phosphate particles comprises the steps of slowly dropwise adding 250ml of 2mol/L sodium dihydrogen phosphate solution into a three-neck flask filled with 500ml of 1mol/L ferric sulfate solution through a dropping funnel, heating the flask in a water bath at 50 ℃ to maintain the reaction temperature, then slowly adding 35g of 27.5% industrial grade hydrogen peroxide solution, adjusting the mechanical stirring speed to be 500rpm, reacting for 1.5h, obtaining mixed liquid containing nano iron phosphate after the system turns white in color, filtering, washing, dehydrating and drying at 350 ℃ for 12h, carrying out airflow crushing to obtain iron phosphate powder with the D50 of 7.38 mu m, and measuring the compaction density of 2.62g/cm3。
Feeding the iron phosphate, lithium carbonate and sucrose according to the proportion of 1:1.01:0.2, dissolving in pure water, sanding for 2h in a sand mill, spray-drying the slurry, calcining for 10h at 650 ℃ under the protection of N2 atmosphere, raising the temperature at the rate of 5 ℃/min, naturally cooling to room temperature, crushing by using a crusher to obtain the lithium iron phosphate anode material with the particle size D50 of 6.62 mu m, and measuring the compacted density of 2.57g/cm3。
Example 4
A preparation method of high-compaction iron phosphate particles comprises the steps of slowly dripping 500ml of 2mol/L ammonium dihydrogen phosphate solution into a three-neck flask filled with 500ml of 2mol/L ferric sulfate solution through a dropping funnel, heating the flask in a water bath at 80 ℃ to maintain the reaction temperature, then slowly adding 70g of 27.5% industrial grade hydrogen peroxide solution, adjusting the mechanical stirring speed to 300rpm, reacting for 2 hours, obtaining mixed liquid containing nano iron phosphate after the system turns white in color, filtering, washing, dehydrating and drying at 350 ℃ for 12 hours, carrying out airflow crushing to obtain iron phosphate powder with D50 of 12.18 mu m, and measuring the compaction density to be 2.55g/cm3。
Mixing the iron phosphate with lithium carbonate and sucrose according to the ratio of 1Feeding materials according to the proportion of 1.02:0.2, dissolving in pure water, sanding for 2h in a sand mill, spray-drying the slurry, calcining at 800 ℃ for 10h under the protection of N2 atmosphere, raising the temperature at the rate of 5 ℃/min, naturally cooling to room temperature, crushing by using a crusher to obtain a lithium iron phosphate anode material with the particle size D50 of 8.34 mu m, and measuring the compaction density of 2.6g/cm3。
Additional Table 1 shows the D50 particle size and compacted density g/cm for the iron phosphate intermediates and lithium iron phosphate of examples 1-43。
Attached table 1
Claims (7)
1. A preparation method of a high-performance nanoscale lithium iron phosphate cathode material comprises the following steps:
A) preparing precursor iron phosphate:
respectively preparing a ferrous salt aqueous solution, a phosphorus source aqueous solution and a hydrogen peroxide solution according to a mol ratio, adding the ferrous salt aqueous solution and the phosphate aqueous solution into a reaction kettle according to a certain stoichiometric ratio, controlling the concentration of the added hydrogen peroxide solution, reacting at a stirring speed of 100-1000 rpm for 0.5-6 h at 20-80 ℃ to generate an iron phosphate (III) mixed solution with a certain particle size distribution, and performing filter pressing, washing, drying and crushing to obtain spherical or quasi-spherical particles with a compaction density of 2.35-2.65g/cm3-2.6g/cm3Powdered iron phosphate powder intermediate;
B) weighing the powder ferric phosphate powder intermediate obtained in the step A), adding a lithium source and a carbon source according to the proportion of 1:1.01-0.02:0.1-0.2, dissolving in pure water, sanding for 2h in a sand mill, spray-drying the slurry, and then N2Calcining at 700 ℃ for 12h under the protection of atmosphere, raising the temperature at the rate of 5 ℃/min, naturally cooling to room temperature, crushing by using a crusher to obtain a spherical or spheroidal lithium iron phosphate anode material with the particle size D50 of 3.8-8.34 mu m, and measuring the compaction density of 2.42-2.6g/cm3。
2. The preparation method of the high-performance nanoscale lithium iron phosphate positive electrode material according to claim 1, characterized by comprising the following steps: the concentration of the ferrous salt solution in the step A) is 0.5-2mol/L, and the ferrous salt solution is one or more of ferric sulfate, ferric nitrate and ferric chloride; the concentration of the phosphorus source solution is 0.5-2mol/L, and the phosphorus source solution is one or more of phosphoric acid, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, potassium monohydrogen phosphate, potassium dihydrogen phosphate, potassium phosphate, sodium monohydrogen phosphate, sodium dihydrogen phosphate and sodium phosphate; the hydrogen peroxide solution is industrial grade or analytically pure hydrogen peroxide solution, and the concentration is 27.5% -50%.
3. The preparation method of the high-performance nanoscale lithium iron phosphate positive electrode material according to claim 1, characterized by comprising the following steps: the drying temperature in the step A) is 200-800 ℃, and the drying time is 0.5-3 h.
4. The preparation method of the high-performance nanoscale lithium iron phosphate positive electrode material according to claim 1, characterized by comprising the following steps: the particle size of the iron phosphate powder crushed in the step A) is 7.38-17.85 microns.
5. The preparation method of the high-performance nanoscale lithium iron phosphate positive electrode material according to claim 1, characterized by comprising the following steps: the ferric phosphate intermediate with a certain particle size distribution in the step B) takes the particle size of D50 as a standard; the lithium source is one or more of lithium carbonate, lithium oxalate, lithium acetate and lithium hydroxide; the carbon source is one or more of glucose, sucrose, PEG, acetylene black, graphene and carbon black.
6. The preparation method of the high-performance nanoscale lithium iron phosphate positive electrode material according to claim 1, characterized by comprising the following steps: the inert gas in the step B) is one or more of nitrogen, argon, carbon dioxide and the like.
7. The preparation method of the high-performance nanoscale lithium iron phosphate positive electrode material according to claim 1, characterized by comprising the following steps: the calcination temperature in the step B) is 400-800 ℃, and the calcination time is 4-24 h; the particle size of the crushed D50 is 1-20 μm.
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