CN115448281B - LiAlF coated on surface 4 Preparation method of low-temperature lithium iron phosphate of fast ion conductor - Google Patents
LiAlF coated on surface 4 Preparation method of low-temperature lithium iron phosphate of fast ion conductor Download PDFInfo
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- CN115448281B CN115448281B CN202211109759.4A CN202211109759A CN115448281B CN 115448281 B CN115448281 B CN 115448281B CN 202211109759 A CN202211109759 A CN 202211109759A CN 115448281 B CN115448281 B CN 115448281B
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- iron phosphate
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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 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000010416 ion conductor Substances 0.000 title claims abstract description 24
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 63
- 239000002243 precursor Substances 0.000 claims abstract description 61
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 59
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 59
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 59
- 238000005243 fluidization Methods 0.000 claims abstract description 38
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- NUVIPRKSJRNEQS-UHFFFAOYSA-N 1h-pyrrole;hydrofluoride Chemical compound F.C=1C=CNC=1 NUVIPRKSJRNEQS-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000004114 Ammonium polyphosphate Substances 0.000 claims abstract description 23
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims abstract description 23
- 229920001276 ammonium polyphosphate Polymers 0.000 claims abstract description 23
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims abstract description 14
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 claims abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 11
- 239000011574 phosphorus Substances 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 91
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 68
- 229910052757 nitrogen Inorganic materials 0.000 claims description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 23
- 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 22
- 239000002077 nanosphere Substances 0.000 claims description 20
- 239000000725 suspension Substances 0.000 claims description 18
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 16
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 16
- GRJJQCWNZGRKAU-UHFFFAOYSA-N pyridin-1-ium;fluoride Chemical compound F.C1=CC=NC=C1 GRJJQCWNZGRKAU-UHFFFAOYSA-N 0.000 claims description 15
- 239000012266 salt solution Substances 0.000 claims description 10
- 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 9
- 239000008103 glucose Substances 0.000 claims description 9
- 239000011164 primary particle Substances 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 230000001351 cycling effect Effects 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 3
- 230000002776 aggregation Effects 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 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 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 238000005054 agglomeration Methods 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
- 239000013078 crystal Substances 0.000 claims description 2
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 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 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Inorganic materials [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 29
- 239000011248 coating agent Substances 0.000 abstract description 26
- 230000008569 process Effects 0.000 abstract description 19
- 238000005530 etching Methods 0.000 abstract description 17
- 229910010227 LiAlF4 Inorganic materials 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 239000007774 positive electrode material Substances 0.000 abstract description 2
- 238000007600 charging Methods 0.000 description 27
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 15
- 238000001816 cooling Methods 0.000 description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 13
- 239000007789 gas Substances 0.000 description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 9
- 238000004321 preservation Methods 0.000 description 8
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 230000001681 protective effect Effects 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000009831 deintercalation Methods 0.000 description 4
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 3
- 238000009690 centrifugal atomisation Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- PPTSBERGOGHCHC-UHFFFAOYSA-N boron lithium Chemical compound [Li].[B] PPTSBERGOGHCHC-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000010278 pulse charging Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/50—Fluorides
- C01F7/54—Double compounds containing both aluminium and alkali metals or alkaline-earth metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- 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
- C01P2006/12—Surface area
-
- 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
-
- 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 low-temperature lithium iron phosphate with a LiAlF4 fast ion conductor coated on the surface, which comprises the following steps: s1: mixing a porous ferric phosphate precursor, a lithium source and a carbon source, and calcining to obtain lithium iron phosphate; s2: putting the lithium iron phosphate obtained in the step S1 into a fluidization device and heating to 250-280 ℃; s3: sequentially pulse-introducing steam of trimethylaluminum, a hydrogen fluoride pyrrole solution, lithium tert-butoxide and the hydrogen fluoride pyrrole solution to obtain the lithium iron phosphate with the surface coated with the LiAlF4 fast ion conductor. The ammonium polyphosphate is used as a phosphorus source, so that the cost for preparing the lithium iron phosphate is reduced. The lithium iron phosphate is firstly etched when being prepared, and then the LiAlF4 fast ion conductor is adopted for coating, so that the coating effect is better, the defects generated in the etching process are also overcome, and the charge and discharge performance of the lithium iron phosphate as a positive electrode material is greatly improved; the invention also realizes the uniform coating of the surface of the lithium iron phosphate; meanwhile, the preparation process is greatly simplified, and the preparation efficiency is improved.
Description
Technical Field
The invention relates to the technical field of production of lithium ion battery anode materials, in particular to a surface-coated LiAlF 4 A preparation method of low-temperature lithium iron phosphate of a fast ion conductor.
Background
The fast ion conductor coating can solve the problems of poor electrochemical performance, thermal stability and structural stability of the battery anode material to a certain extent, and the fast ion conductor coating modification has great significance on improving the performance of the lithium ion battery anode material. As disclosed in CN104332618A, a method for preparing a ternary nickel cobalt lithium manganate anode material coated by a boron-lithium composite oxide by a liquid phase coating method is specifically prepared by adding a ternary nickel cobalt lithium manganate material into a mixed alcohol solution of a lithium source and a boron source, uniformly dispersing the ternary nickel cobalt lithium manganate material by ultrasound, adding a dispersing agent to fully infiltrate the material, evaporating a solvent, and performing heat treatment to obtain a surface-coated material, wherein the heat treatment is carried out for 25 hours at a constant temperature of 900 ℃, and then cooling along with a furnace. The liquid phase coating method can cause the problems of low coating efficiency and uneven coating, and meanwhile, the uneven coating distribution of the fast ion conductor also influences the improvement effect of the fast ion conductor coating on the electrochemical performance. Similar coating methods are also disclosed in patents CN104362330a and CN103236521 a. The materials filtering, washing and sintering processes brought by the liquid phase mixing and sintering processes in the patents have complex processes and long treatment time, and can cause the reduction of production efficiency and the increase of cost.
In addition, the viscosity of the electrolyte at low temperature is increased, and the conductivity of the lithium iron phosphate is too poor, so that the charge and discharge electrode is increased, the overpotential in the battery is increased, and lithium is separated from the anode during charging; the low temperature and large current discharge, the battery is easily reached to the lower limit voltage cutoff due to large polarization, and thus cannot be discharged. In order to meet the requirement of charging and discharging at low temperature, many battery manufacturers wrap a layer of heat preservation cotton on the outer surface of the battery core, heat treatment is performed on the battery before the battery is charged and discharged at low temperature, and charging and discharging are started when the safe working temperature of the battery is reached. However, the battery cost is too high, the heating time of the heating cotton is too long, and the effect is not good in practical use. Therefore, development of low-temperature lithium iron phosphate is necessary.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art and provides a surface-coated LiAlF 4 Preparation method of low-temperature lithium iron phosphate of fast ion conductor, wherein lithium iron phosphate is in fluidization state through fluidization device and is filled with gas phase cladding in cooperation with pulseMaterial for coating lithium iron phosphate with LiAlF 4 And the porous ferric phosphate precursor is used for preparing the lithium iron phosphate, so that a lithium ion deintercalation channel in the lithium iron phosphate is increased, and the deintercalation channel is matched with LiAlF 4 The coating realizes the preparation of low-temperature type lithium iron phosphate with rapid charge and discharge and high stability. The specific technical scheme is as follows:
LiAlF coated on surface 4 The preparation method of the low-temperature lithium iron phosphate of the fast ion conductor comprises the following steps:
s1: mixing a porous ferric phosphate precursor, a lithium source and a carbon source, and calcining to obtain lithium iron phosphate;
s2: putting the lithium iron phosphate obtained in the step S1 into a fluidization device and heating to 250-280 ℃;
s3: sequentially pulse-introducing steam of trimethylaluminum, a hydrogen fluoride pyrrole solution, lithium tert-butoxide and the hydrogen fluoride pyrrole solution to obtain the lithium iron phosphate with the surface coated with the LiAlF4 fast ion conductor.
The lithium source in the S1 is one or two of lithium carbonate or lithium hydroxide;
the carbon source in the S1 is one or the combination of two or more of glucose, sucrose and polyethylene glycol.
In the S1, the molar ratio of the porous ferric phosphate precursor to the lithium source is (1-1.15) according to the mole ratio of Li to Fe: 1.
The addition amount of the carbon source in the S1 is 2-8% of the total mass of the porous ferric phosphate and the lithium source;
the preparation method of the porous ferric phosphate precursor in the step S1 comprises the following steps:
(1) Dissolving ammonium polyphosphate crystals in deionized water to obtain an ammonium polyphosphate solution;
(2) Dissolving an iron source in deionized water to obtain an iron salt solution;
(3) Mixing the solutions obtained in step (1) and step (2) according to the quantitative Fe/P to obtain a mixed salt solution;
(4) Adding TiO to the mixed salt solution in (3) 2 The nanospheres obtain suspension solution, and the suspension solution is atomized and then heated to 500-600 ℃ to obtain an iron phosphate precursor;
(5) Placing the ferric phosphate precursor in a fluidization device to enable the ferric phosphate precursor to be in a fluidization state;
(6) Under certain conditions, hydrogen fluoride pyridine steam is pulse-fed into the fluidization device to obtain a porous ferric phosphate precursor;
the phosphorus content of the ammonium polyphosphate solution in the step (1) is 5-10wt%.
The concentration of ferric iron in the iron salt solution in the step (2) is 0.8-1.5 mol/L.
The iron source in the step (2) is soluble ferric salt, and is selected from one or a mixture of any of ferric chloride, ferric sulfate, ferric oxalate and ferric nitrate, preferably ferric nitrate.
The molar concentration ratio of Fe/P in the mixed salt solution in the step (3) is 0.96-1.05.
The TiO of (4) 2 The primary particle size of the nanospheres is 50-100nm, and the secondary agglomeration particle size is 1-3 mu m.
The atomization mode in the step (4) is high-speed centrifugal atomization.
The TiO in (4) 2 The molar mass ratio of the nanospheres to Fe in the mixed solution is (0.02-0.1): 1.
the vacuum degree in the fluidization device in the step (5) is kept to be less than 5torr, and the temperature is controlled to be 200-250 ℃.
(5) And nitrogen is introduced, and the flow rate of the nitrogen in the step S5 is controlled to be 30-500 sccm.
The hydrofluoric acid in the step (6) is sourced from a source device filled with the hydrogen fluoride pyridine solution, and the temperature of the source device and a pipeline of the hydrogen fluoride pyridine solution is controlled at 40-60 ℃;
the condition of pulse feeding of the hydrogen fluoride pyridine steam in the step (6) is that the single feeding time is controlled to be 0.1-2 s, the gap time is 10-100 s, and the pulse times are 1-100 times.
The fluidization device also comprises an exhaust gas treatment device and/or a reagent.
The lithium iron phosphate prepared by the method also comprises a small amount of titanium oxide.
And in the step S2, heating to 280 ℃ in a vulcanizing device, introducing nitrogen and controlling the nitrogen flow speed to be 150-250sccm.
Sequentially pulse-introducing the vapor of trimethylaluminum, the hydrogen fluoride pyrrole solution, the lithium tert-butoxide and the hydrogen fluoride pyrrole solution for 8-20S, 3-10S, 15-35S and 3-10S in the step S3, and simultaneously, respectively keeping the interval time at 800-1500S; cycling for 5-20 times.
In a preferred scheme, in the step S3, the vapor of trimethylaluminum, a hydrogen fluoride pyrrole solution, lithium tert-butoxide and the hydrogen fluoride pyrrole solution is sequentially pulsed for 10S,8S, 120S and 8S, and meanwhile, the respective interval time is 1000S; cycling was performed 12 times.
The lithium iron phosphate prepared by the preparation method can be used as a battery anode material.
The invention has the following beneficial effects:
1. etching is firstly carried out when lithium iron phosphate is prepared, and then LiAlF is adopted 4 The fast ion conductor is coated, so that the coating effect is better, and meanwhile, the defects generated in the etching process are also overcome; the porous ferric phosphate precursor is used for preparing the lithium iron phosphate, so that a lithium ion deintercalation channel in the lithium iron phosphate is increased, and the deintercalation channel is matched with LiAlF 4 Coating, the charge and discharge performance required by taking lithium iron phosphate as a positive electrode material is greatly improved;
2. on the one hand, the ammonium polyphosphate is used as a phosphorus source, so that the p content in the ammonium polyphosphate is high, the price is low, and the cost for preparing the lithium iron phosphate is reduced; on the other hand, the solubility is high, the method is suitable for dissolution in a low-temperature environment, and the preparation efficiency of the ferric phosphate or lithium iron phosphate material in the low-temperature environment can be improved;
3. the hydrogen fluoride pyridine solution is used for replacing hydrofluoric acid solution, the hydrogen fluoride pyridine is stable at normal temperature and normal pressure, hydrofluoric acid and organic matters can be decomposed at high temperature, and the problems that pipelines are corroded and leakage is easy to occur when the hydrofluoric acid solution is directly used are avoided; in addition, the method is used in combination with a fluidization device and a pulse feeding method, so that the consumption can be reduced, the amount of the generated waste liquid is smaller, and the cost of tail gas treatment is reduced;
4. the lithium iron phosphate is in a fluidized state through a fluidization device, and then is matched with pulse to be introduced into a gas phase coating material to coat LiAlF on the lithium iron phosphate 4 The generation of clusters with smaller lithium iron phosphate size is improvedThe problem of uneven coating caused by aggregation and the like is solved, and the uniform coating of the surface of the lithium iron phosphate is realized; meanwhile, the preparation process is greatly simplified, and the preparation efficiency is improved; the pulse mode can avoid raw material waste and reduce preparation cost;
5. according to the invention, the mesoporous ferric phosphate precursor is used for preparing the lithium iron phosphate, and the prepared lithium iron phosphate has a high specific surface area, so that the migration path of lithium ions can be effectively shortened; by coating LiAlF 4 The compact coating layer can be formed, so that side reactions with electrolyte are effectively prevented, and meanwhile, the coating layer has a faster migration rate of lithium ions; the synthesized lithium iron phosphate can be applied to a low-temperature environment.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
Example 1
(1) Preparation of porous ferric phosphate precursor
(1) Preparing ammonium polyphosphate solution with the phosphorus content of 8wt% and ferric nitrate solution with the concentration of 1.2 mol/L; mixing the ammonium polyphosphate solution and the ferric nitrate solution according to the Fe/P molar concentration ratio of 0.96 to obtain a mixed solution; (2) According to TiO 2 Nanospheres (primary particle size 50 nm): the molar ratio of Fe in the mixed solution is 0.06:1 ratio of TiO to the above-mentioned mixed solution 2 The nanospheres are obtained into suspension solution, and then the suspension solution is centrifugally atomized at high speed and then heated to 550 ℃ to obtain ferric phosphate precursor; (3) Placing the ferric phosphate precursor in a fluidization device, introducing nitrogen, controlling the flow rate to be 120sccm, controlling the vacuum degree in a process cavity of the fluidization device to be 3torr, and controlling the temperature of the process cavity to be 200 ℃; (4) Pulse-charging hydrogen fluoride gas, controlling the single-charging time to be 0.8s, the gap time to be 100s, the pulse times to be 20, controlling the temperature of a hydrogen fluoride pyridine solution pipeline and a source device to be 40 ℃,etching; (5) And after etching is finished, continuously introducing nitrogen for more than 10min, and cooling to obtain the porous ferric phosphate precursor.
(2) Preparation of lithium iron phosphate
According to Li: fe is 1.05:1, mixing a porous ferric phosphate precursor and lithium carbonate, adding glucose accounting for 5% of the total mass of the porous ferric phosphate precursor and the lithium carbonate, uniformly mixing, calcining under a protective atmosphere, heating to 580 ℃ at a heating rate of 8 ℃/min, and naturally cooling after heat preservation for 4 hours to obtain lithium iron phosphate;
charging lithium iron phosphate into a fluidization device, heating to 280 ℃, charging nitrogen with the flow rate of the nitrogen controlled at 180sccm, sequentially charging steam of trimethylaluminum, hydrogen fluoride pyrrole solution, lithium tert-butoxide and hydrogen fluoride pyrrole solution for 10s,8s,20s and 8s respectively, with the interval time of 1000s, and circulating for 12 times to obtain LiAlF with the surface coating thickness of 1.5nm 4 Low temperature lithium iron phosphate.
Example 2
(1) Preparation of porous ferric phosphate precursor
Preparing an ammonium polyphosphate solution with the phosphorus content of 10wt% and preparing an iron nitrate solution with the concentration of 1.2 mol/L; mixing the ammonium polyphosphate solution and the ferric nitrate solution according to the Fe/P molar concentration ratio of 1.05 to obtain a mixed solution; (2) according to TiO2 nanospheres (primary particle size 50 nm): the molar ratio of Fe in the mixed solution is 0.1:1, adding TiO2 nanospheres into the mixed solution in proportion to obtain a suspension solution, and then heating the suspension solution to 550 ℃ after high-speed centrifugal atomization to obtain an iron phosphate precursor; (3) Placing the ferric phosphate precursor in a fluidization device, introducing nitrogen, controlling the flow rate to be 120sccm, controlling the vacuum degree in a process cavity of the fluidization device to be 3torr, and controlling the temperature of the process cavity to be 200 ℃; (4) Pulse-introducing hydrogen fluoride gas, controlling the single-time introducing time to be 0.8s, the gap time to be 100s, the pulse times to be 100 times, controlling the temperature of a hydrogen fluoride pyridine solution pipeline and a source device to be 40 ℃, and etching; (5) And after etching is finished, continuously introducing nitrogen for more than 10min, and cooling to obtain the porous ferric phosphate precursor.
(2) Preparation of lithium iron phosphate
According to Li: fe is 1:1, mixing a porous ferric phosphate precursor and lithium carbonate, adding glucose accounting for 5% of the total mass of the porous ferric phosphate precursor and the lithium carbonate, uniformly mixing, calcining under a protective atmosphere, heating to 580 ℃ at a heating rate of 8 ℃/min, and naturally cooling after heat preservation for 4 hours to obtain lithium iron phosphate;
charging lithium iron phosphate into a fluidization device, heating to 280 ℃, charging nitrogen with the flow rate of the nitrogen controlled at 180sccm, sequentially charging steam of trimethylaluminum, hydrogen fluoride pyrrole solution, lithium tert-butoxide and hydrogen fluoride pyrrole solution, wherein the charging time is 10s,8s,20s and 8s respectively, the interval time is 1000s, and circulating for 12 times to obtain LiAlF with the surface coating thickness of 1.5nm 4 Low temperature lithium iron phosphate.
Example 3
(1) Preparation of porous ferric phosphate precursor
Preparing an ammonium polyphosphate solution with the phosphorus content of 10wt% and preparing an iron nitrate solution with the concentration of 1.2 mol/L; mixing the ammonium polyphosphate solution and the ferric nitrate solution according to the Fe/P molar concentration ratio of 1.05 to obtain a mixed solution; (2) according to TiO2 nanospheres (primary particle size of 100 nm): the molar ratio of Fe in the mixed solution is 0.1:1 ratio of TiO to the above-mentioned mixed solution 2 The nanospheres are obtained into suspension solution, and then the suspension solution is centrifugally atomized at high speed and then heated to 550 ℃ to obtain ferric phosphate precursor; (3) Placing the ferric phosphate precursor in a fluidization device, introducing nitrogen, controlling the flow rate to be 120sccm, controlling the vacuum degree in a process cavity of the fluidization device to be 3torr, and controlling the temperature of the process cavity to be 200 ℃; (4) Pulse-introducing hydrogen fluoride gas, controlling the single-time introducing time to be 2s, the gap time to be 10s, the pulse times to be 100 times, controlling the temperature of a hydrogen fluoride pyridine solution pipeline and a source device to be 40 ℃, and etching; (5) And after etching is finished, continuously introducing nitrogen for more than 10min, and cooling to obtain the porous ferric phosphate precursor.
(2) Preparation of lithium iron phosphate
According to Li: fe is 1:1, mixing a porous ferric phosphate precursor and lithium carbonate, adding glucose accounting for 5% of the total mass of the porous ferric phosphate precursor and the lithium carbonate, uniformly mixing, calcining under a protective atmosphere, heating to 580 ℃ at a heating rate of 8 ℃/min, and naturally cooling after heat preservation for 4 hours to obtain lithium iron phosphate;
charging lithium iron phosphate into a fluidization device, heating to 280 ℃, charging nitrogen with the flow rate of the nitrogen controlled at 180sccm, sequentially charging steam of trimethylaluminum, hydrogen fluoride pyrrole solution, lithium tert-butoxide and hydrogen fluoride pyrrole solution for 10s,8s,20s and 8s respectively, with the interval time of 1000s, and circulating for 12 times to obtain LiAlF with the surface coating thickness of 1.5nm 4 Low temperature lithium iron phosphate.
Example 4
(1) Preparation of porous ferric phosphate precursor
Preparing an ammonium polyphosphate solution with the phosphorus content of 10wt% and preparing an iron nitrate solution with the concentration of 1.2 mol/L; mixing the ammonium polyphosphate solution and the ferric nitrate solution according to the Fe/P molar concentration ratio of 1.05 to obtain a mixed solution; (2) according to TiO2 nanospheres (primary particle size of 100 nm): the molar ratio of Fe in the mixed solution is 0.1:1, adding TiO2 nanospheres into the mixed solution in proportion to obtain a suspension solution, and then heating the suspension solution to 550 ℃ after high-speed centrifugal atomization to obtain an iron phosphate precursor; (3) Placing the ferric phosphate precursor in a fluidization device, introducing nitrogen, controlling the flow rate to be 120sccm, controlling the vacuum degree in a process cavity of the fluidization device to be 3torr, and controlling the temperature of the process cavity to be 200 ℃; (4) Pulse-introducing hydrogen fluoride gas, controlling the single-time introducing time to be 2s, the gap time to be 10s, the pulse times to be 100 times, controlling the temperature of a hydrogen fluoride pyridine solution pipeline and a source device to be 40 ℃, and etching; (5) And after etching is finished, continuously introducing nitrogen for more than 10min, and cooling to obtain the porous ferric phosphate precursor.
(2) Preparation of lithium iron phosphate
According to Li: fe is 1.15:1, mixing a porous ferric phosphate precursor and lithium carbonate, adding glucose accounting for 5% of the total mass of the porous ferric phosphate precursor and the lithium carbonate, uniformly mixing, calcining under a protective atmosphere, heating to 580 ℃ at a heating rate of 8 ℃/min, and naturally cooling after heat preservation for 4 hours to obtain lithium iron phosphate;
charging lithium iron phosphate into a fluidization device, heating to 280 ℃, introducing nitrogen and controlling the flow rate of the nitrogen to 180sccm, and sequentiallyIntroducing steam of trimethylaluminum, hydrogen fluoride pyrrole solution, lithium tert-butoxide and hydrogen fluoride pyrrole solution for 10s,8s,20s and 8s respectively, with interval of 1000s, and circulating for 12 times to obtain LiAlF with surface coating thickness of 1.5nm 4 Low temperature lithium iron phosphate.
Example 5
(1) Preparation of porous ferric phosphate precursor
Preparing an ammonium polyphosphate solution with the phosphorus content of 10wt% and preparing an iron nitrate solution with the concentration of 1.2 mol/L; mixing the ammonium polyphosphate solution and the ferric nitrate solution according to the Fe/P molar concentration ratio of 1.05 to obtain a mixed solution; (2) according to TiO2 nanospheres (primary particle size of 100 nm): the molar ratio of Fe in the mixed solution is 0.1:1 ratio of TiO to the above-mentioned mixed solution 2 The nanospheres are obtained into suspension solution, and then the suspension solution is centrifugally atomized at high speed and then heated to 550 ℃ to obtain ferric phosphate precursor; (3) Placing the ferric phosphate precursor in a fluidization device, introducing nitrogen, controlling the flow rate to be 120sccm, controlling the vacuum degree in a process cavity of the fluidization device to be 3torr, and controlling the temperature of the process cavity to be 200 ℃; (4) Pulse-introducing hydrogen fluoride gas, controlling the single-time introducing time to be 2s, the gap time to be 10s, the pulse times to be 100 times, controlling the temperature of a hydrogen fluoride pyridine solution pipeline and a source device to be 40 ℃, and etching; (5) And after etching is finished, continuously introducing nitrogen for more than 10min, and cooling to obtain the porous ferric phosphate precursor.
(2) Preparation of lithium iron phosphate
According to Li: fe is 1.10:1, mixing a porous ferric phosphate precursor and lithium carbonate, adding glucose accounting for 2% of the total mass of the porous ferric phosphate precursor and the lithium carbonate, uniformly mixing, calcining under a protective atmosphere, heating to 580 ℃ at a heating rate of 8 ℃/min, and naturally cooling after heat preservation for 4 hours to obtain lithium iron phosphate;
charging lithium iron phosphate into a fluidization device, heating to 280 ℃, charging nitrogen, controlling the flow rate of the nitrogen at 180sccm, sequentially charging steam of trimethylaluminum, hydrogen fluoride pyrrole solution, lithium tert-butoxide and hydrogen fluoride pyrrole solution, wherein the charging time is respectively 10s,8s,20s and 8s, the interval time is 1000s, and circulating for 12 times to obtain the surface coating thickness of 1.LiAlF at 5nm 4 Low temperature lithium iron phosphate.
Example 6
(1) Preparation of porous ferric phosphate precursor
Preparing an ammonium polyphosphate solution with the phosphorus content of 10wt% and preparing an iron nitrate solution with the concentration of 1.2 mol/L; mixing the ammonium polyphosphate solution and the ferric nitrate solution according to the Fe/P molar concentration ratio of 1.05 to obtain a mixed solution; (2) According to TiO 2 Nanospheres (primary particle size 100 nm): the molar ratio of Fe in the mixed solution is 0.1:1 ratio of TiO to the above-mentioned mixed solution 2 The nanospheres are obtained into suspension solution, and then the suspension solution is centrifugally atomized at high speed and then heated to 550 ℃ to obtain ferric phosphate precursor; (3) Placing the ferric phosphate precursor in a fluidization device, introducing nitrogen, controlling the flow rate to be 120sccm, controlling the vacuum degree in a process cavity of the fluidization device to be 3torr, and controlling the temperature of the process cavity to be 200 ℃; (4) Pulse-introducing hydrogen fluoride gas, controlling the single-time introducing time to be 2s, the gap time to be 10s, the pulse times to be 100 times, controlling the temperature of a hydrogen fluoride pyridine solution pipeline and a source device to be 40 ℃, and etching; (5) And after etching is finished, continuously introducing nitrogen for more than 10min, and cooling to obtain the porous ferric phosphate precursor.
(2) Preparation of lithium iron phosphate
According to Li: fe is 1.10:1, mixing a porous ferric phosphate precursor and lithium carbonate, adding glucose accounting for 8% of the total mass of the porous ferric phosphate precursor and the lithium carbonate, uniformly mixing, calcining under a protective atmosphere, heating to 580 ℃ at a heating rate of 8 ℃/min, and naturally cooling after heat preservation for 4 hours to obtain lithium iron phosphate;
charging lithium iron phosphate into a fluidization device, heating to 280 ℃, charging nitrogen with the flow rate of the nitrogen controlled at 180sccm, sequentially charging steam of trimethylaluminum, hydrogen fluoride pyrrole solution, lithium tert-butoxide and hydrogen fluoride pyrrole solution for 10s,8s,20s and 8s respectively, with the interval time of 1000s, and circulating for 12 times to obtain LiAlF with the surface coating thickness of 1.5nm 4 Low temperature lithium iron phosphate.
Example 7
(1) Preparation of porous ferric phosphate precursor
Preparing an ammonium polyphosphate solution with the phosphorus content of 10wt% and preparing an iron nitrate solution with the concentration of 1.2 mol/L; mixing the ammonium polyphosphate solution and the ferric nitrate solution according to the Fe/P molar concentration ratio of 1.05 to obtain a mixed solution; (2) According to TiO 2 Nanospheres (primary particle size 100 nm): the molar ratio of Fe in the mixed solution is 0.1:1 ratio of TiO to the above-mentioned mixed solution 2 The nanospheres are obtained into suspension solution, and then the suspension solution is centrifugally atomized at high speed and then heated to 550 ℃ to obtain ferric phosphate precursor; (3) Placing the ferric phosphate precursor in a fluidization device, introducing nitrogen, controlling the flow rate to be 120sccm, controlling the vacuum degree in a process cavity of the fluidization device to be 3torr, and controlling the temperature of the process cavity to be 200 ℃; (4) Pulse-introducing hydrogen fluoride gas, controlling the single-time introducing time to be 2s, the gap time to be 10s, the pulse times to be 100 times, controlling the temperature of a hydrogen fluoride pyridine solution pipeline and a source device to be 40 ℃, and etching; (5) And after etching is finished, continuously introducing nitrogen for more than 10min, and cooling to obtain the porous ferric phosphate precursor.
(2) Preparation of lithium iron phosphate
According to Li: fe is 1.10:1, mixing a porous ferric phosphate precursor and lithium carbonate, adding glucose accounting for 8% of the total mass of the porous ferric phosphate precursor and the lithium carbonate, uniformly mixing, calcining under a protective atmosphere, heating to 580 ℃ at a heating rate of 8 ℃/min, and naturally cooling after heat preservation for 4 hours to obtain lithium iron phosphate;
charging lithium iron phosphate into a fluidization device, heating to 280 ℃, charging nitrogen with the flow rate of the nitrogen controlled at 180sccm, sequentially charging steam of trimethylaluminum, hydrogen fluoride pyrrole solution, lithium tert-butoxide and hydrogen fluoride pyrrole solution for 20s, 16s,40s and 16s respectively, with the interval time of 1000s, and circulating for 12 times to obtain LiAlF with the surface coating thickness of 1.5nm 4 Low temperature lithium iron phosphate.
Comparative example 1:
based on example 7, the difference was that the charging times were 2.5s,2s,5s,2s, the interval time was 1000s, and the cycle was 12 times, respectively, to obtain LiAlF having a surface coating thickness of 0.5nm 4 Low temperature lithium iron phosphate.
Comparative example 2:
based on example 7, the difference is that the charging time is 10s,8s,20s,8s, the interval time is 1000s, and the LiAlF with the surface coating thickness of 3nm is obtained by 30 times of circulation 4 Low temperature lithium iron phosphate.
The lithium iron phosphate prepared in the examples was tested as follows:
Claims (9)
1. LiAlF coated on surface 4 The preparation method of the low-temperature lithium iron phosphate of the fast ion conductor is characterized by comprising the following steps of:
s1: mixing a porous ferric phosphate precursor, a lithium source and a carbon source, and calcining to obtain lithium iron phosphate;
s2: putting the lithium iron phosphate obtained in the step S1 into a fluidization device and heating to 250-280 ℃;
s3: sequentially pulse-introducing steam of trimethylaluminum, hydrogen fluoride pyrrole solution, lithium tert-butoxide and hydrogen fluoride pyrrole solution to obtain LiAlF coated with surface 4 Lithium iron phosphate of a fast ion conductor;
the preparation method of the porous ferric phosphate precursor in the step S1 comprises the following steps:
(1) Dissolving ammonium polyphosphate crystals in deionized water to obtain an ammonium polyphosphate solution;
(2) Dissolving an iron source in deionized water to obtain an iron salt solution;
(3) Mixing the solutions obtained in step (1) and step (2) according to the quantitative Fe/P to obtain a mixed salt solution;
(4) Adding TiO to the mixed salt solution in (3) 2 The nanospheres obtain suspension solution, and the suspension solution is atomized and then heated to 500-600 ℃ to obtain an iron phosphate precursor;
(5) Placing the ferric phosphate precursor in a fluidization device to enable the ferric phosphate precursor to be in a fluidization state;
(6) And (3) pulse-feeding hydrogen fluoride pyridine steam into the fluidization device to obtain the porous ferric phosphate precursor.
2. A surface-coated LiAlF as claimed in claim 1 4 The preparation method of the low-temperature lithium iron phosphate of the fast ion conductor is characterized in that the lithium source in the S1 is one or two of lithium carbonate or lithium hydroxide;
the carbon source in the S1 is one or the combination of any one of glucose, sucrose and polyethylene glycol;
in the S1, the molar ratio of the porous ferric phosphate precursor to the lithium source is (1-1.15) according to the mole ratio of Li to Fe: 1, mixing;
the addition amount of the carbon source in the S1 is 2% -8% of the total mass of the porous ferric phosphate precursor and the lithium source.
3. A surface-coated LiAlF as claimed in claim 1 4 The preparation method of the low-temperature lithium iron phosphate of the fast ion conductor is characterized in that the phosphorus content in the ammonium polyphosphate solution in the step (1) is 5-10wt%;
the concentration of ferric iron in the ferric salt solution in the step (2) is 0.8-1.5 mol/L, and the iron source is soluble ferric iron salt and is selected from one or a mixture of any of ferric chloride, ferric sulfate, ferric oxalate and ferric nitrate; and (3) the molar concentration ratio of Fe/P in the mixed salt solution in the step (3) is 0.96-1.05.
4. A surface-coated LiAlF as claimed in claim 1 4 A method for preparing low-temperature lithium iron phosphate of a fast ion conductor is characterized in that TiO in the step (4) 2 The primary particle size of the nanospheres is 50-100nm, the secondary agglomeration particle size is 1-3 mu m, and the TiO 2 The molar mass ratio of the nanospheres to Fe in the mixed solution in the step (4) is (0.02-0.1): 1.
5. the method as claimed in claim 1LiAlF coated on surface 4 The preparation method of the low-temperature lithium iron phosphate of the fast ion conductor is characterized in that the vacuum degree in the fluidization device in the step (5) is kept to be less than 5torr, the temperature is controlled to be 200-250 ℃, the condition that the hydrogen fluoride pyridine steam is pulsed in the step (6) is controlled to be single-pass in time of 0.1-2 s, the gap time is 10-100 s, and the pulse times are 1-100 times.
6. A surface-coated LiAlF as claimed in claim 5 4 The preparation method of the low-temperature lithium iron phosphate of the fast ion conductor is characterized in that the fluidization device in the step S2 is heated to 280 ℃, nitrogen is introduced, and the flow speed of the nitrogen is controlled to be 150-250sccm.
7. A surface-coated LiAlF as claimed in claim 5 4 The preparation method of the low-temperature lithium iron phosphate of the fast ion conductor is characterized in that in the step S3, the vapor of trimethylaluminum, hydrogen fluoride pyrrole solution, tertiary butyl alcohol lithium and hydrogen fluoride pyrrole solution is sequentially pulsed for 8-20S, 3-10S, 15-35S and 3-10S, and meanwhile, the respective interval time is 800-1500S; cycling for 5-20 times.
8. A surface-coated LiAlF as claimed in claim 7 4 The preparation method of the low-temperature lithium iron phosphate of the fast ion conductor is characterized in that in the step S3, the time for sequentially pulsing the vapors of trimethylaluminum, hydrogen fluoride pyrrole solution, lithium tert-butoxide and hydrogen fluoride pyrrole solution is 10S,8S,20S and 8S, and meanwhile, the respective interval time is 1000S; cycling was performed 12 times.
9. A surface-coated LiAlF using any one of claims 1 to 8 4 The lithium iron phosphate prepared by the preparation method of the low-temperature lithium iron phosphate of the fast ion conductor is characterized by being used as a battery anode material.
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