WO2022237545A1 - 磷酸铁锂及其制备方法与应用 - Google Patents
磷酸铁锂及其制备方法与应用 Download PDFInfo
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- WO2022237545A1 WO2022237545A1 PCT/CN2022/089583 CN2022089583W WO2022237545A1 WO 2022237545 A1 WO2022237545 A1 WO 2022237545A1 CN 2022089583 W CN2022089583 W CN 2022089583W WO 2022237545 A1 WO2022237545 A1 WO 2022237545A1
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- Prior art keywords
- lithium
- preparation
- source
- intermediate product
- iron phosphate
- Prior art date
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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 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 66
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000013067 intermediate product Substances 0.000 claims abstract description 68
- 239000000243 solution Substances 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000003999 initiator Substances 0.000 claims abstract description 46
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 39
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 37
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 31
- 239000011574 phosphorus Substances 0.000 claims abstract description 31
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 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 abstract description 27
- 239000008103 glucose Substances 0.000 claims abstract description 27
- 229910052742 iron Inorganic materials 0.000 claims abstract description 26
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 23
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 239000007800 oxidant agent Substances 0.000 claims abstract description 18
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000007774 positive electrode material Substances 0.000 claims abstract description 6
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 64
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 63
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 55
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 53
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 32
- 239000000725 suspension Substances 0.000 claims description 32
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 30
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 22
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 19
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 19
- -1 polyoxyethylene Polymers 0.000 claims description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 16
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 16
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 16
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 11
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 230000001186 cumulative effect Effects 0.000 claims description 9
- 150000003254 radicals Chemical class 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003945 anionic surfactant Substances 0.000 claims description 6
- 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 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002736 nonionic surfactant Substances 0.000 claims description 6
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 20
- 230000001590 oxidative effect Effects 0.000 abstract description 13
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000010298 pulverizing process Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 28
- 238000003756 stirring Methods 0.000 description 22
- 229910000398 iron phosphate Inorganic materials 0.000 description 20
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 20
- 229920000642 polymer Polymers 0.000 description 20
- 239000002105 nanoparticle Substances 0.000 description 19
- 239000002243 precursor Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000000839 emulsion Substances 0.000 description 14
- 101710134784 Agnoprotein Proteins 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- JRSGPUNYCADJCW-UHFFFAOYSA-K iron(3+);trichlorate Chemical compound [Fe+3].[O-]Cl(=O)=O.[O-]Cl(=O)=O.[O-]Cl(=O)=O JRSGPUNYCADJCW-UHFFFAOYSA-K 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 238000001694 spray drying Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- IVIHUELQQBDVNA-UHFFFAOYSA-L C([O-])([O-])=O.[Fe+2].[Li+] Chemical compound C([O-])([O-])=O.[Fe+2].[Li+] IVIHUELQQBDVNA-UHFFFAOYSA-L 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 230000006911 nucleation Effects 0.000 description 5
- 238000010899 nucleation Methods 0.000 description 5
- 239000001103 potassium chloride Substances 0.000 description 5
- 235000011164 potassium chloride Nutrition 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 229910052754 neon Inorganic materials 0.000 description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 229930006000 Sucrose Natural products 0.000 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 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 102220043159 rs587780996 Human genes 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the invention relates to the technical field of battery anode material manufacturing, in particular to lithium iron phosphate and its preparation method and application.
- lithium-ion batteries have developed rapidly in recent years and have been widely used in mobile phones, computers, new energy vehicles and energy storage fields. Especially driven by the explosive growth of the new energy vehicle market, the rapid development of lithium batteries has led to increasingly fierce competition in the industry, and the gradual rise of local battery giants. Downstream new energy vehicles have entered the growth period from the introduction period. Factors such as subsidy decline and technical performance requirements have intensified the survival of the fittest in the battery industry, and the market concentration has increased. In such a highly competitive environment, it is extremely important to improve the cost performance of materials.
- LiFePO 4 has the characteristics of wide source of raw materials, low price, good thermal stability, excellent cycle performance, outstanding safety performance and zero environmental pollution, making it an ideal electrode material in the field of electric vehicles.
- the object of the present invention is to provide a lithium iron phosphate and its preparation method and application.
- the preparation method can directly obtain nano-scale lithium iron phosphate, and reduce the crushing process and energy consumption in the manufacturing process.
- the elements in the lithium iron phosphate are evenly distributed, and when it is used as an electrode cathode material, it has the effects of simple synthesis process, low cost, excellent gram capacity and rate performance.
- the invention provides a kind of preparation method of lithium iron phosphate, and this preparation method comprises:
- the intermediate product B is a lithium source nanoparticle with a core-shell structure coated with a polymer, and the polymer as a coating layer of the lithium source nanoparticle can effectively prevent the lithium source particle from forming in the subsequent synthesis of iron phosphate particles. Soluble in acidic environment.
- Lithium source nanoparticles coated with a polymer layer can increase the number of nucleation points of iron phosphate, and generate more and smaller iron phosphate particles when the concentration of iron source and phosphorus source remains unchanged, and these iron phosphate particles adhere to On the surface of the lithium source particles coated with polymers, after the polymers are removed by calcination, the iron phosphate and the lithium source particles are fused, and sintered into a lithium iron phosphate material that is uniformly mixed with lithium, phosphorus, and iron elements, omitting the crushing operation Under certain circumstances, nano-scale materials can also be obtained, which helps to improve the gram capacity of lithium iron phosphate materials.
- iron phosphate is generally synthesized first, and then lithium iron phosphate is synthesized.
- the process of synthesizing iron phosphate generally includes solid-phase synthesis, drying, sintering, and crushing; the process of synthesizing lithium iron phosphate generally includes Mixing (including iron phosphate raw materials), sanding, drying, etc.
- the present invention synthesizes lithium iron phosphate in the liquid phase, omits the grinding and pulverizing processes in the conventional process, simplifies the synthesis process to synthesis and drying, and has the technical effects of saving process, reducing energy consumption and low cost.
- the lithium source generally includes one or a combination of two or more of lithium carbonate, lithium hydroxide, lithium chloride, lithium fluoride, lithium acetate, and lithium nitrate.
- the lithium source is generally nanoparticles, and its particle size D50 is generally controlled to be 300nm-400nm.
- the emulsifier in the above preparation method, can include anionic surfactant and/or nonionic surfactant, and the anionic surfactant can include sodium lauryl sulfate, and the nonionic surfactant Polyoxyethylene alkylphenol ethers may be included.
- the mass ratio of the anionic surfactant to the nonionic surfactant is preferably (1-1.5):1, for example, it can be 1.5:1, 1:1 or 1.25:1, that is, the The emulsifier may include sodium lauryl sulfate and polyoxyethylene alkylphenol ether in a mass ratio of (1-1.5):1.
- the molar ratio of the emulsifier to the lithium source is generally controlled to be (0.5-1):1.
- the first polymerization reaction is a polymerization reaction initiated by free radicals, and the reaction temperature is generally controlled at 60-70° C., and the reaction time is generally controlled at 2-4 hours.
- the first initiator used in the first polymerization reaction may include butyl acrylate and/or divinylbenzene, for example, in a molar ratio of (5-10):(90-95) (preferably 5:95) of divinylbenzene and butyl acrylate.
- the molar ratio of the first initiator to the lithium source is generally controlled to be (0.5-1):1, for example, it can be controlled to be 0.5:1, 0.6:1, 0.7:1, 0.8: 1 or 1:1.
- the molar ratio of the methyl methacrylate to the lithium source is generally controlled to be (0.05-0.5):1, for example, can be controlled to be 0.05:1.
- the molar ratio of the methyl methacrylate, the crosslinking agent, and the second initiator is generally (1-2):0.5:(1-3), for example, it can be 1:0.5 :1, 1.1:0.5:1, 2:0.5:1.5, 1.5:0.5:3, 2:0.5:1, or 2:0.5:3.
- the crosslinking agent generally includes divinylbenzene.
- the second initiator in S2, generally includes one or a combination of two or more of ammonium persulfate, potassium persulfate and hydrogen peroxide.
- the methyl methacrylate, the crosslinking agent and the second initiator are generally added in the intermediate product A in the form of a mixed solution of the three, and in the mixed solution, the crosslinking agent
- the molar concentration of the second initiator can be 0.5%
- the molar concentration of the second initiator can be 1-3%
- the molar concentration of the methyl methacrylate can be 1-2%.
- the reaction temperature of the second polymerization reaction is generally controlled to be 75-85° C.
- the reaction time is generally controlled to be 4 hours.
- the product after the second polymerization reaction is generally an emulsion, which generally needs to be cooled to room temperature (25°C), demulsified, washed with water, dried and other post-treatments to obtain the intermediate product B.
- the demulsification can adopt ethanol, sodium chloride aqueous solution, potassium chloride aqueous solution. If ethanol is used for demulsification, the product after demulsification can be dried directly; if sodium chloride aqueous solution or potassium chloride aqueous solution is used for demulsification, the product needs to be washed with water until the product is tested with AgNO3 solution. The degree of Cl - is then dried.
- the above-mentioned drying generally adopts the method of spray drying, and the drying temperature is generally 70-80°C.
- the intermediate product B is specifically polymer-wrapped lithium carbonate nanoparticles, which have a core-shell structure, wherein lithium carbonate nanoparticles are used as the core during the subsequent synthesis of iron phosphate.
- the polymer can effectively prevent the lithium carbonate core from dissolving in an acidic solution and ensure the normal nucleation of iron phosphate on the lithium carbonate surface.
- a nanoscale lithium iron phosphate precursor in S3, can be generated during the third reaction process of the intermediate product B with an iron source and a phosphorus source.
- iron phosphate nucleates in large quantities with polymer-coated lithium carbonate as the nucleation point, forming fine iron phosphate particles attached to the surface of lithium carbonate nanoparticles with a shell structure.
- the temperature of the third reaction can be controlled to be 70-80°C, and the reaction time can be controlled to be 4h-8h.
- an iron source and an oxidant are generally added to the intermediate product B in sequence and stirred rapidly to obtain a suspension, and then a phosphorus source is added to the suspension and stirred uniformly to obtain the intermediate product C.
- adding the phosphorus source generally keep the pH of the reaction system at 2.1-2.3, then adding the phosphorus source may also include adding (generally slowly dropping) ammonia water (mass concentration generally ⁇ 6.5%). Dropping ammonia water can adjust the pH value to ensure uniform reaction speed and avoid excessive growth of iron phosphate.
- the iron source generally adopts ferric salt, such as one or a combination of two or more of ferric chlorate, ferric sulfate, ferric nitrate and the like.
- the molar ratio of the iron element in the iron source to the lithium element in the lithium source is generally controlled to be 1: (0.95-1.25), for example, it can be 1:1.25, 1:0.95 or 1: 1.
- the molar ratio of the iron element in the iron source to the oxidant is generally controlled to be 1:(0.2-0.5), for example, it can be 1:0.5, 1:0.2 or 1:0.35.
- the oxidizing agent generally adopts hydrogen peroxide, and the hydrogen peroxide can be a hydrogen peroxide solution with a mass concentration ⁇ 20%.
- the phosphorus source is generally one or a combination of phosphoric acid (solution concentration generally ⁇ 75%), ammonium dihydrogen phosphate, ammonium phosphate, etc.
- the molar ratio of the phosphorus element in the phosphorus source to the iron element in the iron source is generally controlled to be 1:(0.95-1), for example, 1:(0.95-0.98).
- the reaction system of the intermediate product B, the iron source, the phosphorus source and the oxidizing agent is generally in the form of a suspension, and generally undergoes post-treatments such as filtration and water washing before being dispersed with a glucose solution. After washing with water, it is necessary to check that the product does not contain Cl - with AgNO 3 solution and that there is no SO 4 2- with Ba(NO 3 ) 2 .
- the mass of glucose in the glucose solution is generally controlled to be 40%-50% of the mass of lithium carbonate, for example, it can be 40%, 45% or 50%.
- the calcination process can remove the polymer layer between lithium carbonate and iron phosphate, so that lithium elements, iron elements and phosphorus elements can be fully contacted to form phosphoric acid with uniform element distribution. lithium iron.
- the calcination temperature is 700°C-800°C, and the calcination time is 6h-10h.
- the calcination process is generally carried out in nitrogen, neon, argon and other protective gases, generally high-purity nitrogen, high-purity neon, high-purity argon and the like.
- the above-mentioned preparation method may include:
- the present invention also provides a lithium iron phosphate prepared by the above preparation method.
- the present invention further provides a positive electrode material, which includes the above-mentioned lithium iron phosphate.
- the above-mentioned lithium iron phosphate as a positive electrode material has the properties of simple synthesis process, low cost, excellent gram capacity and rate performance.
- the emulsifier can ensure that the lithium source nanoparticles are well coated by polymers, thereby forming lithium source nanoparticles with a core-shell structure coated with polymers. Particles, to avoid the dissolution of lithium source nanoparticles in acidic environment during the synthesis of iron phosphate.
- the lithium source nanoparticles covered by polymers can provide more nucleation sites for the synthesis of iron phosphate, so that iron phosphate grows on the surface of lithium carbonate nanoparticles with a shell structure, increasing the number of nucleation of iron phosphate, forming Lithium carbonate nanocomposites with a shell structure coated with multiple nano-iron phosphates, and then the polymer shells are removed through the calcination process, so that lithium, iron, and phosphorus elements are fully mixed and sintered into phases, which improves the gram capacity of the material.
- the above-mentioned process is carried out in the liquid phase, which is also conducive to the thorough mixing of the elements and the uniform distribution in the final product.
- the reaction system is acidic by dripping ammonia water, and by controlling the drip rate of ammonia water, that is At the beginning of the third reaction, when the reactant concentration is low (less phosphorus source is added), the ammonia drop rate is slow, and when the reactant concentration is high in the later stage of the reaction, the ammonia drop rate is fast, which can ensure a stable reaction rate and uniform particle size distribution of the synthesized material.
- the preparation method of lithium iron phosphate provided by the present invention can directly obtain nanoscale lithium iron phosphate without pulverizing the product, avoiding the large energy consumption caused by stirring and ball milling in the preparation process of conventional lithium iron phosphate cathode materials
- the problem also reduces the drying and crushing of iron phosphate and the mixing and sanding of lithium iron phosphate, which greatly reduces the cost of material manufacturing.
- the preparation method of lithium iron phosphate provided by the present invention has a simple synthesis process and low cost, and can obtain lithium iron phosphate with excellent gram capacity and rate performance.
- FIG. 1 is a scanning electron microscope image of the lithium iron phosphate material prepared in Example 1 of the present invention.
- FIG. 3 is the charging and discharging curves of lithium iron phosphate materials prepared in Example 1 and Comparative Example 1 of the present invention.
- This embodiment provides a preparation method of lithium iron phosphate, the preparation method comprising:
- the particle diameter is added in the emulsifier solution that is formed by sodium lauryl sulfate and polyoxyethylene alkylphenol ether after vacuum-drying the nano lithium carbonate of 400nm, keeps stirring; Then add butyl acrylate and divinylbenzene ( The two are used as the first initiator), the free radical is used to initiate the first polymerization reaction, the temperature of the first polymerization reaction is 70° C., and the time is 4 hours to obtain the intermediate product A.
- the ratio of emulsifying agent and lithium carbonate mol ratio is 0.5:1;
- the mass ratio of sodium lauryl sulfate and polyoxyethylene alkylphenol ether is 1.5:1, and the mol ratio of divinylbenzene in the first initiator is 5%, the mol ratio of the first initiator and lithium carbonate is 0.5:1.
- the molar ratio of methyl methacrylate to lithium carbonate is 0.05:1, and the molar ratio of methyl methacrylate, divinylbenzene, and hydrogen peroxide is 1:0.5:1.
- the nanoscale lithium iron phosphate precursor is calcined at 750°C for 10 hours to obtain a lithium iron phosphate material.
- This embodiment provides a preparation method of lithium iron phosphate, the preparation method comprising:
- the particle diameter is added in the emulsifier solution that is formed by sodium lauryl sulfate and polyoxyethylene alkylphenol ether after vacuum-drying the nano lithium carbonate of 400nm, keeps stirring; Then add butyl acrylate and divinylbenzene ( The two are used as the first initiator), the free radical is used to initiate the first polymerization reaction, the temperature of the first polymerization reaction is 70° C., and the time is 4 hours to obtain the intermediate product A.
- the molar ratio of emulsifier to lithium carbonate is 0.5:1.
- the mass ratio of sodium lauryl sulfate and polyoxyethylene alkylphenol ether is 1.5:1, and the mol ratio of divinylbenzene in the first initiator is 5%, and the mol ratio of the first initiator and lithium carbonate is 0.6: 1.
- the molar ratio of methyl methacrylate to lithium carbonate is 0.05:1
- the molar ratio of methyl methacrylate, divinylbenzene, and hydrogen peroxide is 1.1:0.5:1.
- the nanoscale lithium iron phosphate precursor is calcined at 800° C. for 10 hours to obtain a lithium iron phosphate material.
- This embodiment provides a preparation method of lithium iron phosphate, the preparation method comprising:
- the mol ratio of emulsifier and lithium carbonate is 0.5:1.
- the mass ratio of sodium lauryl sulfate and polyoxyethylene alkylphenol ether is 1:1, and the mol ratio of divinylbenzene in the first initiator is 5%, and the mol ratio of the first initiator and lithium carbonate is 0.6: 1.
- the molar ratio of methyl methacrylate to lithium carbonate is 0.05:1
- the molar ratio of methyl methacrylate, divinylbenzene, and hydrogen peroxide is 2:0.5:1.5.
- the nanoscale lithium iron phosphate precursor in step 5 is calcined at 700° C. for 10 hours to obtain a lithium iron phosphate material.
- This embodiment provides a preparation method of lithium iron phosphate, the preparation method comprising:
- the molar ratio of emulsifier to lithium carbonate is 0.5:1.
- the mass ratio of sodium lauryl sulfate and polyoxyethylene alkylphenol ether is 1.25:1, and the mol ratio of divinylbenzene in the first initiator is 5%, and the mol ratio of the first initiator and lithium carbonate is 0.7: 1.
- the molar ratio of methyl methacrylate to lithium carbonate is 0.05:1
- the molar ratio of methyl methacrylate, divinylbenzene, and hydrogen peroxide is 1.5:0.5:3.
- the nanoscale lithium iron phosphate precursor in step 5 is calcined at 750° C. for 10 hours to obtain a lithium iron phosphate material.
- This embodiment provides a preparation method of lithium iron phosphate, the preparation method comprising:
- the molar ratio of emulsifier to lithium carbonate is 0.5:1.
- the mass ratio of sodium lauryl sulfate and polyoxyethylene alkylphenol ether is 1:1, and the mol ratio of divinylbenzene in the first initiator is 5%, and the mol ratio of the first initiator and lithium carbonate is 0.8: 1.
- the molar ratio of methyl methacrylate to lithium carbonate is 0.05:1, and the molar ratio of methyl methacrylate, divinylbenzene, and hydrogen peroxide is 2:0.5:1.
- the nanoscale lithium iron phosphate precursor in step 5 is calcined at 750° C. for 10 hours to obtain a lithium iron phosphate material.
- This embodiment provides a preparation method of lithium iron phosphate, the preparation method comprising:
- the particle diameter is added in the emulsifier solution that is formed by sodium lauryl sulfate and polyoxyethylene alkylphenol ether after vacuum-drying the nano lithium carbonate of 400nm, keeps stirring; Then add butyl acrylate and divinylbenzene ( The two are used as the first initiator), the free radical is used to initiate the first polymerization reaction, the temperature of the first polymerization reaction is 70° C., and the time is 4 hours to obtain the intermediate product A.
- the molar ratio of emulsifier to lithium carbonate is 0.5:1.
- the mass ratio of sodium lauryl sulfate and polyoxyethylene alkylphenol ether is 1.5:1, and the mol ratio of divinylbenzene in the first initiator is 5%, and the mol ratio of the first initiator and lithium carbonate is 1: 1.
- the molar ratio of methyl methacrylate to lithium carbonate is 0.05:1
- the molar ratio of methyl methacrylate, divinylbenzene, and hydrogen peroxide is 2:0.5:3.
- the nanoscale lithium iron phosphate precursor in step 5 is calcined at 750° C. for 10 hours to obtain a lithium iron phosphate material.
- Figure 1 and Figure 2 are the SEM photographs of the lithium iron phosphate material prepared in Example 1 and Comparative Example 1 respectively, as can be seen from Figure 1, the lithium iron phosphate material particles prepared in Example 1 are small and uniform; as can be seen from Figure 2 , the particle size of the lithium iron phosphate material prepared in Comparative Example 1 was different, and the particle size distribution was not uniform.
- the battery used in the embodiments and test examples of the present invention is a simulated battery assembled with the material prepared by the present invention as the positive electrode material, battery-grade lithium sheet as the negative electrode material, and lithium hexafluorophosphate as the electrolyte.
- the window is 2.0-4.0V.
- Fig. 3 is the deduction charging and discharging curve of the lithium iron phosphate material prepared in Example 1 and Comparative Example 1. It can be seen from Fig. 3 that the lithium iron phosphate prepared in Example 1 has a higher gram capacity and rate performance.
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Abstract
Description
Claims (16)
- 一种磷酸铁锂的制备方法,包括:S1、将锂源用乳化剂分散,加入第一引发剂进行第一聚合反应,得到中间产物A;其中,所述第一引发剂包括丙烯酸丁酯和二乙烯苯,所述第一聚合反应为自由基引发聚合反应;S2、将甲基丙烯酸甲酯、交联剂和第二引发剂的混合溶液加入中间产物A中,进行第二聚合反应,得到中间产物B;S3、先将中间产物B、铁源、氧化剂混合得到悬浮液,再向该悬浮液中添加磷源进行第三反应,得到中间产物C;其中,通过加入氨水使所述第三反应的反应体系的pH值保持为2.1-2.3;所述氨水的加入速度为:V=10t 2+5,其中,V为氨水的加入速度,单位为mL/min;t为氨水累计加入时间,单位为min;S4、将中间产物C用葡萄糖溶液分散,干燥,700℃-800℃煅烧6h-10h,所述煅烧在保护气体中进行,得到所述磷酸铁锂。
- 根据权利要求1所述的制备方法,S1中,所述锂源包括碳酸锂、氢氧化锂、氯化锂、氟化锂、醋酸锂和硝酸锂中的一种或两种以上的组合;和/或,S1中,所述锂源的粒径D50为300nm-400nm。
- 根据权利要求1所述的制备方法,S1中,所述乳化剂包括阴离子表面活性剂和非离子表面活性剂;所述阴离子表面活性剂和所述非离子表面活性剂的质量比为(1-1.5):1。
- 根据权利要求3所述的制备方法,其中,所述阴离子表面活性剂包括十二烷基硫酸钠;和/或,所述非离子表面活性剂包括聚氧乙烯烷基酚醚。
- 根据权利要求1所述的制备方法,其中,所述第一引发剂包括摩尔比为(5-10):(90-95)的二乙烯苯与丙烯酸丁酯。
- 根据权利要求1或2所述的制备方法,S1中,所述乳化剂与所述锂源的摩尔比为(0.5-1):1;所述第一引发剂与锂源的摩尔比为(0.5-1):1。
- 根据权利要求1-6任一项所述的制备方法,S1中,所述第一聚合反应的温度为60℃-70℃,所述第一聚合反应的时间为2h-4h。
- 根据权利要求1所述的制备方法,S2中,所述甲基丙烯酸甲酯与所述锂源的摩尔比为(0.05-0.5):1;所述甲基丙烯酸甲酯、交联剂、第二引发剂的摩尔比为(1-2):0.5:(1-3)。
- 根据权利要求1或8所述的制备方法,S2中,所述交联剂包括二乙烯苯;所述第二引发剂包括过硫酸铵、过硫酸钾和双氧水中的一种或两种以上的组合。
- 根据权利要求1、8或9所述的制备方法,S2中,所述第二聚合反应的温度为75-85℃,所述第二聚合反应的时间为4h-8h。
- 根据权利要求1所述的制备方法,S3中,所述铁源包括三价铁盐;所述三价铁盐包括氯化铁、硫酸铁、硝酸铁中的一种或两种以上的组合;所述氧化剂包括双氧水;所述磷源包括磷酸、磷酸二氢铵、磷酸铵中的一种或两种以上的组合。
- 根据权利要求1或11任一项所述的制备方法,S3中,所述铁源中的铁元素与锂源中锂元素的摩尔比为1:(0.95-1.25);所述铁源中铁元素与氧化剂的摩尔比为1:(0.2-0.5);所述磷源中的磷元素与所述铁源中的铁元素的摩尔比为1:(0.95-1)。
- 根据权利要求1、11或12任一项所述的制备方法,S3中,所述第三反应的温度为70℃-80℃、所述第三反应的时间为4h-8h。
- 根据权利要求1所述的制备方法,S4中,所述葡萄糖溶液中葡萄糖的质量为所述锂源质量的40%-50%。
- 一种磷酸铁锂,其是由权利要求1-14任一项所述的制备方法制备得到的。
- 一种正极材料,其包括权利要求15所述的磷酸铁锂。
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