CN114899392A - Preparation method of lithium iron phosphate or lithium ferromanganese anode material of lithium ion battery - Google Patents
Preparation method of lithium iron phosphate or lithium ferromanganese anode material of lithium ion battery Download PDFInfo
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- CN114899392A CN114899392A CN202210442173.3A CN202210442173A CN114899392A CN 114899392 A CN114899392 A CN 114899392A CN 202210442173 A CN202210442173 A CN 202210442173A CN 114899392 A CN114899392 A CN 114899392A
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- lithium
- phosphate
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- manganese
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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 37
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 34
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000010405 anode material Substances 0.000 title claims abstract description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 19
- 229910000616 Ferromanganese Inorganic materials 0.000 title claims abstract description 16
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002243 precursor Substances 0.000 claims abstract description 37
- 238000001035 drying Methods 0.000 claims abstract description 27
- 229910052742 iron Inorganic materials 0.000 claims abstract description 27
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims abstract description 27
- 239000000725 suspension Substances 0.000 claims abstract description 27
- 239000000706 filtrate Substances 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 26
- 238000001914 filtration Methods 0.000 claims abstract description 24
- 239000002244 precipitate Substances 0.000 claims abstract description 24
- 238000001816 cooling Methods 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 239000011572 manganese Substances 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 239000005416 organic matter Substances 0.000 claims abstract description 6
- 238000005245 sintering Methods 0.000 claims abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- OEMGCAOEZNBNAE-UHFFFAOYSA-N [P].[Li] Chemical compound [P].[Li] OEMGCAOEZNBNAE-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 66
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 40
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 25
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 25
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 20
- -1 iron ions Chemical class 0.000 claims description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 229920002472 Starch Polymers 0.000 claims description 8
- 229910001437 manganese ion Inorganic materials 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- 239000008107 starch Substances 0.000 claims description 8
- 235000019698 starch Nutrition 0.000 claims description 8
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 7
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 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 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000010406 cathode material Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 4
- 239000008103 glucose Substances 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
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000007774 positive electrode material Substances 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 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 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
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 3
- 239000011654 magnesium acetate Substances 0.000 claims description 3
- 235000011285 magnesium acetate Nutrition 0.000 claims description 3
- 229940069446 magnesium acetate Drugs 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 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
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid 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
- 229960002413 ferric citrate Drugs 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-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
- 229940071264 lithium citrate Drugs 0.000 claims description 2
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 claims description 2
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 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
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000008367 deionised water Substances 0.000 description 45
- 229910021641 deionized water Inorganic materials 0.000 description 45
- 239000000243 solution Substances 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 229910015855 LiMn0.7Fe0.3PO4 Inorganic materials 0.000 description 6
- 239000011790 ferrous sulphate Substances 0.000 description 5
- 235000003891 ferrous sulphate Nutrition 0.000 description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 5
- 229940099596 manganese sulfate Drugs 0.000 description 5
- 239000011702 manganese sulphate Substances 0.000 description 5
- 235000007079 manganese sulphate Nutrition 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 4
- 229910015944 LiMn0.8Fe0.2PO4 Inorganic materials 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 229910010710 LiFePO Inorganic materials 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000010450 olivine Substances 0.000 description 3
- 229910052609 olivine Inorganic materials 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910015831 LiMn0.6Fe0.4PO4 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a lithium iron phosphate or lithium ferromanganese anode material of a lithium ion battery, which comprises the following steps: adding a lithium source and a phosphorus source into water, and uniformly stirring to obtain suspensions with lithium ion and phosphorus lithium ion concentrations of 0.1-4 mol/L respectively; adding a salt source into water to obtain a mixed solution with the pH value of 1-4, wherein the salt source is an iron source or a combination of the iron source and a manganese source, preheating the suspension to 70-101 ℃, adding the mixed solution, preserving the heat for 4-12 h, naturally cooling, and filtering to obtain a filtrate and a precipitate; washing and drying the precipitate to obtain a lithium iron phosphate precursor or a lithium manganese iron phosphate precursor; and mixing the precursor with an organic matter and an additive, grinding, drying, sintering and crushing to obtain the lithium iron phosphate anode material or the ferromanganese lithium anode material of the lithium ion battery. The invention has simple and easy process, low-temperature synthesis, reduced production cost, controllable particle size of the anode material and excellent material performance.
Description
Technical Field
The invention belongs to the field of lithium ion battery electrode materials, and particularly relates to a preparation method of a lithium iron phosphate or lithium ferromanganese anode material of a lithium ion battery.
Background
The olivine phosphate is a novel lithium ion battery electrode material and is characterized by large discharge capacity, low price, no toxicity and no environmental pollution. The production processes of lithium iron phosphate and lithium manganese iron phosphate of different enterprises are different, and the current mainstream processes are a high-temperature solid phase method and a liquid phase method.
The high-temperature solid phase method is generally to grind and calcine a mixed material of lithium carbonate and iron phosphate, and has the advantages of simple process and suitability for large-scale production, and has the defects that the mixed material of two different substances is difficult to realize uniformity, the batch stability is poor, and the prepared lithium iron phosphate has slightly insufficient performance. The liquid phase method can fully mix raw materials and can realize controllable synthesis of particle size, but the synthesis process of the liquid phase method is more complex, if a hydrothermal method needs high-temperature and high-pressure resistant reaction kettle equipment, great potential safety hazards exist, and the mother liquor contains an organic solvent, so that the recovery cost is high, and the large-scale industrial development is not facilitated.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a preparation method of a lithium iron phosphate or lithium ferromanganese anode material of a lithium ion battery, which can prepare a pure-phase lithium iron phosphate or lithium iron manganese phosphate anode material with excellent electrochemical performance in a low-temperature pure water phase.
The invention is realized in such a way that a preparation method of lithium iron phosphate or lithium ferromanganese anode material of a lithium ion battery comprises the following steps:
(1) adding a lithium source and a phosphorus source into water, and uniformly stirring to obtain suspensions with lithium ion and phosphorus lithium ion concentrations of 0.1-4 mol/L respectively;
adding a salt source into water to obtain a mixed solution with a pH value of 1-4, wherein the salt source is an iron source, and the concentration of iron ions in the mixed solution is 0.1-4 mol/L, or the salt source is a combination of the iron source and a manganese source, and the concentration of the iron ions in the mixed solution is 0.1-4 mol/L and the concentration of ferromanganese ions is 0.1-4 mol/L;
(2) preheating the suspension to 70-101 ℃, adding the mixed solution, preserving the heat for 4-12 hours, naturally cooling, and filtering to obtain filtrate and precipitate; washing and drying the precipitate to obtain a lithium iron phosphate precursor or a lithium manganese iron phosphate precursor; wherein,
in the lithium iron phosphate precursor, the molar ratio of lithium ions to iron ions to phosphate ions is 1-4: 0.01-1: 1-3;
in the lithium iron manganese phosphate precursor, the molar ratio of lithium ions, iron ions, manganese ions and phosphate ions is 1-4: 0.01-1: 0.01-1: 1-3;
(3) mixing the precursor obtained in the step (2) with an organic matter and an additive, grinding, drying, sintering and crushing to obtain a lithium iron phosphate anode material or a lithium ferromanganese anode material of the lithium ion battery; wherein the mass of the organic matter is 1-10% of the mass of the precursor, and the mass of the additive is 0.05-5% of the mass of the precursor.
Preferably, step (2) is followed by the step of: (4) and adding acid into the filtrate to adjust the pH value, adding a precipitator, and recovering valuable metals.
Preferably, in step (1), the lithium source is selected from at least one of lithium carbonate, lithium bicarbonate, lithium hydroxide, lithium acetate, lithium citrate, lithium dihydrogen phosphate, and lithium phosphate; the phosphorus source is selected from at least one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, lithium dihydrogen phosphate, phosphoric acid and lithium phosphate.
Preferably, in step (1), the iron source is selected from at least one of ferrous sulfate heptahydrate, ferric nitrate, ferric citrate, ferric chloride, ferrous acetate, ferrous dihydrogen phosphate, iron powder, and iron ingot; the manganese source is selected from at least one of manganese sulfate monohydrate, manganese acid phosphate, manganese acetate and manganese nitrate.
Preferably, in the step (3), the organic substance is at least one selected from glucose, sucrose, polyethylene glycol, starch and ascorbic acid;
the additive is at least one of magnesium oxide, zirconium oxide, titanium dioxide, magnesium acetate and tetrabutyl titanate.
Preferably, in the step (4), the pH of the acid is 1-6, and the acid is selected from at least one of sulfuric acid, phosphoric acid, hydrochloric acid, acetic acid and citric acid; the precipitant is selected from at least one of sodium carbonate, sodium hydroxide, lithium hydroxide and sodium phosphate.
The invention overcomes the defects of the prior art and provides a preparation method of a lithium iron phosphate or lithium ferromanganese anode material of a lithium ion battery.
Compared with the defects and shortcomings of the prior art, the invention has the following beneficial effects: the lithium iron phosphate and lithium manganese iron phosphate anode material is prepared at low temperature, so that the dependence on a high-temperature high-pressure reaction kettle can be greatly reduced, the production cost is reduced, and the safety performance is improved; in addition, the method is simple and feasible in process and meets the requirement of high-performance power battery materials.
Drawings
Fig. 1 is an XRD pattern of the lithium iron phosphate material prepared in example 1 of the present invention;
fig. 2 is an SEM image of the lithium iron phosphate material prepared in example 1 of the present invention;
fig. 3 is an XRD pattern of the lithium iron manganese phosphate positive electrode material prepared in example 2 of the present invention;
fig. 4 is an SEM image of the lithium iron manganese phosphate positive electrode material prepared in example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
(1) Weighing 67.3Kg of lithium hydroxide to dissolve in 1.25 cubic meter of deionized water, stirring and dissolving, adding 58.8Kg of concentrated phosphoric acid into the lithium hydroxide solution, and stirring for 30min to generate white suspension (the concentration of lithium ions is 1.28mol/L, and the concentration of phosphate radical is 0.41 mol/L);
adding 0.4 cubic meter of deionized water into a storage tank, then adding 149.8Kg of concentrated phosphoric acid, then adding 30.5Kg of reduced iron powder, keeping the pH value of the solution at 1.5, and then filtering, wherein the filtrate is used as a mixed solution (the concentration of iron ions is 1.25mol/L) for later use;
(2) heating the suspension to 95 deg.C, and addingKeeping the temperature of the mixed solution for 6 hours, then naturally cooling and cooling, filtering to obtain filtrate and precipitate, washing the precipitate with deionized water, and drying at normal temperature to obtain the lithium iron phosphate LiFePO 4 A precursor;
(3) 50Kg of the precursor is dispersed in 70Kg of deionized water, 3Kg of soluble starch and 0.5Kg of nano titanium dioxide are added, and the lithium iron phosphate anode material LiFePO is obtained by grinding, drying, sintering, crushing and packaging 4 /C；
(4) And (3) adding 115.3Kg of concentrated phosphoric acid into the filtrate obtained in the step (2), adding 47.1Kg of lithium hydroxide, controlling the pH value of the solution to be 11 and the temperature of the solution to be 90 ℃, cooling after complete reaction, washing with deionized water, filtering, drying and recovering to obtain white solid lithium phosphate.
Example 2
(1) Weighing 67.3Kg of lithium hydroxide to dissolve in 0.75 cubic meter of deionized water, stirring and dissolving, then adding 58.8Kg of concentrated phosphoric acid into the lithium hydroxide solution, stirring for 30min after complete reaction, and generating white suspension (the concentrations of lithium ions and phosphate ions are respectively 2.14mol/L and 0.68 mol/L);
dissolving 32.7Kg and 79.5Kg of ferrous sulfate and manganese sulfate in 1 cubic meter of deionized water to generate a mixed solution (the concentrations of iron ions and manganese ions are 0.11mol/L and 0.47mol/L respectively), stirring for 30min, and controlling the pH value to be 2.5;
(2) heating the suspension to 100 ℃, adding the mixed solution, keeping the temperature for 4 hours, naturally cooling, filtering to obtain filtrate and precipitate, washing the precipitate with deionized water, and drying at normal temperature to obtain the lithium iron manganese phosphate LiMn 0.8 Fe 0.2 PO 4 A precursor;
(3) 50Kg of the precursor is dispersed in 70Kg of deionized water, 2.5Kg of soluble starch, 1Kg of polyethylene glycol and 0.3Kg of nano-magnesium oxide are added, and the mixture is ground, dried, sintered, crushed and packaged to obtain the lithium iron manganese phosphate anode material LiMn 0.8 Fe 0.2 PO 4 /C；
(4) And (3) adding 109.2Kg of concentrated phosphoric acid into the filtrate obtained in the step (2), adding 46.8Kg of lithium hydroxide, controlling the pH value of the solution to be 10 and the temperature of the solution to be 90 ℃, cooling after complete reaction, washing with deionized water, filtering, drying and recovering to obtain white solid lithium phosphate.
Example 3
(1) Weighing 68.1Kg of lithium phosphate, dissolving the lithium phosphate in 1 cubic meter of deionized water, and stirring for 30min to generate white suspension (the concentration of the lithium phosphate suspension is 0.59 mol/L));
dissolving 32.7Kg and 114Kg of ferrous sulfate and manganese sulfate in 0.65 cubic meter of deionized water to generate a mixed solution (the concentrations of iron ions and manganese ions are 0.18mol/L and 1.04mol/L), and controlling the pH value to be 1.5;
(2) heating the suspension to 90 ℃, adding the mixed solution, keeping the temperature for 12 hours, naturally cooling, filtering to obtain filtrate and precipitate, washing the precipitate with deionized water, and drying at normal temperature to obtain the lithium iron manganese phosphate LiMn 0.8 Fe 0.2 PO 4 A precursor;
(3) 50Kg of the precursor is dispersed in 70Kg of deionized water, 3.2Kg of glucose and 0.5Kg of nano titanium dioxide are added, and the mixture is ground, dried, sintered, crushed and packaged to obtain the lithium iron manganese phosphate anode material LiMn 0.8 Fe 0.2 PO 4 /C；
(4) And (3) adding 113.2Kg of concentrated phosphoric acid into the filtrate obtained in the step (2), adding 45.7Kg of lithium hydroxide, controlling the pH value of the solution to be 11 and the temperature of the solution to be 90 ℃, cooling after complete reaction, washing with deionized water, filtering and drying to obtain white solid lithium phosphate.
Example 4
(1) Weighing 64.5Kg of lithium hydroxide to dissolve in 0.55 cubic meter of deionized water, stirring and dissolving, then adding 54.8Kg of concentrated phosphoric acid into the lithium hydroxide solution, and stirring for 30min after complete reaction to generate white suspension (the concentration of lithium ions is 2.79mol/L, and the concentration of phosphate radical is 0.86 mol/L);
dissolving 55.6Kg and 50.7Kg of ferrous sulfate and manganese sulfate in 0.65 cubic meter of deionized water to generate a mixed solution (the concentrations of iron ions and manganese ions are 0.31mol/L and 0.46mol/L), and controlling the pH value to be 2.5;
(2) heating the suspension to 95 deg.C, adding the above mixture, maintaining the temperature for 8 hr, and collecting the supernatantThen cooling, filtering to obtain filtrate and precipitate, washing the precipitate with deionized water, and drying at normal temperature to obtain the lithium iron manganese phosphate LiMn 0.6 Fe 0.4 PO 4 A precursor;
(3) 50Kg of the precursor is dispersed in 70Kg of deionized water, and 3Kg of soluble starch and 2Kg of tetrabutyl titanate are added, ground, dried, sintered, crushed and packaged to obtain the lithium iron manganese phosphate anode material LiMn 0.6 Fe 0.4 PO 4 /C；
(4) And (3) adding 108.5Kg of concentrated phosphoric acid into the filtrate obtained in the step (2), adding 43.5Kg of lithium hydroxide, controlling the pH value of the solution to be 11 and the temperature of the solution to be 90 ℃, cooling after complete reaction, washing with deionized water, filtering and drying to obtain white solid lithium phosphate. .
Example 5
(1) Weighing 63.3Kg of lithium hydroxide, dissolving the lithium hydroxide in 1 cubic meter of deionized water, stirring and dissolving, adding 57.9Kg of concentrated phosphoric acid into the lithium hydroxide solution, and stirring for 30min after complete reaction to generate white suspension (the concentrations of lithium ions and phosphate ions are 1.51mol/L and 0.5mol/L respectively);
dissolving 49.1Kg and 69.6Kg of ferrous sulfate and manganese sulfate with 0.5 cubic meter of deionized water to generate a mixed solution (the concentration of iron ions and manganese ions is 0.35mol/L and 0.82mol/L), and controlling the pH value to be 1.5;
(2) heating the suspension to 100 ℃, adding the mixed solution, keeping the temperature for 4 hours, naturally cooling, filtering to obtain filtrate and precipitate, washing the precipitate with deionized water, and drying at normal temperature to obtain the lithium iron manganese phosphate LiMn 0.7 Fe 0.3 PO 4 A precursor;
(3) 50Kg of the precursor is dispersed in 70Kg of deionized water, 3Kg of soluble starch and 0.25Kg of nano zirconia are added, and the mixture is ground, dried, sintered, crushed and packaged to obtain the lithium iron manganese phosphate anode material LiMn 0.7 Fe 0.3 PO 4 /C；
(4) And (3) adding 107.1Kg of concentrated phosphoric acid into the filtrate obtained in the step (2), adding 45.5Kg of lithium hydroxide, controlling the pH of the solution to be 10 and the temperature of the solution to be 90 ℃, cooling after complete reaction, washing with deionized water, filtering and drying to obtain white solid lithium phosphate. .
Example 6
(1) Weighing 69.1Kg of lithium phosphate, dissolving the lithium phosphate in 1.2 cubic meters of deionized water, and stirring for 30min to generate white suspension (the concentration of the lithium phosphate suspension is 0.5 mol/L);
dissolving 49.1Kg and 69.6Kg of ferrous sulfate and manganese sulfate with 0.5 cubic meter of deionized water to generate a mixed solution (the concentration of iron ions and manganese ions is 0.35mol/L and 0.12mol/L), and controlling the pH value to be 1;
(2) heating the suspension to 100 ℃, adding the mixed solution, keeping the temperature for 4 hours, naturally cooling, filtering to obtain filtrate and precipitate, washing the precipitate with deionized water, and drying at normal temperature to obtain the lithium iron manganese phosphate LiMn 0.7 Fe 0.3 PO 4 A precursor;
(3) 50Kg of the precursor is dispersed in 70Kg of deionized water, 3Kg of soluble starch and 0.5Kg of nano titanium dioxide are added, and the mixture is ground, dried, sintered, crushed and packaged to obtain the lithium iron manganese phosphate anode material LiMn 0.7 Fe 0.3 PO 4 /C；
(4) And (3) adding 112.4Kg of concentrated phosphoric acid into the filtrate obtained in the step (2), adding 43.7Kg of lithium hydroxide, controlling the pH value of the solution to be 11 and the temperature of the solution to be 90 ℃, cooling after complete reaction, washing with deionized water, filtering and drying to obtain white solid lithium phosphate.
Example 7
(1) Weighing 5.26Kg of lithium phosphate, dissolving the lithium phosphate in 1.25 cubic meters of deionized water, stirring and dissolving, adding 13.4Kg of diammonium phosphate into the lithium phosphate solution, and stirring for 30min to generate white suspension (the concentration of lithium ions is 0.1mol/L, and the concentration of phosphate radicals is 0.1 mol/L);
adding 0.4 cubic meter of deionized water into a storage tank, then adding 149.8Kg of concentrated phosphoric acid, then adding 2.44Kg of ferrous dihydrogen phosphate, keeping the pH value of the solution at 1, and then filtering, wherein the filtrate is used as a mixed solution (the concentration of iron ions is 0.1mol/L) for later use;
(2) heating the suspension to 101 deg.C, adding the above mixture, and maintaining the temperatureCooling naturally for 12h, filtering to obtain filtrate and precipitate, washing the precipitate with deionized water, and drying at normal temperature to obtain lithium iron phosphate LiFePO 4 A precursor;
(3) dispersing 5Kg of the precursor in 7Kg of deionized water, adding 0.51Kg of glucose and 0.5g of nano magnesium acetate, grinding, drying, sintering, crushing and packaging to obtain the lithium iron phosphate anode material LiFePO 4 /C；
(4) And (3) adding 11.3Kg of concentrated phosphoric acid into the filtrate obtained in the step (2), adding 4.1Kg of lithium hydroxide, controlling the pH value of the solution to be 11 and the temperature of the solution to be 90 ℃, cooling after complete reaction, washing with deionized water, filtering, drying and recovering to obtain white solid lithium phosphate.
Example 8
(1) Weighing 210Kg of lithium carbonate to dissolve in 1.25 cubic meters of deionized water, stirring and dissolving, adding 585Kg of ammonium dihydrogen phosphate into the lithium carbonate solution, and stirring for 30min to generate white suspension (the concentration of lithium ions is 1.28mol/L, and the concentration of phosphate radical is 4 mol/L);
adding 0.4 cubic meter of deionized water into a storage tank, then adding 149.8Kg of concentrated phosphoric acid, then adding 97.5Kg of reduced iron powder, keeping the pH value of the solution at 4, and then filtering, wherein the filtrate is used as a mixed solution (the concentration of iron ions is 4mol/L) for later use;
(2) heating the suspension to 70 ℃, adding the mixed solution, preserving heat for 4 hours, naturally cooling, filtering to obtain filtrate and precipitate, washing the precipitate with deionized water, and drying at normal temperature to obtain lithium iron phosphate LiFePO 4 A precursor;
(3) 50Kg of the precursor is dispersed in 70Kg of deionized water, 3Kg of soluble starch and 0.5Kg of nano titanium dioxide are added, and the lithium iron phosphate anode material LiFePO is obtained by grinding, drying, sintering, crushing and packaging 4 /C；
(4) And (3) adding 115.3Kg of concentrated phosphoric acid into the filtrate obtained in the step (2), adding 47.1Kg of lithium hydroxide, controlling the pH value of the solution to be 11 and the temperature of the solution to be 90 ℃, cooling after complete reaction, washing with deionized water, filtering, drying and recovering to obtain white solid lithium phosphate.
Example 9
(1) Weighing 34.5Kg of lithium phosphate, dissolving the lithium phosphate in 1.2 cubic meters of deionized water, and stirring for 30min to generate white suspension (the concentration of the lithium phosphate suspension is 0.1 mol/L);
dissolving 14.0Kg and 69.2Kg of ferrous dihydrogen phosphate and manganese acid phosphate in 0.5 cubic meter of deionized water to generate a mixed solution (the concentration of iron ions and manganese ions is 0.1mol/L and 0.1mol/L), and controlling the pH value to be 4;
(2) heating the suspension to 100 ℃, adding the mixed solution, keeping the temperature for 12 hours, naturally cooling, filtering to obtain filtrate and precipitate, washing the precipitate with deionized water, and drying at normal temperature to obtain the lithium iron manganese phosphate LiMn 0.7 Fe 0.3 PO 4 A precursor;
(3) 50Kg of the precursor is dispersed in 70Kg of deionized water, 5.56Kg of polyethylene glycol and 0.5Kg of zirconia are added, and the mixture is ground, dried, sintered, crushed and packaged to obtain the lithium iron manganese phosphate anode material LiMn 0.7 Fe 0.3 PO 4 /C；
(4) And (3) adding 112.4Kg of concentrated phosphoric acid into the filtrate obtained in the step (2), adding 43.7Kg of lithium hydroxide, controlling the pH of the solution to be 11 and the temperature of the solution to be 90 ℃, cooling after complete reaction, washing with deionized water, filtering and drying to obtain white solid lithium phosphate.
Effects of the embodiment
The lithium iron phosphate cathode material LiFePO prepared in the above example 1 4 The XRD and SEM test is carried out on the/C, and the test results are shown in figures 1 and 2. As can be seen from fig. 1, the lithium iron phosphate precursor has a pure-phase olivine structure; as can be seen from FIG. 2, the lithium iron phosphate cathode material has uniform primary particle size and good particle dispersibility, and the primary particles are between 100 nm and 200nm, which is beneficial to the exertion of electrochemical performance.
The lithium iron manganese phosphate cathode material LiMn prepared in the embodiment 2 0.8 Fe 0.2 PO 4 XRD and SEM tests are carried out on the/C, and the test results are shown in figures 3 and 4. As can be seen from fig. 3, the lithium iron manganese phosphate precursor has a pure-phase olivine structure; as can be seen from fig. 4, the lithium iron manganese phosphate positive electrode materialThe primary particles are uniform in size and good in particle dispersibility, and the primary particles are between 50nm, so that the electrochemical performance is favorably exerted.
Electrochemical performance tests are performed on the anode materials prepared in the above examples 1 to 6, the voltage platform is 2.0 to 4.5V, and the electrical performance test results are shown in the following table 1:
TABLE 1 electrochemical Performance data
From the test result of the electrochemical performance, the lithium iron phosphate prepared by the method has excellent electrochemical performance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (6)
1. A preparation method of a lithium iron phosphate or lithium ferromanganese anode material of a lithium ion battery is characterized by comprising the following steps:
(1) adding a lithium source and a phosphorus source into water, and uniformly stirring to obtain suspensions with lithium ion and phosphorus lithium ion concentrations of 0.1-4 mol/L respectively;
adding a salt source into water to obtain a mixed solution with a pH value of 1-4, wherein the salt source is an iron source, and the concentration of iron ions in the mixed solution is 0.1-4 mol/L, or the salt source is a combination of the iron source and a manganese source, and the concentration of the iron ions in the mixed solution is 0.1-4 mol/L and the concentration of ferromanganese ions is 0.1-4 mol/L;
(2) preheating the suspension to 70-101 ℃, adding the mixed solution, preserving the heat for 4-12 hours, naturally cooling, and filtering to obtain filtrate and precipitate; washing and drying the precipitate to obtain a lithium iron phosphate precursor or a lithium manganese iron phosphate precursor; wherein,
in the lithium iron phosphate precursor, the molar ratio of lithium ions to iron ions to phosphate ions is 1-4: 0.01-1: 1-3;
in the lithium iron manganese phosphate precursor, the molar ratio of lithium ions, iron ions, manganese ions and phosphate ions is 1-4: 0.01-1: 0.01-1: 1-3;
(3) mixing the precursor obtained in the step (2) with an organic matter and an additive, grinding, drying, sintering and crushing to obtain a lithium iron phosphate anode material or a lithium ferromanganese anode material of the lithium ion battery; wherein the mass of the organic matter accounts for 1-10% of the mass of the precursor, and the mass of the additive accounts for 0.05-5% of the mass of the precursor.
2. The method for preparing the lithium iron phosphate or lithium ferromanganese anode material for the lithium ion battery according to claim 1, further comprising the step of, after the step (2): (4) and adding acid into the filtrate to adjust the pH value, adding a precipitator, and recovering valuable metals.
3. The method for preparing a lithium iron phosphate or lithium manganese iron phosphate positive electrode material for a lithium ion battery according to claim 1, wherein in step (1), the lithium source is at least one selected from lithium carbonate, lithium bicarbonate, lithium hydroxide, lithium acetate, lithium citrate, lithium dihydrogen phosphate, and lithium phosphate; the phosphorus source is selected from at least one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, lithium dihydrogen phosphate, phosphoric acid and lithium phosphate.
4. The method for preparing lithium iron phosphate or lithium ferromanganese positive electrode material for lithium ion battery according to claim 1, wherein in the step (1), the iron source is at least one selected from ferrous sulfate heptahydrate, ferric nitrate, ferric citrate, ferric chloride, ferrous acetate, ferrous dihydrogen phosphate, iron powder, and iron ingot; the manganese source is selected from at least one of manganese sulfate monohydrate, manganese acid phosphate, manganese acetate and manganese nitrate.
5. The method for preparing the lithium iron phosphate or lithium iron manganese phosphate cathode material of the lithium ion battery according to claim 1, wherein in the step (3), the organic matter is at least one selected from glucose, sucrose, polyethylene glycol, starch and ascorbic acid;
the additive is at least one of magnesium oxide, zirconium oxide, titanium dioxide, magnesium acetate and tetrabutyl titanate.
6. The method for preparing the lithium iron phosphate or lithium ferromanganese anode material for the lithium ion battery according to claim 2, wherein in the step (4), the pH of the acid is 1-6, and the acid is selected from at least one of sulfuric acid, phosphoric acid, hydrochloric acid, acetic acid and citric acid; the precipitant is selected from at least one of sodium carbonate, sodium hydroxide, lithium hydroxide and sodium phosphate.
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