WO2022242184A1 - Doped iron phosphate, and preparation method therefor and application thereof - Google Patents
Doped iron phosphate, and preparation method therefor and application thereof Download PDFInfo
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- WO2022242184A1 WO2022242184A1 PCT/CN2021/142927 CN2021142927W WO2022242184A1 WO 2022242184 A1 WO2022242184 A1 WO 2022242184A1 CN 2021142927 W CN2021142927 W CN 2021142927W WO 2022242184 A1 WO2022242184 A1 WO 2022242184A1
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- Prior art keywords
- phosphate
- iron
- iron phosphate
- doped
- preparation
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- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 69
- 229910000398 iron phosphate Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 33
- 239000002245 particle Substances 0.000 claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 29
- 239000005955 Ferric phosphate Substances 0.000 claims description 28
- 229940032958 ferric phosphate Drugs 0.000 claims description 28
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 28
- 230000002378 acidificating effect Effects 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 5
- 239000003929 acidic solution Substances 0.000 claims description 5
- 238000005273 aeration Methods 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 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
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 239000000203 mixture Substances 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-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
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 239000002893 slag Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- FDGBQHCDMSYZRC-UHFFFAOYSA-N 2-hydroxy-2-oxo-1,3,2$l^{5}-dioxaphosphinan-4-amine Chemical compound NC1CCOP(O)(=O)O1 FDGBQHCDMSYZRC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- WCBWLLSPCIWUOI-UHFFFAOYSA-N OC1COP(=O)OP(=O)O1 Chemical compound OC1COP(=O)OP(=O)O1 WCBWLLSPCIWUOI-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229940117975 chromium trioxide Drugs 0.000 claims description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 238000010979 pH adjustment Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 239000002699 waste material Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 229910052595 hematite Inorganic materials 0.000 claims 1
- 239000011019 hematite Substances 0.000 claims 1
- 238000001694 spray drying Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000005056 compaction Methods 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 238000009827 uniform distribution Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000843 powder Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 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 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Images
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
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- C01P2004/01—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
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
- C01P2006/10—Solid density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
-
- 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
Definitions
- the invention belongs to the technical field of battery materials, and in particular relates to a doped iron phosphate and a preparation method and application thereof.
- Olivine-type lithium iron phosphate has the advantages of high energy density, stable voltage platform, long life, low cost, and good safety performance. It is considered to be a promising cathode material and is widely used in industries such as power vehicles and energy storage. However, due to the structure of lithium iron phosphate materials, the electronic conductivity is low and the diffusion coefficient of lithium ions is small, which greatly restricts the development of lithium iron phosphate. In order to overcome this problem, researchers have done a lot of research and found that by trying a small amount Doping can improve the conductivity of electrons, reduce impedance and polarization, so that the electrochemical performance of the battery can be significantly improved.
- the present invention aims to solve at least one of the technical problems in the above-mentioned prior art. For this reason, the present invention proposes a doped ferric phosphate and its preparation method and application.
- the preparation conditions and components of the doped ferric phosphate are easy to control and easy to industrialized production.
- the density is 0.71-0.8g/cm 3
- the specific surface area is 8.56-9.3m 2 /g, which avoids the problems of difficult doping and compaction caused by doping during the synthesis of lithium iron phosphate.
- the present invention adopts the following technical solutions:
- a doped iron phosphate has a particle diameter of 2.5-3.5 ⁇ m, a tap density of 0.71-0.8 g/cm 3 and a specific surface area of 8.56-9.3 m 2 /g.
- a preparation method of doped iron phosphate comprising the following steps:
- the phosphorus source is a substance containing phosphate; the substance containing phosphate includes organic phosphate and inorganic phosphate.
- the phosphate-containing substance is at least one of phosphoric acid, dihydrogen phosphate, hydrogen phosphate, hydroxyethylene diphosphonate or aminotrimethylene phosphate.
- the phosphate-containing substance is phosphoric acid.
- the iron source is a substance containing iron element; the iron source is ferrophosphorus waste, ferrophosphorus leaching slag, iron powder, magnetite (Fe 3 O 4 ), hematite (Fe 2 O 3 ), iron phosphate, lithium iron phosphate, ferric sulfate, ferrous sulfate, ferric chloride, ferrous chloride, ferric nitrate or ferrous nitrate.
- the acidic solution is at least one of sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid.
- the concentration of the acidic solution is 1-16 mol/L. Further preferably, the acidic solution has a concentration of 2-10 mol/L.
- the ratio of iron to phosphorus in the phosphorus-iron solution is 1: (1-1.20).
- the doping element is at least one of Ti, Al, V, Ni, Co, Mn, Mg, Cr and Mo.
- the doping element substance is a solution of a soluble salt or oxide of a doping element.
- the substance containing doping elements is at least one of titanium trichloride, titanium oxide, aluminum oxide, aluminum sulfate, aluminum chloride, nickel sulfate, magnesium chloride, chromium trioxide or molybdenum trioxide.
- the doping amount of the doping element in the substance containing the doping element is 0.1-10%.
- step (2) when the iron source is ferrous iron, aeration oxidation is also included before the pH adjustment; the gas used in the aeration oxidation is oxygen.
- the aeration oxidation is to oxidize the Fe 2+ present in the solution to Fe 3+ to improve the subsequent iron precipitation rate.
- the substance used to adjust the pH is at least one of sodium hydroxide, ammonia water or sodium carbonate.
- the stirring rate is 100-1300 r/min, more preferably 350-800 r/min.
- the present invention also provides a method for preparing doped and coated carbon-type lithium iron phosphate, comprising the following steps:
- the molar ratio of iron phosphate in the doped iron phosphate to lithium in the lithium source is 1: (0.98-1.05).
- the temperature of the calcination is 750-800° C.
- the atmosphere of the calcination is nitrogen or argon.
- the lithium source is selected from at least one of lithium carbonate, lithium hydroxide, lithium nitrate or lithium acetate.
- the carbon source is glucose
- the mass fraction of the glucose is 5-10%.
- the present invention prepares battery-grade iron phosphate with uniform distribution of doping elements.
- the conditional components are easy to control and industrialized production.
- the particle size of doped iron phosphate is 2.5-3.5 ⁇ m, and the tap density is 0.71-0.8g/cm 3.
- the specific surface area is 8.56-9.3m 2 /g, which avoids the problems of difficult doping and compaction caused by doping during the synthesis of lithium iron phosphate.
- the preparation method of doped ferric phosphate of the present invention is simple to operate. Adding a substance containing doping elements to ferric phosphate liquid to synthesize ferric phosphate, so that the doping process and the precipitation process are carried out simultaneously, avoiding the synthesis of lithium iron phosphate
- the problem of difficult doping and compaction caused by doping in the process, the conditional composition is easy to control, and battery-grade iron phosphate with uniform distribution of doping elements can be obtained; the precursor with uniform distribution of doping elements has a great impact on the performance of lithium iron phosphate The influence is large, and uniform doping can further improve the electrochemical performance of lithium iron phosphate.
- the electrochemical performance of the lithium iron phosphate material prepared by doping iron phosphate of the present invention is significantly improved, because improving the uniformity of doping elements can improve the lithium iron phosphate Electrochemical properties of materials.
- FIG. 1 is an SEM image of titanium-doped iron phosphate according to Example 1 of the present invention.
- the preparation method of the doped ferric phosphate of this embodiment specifically the preparation method of titanium doped ferric phosphate, comprises the following steps:
- Phosphoric acid is taken as the phosphorus source, and reduced iron powder is used as the iron source.
- the reduced iron powder is first dissolved in 2mol/L sulfuric acid to obtain an acidic iron solution, and phosphoric acid is added to the acidic iron solution at an iron-to-phosphorus ratio of 1:1.03.
- Fig. 1 is the SEM picture of the ferric phosphate doped with titanium of the embodiment 1 of the present invention;
- the magnification in the a of Fig. 1 is 50000, and the magnification in the b of Fig. 1 is 10000, as can be seen from the a and b of Fig. 1
- the doped ferric phosphate with good sphericity and uniform doping was prepared.
- the preparation method of the doped ferric phosphate of this embodiment specifically the preparation method of titanium doped ferric phosphate, comprises the following steps:
- the preparation method of the doped iron phosphate of the present embodiment specifically the preparation method of nickel doped iron phosphate, comprises the following steps:
- nickel sulfate Add 0.2g/L nickel sulfate to the ferrophosphorus solution and stir to dissolve it. After the dissolution is complete, add sodium carbonate to adjust the pH to 3, react at 90°C for 3 hours, and separate the liquid and solid to obtain nickel-doped iron phosphate ;
- the preparation method of the doped ferric phosphate of this embodiment specifically the preparation method of titanium doped ferric phosphate, comprises the following steps:
- the preparation method of the ferric phosphate of this comparative example comprises the following steps:
- Phosphoric acid and magnetite are dissolved in the sulfuric acid of 2mol/L respectively to obtain acidic iron solution and acidic phosphorus solution, be mixed with acidic phosphorus iron solution for 1: 1.03 by iron-phosphorus ratio;
- the preparation method of the zinc-doped lithium iron phosphate/carbon composite material of this comparative example comprises the following steps:
- the primary crushed particles are calcined at a high temperature under a protective atmosphere, and then secondary crushed to obtain lithium iron phosphate.
- Table 2 The specific detection data of the doped iron phosphate of embodiment 1-3 and the iron phosphate of comparative example 1
- the doped ferric phosphate particle size, tap density, specific surface area and the data of the ferric phosphate prepared by comparative example 1 prepared by embodiment 1-3 are not much different, indicating that doping elements have a significant effect on the physical index of ferric phosphate The effect is not large, which further shows that the doping elements of the present invention are evenly distributed on the iron phosphate.
- Table 3 is a comparison table of the compaction density and electrical performance test results of the doped iron phosphate of Examples 1-3 and the comparative example synthetic lithium iron phosphate powder. From the data in the table, it can be seen that the iron phosphate prepared by element doping Compared with the lithium iron phosphate prepared by undoped iron phosphate, the electrochemical performance of the lithium iron phosphate material is significantly improved, because the introduction of doping elements improves the electrical conductivity of the lithium iron phosphate material, thereby improving the lithium iron phosphate material.
- Electrochemical properties compared with the performance of the lithium iron phosphate prepared in Comparative Example 2 (doping by solid phase method), it is found that the performance of the lithium iron phosphate prepared by the doped iron phosphate of Examples 1-3 is better, indicating that the lithium iron phosphate prepared by the liquid phase Improving the uniformity of doping elements by method doping can improve the electrochemical performance of lithium iron phosphate materials.
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Abstract
The present invention relates to the technical field of battery materials, and disclosed are doped iron phosphate, and a preparation method therefor and an application thereof. The doped iron phosphate has a particle size of 2.5-3.5 μm, tap density of 0.71-0.8 g/cm3 and a specific surface area of 8.56-9.3 m2/g. According to the present invention, battery-grade iron phosphate with uniform distribution of doping elements can be prepared, condition components are easy to control, and industrial production is facilitated; the doped iron phosphate has the particle size of 2.5-3.5 μm and the tap density of 0.71-0.8 g/cm3. The problems of difficulty in doping and difficulty in improving the compaction caused by doping during the synthesis of lithium iron phosphate are avoided.
Description
本发明属于电池材料技术领域，具体涉及一种掺杂磷酸铁及其制备方法和应用。The invention belongs to the technical field of battery materials, and in particular relates to a doped iron phosphate and a preparation method and application thereof.
橄榄石型磷酸铁锂具有能量密度高、电压平台稳定、寿命长、成本低、安全性能好等优点，被认为是很有前途的正极材料，在动力汽车和储能等行业应用广泛。但由于磷酸铁锂材料结构的原因导致电子导电率低，锂离子扩散系数小，从而极大的制约了磷酸铁锂的发展，为了克服这一问题，研究学者做了大量的研究发现通过尝试少量掺杂，可以提高电子的导电性，减少阻抗和极化，从而使得电池的电化学性能显著提高。Olivine-type lithium iron phosphate has the advantages of high energy density, stable voltage platform, long life, low cost, and good safety performance. It is considered to be a promising cathode material and is widely used in industries such as power vehicles and energy storage. However, due to the structure of lithium iron phosphate materials, the electronic conductivity is low and the diffusion coefficient of lithium ions is small, which greatly restricts the development of lithium iron phosphate. In order to overcome this problem, researchers have done a lot of research and found that by trying a small amount Doping can improve the conductivity of electrons, reduce impedance and polarization, so that the electrochemical performance of the battery can be significantly improved.
然而，目前磷酸铁锂的掺杂方法大多是在磷酸铁锂合成时，在其混料的过程中加入掺杂元素，再经后续焙烧等工序得到掺杂改性磷酸铁锂材料，但是上述的改性方法的成分和条件难以控制，还有掺杂元素不均匀，不易于工业化生产。However, at present, most of the doping methods of lithium iron phosphate are to add doping elements in the process of mixing lithium iron phosphate during the synthesis of lithium iron phosphate, and then obtain doped modified lithium iron phosphate materials through subsequent roasting and other processes, but the above-mentioned The composition and conditions of the modification method are difficult to control, and the doping elements are not uniform, so it is not easy for industrial production.
发明内容Contents of the invention
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此，本发明提出一种掺杂磷酸铁及其制备方法和应用，该掺杂磷酸铁的制备条件成分易于控制，易于工业化生产，掺杂磷酸铁的粒径为2.5-3.5μm，振实密度为0.71-0.8g/cm
3，比表面积为8.56-9.3m
2/g，避免了磷酸铁锂合成过程中掺杂所带来的难以掺杂及难以提高压实的问题。
The present invention aims to solve at least one of the technical problems in the above-mentioned prior art. For this reason, the present invention proposes a doped ferric phosphate and its preparation method and application. The preparation conditions and components of the doped ferric phosphate are easy to control and easy to industrialized production. The density is 0.71-0.8g/cm 3 , and the specific surface area is 8.56-9.3m 2 /g, which avoids the problems of difficult doping and compaction caused by doping during the synthesis of lithium iron phosphate.
为实现上述目的，本发明采用以下技术方案：To achieve the above object, the present invention adopts the following technical solutions:
一种掺杂磷酸铁，所述掺杂磷酸铁的粒径为2.5-3.5μm，振实密度为0.71-0.8g/cm
3，比表面积为8.56-9.3m
2/g。
A doped iron phosphate, the doped iron phosphate has a particle diameter of 2.5-3.5 μm, a tap density of 0.71-0.8 g/cm 3 and a specific surface area of 8.56-9.3 m 2 /g.
一种掺杂磷酸铁的制备方法，包括以下步骤：A preparation method of doped iron phosphate, comprising the following steps:
(1)将磷源、铁源溶于酸性溶液中，过滤并收集滤液，得到酸性磷铁液；(1) dissolving the phosphorus source and the iron source in the acidic solution, filtering and collecting the filtrate to obtain the acidic phosphorus iron solution;
(2)向所述酸性磷铁液中加入含掺杂元素的物质，调节pH，并加热搅拌，反应，液固分离，得到掺杂磷酸铁。(2) Adding substances containing doping elements to the acidic ferrophosphorus liquid, adjusting the pH, heating and stirring, reacting, liquid-solid separation, and obtaining doped ferric phosphate.
优选地，步骤(1)中，所述磷源为含有磷酸根的物质；所述含有磷酸根的物质包括有机磷酸盐和无机磷酸盐。Preferably, in step (1), the phosphorus source is a substance containing phosphate; the substance containing phosphate includes organic phosphate and inorganic phosphate.
进一步优选地，所述含有磷酸根的物质为磷酸、磷酸二氢盐、磷酸氢盐、羟基亚乙基二膦酸盐或氨基三亚甲基磷酸盐中的至少一种。Further preferably, the phosphate-containing substance is at least one of phosphoric acid, dihydrogen phosphate, hydrogen phosphate, hydroxyethylene diphosphonate or aminotrimethylene phosphate.
更优选地，所述含有磷酸根的物质为磷酸。More preferably, the phosphate-containing substance is phosphoric acid.
优选地，步骤(1)中，所述铁源为含有铁元素的物质；所述铁源为磷铁废料、磷铁浸出渣、铁粉、磁铁矿(Fe
3O
4)、赤铁矿(Fe
2O
3)、磷酸铁、磷酸铁锂、硫酸铁、硫酸亚铁、氯化铁、氯化亚铁、硝酸铁或硝酸亚铁中的至少一种。
Preferably, in step (1), the iron source is a substance containing iron element; the iron source is ferrophosphorus waste, ferrophosphorus leaching slag, iron powder, magnetite (Fe 3 O 4 ), hematite (Fe 2 O 3 ), iron phosphate, lithium iron phosphate, ferric sulfate, ferrous sulfate, ferric chloride, ferrous chloride, ferric nitrate or ferrous nitrate.
优选地，步骤(1)中，所述酸性溶液为硫酸、盐酸、硝酸、磷酸中的至少一种。Preferably, in step (1), the acidic solution is at least one of sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid.
优选地，步骤(1)中，所述酸性溶液的浓度为1～16mol/L。进一步优选，所述酸性溶液的浓度为2～10mol/L。Preferably, in step (1), the concentration of the acidic solution is 1-16 mol/L. Further preferably, the acidic solution has a concentration of 2-10 mol/L.
优选地，步骤(1)中，所述磷铁液中的铁磷比为1：(1～1.20)。Preferably, in step (1), the ratio of iron to phosphorus in the phosphorus-iron solution is 1: (1-1.20).
优选地，步骤(2)中，所述掺杂元素为Ti、Al、V、Ni、Co、Mn、Mg、Cr、Mo中的至少一种。Preferably, in step (2), the doping element is at least one of Ti, Al, V, Ni, Co, Mn, Mg, Cr and Mo.
优选地，步骤(2)中，所述掺杂元素物质为掺杂元素的可溶性盐或氧化物的溶液。Preferably, in step (2), the doping element substance is a solution of a soluble salt or oxide of a doping element.
更优选地，所述含掺杂元素的物质为三氯化钛、氧化钛、氧化铝、硫酸铝、氯化铝、硫酸镍、氯化镁、三氧化二铬或三氧化钼中的至少一种。More preferably, the substance containing doping elements is at least one of titanium trichloride, titanium oxide, aluminum oxide, aluminum sulfate, aluminum chloride, nickel sulfate, magnesium chloride, chromium trioxide or molybdenum trioxide.
优选地，步骤(2)中，所述含掺杂元素的物质中掺杂元素掺杂量为0.1～10％。Preferably, in step (2), the doping amount of the doping element in the substance containing the doping element is 0.1-10%.
优选地，步骤(2)中，所述铁源为二价铁时，所述调节pH前还包括通气氧化；所述通气氧化所使用的气体为氧气。通气氧化是将溶液中存在的Fe
2+氧化成Fe
3+提高后续铁的沉淀率。
Preferably, in step (2), when the iron source is ferrous iron, aeration oxidation is also included before the pH adjustment; the gas used in the aeration oxidation is oxygen. The aeration oxidation is to oxidize the Fe 2+ present in the solution to Fe 3+ to improve the subsequent iron precipitation rate.
优选地，步骤(2)中，所述调节pH所使用的物质为氢氧化钠、氨水或碳酸钠中的至少一种。Preferably, in step (2), the substance used to adjust the pH is at least one of sodium hydroxide, ammonia water or sodium carbonate.
优选地，步骤(2)中，所述搅拌的速率为100～1300r/min，进一步优选为350～800r/min。Preferably, in step (2), the stirring rate is 100-1300 r/min, more preferably 350-800 r/min.
本发明还提供一种掺杂包覆碳型磷酸铁锂的制备方法，包括以下步骤：The present invention also provides a method for preparing doped and coated carbon-type lithium iron phosphate, comprising the following steps:
将所述掺杂磷酸铁和锂源混合，加入碳源，加入水进行砂磨处理，再喷雾干燥，焙烧，制得掺杂型磷酸铁锂。Mix the doped iron phosphate and lithium source, add carbon source, add water to carry out sand milling treatment, then spray dry and roast to prepare doped lithium iron phosphate.
优选地，所述掺杂磷酸铁中磷酸铁和锂源中锂的摩尔比1：(0.98～1.05)。Preferably, the molar ratio of iron phosphate in the doped iron phosphate to lithium in the lithium source is 1: (0.98-1.05).
优选地，所述焙烧的温度为750-800℃，所述焙烧的氛围为氮气或氩气。Preferably, the temperature of the calcination is 750-800° C., and the atmosphere of the calcination is nitrogen or argon.
优选地，所述锂源选自碳酸锂、氢氧化锂、硝酸锂或乙酸锂中的至少一种。Preferably, the lithium source is selected from at least one of lithium carbonate, lithium hydroxide, lithium nitrate or lithium acetate.
优选地，所述碳源为葡萄糖。Preferably, the carbon source is glucose.
进一步优选地，所述葡萄糖的质量分数为5-10％。Further preferably, the mass fraction of the glucose is 5-10%.
相对于现有技术，本发明的有益效果如下：Compared with the prior art, the beneficial effects of the present invention are as follows:
1、本发明制备的是掺杂元素分布均匀的电池级磷酸铁，条件成分易于控制，易于工业化生产，掺杂磷酸铁的粒径为2.5-3.5μm，振实密度为0.71-0.8g/cm
3，比表面积为8.56-9.3m
2/g，避免了磷酸铁锂合成过程中掺杂所带来的难以掺杂及难以提高压实的问题。
1. The present invention prepares battery-grade iron phosphate with uniform distribution of doping elements. The conditional components are easy to control and industrialized production. The particle size of doped iron phosphate is 2.5-3.5 μm, and the tap density is 0.71-0.8g/cm 3. The specific surface area is 8.56-9.3m 2 /g, which avoids the problems of difficult doping and compaction caused by doping during the synthesis of lithium iron phosphate.
2、本发明的掺杂磷酸铁的制备方法，操作简单，在磷铁液中加入含有掺杂元素的物质进行磷酸铁的合成，使得掺杂过程和沉淀过程同时进行，避免了磷酸铁锂合成过程中掺杂所带来的难以掺杂及难以提高压实的问题，条件成分易于控制，可以得到掺杂元素分布均匀的电池级磷酸铁；掺杂元素分布均匀的前驱体对磷酸铁锂性能影响较大，均匀掺杂可以进一步提高磷酸铁锂的电化学性能。2. The preparation method of doped ferric phosphate of the present invention is simple to operate. Adding a substance containing doping elements to ferric phosphate liquid to synthesize ferric phosphate, so that the doping process and the precipitation process are carried out simultaneously, avoiding the synthesis of lithium iron phosphate The problem of difficult doping and compaction caused by doping in the process, the conditional composition is easy to control, and battery-grade iron phosphate with uniform distribution of doping elements can be obtained; the precursor with uniform distribution of doping elements has a great impact on the performance of lithium iron phosphate The influence is large, and uniform doping can further improve the electrochemical performance of lithium iron phosphate.
3、本发明的掺杂磷酸铁所制备的磷酸铁锂材料相比于合成段掺杂所制备的磷酸铁锂的电化学性能明显改善，是因为提高掺杂元素的均匀性可以提高磷酸铁锂材料的电化学性能。3. Compared with the lithium iron phosphate prepared by doping in the synthesis section, the electrochemical performance of the lithium iron phosphate material prepared by doping iron phosphate of the present invention is significantly improved, because improving the uniformity of doping elements can improve the lithium iron phosphate Electrochemical properties of materials.
图1为本发明实施例1的掺杂钛的磷酸铁的SEM图。FIG. 1 is an SEM image of titanium-doped iron phosphate according to Example 1 of the present invention.
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述，以充分地理解本发明的目的、特征和效果。显然，所描述的实施例只是本发明的一部分实施例，而不是全部实施例，基于本发明的实施例，本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例，均属于本发明保护的范围。The conception and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments, so as to fully understand the purpose, features and effects of the present invention. Apparently, the described embodiments are only some of the embodiments of the present invention, rather than all of them. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without creative efforts belong to The protection scope of the present invention.
实施例1Example 1
本实施例的掺杂磷酸铁的制备方法，具体为钛掺杂磷酸铁的制备方法，包括以下步骤：The preparation method of the doped ferric phosphate of this embodiment, specifically the preparation method of titanium doped ferric phosphate, comprises the following steps:
(1)取磷源为磷酸，铁源为还原铁粉，将还原铁粉先溶于2mol/L的硫酸中得到酸 性铁溶液，按铁磷比为1∶1.03向酸性铁溶液中补加磷酸得到酸性磷铁液；(1) Phosphoric acid is taken as the phosphorus source, and reduced iron powder is used as the iron source. The reduced iron powder is first dissolved in 2mol/L sulfuric acid to obtain an acidic iron solution, and phosphoric acid is added to the acidic iron solution at an iron-to-phosphorus ratio of 1:1.03. Obtain acidic ferrophosphorus solution;
(2)向酸性磷铁液中加入0.2g/L的三氯化钛溶液，并通入氧气氧化1h至溶液中的Fe
2+氧化为Fe
3+，加入氢氧化钠调节pH至3，在90℃下反应3h，液固分离得到钛掺杂磷酸铁；
(2) Add 0.2g/L titanium trichloride solution to the acidic ferrophosphorus solution, and pass through oxygen to oxidize for 1h until the Fe 2+ in the solution is oxidized to Fe 3+ , add sodium hydroxide to adjust the pH to 3, and Reaction at 90°C for 3 hours, liquid-solid separation to obtain titanium-doped iron phosphate;
(3)将得到的钛掺杂磷酸铁进行洗涤、过滤、干燥、脱水，即得钛掺杂磷酸铁成品。(3) Washing, filtering, drying and dehydrating the obtained titanium-doped ferric phosphate to obtain the finished product of titanium-doped ferric phosphate.
图1为本发明实施例1的掺杂钛的磷酸铁的SEM图；图1的a中的倍率为50000，图1的b中的倍率为10000，从图1的a和b中可以看出制备得到了球形度良好的掺杂磷酸铁，而且掺杂均匀。Fig. 1 is the SEM picture of the ferric phosphate doped with titanium of the embodiment 1 of the present invention; The magnification in the a of Fig. 1 is 50000, and the magnification in the b of Fig. 1 is 10000, as can be seen from the a and b of Fig. 1 The doped ferric phosphate with good sphericity and uniform doping was prepared.
实施例2Example 2
本实施例的掺杂磷酸铁的制备方法，具体为钛掺杂磷酸铁的制备方法，包括以下步骤：The preparation method of the doped ferric phosphate of this embodiment, specifically the preparation method of titanium doped ferric phosphate, comprises the following steps:
(1)将提锂后得到的磷铁浸出渣溶于2mol/L的硫酸中得到酸性磷铁溶液；(1) the ferrophosphorus leaching slag obtained after lithium extraction is dissolved in the sulfuric acid of 2mol/L to obtain an acidic ferrophosphorus solution;
(2)向酸性磷铁液中加入0.3g/L的硫酸矾进行搅拌溶解，等溶解完全后加入氢氧化钠调节pH至3，在85℃下反应4h，液固分离得到钒掺杂磷酸铁；(2) Add 0.3g/L of alum sulfate into the acidic ferrophosphorus liquid to stir and dissolve, add sodium hydroxide to adjust the pH to 3 after the dissolution is complete, react at 85°C for 4 hours, and separate liquid and solid to obtain vanadium-doped ferric phosphate ;
(3)将得到的钒掺杂磷酸铁进行洗涤、过滤、干燥、脱水，即得钛掺杂磷酸铁成品。(3) Washing, filtering, drying and dehydrating the obtained vanadium-doped iron phosphate to obtain the finished product of titanium-doped iron phosphate.
实施例3Example 3
本实施例的掺杂磷酸铁的制备方法，具体为镍掺杂磷酸铁的制备方法，包括以下步骤：The preparation method of the doped iron phosphate of the present embodiment, specifically the preparation method of nickel doped iron phosphate, comprises the following steps:
(1)将磷酸二氢钠和硫酸铁分别溶于2mol/L的硫酸中得到酸性铁溶液和酸性磷溶液，按铁磷比为1∶1.05配制成酸性磷铁液；(1) sodium dihydrogen phosphate and ferric sulfate are dissolved in the sulfuric acid of 2mol/L respectively to obtain acidic iron solution and acidic phosphorus solution, be mixed with acidic phosphorus ferric solution by iron-phosphorus ratio of 1: 1.05;
(2)向所述磷铁液中加入0.2g/L的硫酸镍进行搅拌溶解，等溶解完全后加入碳酸钠调节pH至3，在90℃下反应3h，液固分离得到镍掺杂磷酸铁；(2) Add 0.2g/L nickel sulfate to the ferrophosphorus solution and stir to dissolve it. After the dissolution is complete, add sodium carbonate to adjust the pH to 3, react at 90°C for 3 hours, and separate the liquid and solid to obtain nickel-doped iron phosphate ;
(3)将得到的镍掺杂磷酸铁进行洗涤、过滤、干燥、脱水，即得镍掺杂磷酸铁。(3) Washing, filtering, drying and dehydrating the obtained nickel-doped iron phosphate to obtain nickel-doped iron phosphate.
实施例4Example 4
本实施例的掺杂磷酸铁的制备方法，具体为钛掺杂磷酸铁的制备方法，包括以下步骤：The preparation method of the doped ferric phosphate of this embodiment, specifically the preparation method of titanium doped ferric phosphate, comprises the following steps:
(1)将磷酸氢钠和硝酸亚铁分别溶于4mol/L的硝酸中得到酸性铁溶液和酸性磷溶液，按铁磷比为1∶1.03配制成酸性磷铁液；(1) Sodium hydrogen phosphate and ferrous nitrate are dissolved in the nitric acid of 4mol/L respectively to obtain acid iron solution and acid phosphorus solution, and it is 1: 1.03 to be mixed with acid iron phosphorus solution by iron phosphorus ratio;
(2)向酸性磷铁液中加入0.2g/L的三氯化钛溶液，并通入氧气氧化2h至溶液中的Fe
2+氧化为Fe
3+，加入氢氧化钠调节pH至3，在90℃下反应3h，液固分离得到钛掺杂磷酸铁；
(2) Add 0.2g/L titanium trichloride solution to the acidic ferrophosphorus solution, and pass through oxygen for 2h to oxidize Fe 2+ in the solution to Fe 3+ , add sodium hydroxide to adjust the pH to 3, and Reaction at 90°C for 3 hours, liquid-solid separation to obtain titanium-doped iron phosphate;
(3)将得到的钛掺杂磷酸铁进行洗涤、过滤、干燥、脱水，即得钛掺杂磷酸铁成品。(3) Washing, filtering, drying and dehydrating the obtained titanium-doped ferric phosphate to obtain the finished product of titanium-doped ferric phosphate.
对比例1Comparative example 1
本对比例的磷酸铁的制备方法，包括以下步骤：The preparation method of the ferric phosphate of this comparative example, comprises the following steps:
(1)将磷酸和磁铁矿分别溶于2mol/L的硫酸中得到酸性铁溶液和酸性磷溶液，按铁磷比为1∶1.03配制成酸性磷铁液；(1) Phosphoric acid and magnetite are dissolved in the sulfuric acid of 2mol/L respectively to obtain acidic iron solution and acidic phosphorus solution, be mixed with acidic phosphorus iron solution for 1: 1.03 by iron-phosphorus ratio;
(2)向所述磷铁液中通入空气氧化1h至溶液中的Fe
2+氧化为Fe
3+，加入氨水调节pH至3，在90℃下反应4h，液固分离得到磷酸铁；
(2) Pass air into the ferrophosphorus solution for 1 hour to oxidize Fe 2+ in the solution to Fe 3+ , add ammonia water to adjust the pH to 3, react at 90° C. for 4 hours, and separate the liquid and solid to obtain ferric phosphate;
(3)将磷酸铁进行洗涤、过滤、干燥、脱水，即得磷酸铁成品。(3) Washing, filtering, drying and dehydrating the ferric phosphate to obtain the finished ferric phosphate.
对比例2Comparative example 2
本对比例的锌掺杂磷酸铁锂/碳复合材料的制备方法，包括以下步骤：The preparation method of the zinc-doped lithium iron phosphate/carbon composite material of this comparative example comprises the following steps:
(1)以磷酸铁、碳酸锂、葡萄糖、乙酸锌为原料，以去离子水为分散剂形成浆料，浆料搅拌处理后进行超声分散；(1) Using iron phosphate, lithium carbonate, glucose, and zinc acetate as raw materials, using deionized water as a dispersant to form a slurry, and ultrasonically dispersing after the slurry is stirred;
(2)将分散均匀的浆料置于玛瑙罐中，在行星式球磨机上湿法球磨处理，球磨后的浆料进行微波处理；(2) The uniformly dispersed slurry is placed in an agate jar, and wet ball milling is performed on a planetary ball mill, and the slurry after the ball milling is subjected to microwave treatment;
(3)微波处理后的浆液通过喷雾干燥机干燥后得到半成品粉末，半成品粉末在球磨罐干磨处理，进行一次粉碎；(3) The slurry after the microwave treatment is dried by a spray dryer to obtain a semi-finished powder, and the semi-finished powder is dry-milled in a ball mill tank for primary pulverization;
(4)一次粉碎颗粒在保护气氛下进行高温煅烧处理后进行二次粉碎后制得磷酸铁锂。(4) The primary crushed particles are calcined at a high temperature under a protective atmosphere, and then secondary crushed to obtain lithium iron phosphate.
结果对比：Comparative Results:
表1 实施例1制备的磷酸铁的主元素分析表Table 1 The main element analysis table of the ferric phosphate prepared in Example 1
| 元素element | FeFe | PP | Oo | TiTi |
| 质量(％)quality(%) | 36.4536.45 | 20.6120.61 | 42.5542.55 | 0.150.15 |
表2 实施例1-3的掺杂磷酸铁与对比例1的磷酸铁的具体检测数据Table 2 The specific detection data of the doped iron phosphate of embodiment 1-3 and the iron phosphate of comparative example 1
| 序号serial number | 粒径D50(μm)Particle size D50(μm) | 振实密度(g/cm 3) Tap density (g/cm 3 ) | 比表(m 2/g) Specific table (m 2 /g) |
| 实施例1Example 1 | 2.712.71 | 0.710.71 | 8.838.83 |
| 实施例2Example 2 | 3.233.23 | 0.750.75 | 9.279.27 |
| 实施例3Example 3 | 2.962.96 | 0.730.73 | 8.568.56 |
| 对比例1Comparative example 1 | 2.852.85 | 0.720.72 | 8.558.55 |
从表2可得，实施例1-3制备的掺杂磷酸铁粒径、振实密度、比表面积和对比例1制备的磷酸铁的数据相差不大，说明掺杂元素对磷酸铁的物理指标影响不大，也进一步说明本发明的掺杂元素均匀分布在磷酸铁上。As can be seen from Table 2, the doped ferric phosphate particle size, tap density, specific surface area and the data of the ferric phosphate prepared by comparative example 1 prepared by embodiment 1-3 are not much different, indicating that doping elements have a significant effect on the physical index of ferric phosphate The effect is not large, which further shows that the doping elements of the present invention are evenly distributed on the iron phosphate.
表3 合成磷酸铁锂粉末压实密度及电性能检测结果对比表Table 3 Comparison of compaction density and electrical performance test results of synthetic lithium iron phosphate powder
表3为实施例1-3的掺杂磷酸铁与对比例合成磷酸铁锂粉末的压实密度及电性能检测结果对比表，从表中数据可以看出经过元素掺杂后的磷酸铁所制备的磷酸铁锂材料相比于不掺杂的磷酸铁所制备的磷酸铁锂的电化学性能明显改善，是因为掺杂元素的引入提高了磷酸铁锂材料的导电性能，从而提高磷酸铁锂材料的电化学性能；与对比例2(固相法掺杂)制备的磷酸铁锂的性能对比发现，实施例1-3的掺杂磷酸铁制备的磷酸铁锂的性能更佳，说明通过液相法掺杂提高掺杂元素的均匀性可以提高磷酸铁锂材料的电化学性能。Table 3 is a comparison table of the compaction density and electrical performance test results of the doped iron phosphate of Examples 1-3 and the comparative example synthetic lithium iron phosphate powder. From the data in the table, it can be seen that the iron phosphate prepared by element doping Compared with the lithium iron phosphate prepared by undoped iron phosphate, the electrochemical performance of the lithium iron phosphate material is significantly improved, because the introduction of doping elements improves the electrical conductivity of the lithium iron phosphate material, thereby improving the lithium iron phosphate material. Electrochemical properties; compared with the performance of the lithium iron phosphate prepared in Comparative Example 2 (doping by solid phase method), it is found that the performance of the lithium iron phosphate prepared by the doped iron phosphate of Examples 1-3 is better, indicating that the lithium iron phosphate prepared by the liquid phase Improving the uniformity of doping elements by method doping can improve the electrochemical performance of lithium iron phosphate materials.
上面结合附图对本发明实施例作了详细说明，但是本发明不限于上述实施例，在所 属技术领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。此外，在不冲突的情况下，本发明的实施例及实施例中的特征可以相互组合。The embodiments of the present invention have been described in detail above in conjunction with the accompanying drawings, but the present invention is not limited to the above-mentioned embodiments, and within the scope of knowledge of those of ordinary skill in the art, various modifications can be made without departing from the spirit of the present invention. Variety. In addition, the embodiments of the present invention and the features in the embodiments can be combined with each other if there is no conflict.
Claims (10)
- 一种掺杂磷酸铁，其特征在于，所述掺杂磷酸铁的粒径为2.5-3.5μm，振实密度为0.71-0.8g/cm 3，比表面积为8.56-9.3m 2/g。 A doped iron phosphate, characterized in that the doped iron phosphate has a particle size of 2.5-3.5 μm, a tap density of 0.71-0.8 g/cm 3 , and a specific surface area of 8.56-9.3 m 2 /g.
- 权利要求1所述的掺杂磷酸铁的制备方法，其特征在于，包括以下步骤：The preparation method of doped iron phosphate according to claim 1, is characterized in that, comprises the following steps:(1)将磷源、铁源溶于酸性溶液中，过滤并收集滤液，得到酸性磷铁液；(1) dissolving the phosphorus source and the iron source in the acidic solution, filtering and collecting the filtrate to obtain the acidic phosphorus iron solution;(2)向所述酸性磷铁液中加入含掺杂元素的物质，调节pH，加热搅拌，反应，液固分离，得到掺杂磷酸铁。(2) Adding substances containing doping elements to the acidic ferrophosphorus liquid, adjusting the pH, heating and stirring, reacting, liquid-solid separation, and obtaining doped ferric phosphate.
- 根据权利要求2所述的制备方法，其特征在于，步骤(1)中，所述磷源为含有磷酸根的物质；所述含有磷酸根的物质为磷酸、磷酸二氢盐、磷酸氢盐、羟基亚乙基二膦酸盐或氨基三亚甲基磷酸盐中的至少一种。The preparation method according to claim 2, characterized in that, in step (1), the phosphorus source is a substance containing phosphate; the substance containing phosphate is phosphoric acid, dihydrogen phosphate, hydrogen phosphate, At least one of hydroxyethylene diphosphonate or aminotrimethylene phosphate.
- 根据权利要求2所述的制备方法，其特征在于，步骤(1)中，所述铁源为磷铁废料、磷铁浸出渣、铁粉、磁铁矿、赤铁矿、磷酸铁、磷酸铁锂、硫酸铁、硫酸亚铁、氯化铁、氯化亚铁、硝酸铁或硝酸亚铁中的至少一种。The preparation method according to claim 2, characterized in that, in step (1), the iron source is iron phosphorus waste, iron phosphorus leaching slag, iron powder, magnetite, hematite, iron phosphate, iron phosphate At least one of lithium, ferric sulfate, ferrous sulfate, ferric chloride, ferrous chloride, ferric nitrate or ferrous nitrate.
- 根据权利要求2所述的制备方法，其特征在于，步骤(2)中，所述掺杂元素为Ti、Al、V、Ni、Co、Mn、Mg、Cr或Mo中的至少一种。The preparation method according to claim 2, characterized in that, in step (2), the doping element is at least one of Ti, Al, V, Ni, Co, Mn, Mg, Cr or Mo.
- 根据权利要求2所述的制备方法，其特征在于，步骤(2)中，所述掺杂元素物质为掺杂元素的可溶性盐或氧化物的溶液；所述含掺杂元素的物质为三氯化钛、氧化钛、氧化铝、硫酸铝、氯化铝、硫酸镍、氯化镁、三氧化二铬或三氧化钼中的至少一种。The preparation method according to claim 2, characterized in that, in step (2), the doping element substance is a solution of a soluble salt or an oxide of the doping element; the substance containing the doping element is trichloro At least one of titanium oxide, titanium oxide, aluminum oxide, aluminum sulfate, aluminum chloride, nickel sulfate, magnesium chloride, chromium trioxide or molybdenum trioxide.
- 根据权利要求2所述的制备方法，其特征在于，步骤(2)中，当所述铁源为二价铁时，所述调节pH前还包括通气氧化；所述通气氧化所使用的气体为氧气。The preparation method according to claim 2, characterized in that, in step (2), when the iron source is ferrous iron, aeration oxidation is also included before the pH adjustment; the gas used in the aeration oxidation is oxygen.
- 根据权利要求2所述的制备方法，其特征在于，步骤(2)中，所述调节pH所使用的物质为氢氧化钠、氨水或碳酸钠中的至少一种。The preparation method according to claim 2, characterized in that, in step (2), the substance used to adjust the pH is at least one of sodium hydroxide, ammonia or sodium carbonate.
- 一种掺杂包覆碳型磷酸铁锂的制备方法，其特征在于，包括以下步骤：A method for preparing doped and coated carbon-type lithium iron phosphate, characterized in that it comprises the following steps:将权利要求1所述的掺杂磷酸铁和锂源混合，加入碳源，再加入水进行砂磨处理，喷雾干燥，焙烧，制得所述掺杂包覆碳型磷酸铁锂。Mix the doped iron phosphate and lithium source according to claim 1, add carbon source, and then add water for sanding treatment, spray drying, and roasting to obtain the doped and coated carbon-type lithium iron phosphate.
- 根据权利要求9所述的制备方法，其特征在于，所述碳源为葡萄糖。The preparation method according to claim 9, characterized in that the carbon source is glucose.
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