CN114649517A - 一种锂离子电池用纳米级碳复合磷酸锰铁锂正极材料的制备方法 - Google Patents
一种锂离子电池用纳米级碳复合磷酸锰铁锂正极材料的制备方法 Download PDFInfo
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- CN114649517A CN114649517A CN202210241338.0A CN202210241338A CN114649517A CN 114649517 A CN114649517 A CN 114649517A CN 202210241338 A CN202210241338 A CN 202210241338A CN 114649517 A CN114649517 A CN 114649517A
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- lithium
- manganese
- phosphate
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- 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 title claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 27
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 21
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000010406 cathode material Substances 0.000 title claims description 16
- 238000000034 method Methods 0.000 claims abstract description 25
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002002 slurry Substances 0.000 claims abstract description 16
- 229940062993 ferrous oxalate Drugs 0.000 claims abstract description 15
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 230000001681 protective effect Effects 0.000 claims abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000011265 semifinished product Substances 0.000 claims abstract description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 66
- 235000006408 oxalic acid Nutrition 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 16
- 239000002270 dispersing agent Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000001694 spray drying Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 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 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- 235000006708 antioxidants Nutrition 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 229920001030 Polyethylene Glycol 4000 Polymers 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
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 5
- -1 polyethylene Polymers 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000008118 PEG 6000 Substances 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 239000007787 solid Substances 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 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 235000006748 manganese carbonate Nutrition 0.000 claims description 3
- 239000011656 manganese carbonate Substances 0.000 claims description 3
- 229940093474 manganese carbonate Drugs 0.000 claims description 3
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 3
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 3
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 239000005955 Ferric phosphate Substances 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 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
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 229940010556 ammonium phosphate Drugs 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 229910052786 argon Inorganic materials 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
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims description 2
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 claims description 2
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 235000019700 dicalcium phosphate Nutrition 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 229940032958 ferric phosphate Drugs 0.000 claims description 2
- 229940116007 ferrous phosphate Drugs 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229910000155 iron(II) phosphate Inorganic materials 0.000 claims description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 2
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 claims description 2
- 238000010902 jet-milling Methods 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 2
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- VKFFEYLSKIYTSJ-UHFFFAOYSA-N tetraazanium;phosphonato phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])([O-])=O VKFFEYLSKIYTSJ-UHFFFAOYSA-N 0.000 claims description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims 2
- AAEGEOXHMYAZAY-UHFFFAOYSA-N [Ar].O=C=O Chemical compound [Ar].O=C=O AAEGEOXHMYAZAY-UHFFFAOYSA-N 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract description 8
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 4
- 229910000616 Ferromanganese Inorganic materials 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 2
- IEBUJWPMONWWDM-UHFFFAOYSA-N manganese;oxalic acid Chemical compound [Mn].OC(=O)C(O)=O IEBUJWPMONWWDM-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- DOCYQLFVSIEPAG-UHFFFAOYSA-N [Mn].[Fe].[Li] Chemical compound [Mn].[Fe].[Li] DOCYQLFVSIEPAG-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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Abstract
本发明提供了一种锂离子电池用纳米级碳复合磷酸锰铁锂正极材料的制备方法,所述方法包括以下步骤:(1)制备纳米级草酸锰前驱体;(2)制备纳米级草酸亚铁前驱体;(3)将所述前驱体和锂源、碳源、磷源混合研磨或者砂磨获得浆料;(4)叫所述浆料喷雾干燥造粒,获得半成品粉体;(5)将所述半成品粉体在保护气体氛围烧结;(6)将所述烧结后的粉体,经过粉碎得到纳米级磷酸锰铁锂正极材料。通过此方法合成得到的纳米级磷酸锰铁锂正极材料同时具备了高容量和长循环寿命。本发明提出的纳米级磷酸锰铁锂制备方法,使用纯水系溶剂,工艺简单环保,具备大规模生产的条件,可为锂离子电池厂家提供高容量、长寿命磷酸锰铁锂电池优质正极原材料。
Description
技术领域
本发明属于新能源材料技术领域,是一种锂离子电池用纳米级碳复合磷酸锰铁锂正极材料的制备方法。
背景技术
在电动自行车领域,磷酸锰铁锂已成为锂离子电池研究的重点材料之一。在磷酸锰铁锂的复合技术上,比如将锰酸锂和磷酸锰铁锂混掺,使电池的低温、安全、循环等性能有不错的提升。同样通过使用磷酸锰铁锂包覆三元材料,可以改善三元材料的安全性能、低温性能及成本,也可以拓宽三元材料本身的应用领域。
不过磷酸锰铁锂也存在性能缺陷和产业化瓶颈:1)导电性能较差:锰接近绝缘体的特性导致磷酸锰铁锂的导电性能较差,磷酸锰锂电导率为 10--(-14)S/cm,与磷酸铁锂相比 存在数量级差异;2)压实密度较低:为了提升锰铁锂导电性,需要将材料粒径做到相对较小,从而导致成品的压实密度相对较低,如果磷酸锰铁锂的压实密度低于磷酸铁锂,则将弱化电压平台提升带来的收益;3)循环性能较差:一方面由于锰元素的存在,锂离子脱嵌与移动难度上升,从而导致较差的导电性能,另一方面由于常规电解液体系与锰发生副反应,表面形成钝化层,两方面因素共同造成锰铁锂的循环性能降低。相对于磷酸铁锂的半导体性能,磷酸锰铁锂是绝缘体,要求具备更小的一次颗粒,配合导电剂才能提升其导电性能。目前磷酸锰铁锂受限于其较低的导电性能与倍率性能,商业化的进程缓慢。
针对目前存在的产业化瓶颈,理论上可以通过小粒径、碳包覆以及添加碳纳米管来改善导电性能,通过烧结工艺优化提升压实密度,以及通过补锂技术提升循环性能。不过本质上是要做到性能指标的平衡以及成本的可控性,例如液相法更利于做出小粒径材料,但需要通过烧结二次结晶以提升压实密度;碳纳米管的添加、补锂技术的应用会改善导电性能、循环次数,但也要考虑工艺、材料应用所带来成本增加。
目前将磷酸锰铁锂纳米化是提高其性能的研究路径之一,较小的粒径可以增大比表面积,有利于锂离子扩散,改善倍率性能,进而提升其电化学性能。
发明内容
基于以上技术背景,本发明提供了一种锂离子电池用纳米级碳复合磷酸锰铁锂正极材料的制备方法,为制备高容量、长寿命的磷酸锰铁锂电池提供了优质正极材料。
本发明的技术方案是通过以下方式实现的:一种锂离子电池用纳米级碳复合磷酸锰铁锂正极材料的制备方法,包括以下步骤:
(1)制备纳米级草酸锰前驱体;在草酸和锰源的摩尔比为1.0~1.5:1.0的条件下,将配制好的质量百分比浓度为5%~75%的草酸溶液、锰源和分散剂,在搅拌转速为100rpm-1000rpm的状态下,20℃-90℃保温反应1h-5h,待反应体系中生成白色沉淀后进行压滤,使用纯水洗涤,然后将滤渣在温度为100℃-200℃下脱水干燥1h-8h,得到纳米级别的草酸锰前驱体;
所述的锰源是一氧化锰、二氧化锰、四氧化三锰、碳酸锰、氢氧化锰中的一种或者它们的几种组合;
所述的分散剂为PEG2000、PEG4000、PEG6000、聚乙烯蜡中的一种或几种;所述的分散剂质量分数为0.1%~10%;
(2)制备纳米级草酸亚铁前驱体;在草酸和铁源的摩尔比为1.0~1.5:1.0的条件下,将配制好的百分比浓度为5%~75%的草酸溶液、铁源、分散剂和抗氧化剂,在搅拌转速为100rpm-1000rpm、反应温度20℃-90℃、保温反应1h-5h;待反应体系中生成淡黄色沉淀后进行压滤,使用纯水洗涤,然后将滤渣在温度为100℃-200℃、干燥时间为1h-8h下脱水,得到纳米级别的草酸亚铁前驱体;
所述铁源为铁源为铁粉、硫酸亚铁、醋酸铁、磷酸铁、磷酸亚铁、磷酸一氢铁、磷酸二氢铁、硝酸铁、氯化铁等中的一种或几种;
所述的分散剂为PEG2000、PEG4000、PEG6000、聚乙烯蜡中的一种或几种;
所述的分散剂质量分数为0.1%~10%;
所述的抗氧化剂质量分数为0.01%~30%;
所述的抗氧化剂为抗坏血酸。
(3)混合研磨或者砂磨:将所述前驱体和锂源、碳源、磷源混合研磨或者砂磨获得浆料;所述的浆料粒径分布在D50:0.1μm~1.0μm;所述的浆料固含在30%~70%,温度≤50℃;所述锂源:草酸锰:草酸亚铁的摩尔比为1~1.03/2:x:1-x,0.5≤x≤1;
所述的锂源为碳酸锂、氢氧化锂、草酸锂、醋酸锂、氯化锂、磷酸锂、硝酸锂、氯化锂中的一种或几种;碳源为葡萄糖、蔗糖、聚乙二醇、聚乙烯醇、柠檬酸、炭黑、乙炔黑、石墨烯等中的一种或几种;磷源为磷酸、磷酸二氢铵、磷酸一氢铵、磷酸铵、磷酸钙、磷酸二氢钙、磷酸一氢钙、焦磷酸铵等中的一种或几种;
(4)喷雾干燥造粒:将上述浆料喷雾干燥造粒,获得半成品粉体;所述的喷雾干燥进风温度为180℃~360℃、出风温度为60℃-130℃、雾化盘转速在3000rpm~20000rpm;
(5)烧结:将所述半成品粉体在保护气体氛围烧结;所述的烧结温度为700℃-800℃;烧结时间为5h~20h;
所述的保护气为氮气、氩气二氧化碳等中的一种或几种。
(6)粉碎:将所述烧结后的粉体,经过机械粉碎或气流粉碎粉碎得到粉碎粒径范围为D50:2μm~20μm、磷酸锰铁锂成品的碳含量为0.8%~5%的纳米级磷酸锰铁锂正极材料。
本发明,通过制备纳米级前驱体,制备出纳米级别磷酸铁锂正极材料,进一步提高了磷酸锰铁锂正极材料的电化学性能,此方法具备大规模生产的条件,可为新能源电池厂家生产高容量、长寿命磷酸锰铁锂电池提供优质原材料。
附图说明
附图1为本发明实施例1中纳米级草酸锰SEM图。
附图2为本发明实施例1中纳米级草酸锰XRD图。
附图3为本发明实施例1中纳米级草酸亚铁SEM图。
附图4为本发明实施例中2中纳米级草酸亚铁XRD图。
附图5为本发明实施例2中纳米级磷酸锰铁锂SEM图。
附图6为本发明实施例中2中纳米级磷酸锰铁锂XRD图。
具体实施方式
实施案例1
一种锂离子电池用纳米级碳复合磷酸锰铁锂正极材料的制备方法,包括以下步骤:
1、纳米草酸锰的制备:配制20%草酸溶液:称取20g草酸(换算成无结晶水),加入到100g纯水中搅拌使其完全溶解。
制备草酸锰:在500rpm搅拌状态下,按照摩尔数草酸:锰源=1.1倍,向上述草酸溶液中加入碳酸锰16.58g,同时按照1%比例,将0.166g分散剂PEG2000加入到体系中,保持搅拌状态,65℃保温反应4h,生成了白色沉淀后,压滤后使用纯水洗涤,滤饼在120℃烘干4h,得到纳米级的草酸锰前驱体。
2、纳米草酸亚铁的制备:同上先制备40%草酸溶液,在烧瓶中依次加入配制好的草酸溶液,在600rpm搅拌状态下,按照摩尔数草酸:铁源=1.15倍,向草酸溶液中加入硫酸亚铁(不计结晶水)20.98g,分别按照1%和5%的比例,加入0.2g分散剂PEG2000和1.05g抗氧化剂抗坏血酸,保持搅拌状态,60℃保温反应3h,待反应体系中生成淡黄色沉淀,3h后进行压滤,使用纯水洗涤,滤渣在120℃烘干3h,得到纳米级草酸亚铁前驱体。
3、混合研磨或者砂磨:按照锂源:草酸锰:草酸亚铁的摩尔比为0.515:0.7:0.3,分别将碳酸锂38.05g碳酸锂、100.03g草酸锰和43.2g草酸亚铁混合,按照50% 固含加纯水362.56g,再加入葡萄糖16.22g和115g磷酸二氢铵,使用含有直径为0.3μm的锆珠的砂磨机研磨至浆料粒径D50至0.4μm,控制过程中料浆的温度不超过40℃。
4、喷雾干燥造粒:将上述浆料喷雾干燥造粒,喷雾干燥塔进风温度260℃,出风温度100℃,述雾化盘转速稳定在12000rpm。
5、烧结:所得造粒后的粉体在氮气保护下,730℃烧结10h,
6、粉碎:将所述烧结后的粉体,经过机械粉碎得到粉碎粒径为D50为6μm、碳含量为1%的纳米级磷酸锰铁锂正极材料。由附图1为本发明实施例1中纳米级草酸锰SEM图。
由附图1得知,为本发明实施例1中纳米级草酸锰SEM图。附图2为本发明实施例1中纳米级草酸锰XRD图。附图3为本发明实施例1中纳米级草酸亚铁SEM图。
实施案例2
一种锂离子电池用纳米级碳复合磷酸锰铁锂正极材料的制备方法,包括以下步骤:
1、纳米草酸锰的制备:配制40%草酸溶液:称取40g草酸(换算成无结晶水),加入到100g纯水中搅拌使其完全溶解。
制备草酸锰:在700rpm搅拌状态下,按照摩尔数草酸:锰源=1.2倍,向上述草酸溶液中加入氢氧化锰19.05g,同时按照1%比例,将0.19g分散剂PEG4000加入到体系中,保持搅拌状态,60℃保温反应3h,生成了白色沉淀后,压滤后使用纯水洗涤,滤饼在120℃烘干3h,得到纳米级的草酸锰前驱体。
2、纳米草酸亚铁的制备:同上先制备40%草酸溶液,在烧瓶中依次加入配制好的草酸溶液,在600rpm搅拌状态下,按照摩尔数草酸:铁源=1.20倍,向草酸溶液中加入硝酸铁(不计结晶水)64.02g,分别按照2.5%和8%的比例,加入1.6g分散剂PEG4000和5.12g抗氧化剂抗坏血酸,保持搅拌状态,70℃保温反应4h,待反应体系中生成淡黄色沉淀,4h后进行压滤,使用纯水洗涤,滤渣在130℃烘干4h,得到纳米级草酸亚铁前驱体。
3、混合研磨或者砂磨:按照锂源:草酸锰:草酸亚铁的摩尔比为0.51:0.8:0.2,分别将122.1g氢氧化锂、1008g草酸锰和288g草酸亚铁混合,按照55% 固含加纯水780g,再加入淀粉162.7g和85%磷酸588g,使用含有直径为0.3μm的锆珠的砂磨机研磨至浆料粒径D50至0.6μm,控制过程中料浆的温度不超过50℃。
4、喷雾干燥造粒:将上述浆料喷雾干燥造粒,喷雾干燥塔进风温度280℃,出风温度110℃,述雾化盘转速稳定在15000rpm。
5、烧结:所得造粒后的粉体在氮气保护下,740℃烧结12h。
6、粉碎:将所述烧结后的粉体,经过机械粉碎得到粉碎粒径为D50为8μm、碳含量为4%的纳米级磷酸锰铁锂正极材料。
由附图4知,为本发明实施例中2中纳米级草酸亚铁XRD图。附图5为本发明实施例2中纳米级磷酸锰铁锂SEM图。附图6为本发明实施例中2中纳米级磷酸锰铁锂XRD图。
Claims (9)
1.一种锂离子电池用纳米级碳复合磷酸锰铁锂正极材料的制备方法,其特征在于:包括以下步骤:
(1)制备纳米级草酸锰前驱体;在草酸和锰源的摩尔比为1.0~1.5:1.0的条件下,将配制好的质量百分比浓度为5%~75%的草酸溶液、锰源和分散剂,在搅拌转速为100rpm-1000rpm的状态下,20℃-90℃保温反应1h-5h,待反应体系中生成白色沉淀后进行压滤,使用纯水洗涤,然后将滤渣在温度为100℃-200℃下脱水干燥1h-8h,得到纳米级别的草酸锰前驱体;
(2)制备纳米级草酸亚铁前驱体;在草酸和铁源的摩尔比为1.0~1.5:1.0的条件下,将配制好的百分比浓度为5%~75%的草酸溶液、铁源、分散剂和抗氧化剂,在搅拌转速为100rpm-1000rpm、反应温度20℃-90℃、保温反应1h-5h;待反应体系中生成淡黄色沉淀后进行压滤,使用纯水洗涤,然后将滤渣在温度为100℃-200℃、干燥时间为1h-8h下脱水,得到纳米级别的草酸亚铁前驱体;
(3)混合研磨或者砂磨:将所述前驱体和锂源、碳源、磷源混合研磨或者砂磨获得浆料;所述的浆料粒径分布在D50:0.1μm~1.0μm;所述的浆料固含在30%~70%,温度≤50℃;所述锂源:草酸锰:草酸亚铁的摩尔比为1~1.03/2:x:1-x,0.5≤x≤1;
(4)喷雾干燥造粒:将上述浆料喷雾干燥造粒,获得半成品粉体;所述的喷雾干燥进风温度为180℃~360℃、出风温度为60℃-130℃、雾化盘转速在3000rpm~20000rpm;
(5)烧结:将所述半成品粉体在保护气体氛围烧结;所述的烧结温度为700℃-800℃;烧结时间为5h~20h;
所述的保护气为氮气、氩气二氧化碳等中的一种或几种;
(6)粉碎:将所述烧结后的粉体,经过机械粉碎或气流粉碎粉碎得到粉碎粒径范围为D50:2μm~20μm、磷酸锰铁锂成品的碳含量为0.8%~5%的纳米级磷酸锰铁锂正极材料。
2.如权利要求1中所述的一种锂离子电池用纳米级碳复合磷酸锰铁锂正极材料的制备方法,其特征在于在:所述的步骤(1)中的锰源是一氧化锰、二氧化锰、四氧化三锰、碳酸锰、氢氧化锰中的一种或者它们的几种组合。
3.如权利要求1中所述的一种锂离子电池用纳米级碳复合磷酸锰铁锂正极材料的制备方法,其特征在于:所述的步骤(1)中的分散剂为PEG2000、PEG4000、PEG6000、聚乙烯蜡中的一种或几种;所述的分散剂质量分数为0.1%~10%。
4.如权利要求1中所述的一种锂离子电池用纳米级碳复合磷酸锰铁锂正极材料的制备方法,其特征在于:所述的步骤(2)中的铁源为铁源为铁粉、硫酸亚铁、醋酸铁、磷酸铁、磷酸亚铁、磷酸一氢铁、磷酸二氢铁、硝酸铁、氯化铁中的一种或几种。
5.如权利要求1中所述的一种锂离子电池用纳米级碳复合磷酸锰铁锂正极材料的制备方法,其特征在于:所述的步骤(2)中的分散剂为PEG2000、PEG4000、PEG6000、聚乙烯蜡中的一种或几种。
6.如权利要求1中所述的一种锂离子电池用纳米级碳复合磷酸锰铁锂正极材料的制备方法,其特征在于:所述的步骤(2)中的分散剂质量分数为0.1%~10%。
7.如权利要求1中所述的一种锂离子电池用纳米级碳复合磷酸锰铁锂正极材料的制备方法,其特征在于:所述的步骤(2)中的抗氧化剂质量分数为0.01%~30%;抗氧化剂为抗坏血酸。
8.如权利要求1中所述的一种锂离子电池用纳米级碳复合磷酸锰铁锂正极材料的制备方法,其特征在于:所述的步骤(3)中锂源为碳酸锂、氢氧化锂、草酸锂、醋酸锂、氯化锂、磷酸锂、硝酸锂、氯化锂中的一种或几种;碳源为葡萄糖、蔗糖、聚乙二醇、聚乙烯醇、柠檬酸、炭黑、乙炔黑、石墨烯中的一种或几种;磷源为磷酸、磷酸二氢铵、磷酸一氢铵、磷酸铵、磷酸钙、磷酸二氢钙、磷酸一氢钙、焦磷酸铵中的一种或几种。
9.如权利要求1中所述的一种锂离子电池用纳米级碳复合磷酸锰铁锂正极材料的制备方法,其特征在于:所述的步骤(4)中的保护气为氮气、氩气二氧化碳中的一种或几种。
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