CN113659133A - 一种高压实磷酸铁锰锂正极材料的制备方法 - Google Patents
一种高压实磷酸铁锰锂正极材料的制备方法 Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 36
- 238000005056 compaction Methods 0.000 title claims abstract description 30
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 title claims abstract description 30
- 239000010406 cathode material Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 27
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 claims abstract description 21
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 21
- 239000011572 manganese Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000010405 anode material Substances 0.000 claims abstract description 12
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 3
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 3
- 230000035484 reaction time Effects 0.000 claims abstract 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 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 description 18
- 238000000034 method Methods 0.000 claims description 17
- 229910019142 PO4 Inorganic materials 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 7
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 7
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 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 6
- 229930006000 Sucrose Natural products 0.000 claims description 6
- 229910052799 carbon Inorganic materials 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
- 238000001914 filtration Methods 0.000 claims description 6
- 239000012535 impurity Substances 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 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000004576 sand Substances 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 229940099596 manganese sulfate Drugs 0.000 claims description 5
- 239000011702 manganese sulphate Substances 0.000 claims description 5
- 235000007079 manganese sulphate Nutrition 0.000 claims description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 239000007774 positive electrode material Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere 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
- 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
- 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
- 230000003647 oxidation Effects 0.000 claims description 4
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 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 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 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
- 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
- 239000007864 aqueous solution Substances 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
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 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
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 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
- NAAXGLXYRDSIRS-UHFFFAOYSA-L dihydrogen phosphate;manganese(2+) Chemical compound [Mn+2].OP(O)([O-])=O.OP(O)([O-])=O NAAXGLXYRDSIRS-UHFFFAOYSA-L 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
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 2
- 229940116007 ferrous phosphate Drugs 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 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
- 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
- 229910000359 iron(II) sulfate 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
- 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
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride 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
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 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
- 239000012286 potassium permanganate 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
- 239000012467 final product Substances 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 239000000543 intermediate Substances 0.000 abstract description 28
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 3
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 5
- 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 description 5
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910014985 LiMnxFe1-xPO4 Inorganic materials 0.000 description 1
- 229910014982 LiMnxFe1−xPO4 Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013292 LiNiO Inorganic materials 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002699 waste material Substances 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- 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
- 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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- 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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- Crystallography & Structural Chemistry (AREA)
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Abstract
本发明提供了一种高压实磷酸铁锰锂正极材料的制备方法,此方法1)使用铁源与磷源混合,通过控制反应过程pH、反应时间及温度、干燥时间及温度,制备不同粒径及压实的磷酸铁中间体;2)将选中的锰源、铁源、磷源按照配比进行混合,然后控制反应过程pH、反应时间及温度、干燥时间及温度,制备不同粒径及压实的磷酸铁锰中间体;3)然后根据压实需求,将不同粒径及压实的磷酸铁、磷酸铁锰中间体进行混合,砂磨,煅烧,粉碎,得到所需压实密度的磷酸铁锰锂正极材料。本发明,极大的提高原料的利用率,减少报废发生;合成制备的高压实磷酸铁锰锂正极材料最高压实密度可达3.0g/cm3,极大的提高了克容量。
Description
技术领域
本发明属于新能源材料技术领域,是一种新型的制备高压实的磷酸铁锰锂正极材料方法。具体为先通过制备不同粒径及压实密度的磷酸铁、磷酸铁锰中间体,然后将大颗粒与小颗粒进行组合,制备出高压实的纳米级磷酸铁锰锂材料。本发明为规模化磷酸铁锰锂的生产提供便利条件,为锂离子电池的制备提供可靠的正极材料。
技术背景
磷酸锰铁锂电池,具有4.1V和3.5V两个放电平台,理论克容量为170mAh/g,与其它的锂离子电池相比,具有原材料资源丰富、价格低廉、热稳定性好、循环寿命长以及环境友好等优点。与磷酸铁锂电池相比,具有更高的放电平台和材料稳定性;与钴酸锂(LiCoO2)、锰酸锂(LiMn2O4)、镍酸锂(LiNiO2)、三元素材料(LiNi0.3Co0.3Mn0.3O2)相比,磷酸铁锰锂电池的循环性能、低温性能、安全性能、性价比等方面较为突出;因此磷酸铁锰锂电池得到商业重视,已有多家厂商进行针对性研究,且在新能源汽车方面得到广泛应用。
作为磷酸铁锰锂电池的核心材料,磷酸铁锰锂正极材料自然受到多方研究。磷酸铁锰锂通式为LiMnxFe1-xPO4,结构简式为LMFP,它是一种橄榄石结构的晶体,Li+离子可以在晶体中嵌入、脱出,实现锂离子电池的充放电,并由于其独特的结构,在锂离子嵌入、脱出的过程中,能够维持晶型的稳定,具有很好的稳定性,从而保证磷酸铁锰锂电池的安全性和高循环性;但另一方面目前市售的传统磷酸铁锰锂的普遍压实密度在2.1~2.2g/cm3、克容量在135~150mAh/g之间,这对于急需要提升能量密度的动力电池厂商而言不能满足要求,因而更高性能的磷酸铁锰锂正极材料的研发势在必行。
提高磷酸铁锰锂电池能量密度的一个好的解决办法是提高正极材料的压实密度,现在市场上普遍的方法是在生产时采用三段压实煅烧法,这极大的增加了工艺的复杂性、过程的不可控性和能源的浪费、成本的增加。为了提高大规模生产时的磷酸铁锰锂正极材料的能量密度,可从以下几个方面进行考虑:1、大幅度提高磷酸铁锰锂的导电性能,减少电阻,使倍率性能与低温性能得到同步的提高;2、提高磷酸铁锰锂正极材料的压实密度;3、改善Fe/Mn配比,寻求更好的材料配比;4、改善磷酸铁锰锂微观形貌,改善晶体晶型。
发明内容
针对以上不足,本发明的目的是提供一种高压实磷酸铁锰锂正极材料的制备方法,是先预制出不同颗粒大小的磷酸铁、磷酸铁锰中间体,以此为原料,通过与锂源、碳源煅烧得到高压实磷酸铁锰锂正极材料,为锂离子电池的制备提供了很好的原材料。
本发明的技术方案是通过以下方式实现的:一种高压实磷酸铁锰锂正极材料的制备方法,包括以下步骤:
A)、将可溶性铁源、磷酸盐溶于水中,使用氨水、氢氧化钠、氢氧化钙、碳酸钙中的一种或多种调节pH1.0-3.0,反应温度30-90℃,然后加入过氧化氢进行氧化,反应2-3h,过滤,将滤饼在75℃-90℃环境下干燥10-12h,得到粒径分布为10-600nm、压实密度1.96g/cm3-2.18g/cm3的纳米级球形或类球形形貌的磷酸铁(III)中间体;
B)、将锰源、铁源、磷源分别溶于水溶液中,按照摩尔计量比x:1-x:1=(0.4-0.9):1-(0.4-0.9):1,搅拌0.5小时,加入氨水调节pH为1-3,再添加氧化剂进行氧化充分反应,反应温度40-80℃,反应1-3h,压滤,使用去离子水进行洗涤去杂质,在40-80℃干燥箱中干燥12h,得到粒径分布500-700nm之间、压实密度2.4-3.2g/cm3的磷酸铁锰MnxFe1-xPO4中间体;
C)、按照压实密度的需求,将磷酸铁(III)中间体、磷酸铁锰MnxFe1-xPO4中间体与锂源、碳源按1:1:1.01:0.03比例投料混合溶于纯水中,再在砂磨机中砂磨1-3h,将此浆料进行喷雾干燥,在N2气氛保护下300-800℃煅烧6-20h,升温速度为5℃/min,最后自然冷却至室温,使用粉碎机进行粉碎得到粒径200-1200nm范围,压实密度2.4-2.6g/cm3的产品,即为球形或类球形纳米磷酸铁锰锂正极材料磷。
优选的,上述步骤A)的可溶性铁源为硫酸亚铁、醋酸铁、草酸铁、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;步骤B)中的锰源为硫酸锰、醋酸锰、草酸锰、磷酸锰、磷酸一氢锰、磷酸二氢锰、硝酸锰、氯化锰,二氧化锰、一氧化锰、碳酸锰中的一种或几种;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。
所述的步骤C)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。
所述的步骤A)、B)中的氧化剂为过氧化氢、高锰酸钾、高氯酸、次氯酸中的一种或多种。
所述步骤C)中溶剂为水、乙醇中的一种或多种。
优选的,上述步骤C)中惰性气体为氮气、氩气、二氧化碳中的一种或多种。
本发明,通过掺杂碳的方法提高了磷酸铁锰锂的导电性能,纳米结构及高压实密度使得制备的材料拥有更高的克容量;通过控制预制备的中间体粒径、压实密度最终制备高压实密度的磷酸铁锰锂正极材料;制备过程产生的各种粒径、压实密度的中间体可以相互组合,极大的提高原料的利用率,减少报废情况;合成制备的高压实磷酸铁锰锂正极材料最高压实密度可达3.0g/cm3,极大的提高了磷酸铁锰锂正极材料的克容量。
附图说明
附图1为本发明实施例1中纳米级球形磷酸铁SEM图。
附图2为本发明实施例1中纳米级球形磷酸铁锰SEM图。
附图3为本发明实施例1中LiMn0.5Fe0.5PO4/C的SEM图。
附图4为本发明实施例1中0.2C条件下的放电曲线图。
附图5为本发明实施例2中0.2C条件下的放电曲线图。
附图6为本发明实施例3中0.2C条件下的放电曲线图。
附图7为本发明实施例4中0.2C条件下的放电曲线图。
具体实施方式
实施例1:
将硫酸铁、磷酸二氢铵溶于水中,加入氨水调节pH2.0、反应温度40-50℃,然后加入过氧化氢进行氧化,反应3h,过滤,用去离子水洗涤,再将滤饼在75℃环境下干燥12h,得到粒径分布10-300nm,压实密度2.13g/cm3-2.18g/cm3的磷酸铁(III)中间体,形貌见附图1。
将硫酸锰、硫酸铁、磷酸二氢铵按1:1:1摩尔比加料溶于3L纯水中,搅拌0.5h,加入氨水调节pH为2.0,加入过氧化氢充分反应,反应温度40-50℃,反应时间3h,压滤、清洗、去杂质得到初始纯净的纳米磷酸铁锰,然后,80℃温度下干燥12h,得到磷酸铁锰MnxFe1-xPO4中间体,其粒径分布200-500nm,压实密度2.4-2.6g/cm3,形貌见附图2。
将磷酸铁(III)中间体、磷酸铁锰MnxFe1-xPO4中间体与碳酸锂、蔗糖按照1:1:1.01:0.03比例投料,溶于纯水中,再在砂磨机中砂磨2h形成浆料,将此浆料进行喷雾干燥,然后N2气氛保护下,700℃煅烧12h,升温速率为5℃/min,最后自然冷却至室温,使用粉碎机进行粉碎得到粒径200-600nm范围,压实密度2.4-2.6g/cm3的磷酸铁锰锂正极材料产品,形貌见附图3。
在室温25℃下,以锂片为负极做成扣式电池,它的0.2C放电159.62mAh/g,曲线见附图4。
实施例2:
将氯化铁、磷酸溶于水中,加入氢氧化钠调节pH3.0、反应温度70-90℃,然后加入过氧化氢进行氧化,反应2h,过滤,将滤饼在75℃环境下干燥12h,得到粒径分布150-600nm,压实密度2.0g/cm3-2.1g/cm3的磷酸铁(III)中间体;
将硫酸锰、氯化铁、磷酸按0.6:0.4:1摩尔比加料溶于3L纯水中,搅拌0.5h,加入氢氧化钠溶液调节pH为3.0,加入过氧化氢充分反应,反应温度70-80℃,反应时间2h,压滤、清洗、去杂质得到初始纯净的纳米磷酸铁锰,然后,80℃温度下干燥12h,得到磷酸铁锰Mn0.6Fe0.4PO4中间体,其粒径分布500-700nm,压实密度2.6-2.8g/cm3;
将磷酸铁(III)中间体、磷酸铁锰MnxFe1-xPO4中间体与碳酸锂、蔗糖按照1:1:1.01:0.03比例投料,溶于纯水中,再在砂磨机中砂磨2h形成浆料,将此浆料进行喷雾干燥,然后N2气氛保护下,700℃煅烧12h,升温速率为5℃/min,最后自然冷却至室温,使用粉碎机进行粉碎得到粒径400-900nm范围,压实密度2.5-2.7g/cm3的磷酸铁锰锂正极材料。
在室温25℃下,以锂片为负极做成扣式电池,它的0.2C放电156.57mAh/g,曲线见附图5。
实施例3:
将硫酸铁、磷酸二氢铵溶于水中,加入氨水控制pH1.0、反应温度30-40℃,然后加入过氧化氢进行氧化,反应2h,过滤,将滤饼在90℃环境下干燥10h,得到粒径分布10-100nm,压实密度1.96g/cm3-2.08g/cm3的磷酸铁(III)中间体;
将硫酸锰、氯化铁、磷酸按0.6:0.4:1摩尔比加料溶于3L纯水中,搅拌0.5h,加入氨水调节pH为3.0,加入过氧化氢充分反应,反应温度70-80℃,反应时间2h,压滤、清洗、去杂质得到初始纯净的纳米磷酸铁锰,然后,80℃温度下干燥12h,得到磷酸铁锰Mn0.6Fe0.4PO4中间体,其粒径分布500-700nm,压实密度2.6-2.8g/cm3;
将磷酸铁(III)中间体、磷酸铁锰MnxFe1-xPO4中间体与碳酸锂、蔗糖按照1:1:1.01:0.03比例投料,溶于纯水中,再在砂磨机中砂磨2h,将此浆料进行喷雾干燥,然后N2气氛保护下,700℃煅烧12h,升温速率为5℃/min,最后自然冷却至室温,使用粉碎机进行粉碎得到粒径500-1200nm范围,压实密度2.6-2.7g/cm3的磷酸铁锰锂正极材料。
在室温25℃下,以锂片为负极做成扣式电池,它的0.2C放电160.18mAh/g,曲线见附图6。
实施例4:
将硫酸铁、磷酸二氢铵溶于水中,加入氨水控制pH1.0、反应温度30-40℃,然后加入过氧化氢进行氧化,反应2h,过滤,将滤饼在90℃环境下干燥10h,得到粒径分布10-100nm,压实密度1.96g/cm3-2.08g/cm3的磷酸铁(III)中间体;
将草酸锰、硫酸铁、磷酸二氢铵按0.7:0.3:1摩尔比加料溶于3L纯水中,搅拌0.5h,加入氨水调节pH为1.5,加入过氧化氢充分反应,反应温度40-50℃,反应时间3h,压滤、清洗、去杂质得到初始纯净的纳米磷酸铁锰,然后,65℃温度下干燥12h,得到磷酸铁锰Mn0.7Fe0.3PO4中间体,其粒径分布700-900nm,压实密度2.9-3.2g/cm3;
将磷酸铁(III)中间体、磷酸铁锰MnxFe1-xPO4中间体与碳酸锂、蔗糖按照1:1:1.01:0.03比例投料,溶于纯水中,再在砂磨机中砂磨2h,将此浆料进行喷雾干燥,然后N2气氛保护下,700℃煅烧12h,升温速率为5℃/min,最后自然冷却至室温,使用粉碎机进行粉碎得到粒径500-1200nm范围,压实密度2.8-3.0g/cm3的磷酸铁锰锂正极材料。
在室温25℃下,以锂片为负极做成扣式电池,它的0.2C放电161.38mAh/g,曲线见附图7。
Claims (6)
1.一种高压实磷酸铁锰锂正极材料的制备方法,包括以下步骤:
A)、将可溶性铁源、磷酸盐溶于水中,使用氨水、氢氧化钠、氢氧化钙、碳酸钙中的一种或多种调节pH1.0-3.0,然后加入氧化剂进行氧化,反应2-3h,过滤,将滤饼在75℃-90℃环境下干燥10-12h,得到粒径分布为10-600nm、压实密度1.96g/cm3-2.18g/cm3的纳米级球形或类球形形貌的磷酸铁(III)中间体;
B)、将锰源、铁源、磷源分别溶于水溶液中,按照MnxFe1-xPO4所需摩尔比,进行计量比x:1-x:1=0.4-0.9:1-0.4-0.9:1配料,搅拌0.5小时,加入氨水调节pH为1.0-3.0,再添加氧化剂进行氧化反应,反应温度40-80℃,反应时间1-3h,压滤,使用去离子水洗涤滤饼,去除杂质,然后在40-80℃干燥箱中干燥12h,得到粒径分布在500-700nm之间、压实密度2.4-3.2g/cm3的磷酸铁锰MnxFe1-xPO4中间体;
C)、按照压实密度的需求,将磷酸铁(III)中间体、磷酸铁锰MnxFe1-xPO4中间体与锂源、碳源、溶剂按1:1:1.01:0.03:1比例投料混合,再在砂磨机中砂磨1-3h形成浆料,将此浆料进行喷雾干燥,在N2气氛保护下300-800℃煅烧6-20h,升温速度为5℃/min,最后自然冷却至室温,使用粉碎机进行粉碎得到粒径200-1200nm,压实密度为2.4-2.6g/cm3的球形或类球形纳米磷酸铁锰锂正极材料。
2.根据权利要求1所述的一种高压实磷酸铁锰锂正极材料的制备方法,其特征在于:所述的步骤A)中的可溶性铁源为硫酸亚铁、醋酸铁、草酸铁、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。
3.根据权利要求1所述的一种高压实磷酸铁锰锂正极材料的制备方法,其特征在于:所述的步骤B)中的锰源为硫酸锰、醋酸锰、草酸锰、磷酸锰、磷酸一氢锰、磷酸二氢锰、硝酸锰、氯化锰、二氧化锰、一氧化锰、碳酸锰中的一种或几种;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。
4.根据权利要求1所述的一种高压实磷酸铁锰锂正极材料的制备方法,其特征在于:所述的步骤C)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。
5.根据权利要求1所述的一种高压实磷酸铁锰锂正极材料的制备方法,其特征在于:所述的步骤A)、B)中的氧化剂为过氧化氢、高锰酸钾、高氯酸、次氯酸中的一种或多种。
6.根据权利要求1所述的一种高压实磷酸铁锰锂正极材料的制备,其特征在于:所述步骤C)中溶剂为水、乙醇中的一种或多种,所述的惰性气体为氮气、氩气、二氧化碳中的一种或多种。
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