CN114520318B - 一种动力电池用高镍无钴镍钨锰酸锂正极材料及制备方法 - Google Patents
一种动力电池用高镍无钴镍钨锰酸锂正极材料及制备方法 Download PDFInfo
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- CN114520318B CN114520318B CN202210097950.5A CN202210097950A CN114520318B CN 114520318 B CN114520318 B CN 114520318B CN 202210097950 A CN202210097950 A CN 202210097950A CN 114520318 B CN114520318 B CN 114520318B
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- Prior art keywords
- compound
- nickel
- positive electrode
- electrode material
- lithium
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 78
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 55
- -1 nickel tungsten lithium manganate Chemical compound 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910010100 LiAlSi Inorganic materials 0.000 claims abstract description 12
- 229910052796 boron Inorganic materials 0.000 claims abstract description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 6
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 56
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 39
- 239000011572 manganese Substances 0.000 claims description 35
- 239000011248 coating agent Substances 0.000 claims description 29
- 238000000576 coating method Methods 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 24
- 238000005245 sintering Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000003513 alkali Substances 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 14
- 239000002103 nanocoating Substances 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 238000000975 co-precipitation Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- 239000005543 nano-size silicon particle Substances 0.000 claims description 6
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000012298 atmosphere Substances 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
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-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
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- TYAVIWGEVOBWDZ-UHFFFAOYSA-K cerium(3+);phosphate Chemical compound [Ce+3].[O-]P([O-])([O-])=O TYAVIWGEVOBWDZ-UHFFFAOYSA-K 0.000 claims description 4
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 4
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 150000003657 tungsten Chemical class 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- 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 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 claims description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 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
- 229910039444 MoC Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- ABKDZANKXKCXKG-UHFFFAOYSA-B P(=O)([O-])([O-])[O-].[W+4].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].[W+4].[W+4] Chemical compound P(=O)([O-])([O-])[O-].[W+4].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].[W+4].[W+4] ABKDZANKXKCXKG-UHFFFAOYSA-B 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QDAYJHVWIRGGJM-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QDAYJHVWIRGGJM-UHFFFAOYSA-B 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- ISFLYIRWQDJPDR-UHFFFAOYSA-L barium chlorate Chemical compound [Ba+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O ISFLYIRWQDJPDR-UHFFFAOYSA-L 0.000 claims description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 2
- 229910001626 barium chloride Inorganic materials 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 2
- 229910002113 barium titanate Inorganic materials 0.000 claims description 2
- ZCLVNIZJEKLGFA-UHFFFAOYSA-H bis(4,5-dioxo-1,3,2-dioxalumolan-2-yl) oxalate Chemical compound [Al+3].[Al+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZCLVNIZJEKLGFA-UHFFFAOYSA-H 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims description 2
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 2
- MHJAJDCZWVHCPF-UHFFFAOYSA-L dimagnesium phosphate Chemical compound [Mg+2].OP([O-])([O-])=O MHJAJDCZWVHCPF-UHFFFAOYSA-L 0.000 claims description 2
- 229910000395 dimagnesium phosphate Inorganic materials 0.000 claims description 2
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 235000011147 magnesium chloride Nutrition 0.000 claims description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 claims description 2
- 239000004137 magnesium phosphate Substances 0.000 claims description 2
- 229910000157 magnesium phosphate Inorganic materials 0.000 claims description 2
- 229960002261 magnesium phosphate Drugs 0.000 claims description 2
- 235000010994 magnesium phosphates Nutrition 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 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
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- DAWBXZHBYOYVLB-UHFFFAOYSA-J oxalate;zirconium(4+) Chemical compound [Zr+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O DAWBXZHBYOYVLB-UHFFFAOYSA-J 0.000 claims description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 claims description 2
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 claims description 2
- JOPDZQBPOWAEHC-UHFFFAOYSA-H tristrontium;diphosphate Chemical compound [Sr+2].[Sr+2].[Sr+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JOPDZQBPOWAEHC-UHFFFAOYSA-H 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- QVOIJBIQBYRBCF-UHFFFAOYSA-H yttrium(3+);tricarbonate Chemical compound [Y+3].[Y+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QVOIJBIQBYRBCF-UHFFFAOYSA-H 0.000 claims description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 2
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 2
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 1
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
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Abstract
本发明公开了一种动力电池用高镍无钴镍钨锰酸锂正极材料及制备方法,该正极材料化学分子式为Lia(NixWyMnzMb)1‑cNcO2·Fd,M为Al、Zr、Ba、Mo、Mg或Ce元素中的至少一种;N为Al、Zr、Ba、Mo、Mg、Ce、Ti、Sr、Y、Nb、B或La元素中的至少一种;F为Li2BAlO4、LiBSiO4、LiAlSi2O6或Li2BAlSiO6;其中0.60≤x≤1.0,0.001≤y≤0.050,0≤z≤0.40,0.95≤a≤1.15,0.001≤b≤0.010,0.001≤c≤0.050,0.001≤d≤0.050,x+y+z+b=1。该正极材料具有低成本优势、长循环寿命、优异的高温性能等特点。
Description
技术领域
本发明属于锂离子二次电池材料技术领域,具体涉及一种动力电池用高镍无钴镍钨锰酸锂正极材料及制备方法。
背景技术
近年来,全球变暖、海平面上升、雾霾等现象表明温室效应带来的气候变化正严重影响着人类未来生存。随着全球各国对气候变化的关注,碳达峰、碳中和等一系列碳排放规划逐渐落地。新能源电动汽车逐步替代传统燃油车是实现节能减排的重要路径之一。伴随着锂电池技术进步与规模效应显著,新能源汽车重要配件锂电池价格逐年降低,锂电池能量密度需要不断提升与快充技术的发展,使新能源汽车较传统汽车竞争力不断增强。国内外锂电池厂如宁德时代、日本松下、韩国LG、韩国三星都明确将高能量密度的高镍三元材料作为未来重要的技术路线之一。目前的高镍三元材料还存在如下问题:(1)在高温长循环过程中,颗粒表面会出现从原来的层状结构,到尖晶石结构,再到非活性岩石相的晶相转变,引起电池容量和循环性能大幅度衰减;(2)晶相转变也伴随着电池中释放一定的氧气,对电池的安全性能产生较大隐患。(3)高镍正极材料因自身容量比较高,在深度脱嵌锂的情况下颗粒收缩体积的变化比常规三元材料大,循环过程当中晶体收缩膨胀导致出现微裂纹,这些裂纹一方面会导致电子的短路,另外一方面微裂纹的出现新鲜的表面跟电解液体产生更多的负反应,影响整个电池的容量衰减、循环及安全性能等问题。(4)目前的高镍正极材料镍钴锰酸锂和镍钴铝酸锂中含有较高的钴元素,而钴元素属于稀缺资源,价格波动大,导致高镍正极材料价格昂贵,性价比不高,故开发高镍无钴正极材料成为降低成本的重要路径之一。但无钴化会带来高镍正极材料结构稳定性、循环和高温性能等下降。因此,需要研发一种高镍无钴性能可以满足新能源汽车动力电池用正极材料。
发明内容
本发明目的是为了解决上述现有高镍正极材料存在的晶体结构不稳定和颗粒裂纹等导致的电池性能下降,含钴成本高,无钴性能下降等问题。为此,本发明提出一种动力电池用高镍无钴镍钨锰酸锂正极材料及制备方法,将现有高镍材料无钴化,通过液相共沉淀法和精密形貌控制制备出内部均匀掺杂W和M的镍钨锰氢氧化物前驱体,然后外部表面固相掺杂纳米添加剂N进行高温烧结复合提高高镍无钴正极材料结构稳定性,再通过湿法包覆表面改性纳米涂层转化正极材料残碱为复合锂离子金属导体包覆层提高循环和高温性能等,最后通过动态高温热处理得到低成本和高性能兼顾的高镍无钴镍钨锰酸锂正极材料。
为实现上述目的,本发明采用以下技术方案:
根据本发明的第一方面,提供一种动力电池用高镍无钴镍钨锰酸锂正极材料,该镍钨锰酸锂正极材料的化学分子式为Lia(NixWyMnzMb)1-cNcO2·Fd,M为Al、Zr、Ba、Mo、Mg或Ce元素中的至少一种;N为Al、Zr、Ba、Mo、Mg、Ce、Ti、Sr、Y、Nb、B或La元素中的至少一种;F为Li2BAlO4、LiBSiO4、LiAlSi2O6或Li2BAlSiO6;其中0.60≤x≤1.0,0.001≤y≤0.050,0≤z≤0.40,0.95≤a≤1.15,0.001≤b≤0.010,0.001≤c≤0.050,0.001≤d≤0.050,x+y+z+b=1。
优选地,所述高镍无钴镍钨锰酸锂正极材料的粒径D50为3-15μm,比表面积为0.2-1.2m2/g,振实密度为1.6-2.8g/cm3。
根据本发明的第二方面,提供所述动力电池用高镍无钴镍钨锰酸锂正极材料的制备方法,主要包括以下步骤:
(1)将镍盐、锰盐、钨盐、M盐配置成混合盐溶液,添加碱溶液和氨水络合剂溶液进行共沉淀反应,得到掺杂W和M的高镍无钴镍钨锰氢氧化物前驱体NixWyMnzMb(OH)2;
(2)将上述得到的前驱体NixWyMnzMb(OH)2与锂盐、添加剂含N化合物固相混合均匀,进行高温烧结,粉碎得到化合物Lia(NixWyMnzMb)1-cNcO2;
(3)将上述得到的化合物Lia(NixWyMnzMb)1-cNcO2进行湿法包覆表面改性转化表面残碱形成含F纳米涂层;
(4)将上述得到的含F纳米涂层的化合物进行高温热处理得到涂层Li2BAlO4、LiBSiO4、LiAlSi2O6或Li2BAlSiO6包覆的高镍无钴镍钨锰酸锂正极材料Lia(NixWyMnzMb)1- cNcO2·Fd。
优选地,步骤(1)中所述镍盐为硫酸镍、草酸镍、乙酸镍、硝酸镍或氯化镍中的至少一种;所述锰盐为硫酸锰、草酸锰、氯化锰或硝酸锰中的至少一种;所述钨盐为钨酸钠、磷酸钨、钨酸铵、仲钨酸铵或偏钨酸铵中的至少一种;所述M盐为Al、Zr、Ba、Mo、Mg或Ce化合物中的至少一种,其中Al化合物为硫酸铝、草酸铝、硝酸铝、氯化铝中的至少一种,Zr化合物为硫酸锆、草酸锆、硝酸锆中的至少一种,Ba化合物为硝酸钡、醋酸钡、氯化钡中的至少一种,Mo化合物为钼酸钠、钼酸铵中的至少一种,Mg化合物为硫酸镁、醋酸镁、氯化镁、硝酸镁中的至少一种;Ce化合物为碳酸铈、氧化铈、磷酸铈中的至少一种。
优选地,步骤(1)中所述共沉淀反应的反应温度为30-90℃;pH为8-14,搅拌转速为50-500r/min,反应时间为30-300小时。
优选地,步骤(2)中所述的锂盐为碳酸锂、氢氧化锂、醋酸锂、氯化锂、氟化锂中的至少一种。
优选地,步骤(2)中所述的含N化合物为Al、Zr、Ba、Mo、Mg、Ce、Ti、Sr、Y、Nb、B或La化合物中的至少一种,其中Al化合物为氧化铝、氢氧化铝、磷酸铝、氟化铝中的至少一种,Zr化合物为氧化锆、磷酸锆中的至少一种,Ba化合物为氢氧化钡、钛酸钡、硝酸钡、氯酸钡、醋酸钡中的至少一种,Mo化合物为三氧化钼、碳化钼、磷酸钼中的至少一种,Mg化合物为碳酸镁、氧化镁、氟化镁、硼酸镁、磷酸镁、磷酸氢镁中的至少一种,Ce化合物为碳酸铈、氧化铈、磷酸铈中的至少一种,Ti化合物为氧化钛、磷酸钛、钛酸四丁酯、钛溶胶中的至少一种,Sr化合物为碳酸锶、氧化锶、磷酸锶中的至少一种,Y化合物为氧化钇、碳酸钇中的至少一种,Nb化合物为氧化铌,B化合物为硼酸、氧化硼中的至少一种,La化合物为氧化镧、氢氧化镧、碳酸镧中的至少一种。所述含N化合物优选采用纳米粉末,利于高温烧结和结构均匀性。
优选地,步骤(2)中所述锂盐与前驱体中的金属元素总量的摩尔比0.95-1.15,烧结温度为500-950℃,烧结时间5-30小时,烧结气氛为氧气、空气或两者混合气中的一种。
优选地,步骤(3)中所述湿法包覆表面改性是使用硼酸、纳米氧化硅、纳米铝溶胶中的至少两种配置成包覆溶液与化合物Lia(NixWyMnzMb)1-cNcO2表面残存LiOH和Li2CO3反应转化形成含F纳米涂层,其中溶剂为去离子水、乙醇、甲醇、甲苯中的至少一种,包覆溶液的固含量在20-80%,搅拌转速20-200r/min,包覆时间为20-120min。
优选地,步骤(4)中所述高温热处理采用动态热处理工艺,动态热处理工艺为使用回转加热炉、搅拌加热釜、喷雾热解机、闪蒸机热处理设备中的至少一种,热处理温度为100-600℃,热处理时间为30-300分钟,热处理后形成Li2BAlO4、LiBSiO4、LiAlSi2O6或Li2BAlSiO6中的其中一种复合化合物。该化合物可以包覆正极材料表面,提高界面稳定性,进而提高电池的循环和高温性能等。
相对于现有技术,本发明的优异效果是:
1.本发明针对高镍镍锰酸锂正极材料无钴降低成本带来的结构稳定性差、倍率性能差、DCR增长大等问题进行改善,通过液相共沉淀法和精密形貌控制制备出内部均匀掺杂W和M多掺杂的镍钨锰氢氧化物前驱体,W、Zr、Al等元素掺杂可以通过晶格坍塌/膨胀的减少以及重复相变引起结构应力的减小,有效改善循环稳定性和电池安全性。另外前驱体共沉淀掺杂原料成本低,掺杂效果比固相更均匀,效果更明显。
2.高温烧结反应前引入固相掺杂纳米添加剂Al、Zr、Ba、Mo、Mg、Ce、Ti、Sr、Y、Nb、B或La等化合物,与前驱体共沉淀掺杂形成复合梯度掺杂,固相掺杂大部分元素富集在颗粒表层,共沉淀掺杂均匀分布在颗粒内部,两者复合可以更有效提高材料结构稳定性,减少深度充放电过程中的有害晶相转变和颗粒应力变化,进而提高高镍材料的循环寿命和高温性能等。
3.针对高镍正极材料表面残碱高、高温性能差等问题,通过湿法包覆表面改性时使用硼酸、纳米氧化硅、纳米铝溶胶中的至少两种配置成包覆溶液与正极材料表面残存LiOH和Li2CO3反应转化形成F纳米涂层可以有效提高高镍正极材料的循环和高温性能。
4.现有固相静态烧结产能低,能耗大,烧结材料均匀性一般,本发明引入动态热处理工艺,使包覆物质硼酸、纳米氧化硅、纳米铝溶胶等与正极材料表面残存的LiOH和Li2CO3动态高温反应转化形成纳米涂层Li2BAlO4、LiBSiO4、LiAlSi2O6或Li2BAlSiO6复合化合物,有效降低高镍正极材料残碱,提高了包覆涂层均匀性,进而提高了电池容量、循环和高温性能;另外引入动态热处理大大缩短热处理时间,降低能耗50%以上,有利于提高高镍无钴正极材料的市场竞争力。
附图说明
图1为实施例1制得的正极材料的SEM。
图2为实施例2制得的正极材料的SEM。
图3为对比例1制得的正极材料的SEM。
图4为对比例2制得的正极材料的SEM。
图5实施例1-2和对比例1-2的正极材料电池性能对比结果。
具体实施方式
为了更好地理解本发明的内容,下面结合具体实施例和对比例作进一步说明。应理解,所描述的实施例只是一部分,而不是全部实施例,这些实施例仅用于对本发明进一步说明,而不用于限制本发明的范围。此外应理解,在阅读了本发明所述的内容后,该领域的技术人员对本发明做出一些非本质的改动或调整,仍属于本发明的保护范围。
实施例1:
本实施例的高镍无钴镍钨锰酸锂正极材料为Li1.05(Ni0.95W0.003Mn0.045Mo0.002)0.998Ba0.002O2·(Li2BAlSiO6)的制备方法,具体步骤如下:
(1)将硫酸镍、钨酸钠、硫酸锰、钼酸钠按Ni:W:Mn:Mo=0.95﹕0.003﹕0.045﹕0.002的摩尔比配置成2.0mol/L混合盐溶液,与氨水溶液和氢氧化钠溶液分别按照10L/min、3.0L/min、6.7L/min的流量通过计量泵打入反应釜中,搅拌转速为200r/min,反应温度在60℃,pH值为13.0,反应80小时后,经洗涤、过滤、干燥、筛分后得到均匀掺杂W和Mo的球形前驱体Ni0.95W0.003Mn0.045Mo0.002(OH)2。
(2)将上述得到的前驱体与氢氧化锂、纳米添加剂硝酸钡按照Li:(Ni0.95W0.003Mn0.045Mo0.002):Ba金属摩尔比1.05:1:0.002进行配料,将高速混合均匀后的物料放置在莫来石匣钵中进行高温烧结,升温速率3℃/min升至730℃,恒温烧结15小时,烧结气氛为氧气,氧含量90%以上,自然冷却后粉碎筛分得到高镍无钴镍钨锰酸锂正极材料Li1.05(Ni0.93W0.003Mn0.045Mo0.002)0.998Ba0.002O2。
(3)将上述得到的镍钨锰酸锂正极材料加入去离子水中得到溶液A,固含量控制50%,搅拌转速为80r/min,分别将对应硼酸、纳米氧化硅和纳米铝溶胶(摩尔比B:Si:Al=1:1:1)与去离子水配置成混合包覆溶液B,将包覆液B匀速加入到溶液A中,搅拌包覆60min后得到表面均匀精密包覆的纳米涂层。
(4)将上述得到的含纳米涂层的正极材料加入搅拌加热釜,进行350℃动态高温热处理,热处理时间为60分钟,将高镍正极表面残存LiOH和Li2CO3转化反应得到涂层为硅酸铝锂Li2BAlSiO6包覆的正极材料Li1.05(Ni0.93W0.003Mn0.045Mo0.002)0.998Ba0.002O2·(Li2BAlSiO6)0.002。最终成品使用电位滴定测试表面残碱含量LiOH和Li2CO3分别为2640ppm和1350ppm。
(5)电性能测试:将上述得到成品高镍无钴正极材料其作为锂离子电池正极材料,乙炔黑为导电剂,聚四氟乙烯为粘接剂,正极材料、导电剂和粘接剂按重量比为90﹕5﹕5分别进行称取,混合均匀后进行制备浆料,以铝箔为集流体进行涂片,以金属锂片为负极,以1.0mol/LiPF6/EC+DEC(1:1Vol.)为电解质,在充满氩气的手套箱中装配成CR2032扣式电池。然后在扣式电池电池性能检测仪上测试该正极材料的容量和循环性能,其中充放电电压范围2.8-4.4V。其0.1C首次放电容量为220.3mAh/g,首次效率为91.6%,高温45℃50周循环保持率为96.0%。
实施例2:
本实施例的高镍无钴镍钨锰酸锂正极材料为Li1.05(Ni0.95W0.005Mn0.043Al0.002)0.998Zr0.002O2·(LiAlSi2O6)的制备方法,具体步骤如下:
(1)将硫酸镍、钨酸钠、硫酸锰、硫酸铝按Ni:W:Mn:Al=0.95﹕0.005﹕0.043﹕0.002的摩尔比配置成2.2mol/L混合盐溶液,与氨水溶液和氢氧化钠溶液分别按照9L/min、3.5L/min、6.8L/min的流量通过计量泵打入反应釜中,搅拌转速为230r/min,反应温度在55℃,pH值为12.8,反应90小时后,经洗涤、过滤、干燥、筛分后得到均匀掺杂W和Al的球形前驱体Ni0.95W0.005Mn0.043Al0.002(OH)2。
(2)将上述得到的前驱体与氢氧化锂、纳米添加剂氧化锆按照Li:(Ni0.95W0.005Mn0.043Al0.002):Zr金属摩尔比1.05:1:0.002进行配料,将高速混合均匀后的物料放置在莫来石匣钵中进行高温烧结,升温速率3℃/min升至740℃,恒温烧结10小时,烧结气氛为氧气,氧含量90%以上,自然冷却后粉碎筛分得到高镍无钴镍钨锰酸锂正极材料Li1.05(Ni0.95W0.005Mn0.043Al0.002)0.998Zr0.02O2。
(3)将上述得到的镍钨锰酸锂正极材料加入去离子水中得到溶液A,固含量控制70%,搅拌转速为60r/min,分别将对应纳米氧化硅和纳米铝溶胶(摩尔比Si:Al=1:1)与去离子水配置成混合包覆溶液B,将包覆液B匀速加入到溶液A中,搅拌包覆45min后得到表面均匀精密包覆的纳米涂层。
(4)将上述得到的含纳米涂层的正极材料加入搅拌加热釜,进行380℃动态高温热处理,热处理时间为45分钟,将高镍正极表面残存LiOH和Li2CO3转化反应得到涂层为硅酸铝锂LiAlSi2O6包覆的正极材料Li1.05(Ni0.95W0.005Mn0.043Al0.002)0.998Zr0.02O2·(LiAlSi2O6)0.002。最终成品使用电位滴定测试表面残碱含量LiOH和Li2CO3分别为2460ppm和1750ppm。
(5)电性能测试:将上述得到成品高镍无钴正极材料其作为锂离子电池正极材料,乙炔黑为导电剂,聚四氟乙烯为粘接剂,正极材料、导电剂和粘接剂按重量比为90﹕5﹕5分别进行称取,混合均匀后进行制备浆料,以铝箔为集流体进行涂片,以金属锂片为负极,以1.0mol/LiPF6/EC+DEC(1:1Vol.)为电解质,在充满氩气的手套箱中装配成CR2032扣式电池。然后在扣式电池电池性能检测仪上测试该正极材料的容量和循环性能,其中充放电电压范围2.8-4.4V。其0.1C首次放电容量为223.5mAh/g,首次效率为92.1%,高温45℃50周循环保持率为95.4%。
对比例1:
实施例的高镍无钴镍钨锰酸锂正极材料为Li1.05(Ni0.95W0.003Mn0.045Mo0.002)0.998Ba0.002O2的制备方法,具体步骤如下:
(1)在实施例1中(2)步骤基础上,将上述得到的正极材料加入去离子水中得到溶液A,固含量控制50%,搅拌转速为80r/min,搅拌洗涤60min后得到表面残碱低的正极材料。
(2)将上述得到的表面残碱低的正极材料加入搅拌加热釜,进行350℃动态高温热处理,热处理时间为60分钟,得到最终产品Li1.05(Ni0.93W0.003Mn0.045Mo0.002)0.998Ba0.002O2。最终成品使用电位滴定测试表面残碱含量LiOH和Li2CO3分别为3070ppm和2560ppm。
(3)电性能测试:将上述得到成品高镍无钴正极材料其作为锂离子电池正极材料,乙炔黑为导电剂,聚四氟乙烯为粘接剂,正极材料、导电剂和粘接剂按重量比为90﹕5﹕5分别进行称取,混合均匀后进行制备浆料,以铝箔为集流体进行涂片,以金属锂片为负极,以1.0mol/LiPF6/EC+DEC(1:1Vol.)为电解质,在充满氩气的手套箱中装配成CR2032扣式电池。然后在扣式电池电池性能检测仪上测试该正极材料的容量和循环性能,其中充放电电压范围2.8-4.4V。其0.1C首次放电容量为210.8mAh/g,首次效率为89.9%,高温45℃50周循环保持率为93.5%。
对比例2:
本对比例的高镍无钴镍锰酸锂正极材料为Li1.05(Ni0.95Mn0.05)0.998Zr0.002O2·(LiAlSi2O6)的制备方法,具体步骤如下:
(1)将硫酸镍、硫酸锰按Ni:Mn=0.95:0.05的摩尔比配置成2.0mol/L混合盐溶液,与氨水溶液和氢氧化钠溶液分别按照10L/min、3.0L/min、6.7L/min的流量通过计量泵打入反应釜中,搅拌转速为200r/min,反应温度在60℃,pH值为13.0,反应80小时后,经洗涤、过滤、干燥、筛分后得到球形前驱体Ni0.95Mn0.05(OH)2。
(2)将上述得到的前驱体与氢氧化锂、纳米添加剂氧化锆按照Li:(Ni0.95Mn0.05):Zr金属摩尔比1.05:1:0.002进行配料,将高速混合均匀后的物料放置在莫来石匣钵中进行高温烧结,升温速率3℃/min升至730℃,恒温烧结12小时,烧结气氛为氧气,氧含量90%以上,自然冷却后粉碎筛分得到高镍无钴镍锰酸锂正极材料Li1.05(Ni0.95Mn0.05)0.998Zr0.002O2。
(3)把上述得到的正极材料Li1.05(Ni0.95Mn0.05)0.998Zr0.002O2使用实施例2中(3)和(4)步骤,得到成品高镍无钴镍锰酸锂正极材料为Li1.05(Ni0.95Mn0.05)0.998Zr0.002O2·(LiAlSi2O6)。最终成品使用电位滴定测试表面残碱含量LiOH和Li2CO3分别为3260ppm和2950ppm。
(4)电性能测试:将上述得到成品高镍无钴正极材料其作为锂离子电池正极材料,乙炔黑为导电剂,聚四氟乙烯为粘接剂,正极材料、导电剂和粘接剂按重量比为90:5:5分别进行称取,混合均匀后进行制备浆料,以铝箔为集流体进行涂片,以金属锂片为负极,以1.0mol/LiPF6/EC+DEC(1:1Vol.)为电解质,在充满氩气的手套箱中装配成CR2032扣式电池。然后在扣式电池电池性能检测仪上测试该正极材料的容量和循环性能,其中充放电电压范围2.8-4.4V。其0.1C首次放电容量为216.5mAh/g,首次效率为91.3%,高温45℃50周循环保持率为94.6%。
如表1和图1-5为实施例1-2和对比例1-2的正极材料的残碱、电池性能及SEM对比结果。实施例1和实施例2的残碱LiOH和Li2CO3分别为2640和1350ppm、2460和1750ppm,明显低于对比例1和2的残碱LiOH和Li2CO3分别为3070和3260ppm,2560和2950ppm。实施例1和实施例2的容量和高温循环分别为220.3mAh/g和96.0%,223.5mAh/g和95.4%,明显优于对比例1和2的容量和高温循环分别为210.8mAh/g和93.5%,216.5mAh/g和94.6%。实施例1和2采用前驱体共沉淀和固相掺杂纳米添加剂烧结制备复合梯度掺杂的高镍无钴正极材料,固相掺杂大部分元素富集在颗粒表层,共沉淀掺杂均匀分布在颗粒内部,复合掺杂可以更有效提高材料结构稳定性,减少深度充放电过程中的有害晶相转变和颗粒应力变化,进而提高高镍材料的循环寿命和高温性能等。从图1-图4可以看出复合掺杂的SEM形貌更均匀,有利于提高循环和高温性能等。从图5可以看出在正极材料表面经过湿法包覆改性和动态热处理将表面残存LiOH和Li2CO3转化为含锂复合化合物导体涂层Li2BAlSiO6和LiAlSi2O6可以有效降低正极材料表面残碱含量、提高高镍正极材料的循环和高温性能;从图1-图4可以看出实施例1和2采用表面湿法包覆改性的SEM形貌表面包覆层更均匀,有利于提高电池循环和高温性能等。
表1实施例1-2和对比例1-2的正极材料的残碱和电池性能对比结果
Claims (8)
1. 一种动力电池用高镍无钴镍钨锰酸锂正极材料,其特征在于,该镍钨锰酸锂正极材料的化学分子式为Lia(NixWyMnzMb)1-cNcO2·Fd,M为Al、Zr、Ba、Mo、Mg或Ce元素中的至少一种;N为Al、Zr、Ba、Mo、Mg、Ce、Ti、Sr、Y、Nb、B或La元素中的至少一种; F为Li2BAlO4、LiBSiO4、LiAlSi2O6或Li2BAlSiO6;其中0.60≤x≤1.0,0.001≤y≤0.050,0≤z≤0.40,0.95≤a≤1.15,0.001≤b≤0.010,0.001≤c≤0.050,0.001≤d≤0.050,x+y+z+b=1;
所述高镍无钴镍钨锰酸锂正极材料的制备方法,包括以下步骤:
(1) 将镍盐、锰盐、钨盐、M盐配置成混合盐溶液,添加碱溶液和氨水络合剂溶液进行共沉淀反应,得到掺杂W和M的高镍无钴镍钨锰氢氧化物前驱体NixWyMnzMb(OH)2;
(2) 将上述得到的前驱体NixWyMnzMb(OH)2与锂盐、添加剂含所述N化合物固相混合均匀,进行高温烧结,粉碎得到化合物Lia(NixWyMnzMb)1-cNcO2;
(3) 将上述得到的化合物Lia(NixWyMnzMb)1-cNcO2进行湿法包覆表面改性转化表面残碱形成含F纳米涂层;所述湿法包覆表面改性是使用硼酸、纳米氧化硅、纳米铝溶胶中的至少两种配置成包覆溶液与化合物Lia(NixWyMnzMb)1-cNcO2表面残存LiOH和Li2CO3反应转化形成含F纳米涂层,其中溶剂为去离子水、乙醇、甲醇、甲苯中的至少一种,包覆溶液的固含量在20-80%,搅拌转速20-200r/min,包覆时间为20-120min;
(4) 将上述得到的含F纳米涂层的化合物进行高温热处理得到涂层Li2BAlO4、LiBSiO4、LiAlSi2O6或Li2BAlSiO6包覆的高镍无钴镍钨锰酸锂正极材料Lia(NixWyMnzMb)1-cNcO2·Fd。
2.根据权利要求1所述的动力电池用高镍无钴镍钨锰酸锂正极材料,其特征在于,所述高镍无钴镍钨锰酸锂正极材料的粒径D50为3-15μm,比表面积为0.2-1.2m2/g,振实密度为1.6-2.8g/cm3。
3.根据权利要求1所述的动力电池用高镍无钴镍钨锰酸锂正极材料,其特征在于,步骤(1)中所述镍盐为硫酸镍、草酸镍、乙酸镍、硝酸镍或氯化镍中的至少一种;所述锰盐为硫酸锰、草酸锰、氯化锰或硝酸锰中的至少一种;所述钨盐为钨酸钠、磷酸钨、钨酸铵、仲钨酸铵或偏钨酸铵中的至少一种。
4.根据权利要求1所述的动力电池用高镍无钴镍钨锰酸锂正极材料,其特征在于,步骤(1)中所述M盐为Al、Zr、Ba、Mo、Mg或Ce化合物中的至少一种,其中Al化合物为硫酸铝、草酸铝、硝酸铝、氯化铝中的至少一种,Zr化合物为硫酸锆、草酸锆、硝酸锆中的至少一种,Ba化合物为硝酸钡、醋酸钡、氯化钡中的至少一种,Mo化合物为钼酸钠、钼酸铵中的至少一种,Mg化合物为硫酸镁、醋酸镁、氯化镁、硝酸镁中的至少一种;Ce化合物为碳酸铈、氧化铈、磷酸铈中的至少一种。
5. 根据权利要求1所述的动力电池用高镍无钴镍钨锰酸锂正极材料,其特征在于,步骤(1)中所述共沉淀反应的反应温度为30-90℃;pH为8-14,搅拌转速为50-500 r/min,反应时间为30-300小时。
6.根据权利要求1所述的动力电池用高镍无钴镍钨锰酸锂正极材料,其特征在于,步骤(2)中所述的锂盐为碳酸锂、氢氧化锂、醋酸锂、氯化锂、氟化锂中的至少一种。
7.根据权利要求1所述的动力电池用高镍无钴镍钨锰酸锂正极材料,其特征在于,步骤(2)中含所述N化合物为Al、Zr、Ba、Mo、Mg、Ce、Ti、Sr、Y、Nb、B或La化合物中的至少一种,其中Al化合物为氧化铝、氢氧化铝、磷酸铝、氟化铝中的至少一种,Zr化合物为氧化锆、磷酸锆中的至少一种,Ba化合物为氢氧化钡、钛酸钡、硝酸钡、氯酸钡、醋酸钡中的至少一种,Mo化合物为三氧化钼、碳化钼、磷酸钼中的至少一种,Mg化合物为碳酸镁、氧化镁、氟化镁、硼酸镁、磷酸镁、磷酸氢镁中的至少一种,Ce化合物为碳酸铈、氧化铈、磷酸铈中的至少一种,Ti化合物为氧化钛、磷酸钛、钛酸四丁酯、钛溶胶中的至少一种,Sr化合物为碳酸锶、氧化锶、磷酸锶中的至少一种,Y化合物为氧化钇、碳酸钇中的至少一种,Nb化合物为氧化铌,B化合物为硼酸、氧化硼中的至少一种,La化合物为氧化镧、氢氧化镧、碳酸镧中的至少一种。
8.根据权利要求1所述的动力电池用高镍无钴镍钨锰酸锂正极材料,其特征在于,步骤(2)中所述锂盐与前驱体中的金属元素总量的摩尔比为0.95-1.15,烧结温度为500-950℃,烧结时间5-30小时,烧结气氛为氧气、空气或两者混合气中的一种。
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