CN113629233A - P2-O3 composite phase lithium-rich manganese-based lithium ion battery positive electrode material and preparation method and application thereof - Google Patents
P2-O3 composite phase lithium-rich manganese-based lithium ion battery positive electrode material and preparation method and application thereof Download PDFInfo
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- CN113629233A CN113629233A CN202110907856.7A CN202110907856A CN113629233A CN 113629233 A CN113629233 A CN 113629233A CN 202110907856 A CN202110907856 A CN 202110907856A CN 113629233 A CN113629233 A CN 113629233A
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- Prior art keywords
- lithium
- phase
- rich manganese
- compound
- acetate
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- 239000011572 manganese Substances 0.000 title claims abstract description 88
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 76
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 75
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 70
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 38
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000007774 positive electrode material Substances 0.000 title claims description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 52
- 239000000463 material Substances 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- 239000011734 sodium Substances 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000010955 niobium Substances 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910013191 LiMO2 Inorganic materials 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000010406 cathode material Substances 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 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 4
- 238000011066 ex-situ storage Methods 0.000 claims description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 150000002500 ions Chemical class 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
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- 239000011656 manganese carbonate Substances 0.000 claims description 3
- 235000006748 manganese carbonate Nutrition 0.000 claims description 3
- 229940093474 manganese carbonate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 2
- PMJNEQWWZRSFCE-UHFFFAOYSA-N 3-ethoxy-3-oxo-2-(thiophen-2-ylmethyl)propanoic acid Chemical compound CCOC(=O)C(C(O)=O)CC1=CC=CS1 PMJNEQWWZRSFCE-UHFFFAOYSA-N 0.000 claims description 2
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical compound [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 claims description 2
- 229910003893 H2WO4 Inorganic materials 0.000 claims description 2
- 229910003206 NH4VO3 Inorganic materials 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 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
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229940009827 aluminum acetate Drugs 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
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 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
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 2
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 2
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims description 2
- 229940116318 copper carbonate Drugs 0.000 claims description 2
- 229940108925 copper gluconate Drugs 0.000 claims description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 2
- 229940112669 cuprous oxide Drugs 0.000 claims description 2
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 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
- 229940062993 ferrous oxalate Drugs 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-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
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 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
- 229960001708 magnesium carbonate Drugs 0.000 claims description 2
- 229960005336 magnesium citrate Drugs 0.000 claims description 2
- 235000002538 magnesium citrate Nutrition 0.000 claims description 2
- 239000004337 magnesium citrate Substances 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 229960000816 magnesium hydroxide Drugs 0.000 claims description 2
- UHNWOJJPXCYKCG-UHFFFAOYSA-L magnesium oxalate Chemical compound [Mg+2].[O-]C(=O)C([O-])=O UHNWOJJPXCYKCG-UHFFFAOYSA-L 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
- 229960000869 magnesium oxide Drugs 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
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 2
- TXCOQXKFOPSCPZ-UHFFFAOYSA-J molybdenum(4+);tetraacetate Chemical compound [Mo+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O TXCOQXKFOPSCPZ-UHFFFAOYSA-J 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 2
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 claims description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 2
- BBJSDUUHGVDNKL-UHFFFAOYSA-J oxalate;titanium(4+) Chemical compound [Ti+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O BBJSDUUHGVDNKL-UHFFFAOYSA-J 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 2
- 229940039790 sodium oxalate Drugs 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- PLSARIKBYIPYPF-UHFFFAOYSA-H trimagnesium dicitrate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PLSARIKBYIPYPF-UHFFFAOYSA-H 0.000 claims description 2
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 claims description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A P2-O3 composite phase lithium-rich manganese-based lithium ion battery anode material and a preparation method and application thereof belong to the technical field of electrochemical lithium ion batteries. The invention provides a material which comprises O3 phase lithium-rich manganese-based oxide and P2 phase layered oxide compounded with the O3 phase lithium-rich manganese-based oxide, wherein the P2 phase accounts for 0.1-20 wt% of the material in percentage by mass. The preparation method comprises the following steps: adding the compound of A and the compound of Mn (a TM compound can be selectively added) into a solvent to obtain a salt solution, adding O3 phase lithium-rich manganese-based oxide, and mixing and dispersing to obtain a precursor suspension; and drying the precursor suspension, and then carrying out heat treatment to obtain the P2-O3 composite phase lithium-rich manganese-based material. According to the invention, because metal ion vacancies existing in the P2 phase layered oxide can additionally store lithium ions, and the material has a high-efficiency lithium ion diffusion channel, the coulombic efficiency of the first circle of the material reaches more than 92.3%, and the cycle stability and the rate capability are obviously improved.
Description
Technical Field
The invention belongs to the technical field of electrochemical lithium ion batteries, and mainly relates to a P2-O3 composite phase lithium-rich manganese-based lithium ion battery anode material, and a preparation method and application thereof.
Background
Lithium ion batteries have been widely used in consumer electronics, electric vehicles, marine, aerospace, and large energy storage devices in recent 10 years of rapid development due to their advantages of long cycle life, high energy density, and high power density. However, in the background of the era in which this rapid charging technology prevails, various applications also put demands on low cost, safety, longer cycle life, higher capacity density and energy density for lithium ion batteries. The positive electrode material, which serves as a supplier of lithium ions, largely determines the capacity and energy density of the battery. Therefore, the search for stable high-capacity high-energy-density cathode materials is the focus of research in the field of lithium ion batteries nowadays.
The chemical formula of the O3 phase lithium-rich manganese-based oxide is xLi2MnO3·(1-x)LiMO2Wherein Li2MnO3Belongs to space group C2/m, LiMO2Belong to space group
Which can be exerted by virtue of the redox behavior of anions and cations>The discharge capacity of 250mgh/g is the layered cathode material with the highest theoretical capacity known at present, and is the most promising material for realizing the energy density of the battery cell to 330 Wh/kg. But the material also suffers from the first coulomb inefficiency (<80%), poor cycling stability and rate capability, which hinders commercialization of the material in the field of power cells. Therefore, it is necessary to develop a lithium-rich manganese-based oxide which has high coulombic efficiency in the first cycle, is stable in cycle performance and is beneficial to large-rate cycle.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to design and provide the P2-O3 composite phase lithium-rich manganese-based lithium ion battery positive electrode material which is easy to industrially produce, low in production cost and simple in process, and the preparation method thereof. After the O3 phase lithium-rich manganese-based material is compounded with the P2 phase layered oxide, the first-turn coulombic efficiency of the P2-O3 composite phase lithium-rich manganese-based lithium ion battery anode material can reach more than 92.3 percent due to the fact that metal ion vacancies exist in the P2 phase layered oxide and a high-efficiency lithium ion diffusion channel is provided, and the cycle stability and the high rate performance are obviously improved.
The P2-O3 composite phase lithium-rich manganese-based lithium ion battery cathode material is characterized by comprising O3 phase lithium-rich manganese-based oxide and P2 phase layered oxide compounded with the O3 phase lithium-rich manganese-based oxide, wherein the P2 phase accounts for 0.1-20 wt% of the material in percentage by mass, preferably 5-10 wt%, and the P2 phase is distributed on the outer side of O3 phase crystal grains.
The P2-O3 composite phase lithium-rich manganese-based lithium ion battery anode material is characterized in that the chemical formula of the O3 phase lithium-rich manganese-based oxide is xLi2MnO3·(1-x)LiMO2Wherein 0 < x < 1, said M comprises any one or a combination of at least two of Na, Mg, Al, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, In, Sn, Ta, W and Ir, and said Li is2MnO3Belongs to space group C2/m, LiMO2Belong to space group
In the O3-phase lithium-rich manganese-based oxide, O represents an octahedral position where Li ions occupy oxygen stacking in a crystal lattice, and 3 represents that the number of stacking layers of the O minimum repeating unit is 3, namely ABCABC …;
the P2 phase layered oxide has a chemical formula of Ay[MnzTM1-z]O2Wherein y is not less than 0.35 and not more than 1.0, z is not less than 0.5 and not more than 1.0, A comprises Na or K, TM comprises any of Li, Mg, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo and WOne or a combination of at least two of Ay[MnzTM1-z]O2Or AyMnzO2Belong to space group P63A/mmc; in the P2 phase layered oxide, P represents a triangular prism position where a ions occupy oxygen packing in the lattice, and 2 represents a stacking layer number of P-minimum repeating units of 2, i.e., ABBA ….
The P2-O3 composite phase lithium-rich manganese-based lithium ion battery anode material is characterized in that the composite mode comprises in-situ composite and ex-situ composite, and the in-situ composite specifically comprises the following steps: co-sintering a precursor of the P2 phase layered oxide and a precursor of the O3 phase lithium-rich manganese-based oxide to obtain the P2 phase layered oxide, or compounding the precursor of the P2 phase layered oxide and the O3 phase lithium-rich manganese-based oxide and sintering to obtain the P3578 phase layered oxide; the ex-situ compounding specifically comprises: the two are mixed by ball milling.
A preparation method of any P2-O3 composite phase lithium-rich manganese-based lithium ion battery positive electrode material is characterized by comprising the following steps:
(1) adding the compound of A, the compound of Mn and the compound of TM into a solvent to obtain a salt solution, adding O3-phase lithium-rich manganese-based oxide, and mixing and dispersing to obtain a precursor suspension;
or adding the compound of A and the compound of Mn into a solvent to obtain a salt solution, adding O3-phase lithium-rich manganese-based oxide, and mixing and dispersing to obtain a precursor suspension;
wherein A is Na or K, TM is any one or combination of at least two of Li, Mg, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo and W;
(2) and (2) drying the precursor suspension obtained in the step (1), and then carrying out heat treatment to obtain the P2-O3 composite phase lithium-rich manganese-based material.
The preparation method is characterized in that in the compound of the step (1) A, when A is Na, the compound of A comprises Na2CO3、NaHCO3、NaOH、Na2O、Na2O2One or more of sodium acetate, sodium oxalate and sodium nitrate; when A is K, the compound of A includes K2CO3、KHCO3、KOH、K2One or more of O, potassium acetate and potassium nitrate; the Mn compound comprises manganese carbonate, manganese acetate, MnO and Mn2O3、Mn3O4、MnO2One or more of; in the TM compound, when the TM contains Li, the TM compound comprises one or more of lithium acetate, lithium nitrate, lithium hydroxide, lithium oxalate and lithium carbonate; when Co is included in TM, compounds of TM include cobalt carbonate, cobalt acetate, Co3O4、Co2O3And CoO; when TM contains Ni, the TM compound includes nickel carbonate, nickel acetate, NiO, Ni2O3One or more of; when Ti is contained in TM, the compound of TM includes TiO2One or more of titanium oxalate; when Al is contained in TM, the compound of TM includes Al2O3One or more of aluminum acetate, aluminum oxalate and aluminum hydroxide; when the TM contains Fe, the compounds of the TM include FeO and Fe2O3、Fe3O4、Fe(OH)2、Fe(OH)3One or more of ferrous oxalate and ferric acetate; when the TM contains Mg, the TM compound includes one or more of magnesium carbonate, magnesium acetate, magnesium hydroxide, magnesium oxide, magnesium oxalate, magnesium citrate; when V is contained in TM, compounds of TM include V2O5、V2O4、NH4VO3One or more of; when TM contains Cr, the TM compound includes chromium acetate and CrO3、Cr2O3One or more of chromic nitrate and ammonium chromate; when Cu is contained in TM, the TM compound comprises one or more of copper citrate, copper gluconate, copper nitrate, copper acetate, copper carbonate and cuprous oxide; when Zn is contained in TM, compounds of TM include zinc acetate, ZnO, zinc nitrate, ZnO2One or more of zinc citrate and basic zinc carbonate; when Zr is contained in TM, the TM compound includes ZrO2Zirconium acetate, ZrH2One or more of zirconium hydroxide, zirconyl nitrate and zirconium carbonate; when Nb is contained in TM, the TM compound includes niobium hydroxide, Nb2O5One or more of; when Mo is contained in TM, the compound of TM comprises one or more of molybdenum acetate and ammonium molybdate; when W is included in TM, compounds of TM include H2WO4、WO2、WO3One or more of ammonium paratungstate and ammonium paratungstate.
The preparation method is characterized in that the solvent in the step (1) comprises any one or a combination of at least two of deionized water, absolute ethyl alcohol, acetone or ethylene glycol, the mass ratio of the O3 phase lithium-rich manganese-based oxide to the solvent is 1: 10-200, the mixing and dispersing method comprises any one or a combination of at least two of ball milling mixing and dispersing, stirring mixing and dispersing, ultrasonic mixing and dispersing and vibration mixing and dispersing, and the mixing and dispersing time is 0.1-5 hours, preferably 0.5-2 hours.
The preparation method is characterized in that the drying temperature in the step (2) is 60-150 ℃, the drying time is 3-15 h, the heat treatment time is 2-24 h, and the heat treatment temperature is 600-1000 ℃, preferably 700-900 ℃.
The application of any one of the materials in the anode of the lithium ion battery.
A positive pole piece is characterized by comprising any P2-O3 composite phase lithium-rich manganese-based lithium ion battery positive pole material.
A lithium ion battery is characterized by comprising the positive pole piece.
In the P2-O3 composite phase lithium-rich manganese-based lithium ion battery anode material, after the O3 phase lithium-rich manganese-based material is compounded with the P2 phase layered oxide, because metal ion vacancies existing in the P2 phase layered oxide can additionally store lithium ions and have a high-efficiency lithium ion diffusion channel, the first-loop coulombic efficiency of the P2-O3 composite phase lithium-rich manganese-based lithium ion battery anode material reaches over 90 percent, and the cycle stability and the high-rate performance are obviously improved.
The specific composition of the O3 phase lithium-rich manganese-based material is not particularly limited, and lithium-rich manganese-based materials commonly used in the art are all suitable for the invention.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention provides a P2-O3 composite phase lithium-rich manganese-based lithium ion battery anode material for the first time, and in the P2-O3 composite phase lithium-rich manganese-based material, because precursors of O3 phase lithium-rich manganese-based oxide and P2 phase layered oxide are combined in a co-firing mode, strong interface bonding performance is provided between O3 phase lithium-rich manganese-based oxide and P2 phase layered oxide, and the two are combined more firmly. The P2-O3 composite phase lithium-rich manganese-based material has a fast ion transmission channel of P2 phase layered oxide and an additional ion storage site, which is beneficial to the transmission of lithium ions, and simultaneously makes up the problem that lithium ions cannot be inserted back due to phase change of a part of O3 phase lithium-rich manganese-based material. Compared with a pure O3 phase lithium-rich manganese-based material, the material shows that the first-turn coulombic efficiency is more than 92.3% (80% of O3 phase lithium-rich manganese-based material), the energy density is higher, and the cycling stability and the high-rate discharge property are more excellent. This result has advanced the commercial use of lithium-rich manganese-based materials.
(2) In the preparation method, the P2-O3 composite phase lithium-rich manganese-based material with high first efficiency and good cycle performance is obtained by adjusting key parameters such as the components and the proportion of P2 phase layered oxide, the heat treatment temperature, the time and the like, and the material has the advantages of simple synthesis process, low cost and contribution to large-scale production.
(3) The battery prepared from the lithium-rich manganese-based composite material has the first charge specific capacity of 311.4mAh/g, the first discharge specific capacity of 287.5mAh/g, the first coulombic efficiency of 92.3 percent, and the cycle retention rate of over 80 percent after 240 cycles under the current density of 200 mA/g.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of a P2-O3 composite phase lithium-rich manganese-based material obtained in example 1;
FIG. 2 is an SEM topography of the P2-O3 composite phase lithium-rich manganese-based material obtained in example 1;
FIG. 3 is a first charge and discharge curve at 0.1C for CR2032 charging prepared in example 1 and comparative example 1;
FIG. 4 is a graph of the rate capability of CR2032 charging obtained in example 1 and comparative example 1;
fig. 5 is a graph showing the charge and discharge cycles-capacity of CR2032 discharge at 1C obtained in example 1 and comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to the following detailed description and accompanying drawings. It should be emphasized that the following description is merely exemplary in nature and is not intended to limit the scope of the invention or its application.
Example 1:
(1) 1.989gNa is added2CO310.6936g of manganese acetate is added into 600mL of ethanol to obtain a salt solution, 50g O3 phase lithium-rich manganese-based oxide is added, and a precursor suspension is obtained after ball milling, mixing and dispersing for 2 hours;
(2) and (2) drying the precursor suspension in the step (1) in a blast drying oven at 100 ℃ for 5h, then carrying out heat treatment at 900 ℃ for 12h, and cooling along with the furnace to obtain the P2-O3 composite phase lithium-rich manganese-based material.
The preparation method of the invention has simple and safe process, low equipment requirement, low cost and high yield, and as shown in figure 1, the phase of the product prepared by the embodiment of the invention is a two-phase composite phase of a P2 phase and an O3 phase through X-ray diffraction (XRD) spectrum analysis. FIG. 2 shows a Scanning Electron Microscope (SEM) photograph of the product obtained in example 1, wherein the material is formed by agglomeration of particles of 200-400 nm.
Comparative example 1:
the present comparative example provides a lithium-rich manganese-based positive electrode material prepared by the following method: 50g of a lithium-rich manganese-based material (0.5 Li)2MnO3·0.5LiNi1/3Co1/3Mn1/3O2) Adding into 500mL ethanol, ball milling and dispersing for 2 h. Drying the lithium-rich manganese-based anode material in a blast drying oven at 100 ℃ for 5h, then carrying out heat treatment at 900 ℃ for 12h, and cooling the lithium-rich manganese-based anode material along with the furnace to obtain the lithium-rich manganese-based anode material.
And (3) performance testing: the positive electrode materials obtained in the example 1 and the comparative example 1 are respectively weighed with conductive carbon black and PVDF according to the mass ratio of 8:1:1, NMP is used as a solvent, the materials are homogenized, mixed, coated on an aluminum foil and dried to obtain two positive electrode pieces, and lithium metal pieces are respectively used as negative electrodes to assemble the CR2032 button cell. Evaluating on a blue battery test cabinet, performing charge and discharge experiments at 25 deg.C and 2.0-4.8V as required, wherein 1C is 200mAh/g, and the first circle charge and discharge curve, multiplying power test and cycle test results are shown in FIGS. 3, 4 and 5. It can be known that the product in embodiment 1 of the invention has a first charge specific capacity of 311.4mAh/g, a first discharge specific capacity of 287.5mAh/g, a first coulomb efficiency of 92.3%, and a cycle retention rate of more than 80% after 240 cycles under a current density of 200 mA/g.
Example 2:
(1) mixing 2.23gNa2Adding O, 8.62g of manganese carbonate and 1.64g of lithium acetate into 500mL of deionized water to obtain a salt solution, adding 30g O3-phase lithium-rich manganese-based oxide, and performing ultrasonic mixing and dispersion for 0.5h to obtain a precursor suspension;
(2) and (2) drying the precursor suspension in the step (1) in a 60 ℃ forced air drying oven for 15h, then carrying out heat treatment at 800 ℃ for 16h, and carrying out furnace cooling to obtain the P2-O3 composite phase lithium-rich manganese-based material.
The foregoing is a more detailed description of the invention in connection with specific/preferred embodiments and is not intended to limit the practice of the invention to those descriptions. It will be apparent to those skilled in the art that various substitutions and modifications can be made to the described embodiments without departing from the spirit of the invention, and such substitutions and modifications are to be considered as within the scope of the invention.
Claims (10)
1. The P2-O3 composite phase lithium-rich manganese-based lithium ion battery cathode material is characterized by comprising O3 phase lithium-rich manganese-based oxide and P2 phase layered oxide compounded with the O3 phase lithium-rich manganese-based oxide, wherein the P2 phase accounts for 0.1-20 wt% of the material in percentage by mass, preferably 5-10 wt%, and the P2 phase is distributed on the outer side of O3 phase crystal grains.
2. The positive electrode material of P2-O3 composite phase lithium-rich manganese-based lithium ion battery as claimed in claim 1, wherein the O3 phase lithium-rich manganese-based oxide is formedHas a chemical formula of xLi2MnO3·(1-x)LiMO2Wherein 0 < x < 1, said M comprises any one or a combination of at least two of Na, Mg, Al, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, In, Sn, Ta, W and Ir, and said Li is2MnO3Belongs to space group C2/m, LiMO2Belong to space group
In the O3-phase lithium-rich manganese-based oxide, O represents an octahedral position where Li ions occupy oxygen stacking in a crystal lattice, and 3 represents that the number of stacking layers of the O minimum repeating unit is 3, namely ABCABC …;
the P2 phase layered oxide has a chemical formula of Ay[MnzTM1-z]O2Wherein y is more than or equal to 0.35 and less than or equal to 1.0, z is more than or equal to 0.5 and less than or equal to 1.0, A comprises Na or K, TM comprises any one or the combination of at least two of Li, Mg, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo and W, and A is more than or equal to 1.0y[MnzTM1-z]O2Or AyMnzO2Belong to space group P63A/mmc; in the P2 phase layered oxide, P represents a triangular prism position where a ions occupy oxygen packing in the lattice, and 2 represents a stacking layer number of P-minimum repeating units of 2, i.e., ABBA ….
3. The P2-O3 composite phase lithium-rich manganese-based lithium ion battery positive electrode material as claimed in claim 1, wherein the composite mode comprises in-situ composite and ex-situ composite, and the in-situ composite is specifically as follows: co-sintering a precursor of the P2 phase layered oxide and a precursor of the O3 phase lithium-rich manganese-based oxide to obtain the P2 phase layered oxide, or compounding the precursor of the P2 phase layered oxide and the O3 phase lithium-rich manganese-based oxide and sintering to obtain the P3578 phase layered oxide; the ex-situ compounding specifically comprises: the two are mixed by ball milling.
4. A method for preparing the positive electrode material of the P2-O3 composite phase lithium-rich manganese-based lithium ion battery as claimed in any one of claims 1 to 3, which is characterized by comprising the following steps:
(1) adding the compound of A, the compound of Mn and the compound of TM into a solvent to obtain a salt solution, adding O3-phase lithium-rich manganese-based oxide, and mixing and dispersing to obtain a precursor suspension;
or adding the compound of A and the compound of Mn into a solvent to obtain a salt solution, adding O3-phase lithium-rich manganese-based oxide, and mixing and dispersing to obtain a precursor suspension;
wherein A is Na or K, TM is any one or combination of at least two of Li, Mg, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo and W;
(2) and (2) drying the precursor suspension obtained in the step (1), and then carrying out heat treatment to obtain the P2-O3 composite phase lithium-rich manganese-based material.
5. The method according to claim 4, wherein the compound of step (1) A comprises Na when A is Na2CO3、NaHCO3、NaOH、Na2O、Na2O2One or more of sodium acetate, sodium oxalate and sodium nitrate; when A is K, the compound of A includes K2CO3、KHCO3、KOH、K2One or more of O, potassium acetate and potassium nitrate; the Mn compound comprises manganese carbonate, manganese acetate, MnO and Mn2O3、Mn3O4、MnO2One or more of; in the TM compound, when the TM contains Li, the TM compound comprises one or more of lithium acetate, lithium nitrate, lithium hydroxide, lithium oxalate and lithium carbonate; when Co is included in TM, compounds of TM include cobalt carbonate, cobalt acetate, Co3O4、Co2O3And CoO; when TM contains Ni, the TM compound includes nickel carbonate, nickel acetate, NiO, Ni2O3One or more of; when Ti is contained in TM, the compound of TM includes TiO2One or more of titanium oxalate; when Al is contained in TM, the compound of TM includes Al2O3One or more of aluminum acetate, aluminum oxalate and aluminum hydroxide; when TM contains FeThe TM compound comprises FeO and Fe2O3、Fe3O4、Fe(OH)2、Fe(OH)3One or more of ferrous oxalate and ferric acetate; when the TM contains Mg, the TM compound includes one or more of magnesium carbonate, magnesium acetate, magnesium hydroxide, magnesium oxide, magnesium oxalate, magnesium citrate; when V is contained in TM, compounds of TM include V2O5、V2O4、NH4VO3One or more of; when TM contains Cr, the TM compound includes chromium acetate and CrO3、Cr2O3One or more of chromic nitrate and ammonium chromate; when Cu is contained in TM, the TM compound comprises one or more of copper citrate, copper gluconate, copper nitrate, copper acetate, copper carbonate and cuprous oxide; when Zn is contained in TM, compounds of TM include zinc acetate, ZnO, zinc nitrate, ZnO2One or more of zinc citrate and basic zinc carbonate; when Zr is contained in TM, the TM compound includes ZrO2Zirconium acetate, ZrH2One or more of zirconium hydroxide, zirconyl nitrate and zirconium carbonate; when Nb is contained in TM, the TM compound includes niobium hydroxide, Nb2O5One or more of; when Mo is contained in TM, the compound of TM comprises one or more of molybdenum acetate and ammonium molybdate; when W is included in TM, compounds of TM include H2WO4、WO2、WO3One or more of ammonium paratungstate and ammonium paratungstate.
6. The preparation method according to claim 4, wherein the solvent in the step (1) comprises any one or a combination of at least two of deionized water, absolute ethyl alcohol, acetone or ethylene glycol, the mass ratio of the O3 phase lithium-rich manganese-based oxide to the solvent is 1: 10-200, and the mixing and dispersing method comprises any one or a combination of at least two of ball milling, mixing and dispersing, stirring, mixing and dispersing, ultrasonic mixing and dispersing and vibrating mixing and dispersing, wherein the mixing and dispersing time is 0.1-5 h, and preferably, the mixing and dispersing time is 0.5-2 h.
7. The preparation method according to claim 4, wherein the drying temperature in the step (2) is 60-150 ℃, the drying time is 3-15 h, the heat treatment time is 2-24 h, and the heat treatment temperature is 600-1000 ℃, preferably 700-900 ℃.
8. Use of a material according to any of claims 1 to 3 in a positive electrode of a lithium ion battery.
9. A positive pole piece, characterized by comprising the P2-O3 composite phase lithium-rich manganese-based lithium ion battery positive pole material as claimed in any one of claims 1 to 3.
10. A lithium ion battery comprising the positive electrode sheet according to claim 9.
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