CN118213526A - A positive electrode active material for a lithium electronic battery, a lithium electronic battery and a preparation method thereof - Google Patents
A positive electrode active material for a lithium electronic battery, a lithium electronic battery and a preparation method thereof Download PDFInfo
- Publication number
- CN118213526A CN118213526A CN202211584335.3A CN202211584335A CN118213526A CN 118213526 A CN118213526 A CN 118213526A CN 202211584335 A CN202211584335 A CN 202211584335A CN 118213526 A CN118213526 A CN 118213526A
- Authority
- CN
- China
- Prior art keywords
- lithium
- positive electrode
- electrode active
- active material
- solution
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 66
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 34
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title description 9
- 238000000034 method Methods 0.000 claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 39
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 38
- 229910001416 lithium ion Inorganic materials 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 22
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- 239000011701 zinc Substances 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 16
- 229910052725 zinc Inorganic materials 0.000 claims description 16
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical class [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000007853 buffer solution Substances 0.000 claims description 3
- 239000002738 chelating agent Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 description 16
- 239000007784 solid electrolyte Substances 0.000 description 16
- 239000011255 nonaqueous electrolyte Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 13
- -1 LiMnO 2 and LiMnO 4 Chemical class 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 239000011572 manganese Substances 0.000 description 10
- 229910052748 manganese Inorganic materials 0.000 description 9
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 8
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 6
- 230000005012 migration Effects 0.000 description 6
- 238000013508 migration Methods 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 239000004202 carbamide Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 159000000002 lithium salts Chemical group 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- 229910014689 LiMnO Inorganic materials 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 4
- 229910001386 lithium phosphate Inorganic materials 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910003480 inorganic solid Inorganic materials 0.000 description 3
- 229940071125 manganese acetate Drugs 0.000 description 3
- 229940099596 manganese sulfate Drugs 0.000 description 3
- 239000011702 manganese sulphate Substances 0.000 description 3
- 235000007079 manganese sulphate Nutrition 0.000 description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229940078494 nickel acetate Drugs 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
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- 230000000087 stabilizing effect Effects 0.000 description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
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- GKZFQPGIDVGTLZ-UHFFFAOYSA-N 4-(trifluoromethyl)-1,3-dioxolan-2-one Chemical compound FC(F)(F)C1COC(=O)O1 GKZFQPGIDVGTLZ-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
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- LEGITHRSIRNTQV-UHFFFAOYSA-N carbonic acid;3,3,3-trifluoroprop-1-ene Chemical compound OC(O)=O.FC(F)(F)C=C LEGITHRSIRNTQV-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229920001973 fluoroelastomer Polymers 0.000 description 2
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- 238000009413 insulation Methods 0.000 description 2
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- 150000002641 lithium Chemical group 0.000 description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 2
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 2
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 2
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- 239000007773 negative electrode material Substances 0.000 description 2
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
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- 229960001763 zinc sulfate Drugs 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- JGZFZZXWCPJDRH-UHFFFAOYSA-N 2-methyloxolane Chemical compound CC1CCCO1.CC1CCCO1 JGZFZZXWCPJDRH-UHFFFAOYSA-N 0.000 description 1
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- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910006210 Li1+xAlxTi2-x(PO4)3 Inorganic materials 0.000 description 1
- 229910006212 Li1+xAlxTi2−x(PO4)3 Inorganic materials 0.000 description 1
- 229910011800 Li2 SiO3 Inorganic materials 0.000 description 1
- 229910008745 Li2O-B2O3-P2O5 Inorganic materials 0.000 description 1
- 229910008523 Li2O-B2O3-ZnO Inorganic materials 0.000 description 1
- 229910008590 Li2O—B2O3—P2O5 Inorganic materials 0.000 description 1
- 229910008627 Li2O—B2O3—ZnO Inorganic materials 0.000 description 1
- 229910008656 Li2O—SiO2 Inorganic materials 0.000 description 1
- 229910009297 Li2S-P2S5 Inorganic materials 0.000 description 1
- 229910009311 Li2S-SiS2 Inorganic materials 0.000 description 1
- 229910009228 Li2S—P2S5 Inorganic materials 0.000 description 1
- 229910009433 Li2S—SiS2 Inorganic materials 0.000 description 1
- 229910012316 Li3.6Si0.6P0.4O4 Inorganic materials 0.000 description 1
- 229910012722 Li3N-LiI-LiOH Inorganic materials 0.000 description 1
- 229910012716 Li3N-LiI—LiOH Inorganic materials 0.000 description 1
- 229910012734 Li3N—LiI—LiOH Inorganic materials 0.000 description 1
- 229910013043 Li3PO4-Li2S-SiS2 Inorganic materials 0.000 description 1
- 229910013035 Li3PO4-Li2S—SiS2 Inorganic materials 0.000 description 1
- 229910012810 Li3PO4—Li2S-SiS2 Inorganic materials 0.000 description 1
- 229910012804 Li3PO4—Li2S—Si2S Inorganic materials 0.000 description 1
- 229910012797 Li3PO4—Li2S—SiS2 Inorganic materials 0.000 description 1
- 229910011244 Li3xLa2/3-xTiO3 Inorganic materials 0.000 description 1
- 229910011245 Li3xLa2/3−xTiO3 Inorganic materials 0.000 description 1
- 229910012050 Li4SiO4-Li3PO4 Inorganic materials 0.000 description 1
- 229910012053 Li4SiO4-Li3VO4 Inorganic materials 0.000 description 1
- 229910012069 Li4SiO4—Li3PO4 Inorganic materials 0.000 description 1
- 229910012072 Li4SiO4—Li3VO4 Inorganic materials 0.000 description 1
- 229910010712 Li5La3Ta2O12 Inorganic materials 0.000 description 1
- 239000002225 Li5La3Ta2O12 Substances 0.000 description 1
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- 229910010833 LiI-Li2S-SiS2 Inorganic materials 0.000 description 1
- 229910010823 LiI—Li2S—B2S3 Inorganic materials 0.000 description 1
- 229910010842 LiI—Li2S—P2O5 Inorganic materials 0.000 description 1
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- 229910010864 LiI—Li3PO4—P2S5 Inorganic materials 0.000 description 1
- 229910015118 LiMO Inorganic materials 0.000 description 1
- 229910014778 LiMn2O 4 Inorganic materials 0.000 description 1
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- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
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- VGYDTVNNDKLMHX-UHFFFAOYSA-N lithium;manganese;nickel;oxocobalt Chemical compound [Li].[Mn].[Ni].[Co]=O VGYDTVNNDKLMHX-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
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- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- VWBWQOUWDOULQN-UHFFFAOYSA-N nmp n-methylpyrrolidone Chemical compound CN1CCCC1=O.CN1CCCC1=O VWBWQOUWDOULQN-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical class [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000004098 selected area electron diffraction Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 239000002203 sulfidic glass Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
- H01M4/48—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
-
- 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
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- 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
-
- 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
- H01M4/48—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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明公开了一种锂电子电池的正极活性材料，该正极电极活性材料以下方式标示：Li1.2NixMn0.8‑x‑yZnyO2，其中x的范围为0＜x≦0.8，y范围为0＜y≦0.1。本发明还包含一种制备该正极活性材料的方法。本发明还另外包含一种使用该正极活性材料的锂电子电池。
The present invention discloses a positive electrode active material for a lithium electronic battery. The positive electrode active material is labeled as follows: Li 1.2 Ni x Mn 0.8-x-y Zn y O 2 , wherein the range of x is 0＜x≦0.8, and the range of y is 0＜y≦0.1. The present invention also includes a method for preparing the positive electrode active material. The present invention also includes a lithium electronic battery using the positive electrode active material.
Description
Technical Field
The invention relates to a positive electrode active material of a lithium electronic battery, in particular to a positive electrode active material of a lithium electronic battery with special chemical composition, a lithium electronic battery and a preparation method thereof.
Background
As technology development and demand for mobile devices increase, the demand of secondary batteries as an energy source also increases rapidly. Among these secondary batteries, commercially available lithium secondary batteries have high energy density and high voltage, long life and low self-charging characteristics, and are widely used.
Lithium-containing cobalt oxide (LiCoO 2) is generally used as a positive electrode active material in lithium secondary batteries. Lithium-containing manganese oxides such as LiMnO 2 having a layered crystal structure and LiMn2O 4 having a spinel crystal structure can be used, and lithium-containing nickel oxides (LiNiO 2) can also be used. Among the above positive electrode active materials, liCoO 2 is most commonly used because of its excellent physical properties (such as excellent cycle characteristics). But LiCoO 2 is low in stability and expensive due to resource limitation of raw cobalt.
Lithium manganese oxides, such as LiMnO 2 and LiMnO 4, are preferably used because: manganese is a raw material, is abundant and environmentally friendly, and thus has been attracting attention as a positive electrode active material for replacing LiCoO 2. However, these lithium manganese oxides have the disadvantages of low capacitance and poor cycle characteristics.
Lithium nickel oxide (such as LiNiO 2) is cheaper than cobalt oxide and also has a higher discharge capacitance when charged to a certain state. Therefore, in recent years, although average discharge voltage and bulk density are low, energy density of a battery including LiNiO 2 as a positive electrode active material is improved, and thus, a great deal of research is actively being conducted on these nickel-based positive electrode active materials to develop a high-capacity battery. In this regard, many prior art techniques have focused on the characteristics of LiNiO 2 -based positive electrode active materials and improved processes for LiNiO 2. However, the LiNiO 2 -based positive electrode active material has disadvantages including high preparation cost, swelling caused by gas generated from the battery, low chemical stability, and high pH, which have not been satisfactory solutions. Accordingly, in the related art, it is suggested to coat a specific material (for example, liF, li 2SO4、Li3PO4) or the like on the surface of lithium nickel-manganese-cobalt oxide in an attempt to improve the performance of the battery. In these cases, the addition of other elements to lithium batteries has certain advantages but also causes defects elsewhere (e.g., complicated processes, etc.), so various manufacturers have been devoted to developing better lithium battery compositions.
However, in spite of various attempts, lithium composite transition metals having satisfactory performance have not been developed yet as positive electrode materials for lithium atom batteries.
Disclosure of Invention
The present invention thus provides a positive electrode material for a lithium atom battery, which has excellent battery performance.
According to one embodiment of the present invention, a positive electrode active material for a lithium battery is provided. The positive electrode active material is labeled in the following manner: li 1.2NixMn0.8-x-yZnyO2, wherein x is in the range of 0 < x+.0.8 and y is in the range of 0 < y+.0.1.
According to another embodiment of the present invention, there is provided a lithium secondary battery using the positive electrode active material, which is labeled in the following manner: li 1.2NixMn0.8-x-yZnyO2, wherein x is in the range of 0 < x+.0.8 and y is in the range of 0 < y+.0.1.
According to another embodiment of the present invention, a method of preparing the positive electrode active material is also included. First, a first solution is provided, which comprises an aqueous solution of manganese metal salts, an aqueous solution of nickel metal salts and an aqueous solution of zinc metal salts. A second solution is then provided, comprising a chelating agent and a buffer solution. Then, the first solution and the second solution are titrated in a preset condition, so that precipitation reaction is generated between the first solution and the second solution, and a material precursor is generated. A lithium-containing compound is then added to the material precursor. Finally, carrying out heat treatment to obtain the positive electrode active material of the lithium-ion battery.
The positive electrode active material and the lithium secondary battery formed by using the positive electrode active material can obtain excellent battery performance.
Drawings
Fig. 1A and 1B are X-ray diffraction patterns according to the first to fourth embodiments of the present invention.
Fig. 2A and 2B are transmission electron microscope images and selective electron diffraction images according to various embodiments of the present invention.
FIG. 3A is a graph showing the relationship between the discharge capacity and the voltage in the positive electrode active material of an electronic battery according to the present invention; fig. 3B is a graph showing the relationship between the cycle number and the discharge capacity/energy density in the positive electrode active material of a lithium-ion battery according to the present invention.
Fig. 4A is a graph showing the relationship between the discharge capacity and the voltage in the positive electrode active material of an electronic battery according to the present invention; fig. 4B is a graph showing the relationship between the cycle number and the discharge capacity/energy density in the positive electrode active material of a lithium-ion battery according to the present invention.
Detailed Description
In order that those skilled in the art to which the invention pertains will further appreciate that a preferred embodiment of the invention is set forth in the following description, together with the drawings, which details the structure and the effects to be achieved.
In order to overcome the problems of the prior art and to avoid using rare cobalt as a raw material, the present invention relates to a positive electrode active material for a lithium-ion battery, represented by the following formula (1):
Li1.2NixMn0.8-x-yZnyO2(1)
Wherein x is in the range of 0 < x +.0.8, and y is in the range of 0 < y +.0.1. In one embodiment of the present invention, x is in the range of 0.1+.x+.0.2, and y is in the range of 0 < y+.0.02. In a preferred embodiment of the present invention, x is in the range of 0.2+.x+.0.3, and y is in the range of 0 < y+.0.02.
The invention further provides a preparation method of the lithium-ion battery anode active material. Firstly, a first solution is provided, which comprises an aqueous solution of manganese metal salts (such as manganese acetate, manganese nitrate, manganese sulfate, but not limited to), an aqueous solution of nickel metal salts (such as nickel acetate, nickel nitrate, nickel sulfate, but not limited to), and an aqueous solution of zinc metal salts (such as zinc acetate, zinc nitrate, zinc sulfate, but not limited to). Then, providing a second solution containing a chelating agent (for example, but not limited to, urea (nickel acetylacetonate, ethylenediamine, 2' -bipyridine, 1, 10-phenanthroline, oxalic acid, 1, 2-bis (dimethylarsine) benzene or ethylenediamine tetraacetic acid) and a buffer solution (for example, but not limited to, sodium carbonate, sodium acetate, sodium hydroxide or sodium bicarbonate), then, titrating the first solution and the second solution in a predetermined condition to cause precipitation reaction of the first solution and the second solution and generate a material precursor, in an embodiment, the predetermined condition means that the first solution and the second solution are respectively dripped into another container in a titration manner to perform precipitation reaction, the first solution is titrated at a speed of 50 milliliters per minute, the second solution is titrated at a speed of maintaining the pH value in a range of 7 to 8, and stirring is performed for 24 hours under the condition of maintaining the water temperature at 70 ℃ and the rotating speed of 1000rpm, then, the first solution and the second solution are titrated at a centrifugal temperature of 70 ℃ until complete precipitation is performed, and lithium is contained in a lithium ion precursor (for example, lithium is completely washed off at a lithium ion precursor solution) in a dry state of lithium salt form, for example, lithium carbonate is not limited to be completely precipitated at least one of lithium acetate is obtained, and a lithium salt is not limited to be dried at least one of lithium acetate (for example, lithium carbonate is not limited to be dried at least 10 ℃ and heat-activated) in a dry material is obtained in a dry state, and a lithium material is not limited to be treated).
According to the above technology, the present invention additionally provides a lithium ion secondary battery that may have a positive electrode including the above positive electrode active material. A configuration example of the secondary battery according to the present embodiment will be described below for each component. The secondary battery of the present embodiment includes, for example, a positive electrode, a negative electrode, and a nonaqueous electrolyte, and can be configured by the same components as those of a lithium ion secondary battery that is generally used. The following embodiments are merely examples, and the lithium ion secondary battery of the present embodiment is based on this embodiment, but various changes and modifications may be made according to the knowledge of those skilled in the art. The use of the secondary battery is not particularly limited.
As for the positive electrode, the positive electrode included in the secondary battery of the present embodiment may include the positive electrode active material described above. An example of a method for producing the positive electrode is described below. First, the positive electrode active material (powder), the conductive material, and the binder (binder) are mixed to form a positive electrode mixture, and if necessary, activated carbon and/or a solvent for viscosity adjustment or the like are added thereto, and then kneaded to prepare a positive electrode mixture paste. The mixing ratio of the various materials in the positive electrode mixture is an element that determines the performance of the lithium ion secondary battery, and thus can be adjusted according to the application. The mixing ratio of the materials may be the same as that of the positive electrode of a known lithium ion secondary battery, and for example, in the case where the total mass of the solid matter of the positive electrode mixture excluding the solvent is made 100 mass%, the positive electrode active material is contained in a proportion of 60 mass% or more and 95 mass% or less, the conductive material is contained in a proportion of 1 mass% or more and 20 mass% or less, and the binder is contained in a proportion of 1 mass% or more and 20 mass% or less. The obtained positive electrode mixture paste is applied to, for example, the surface of an aluminum foil current collector, and then dried to scatter the solvent, whereby a sheet-like positive electrode can be produced. The electrode density may be further increased by pressurizing by rolling or the like as needed. The sheet-like positive electrode thus obtained may be cut into an appropriate size according to a desired battery for use in the production of the battery. As the conductive material, for example, carbon Black materials such as graphite (natural graphite, artificial graphite, expanded graphite, and the like), acetylene Black, ketjen Black (registered trademark), and the like can be used. As the binder, for example, 1 or more kinds selected from polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), fluororubber (fluororubber), ethylene-propylene-diene rubber (Ethylene propylene diene rubber), styrene-butadiene (Styrene butadiene), cellulose resin (Cellulosic resin), polyacrylic acid (Polyacrylic acid), and the like can be used. A solvent in which a positive electrode active material, a conductive material, or the like is dispersed and which is used to dissolve the binder may also be added to the positive electrode mixture, as needed. As the solvent, an organic solvent such as N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone) or the like can be specifically used. In addition, in order to increase the electric double layer capacity, activated carbon may be added to the positive electrode mixture. The method for producing the positive electrode is not limited to the above-described example, and other methods may be employed. For example, the positive electrode mixture may be produced by press-molding and then drying in a vacuum atmosphere.
For the negative electrode, metallic lithium, lithium alloy, or the like can be used for the negative electrode. The negative electrode may be formed by mixing a binder with a negative electrode active material capable of occluding and releasing lithium ions, adding an appropriate solvent to obtain a paste-like negative electrode mixture, and then coating the negative electrode mixture on the surface of a metal foil current collector such as copper, drying the same, and optionally compressing the same to increase the electrode density. Examples of the negative electrode active material include natural graphite, artificial graphite, and a calcined body of an organic compound such as phenol resin, and a powder of a carbonaceous material such as coke. In this case, as the negative electrode binder, a fluorine-containing resin such as PVDF may be used in the same manner as the positive electrode, and as a solvent in which these active materials and binder can be dispersed, an organic solvent such as N-methyl-2-pyrrolidone may be used.
For the separator, the separator may be interposed between the positive electrode and the negative electrode as needed. As the separator for separating the positive electrode and the negative electrode and for holding the electrolyte, a known separator may be used, and for example, a film having a large number of micropores such as polyethylene, polypropylene, or the like may be used.
For the nonaqueous electrolyte, for example, a nonaqueous electrolyte can be used. As the nonaqueous electrolyte, for example, a nonaqueous electrolyte in which a lithium salt as a supporting salt is dissolved in an organic solvent can be used. As the nonaqueous electrolyte, a nonaqueous electrolyte in which a lithium salt is dissolved in an ionic liquid may be used. The ionic liquid is a salt composed of cations and anions other than lithium ions and being liquid even at normal temperature. As the organic solvent, a cyclic carbonate such as ethylene carbonate (Ethylene carbonate), propylene carbonate (Propylene carbonate), trifluoropropene carbonate (Trifluoro propylene carbonate), trifluoropropene carbonate (Trifluoropropylene carbonate) or the like can be used alone; chain carbonates such as diethyl carbonate (Diethyl carbonate), dimethyl carbonate (Dimethyl carbonate), ethylmethyl carbonate (ETHYL METHYL carbonate), dipropyl carbonate (Dipropyl carbonate); ether compounds such as tetrahydrofuran (Tetrahydrofuran), 2-methyltetrahydrofuran (2-methyltetrahydrofuran), and dimethoxyethane (Dimethoxyethane); sulfur compounds such as ethylmethylsulfone (ETHYL METHYL sulfolane) and butane sultone (Butane sultone); one selected from phosphorus compounds such as triethyl phosphate (Triethyl phosphate) and trioctyl phosphate (Trioctyl phosphate), and two or more of them may be used in combination.
As the supporting salt, liPF 6、LiBF4、LiClO4、LiAsF6、LiN(CF3 SO2)2, a complex salt thereof, and the like can be used. In addition, the nonaqueous electrolyte may further contain a radical scavenger, a surfactant, a flame retardant, and the like. As the nonaqueous electrolyte, a solid electrolyte may be used. The solid electrolyte has a property of withstanding high voltage. Examples of the solid electrolyte include an inorganic solid electrolyte and an organic solid electrolyte. Examples of the inorganic solid electrolyte include an oxide solid electrolyte and a sulfide solid electrolyte. The oxide solid electrolyte is not particularly limited, and an oxide solid electrolyte containing oxygen (O) and having lithium ion conductivity and electronic insulation can be preferably used. As the oxide-based solid electrolyte, for example, one or more kinds selected from lithium phosphate (Li3PO4)、Li3PO4NX、LiBO2NX、LiNbO3、LiTaO3、Li2 SiO3、Li4SiO4-Li3PO4、Li4SiO4-Li3VO4、Li2O-B2O3-P2O5、Li2O-SiO2、Li2O-B2O3-ZnO、Li1+XAlXTi2-X(PO4)3(0≦X≦1)、Li1+XAlX Ge2-X(PO4)3(0≦X≦1)、LiTi2(PO4)3、Li3XLa2/3-XTiO3(0≦X≦2/3)、Li5La3Ta2O12、Li7La3Zr2O12、Li6BaLa2Ta2O12、Li3.6Si0.6P0.4O4 and the like can be used. The sulfide-based solid electrolyte is not particularly limited, and for example, sulfide-based solid electrolyte containing sulfur (S) and having lithium ion conductivity and electronic insulation can be preferably used. As the sulfide-based solid electrolyte, for example, one or more kinds selected from Li2S-P2S5、Li2S-SiS2、LiI-Li2S-SiS2、LiI-Li2S-P2S5、LiI-Li2S-B2S3、Li3PO4 Li2S-Si2S、Li3PO4-Li2S-SiS2、LiPO4-Li2S-SiS、LiI-Li2S-P2O5、LiI-Li3PO4-P2S5 and the like can be used. As the inorganic solid electrolyte, materials other than the above may be used, and for example, li 3N、LiI、Li3 N-LiI-LiOH or the like may be used. The organic solid electrolyte is not particularly limited as long as it is a polymer compound having ion conductivity, and for example, polyethylene oxide, polypropylene oxide, and copolymers thereof can be used. In addition, the organic solid electrolyte may further contain a supporting salt (lithium salt).
The lithium ion secondary battery of the present embodiment described above may have various shapes such as a cylindrical shape and a laminated shape. In any shape, when the nonaqueous electrolyte is used as the nonaqueous electrolyte in the secondary battery of the present embodiment, a structure sealed in a battery case can be obtained by laminating a positive electrode and a negative electrode via a separator to form an electrode body, immersing the obtained electrode body in the nonaqueous electrolyte, and connecting a positive electrode collector and a positive electrode terminal to the outside and a negative electrode collector and a negative electrode terminal to the outside using a current collecting lead or the like. As described above, the secondary battery according to the present embodiment is not limited to the form using the nonaqueous electrolyte as the nonaqueous electrolyte, and may be, for example, an all-solid battery which is a secondary battery using a solid nonaqueous electrolyte. In the case of an all-solid-state battery, the structure other than the positive electrode active material may be changed as necessary.
The secondary battery according to the present embodiment is a high-capacity and high-output secondary battery, although it is applicable to various applications, and therefore, for example, it is preferably applied to a power supply for small portable electronic devices (portable computers, mobile phone terminals, etc.) that always require high capacity, and also to a power supply for electric vehicles that require high output. Further, since the secondary battery according to the present embodiment can be miniaturized and has a high output, it is preferable to use the secondary battery as a power source for an electric vehicle in which the installation space is limited. The secondary battery according to the present embodiment can be used not only as a power source for an electric vehicle driven purely by electric energy, but also as a power source for a so-called hybrid vehicle used together with an internal combustion engine such as a gasoline engine or a diesel engine.
Examples and methods of preparation
Referring to tables 1 and 2, the composition data of different examples of the positive electrode active material of a lithium-ion battery according to the present invention are shown. As shown in table 1, the first and second comparative examples are comparative examples in which zinc (Zn) was not doped, the first and second examples are examples in which the specific gravity of zinc gradually increased, and the third and fourth examples are examples in which the specific gravity of zinc gradually increased. The first, first and second examples are groups having a low nickel-manganese ratio (Ni/Mn), and the second, third and fourth examples are groups having a high nickel-manganese ratio.
The preparation methods of the first and second comparative examples were carried out by the coprecipitation method. Firstly, preparing two solutions according to the chemical formula ratio of the first comparative example or the second comparative example, wherein one solution is an aqueous solution of manganese metal salts (such as manganese acetate, manganese nitrate, manganese sulfate and the like) and nickel metal salts (such as nickel acetate, nickel nitrate and nickel sulfate), the other solution is urea and sodium carbonate aqueous solution (the molar volume concentration is 1M), the two solutions are respectively dripped into the other container in a titration mode to carry out precipitation reaction, the metal salt solution is titrated at the speed of 50 milliliters per minute, the titration speed of the other solution (urea and sodium carbonate) is controlled to maintain the pH value to be 7-8, and the water temperature is stirred for 24 hours under the conditions of maintaining 70 ℃ and the rotating speed of 1000rpm to carry out complete precipitation. And then, washing the solution after precipitation in a centrifugal way to remove excessive ions, obtaining salt precipitates (precursor of the positive electrode material), drying to be completely dry, adding lithium carbonate powder according to the chemical formula proportion, uniformly mixing, and carrying out heat treatment at 800-950 ℃ for 12 hours to finally obtain the positive electrode material powder of the first or second comparative example.
The preparation methods of the first, second, third and fourth examples were also carried out by coprecipitation. Firstly, according to the ratios of different chemical formulas of the first embodiment, the second embodiment, the third embodiment and the fourth embodiment, two solutions are respectively prepared, one solution is an aqueous solution of manganese metal salts (such as manganese acetate, manganese nitrate, manganese sulfate and the like), nickel metal salts (such as nickel acetate, nickel nitrate, nickel sulfate and the like) and zinc metal salts (such as zinc acetate, zinc nitrate, zinc sulfate and the like), the other solution is urea and sodium carbonate aqueous solution (the Mohr volume concentration is 1M), the two solutions are respectively dripped into the other container in a titration mode to carry out precipitation reaction, the metal salt solution is titrated at a speed of 50 milliliters per minute, the titration speed of the other solution (urea and sodium carbonate) is controlled to maintain the pH value to be 7 to 8, and the water temperature is stirred for 24 hours under the conditions of maintaining 70 ℃ and the rotating speed of 1000rpm to completely precipitate. And then, washing the solution after precipitation in a centrifugal way to remove excessive ions, obtaining salt precipitates, drying to be completely dry, adding lithium carbonate powder according to the chemical formula proportion, uniformly mixing, and carrying out heat treatment at 800-950 ℃ for 12 hours to finally obtain the positive electrode material powder in the first embodiment, the second embodiment, the third embodiment or the fourth embodiment.
Referring to fig. 1A and fig. 1B, fig. 1A is an X-ray diffraction pattern of the first to second embodiments of the present invention, and fig. 1B is an X-ray diffraction pattern of the third to fourth embodiments of the present invention. For detailed values of each peak in FIGS. 1A and 1B, please refer to Table 2, wherein the void (i.e., the transverse line) between peak 2 and peak 5 refers to the angle atAnd no reflection. Notably, according to FIGS. 1A and 1B, the C2/m space group of monoclinic system (monoclinic) of LiMnO compared to the bottom, and/>, of rhombohedral (Rhombohedral) of LiMO 2 The space group, it is known that zinc doping does not affect the layered structure of the positive electrode material and that no other zinc oxide signals indicate that zinc ions are uniformly incorporated into the material rather than forming oxides on the surface or generating localized byproducts.
TABLE 1
TABLE 2
Referring to fig. 2A and 2B, a transmission electron microscope (Transmission electron microscopy, TEM) image and a selective electron diffraction (SELECTED AREA electron diffraction, SAED) image are shown in accordance with various embodiments of the present invention. In fig. 2A, (a) and (b) are TEM and SAED images of comparative example one; (c) (d) drawing is a TEM drawing and a SAED drawing of the first embodiment; (e) and (f) are TEM and SAED of the second embodiment. In fig. 2B, (a) and (B) are TEM and SAED images of the second comparative example; (c) (d) is a TEM image and a SAED image of the third embodiment; the (e) and (f) graphs are TEM and SAED graphs of the fourth embodiment. Both the TEM and SAED images of fig. 2A and 2B can show that the zinc doping of the first, second, third and fourth embodiments of the present invention still has a uniform layered structure.
Material electrical properties
Regarding the above group of comparative example one/example two (i.e., low nickel/manganese ratio), please refer to fig. 3A and 3B for performance of battery parameters when used as a positive electrode active material. Fig. 3A is a graph showing the relationship between the discharge capacity and the voltage in the positive electrode active material of a lithium battery according to the present invention, wherein the horizontal axis represents the capacity (unit: mAh/g) and the vertical axis represents the voltage (unit: V), and the positive electrode active material is operated under the environment of 0.05C, and the corresponding values are shown in table 3A. As shown in fig. 3A and table 3A, the capacitance in the plateau region at the time of charging decreases as the zinc atom ratio increases (comparative example one→example two) but the charge transfer efficiency can be maintained approximately the same.
TABLE 3A
Referring to fig. 3B, fig. 3B is a graph showing the relationship between the cycle number and the discharge capacity/energy density in the positive electrode active material of a lithium-ion battery according to the present invention, wherein the horizontal axis represents the cycle number (unit: times), the left Fang Zongzhou represents the discharge capacity (unit: mAh/g), the right vertical axis represents the energy density (unit: wh/kg), and the positive electrode active material of a lithium-ion battery according to the present invention is operated in a 0.1C environment, wherein the corresponding values are shown in table 3B. As shown in the data of fig. 3B and table 3B, in the positive electrode active materials of lithium-ion batteries shown in comparative examples one to two, the more zinc atoms are doped, the higher the discharge capacity, and the higher the recovery ratio of the battery capacity after 50 cycles, in the discharge capacity, both after the 1 st cycle and after the 50 th cycle; in the positive electrode active material of the lithium-ion battery of the present invention, the more zinc atoms are doped (from the first comparative example to the second example) in the positive electrode active material of the lithium-ion battery of the present invention, the higher the discharge capacity of the positive electrode active material is, and the higher the recovery ratio of the battery capacity after 50 cycles is, because the lithium-rich material itself has poor conductivity, more cycles are required to induce more lithium migration and extraction, however, the positive electrode material also undergoes irreversible phase change during charging and discharging, which also prevents lithium migration and extraction, and the doped zinc ions can serve as a stable material structure to slow down the generation of phase change, thereby releasing more capacitance values of the lithium-ion battery without the influence of severe phase change.
TABLE 3B
In contrast, the group of comparative example two/example three/example four (i.e., high nickel/manganese ratio), when used as the positive electrode active material, was shown in fig. 4A and 4B for the performance of the battery parameters. Fig. 4A is a graph showing the relationship between the discharge capacity and the voltage in the positive electrode active material of an electronic battery according to the present invention, wherein the horizontal axis represents the capacity (unit: mAh/g) and the vertical axis represents the voltage (unit: V), and the positive electrode active material is operated under the environment of 0.05C, and the corresponding values are shown in table 4A. As shown in fig. 4A and table 4A, the capacitance in the plateau region at the time of charging decreases as the zinc atom ratio increases (from comparative example two to example four), but the charge transfer efficiency can be maintained approximately the same.
TABLE 4A
Referring to fig. 4B, fig. 4B is a graph showing the relationship between the cycle number and the discharge capacity/energy density in the positive electrode active material of a lithium-ion battery according to the present invention, wherein the horizontal axis represents the cycle number (unit: times), the left Fang Zongzhou represents the discharge capacity (unit: mAh/g), the right vertical axis represents the energy density (unit: wh/kg), and the positive electrode active material of a lithium-ion battery according to the present invention is operated in a 0.1C environment, wherein the corresponding values are shown in table 4B. As shown in the data of fig. 4B and table 4B, in the discharge capacity, the discharge capacity is decreased with more zinc atoms (comparative example two to example four) after the 1 st cycle or 50 th cycle, but the recovery ratio of the battery capacity after 50 cycles is gradually increased, because in the case of high nickel, although zinc can be used as the ions of the stabilizing material, nickel can also be used as the stabilizing material, both ions occupy the layer channels of the lithium migration and the migration, so that the excessive zinc doping can decrease the capacitance value of the first cycle, but at the same time, the negative influence of the phase change is also decreased due to the characteristics of the stabilizing material, so that the positive electrode material is continuously activated and more capacitance value is released during the subsequent charge and discharge cycles. In the positive electrode active material of a lithium-ion battery according to the present invention, the discharge capacity decreases with more zinc atoms (from the second comparative example to the fourth example) in the energy density after the 1 st cycle or the 50 th cycle, but the recovery ratio of the battery capacity after the 50 th cycle is also higher, because nickel can act as a crystal phase of a stable material in the positive electrode material, and the nickel generally occupies a channel for lithium ion transport, thereby preventing migration and migration of lithium electrons and further affecting the charge-discharge capacitance. However, after the activation of the subsequent charge-discharge cycle, more capacitance is released, and the nickel stabilizes the material to reduce the capacitance loss associated with the phase change, thereby increasing the capacitance during the subsequent charge-discharge cycle.
TABLE 4B
As can be seen from the above graph, the present invention provides a positive electrode of a lithium battery having excellent performance, having a chemical formula as shown in formula (1)
Li1.2NixMn0.8-x-yZnyO2(1)
X is 0 < x.ltoreq.0.8, y is 0 < y.ltoreq.0.1. According to the foregoing embodiments, as the positive electrode material, either the group having a low nickel/manganese ratio (example one and example two, i.e., the range of x in the formula (1) is 0.1+.x+.0.2, and the range of y is 0 < y+.0.02) or the group having a high nickel/manganese ratio (example three and example four, i.e., the range of x in the formula (1) is 0.2+.x+.0.3, and the range of y is 0 < y+.0.02), the discharge capacity and the energy density are excellent even after the 1 st cycle or up to 50 cycles. Particularly in the embodiment with low nickel/manganese ratio, compared with the condition without doping zinc, the discharge capacity and the energy density can be obviously increased after doping zinc, the increasing amplitude of the discharge capacity and the energy density is slightly better than that of the embodiment with high nickel/manganese ratio, and the positive electrode material doped with zinc can effectively stabilize the material structure under the condition with low nickel/manganese ratio compared with the condition with high nickel/manganese ratio.
In summary, the invention provides a positive electrode of a lithium battery with excellent performance, which is characterized in that zinc is doped, and the preparation method can obtain a structure with uniform lamellar distribution, and experiments prove that the positive electrode has good electrical performance and is suitable for being applied to various electronic products.
Claims (10)
1. A positive electrode active material for a lithium-ion battery, characterized by being represented by the following formula (1):
Li1.2NixMn0.8-x-yZnyO2 (1)
Wherein x is in the range of 0 < x +.0.8, and y is in the range of 0 < y +.0.1.
2. The positive electrode active material of a lithium-ion battery according to claim 1, wherein x is in the range of 0.2+.x+.0.3, and y is in the range of 0 < y+.0.02.
3. The positive electrode active material of a lithium-ion battery according to claim 1, wherein x is in the range of 0.1+.x+.0.2, and y is in the range of 0 < y+.0.02.
4. A lithium-ion battery comprising the active positive electrode material of claim 1.
5. The lithium-ion battery of claim 4, wherein x ranges from 0.2 +.x +.0.3 and y ranges from 0 < y +.0.02.
6. The lithium-ion battery of claim 4, wherein x ranges from 0.1 +.x +.0.2 and y ranges from 0 < y +.0.02.
7. A method for preparing a positive electrode active material of a lithium-ion battery, comprising:
providing a first solution comprising an aqueous solution of manganese metal salts, an aqueous solution of nickel metal salts and an aqueous solution of zinc metal salts;
Providing a second solution comprising a chelating agent and a buffer solution;
Titrating the first solution and the second solution in a preset condition to enable the first solution and the second solution to generate precipitation reaction so as to generate a material precursor;
Adding a lithium-containing compound to the material precursor; and
And performing heat treatment to obtain the positive electrode active material of the lithium-ion battery.
8. The method of claim 7, wherein the predetermined condition comprises: controlling the pH value between 7 and 8.
9. The method of claim 7, wherein the predetermined condition comprises: the temperature is controlled between 60 ℃ and 80 ℃.
10. The method of claim 7, wherein the heat treatment comprises: treating at 800 ℃ to 950 ℃ for at least 10 hours.
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