CN113437264A - Oxide positive electrode material of lithium ion battery and preparation method thereof - Google Patents
Oxide positive electrode material of lithium ion battery and preparation method thereof Download PDFInfo
- Publication number
- CN113437264A CN113437264A CN202010206981.0A CN202010206981A CN113437264A CN 113437264 A CN113437264 A CN 113437264A CN 202010206981 A CN202010206981 A CN 202010206981A CN 113437264 A CN113437264 A CN 113437264A
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- Prior art keywords
- ion battery
- lithium ion
- cathode material
- oxide cathode
- shell
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 98
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000007774 positive electrode material Substances 0.000 title description 47
- 238000005245 sintering Methods 0.000 claims abstract description 47
- 239000002243 precursor Substances 0.000 claims abstract description 40
- 239000011258 core-shell material Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 18
- 239000010406 cathode material Substances 0.000 claims description 62
- 239000003513 alkali Substances 0.000 claims description 44
- 239000000126 substance Substances 0.000 claims description 44
- 150000001875 compounds Chemical class 0.000 claims description 33
- 230000014759 maintenance of location Effects 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 28
- 229910052782 aluminium Inorganic materials 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 25
- 238000001816 cooling Methods 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 9
- 229910052792 caesium Inorganic materials 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 229910052758 niobium Inorganic materials 0.000 claims description 9
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- 239000004094 surface-active agent Substances 0.000 claims description 9
- 229910052721 tungsten Inorganic materials 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- 229910052772 Samarium Inorganic materials 0.000 claims description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 8
- 229910052712 strontium Inorganic materials 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 8
- 150000003624 transition metals Chemical class 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 229910052718 tin Inorganic materials 0.000 claims description 7
- 229910052727 yttrium Inorganic materials 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
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- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract description 31
- 239000000463 material Substances 0.000 abstract description 24
- 230000008569 process Effects 0.000 abstract description 12
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 119
- 239000011572 manganese Substances 0.000 description 73
- 230000000052 comparative effect Effects 0.000 description 37
- 229910052751 metal Inorganic materials 0.000 description 31
- 239000002184 metal Substances 0.000 description 30
- SFKQQYOXXWIJSA-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[O--].[Al+3].[Mn++].[Co++].[Ni++] Chemical compound [Li+].[O--].[O--].[O--].[O--].[O--].[Al+3].[Mn++].[Co++].[Ni++] SFKQQYOXXWIJSA-UHFFFAOYSA-N 0.000 description 27
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 239000000047 product Substances 0.000 description 21
- 239000013078 crystal Substances 0.000 description 20
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 18
- 229910052748 manganese Inorganic materials 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
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- 239000002245 particle Substances 0.000 description 15
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- 238000004140 cleaning Methods 0.000 description 13
- 238000009616 inductively coupled plasma Methods 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000001569 carbon dioxide Substances 0.000 description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 description 12
- 229910052808 lithium carbonate Inorganic materials 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
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- 238000005406 washing Methods 0.000 description 9
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- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 8
- 230000001351 cycling effect Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000011164 primary particle Substances 0.000 description 7
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 150000001868 cobalt Chemical class 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 150000002696 manganese Chemical class 0.000 description 6
- 150000002815 nickel Chemical class 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000012086 standard solution Substances 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- 229910019421 CoxAly Inorganic materials 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 4
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
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- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229910016401 Ni0.34Co0.33Mn0.33 Inorganic materials 0.000 description 2
- 229910017166 Ni0.815CO0.15Al0.035 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
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- 235000015110 jellies Nutrition 0.000 description 2
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- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
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- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
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- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229910010092 LiAlO2 Inorganic materials 0.000 description 1
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
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- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
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- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
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- 238000005054 agglomeration Methods 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
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- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- 235000019341 magnesium sulphate Nutrition 0.000 description 1
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- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- QCAWEPFNJXQPAN-UHFFFAOYSA-N methoxyfenozide Chemical compound COC1=CC=CC(C(=O)NN(C(=O)C=2C=C(C)C=C(C)C=2)C(C)(C)C)=C1C QCAWEPFNJXQPAN-UHFFFAOYSA-N 0.000 description 1
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- 229940078494 nickel acetate Drugs 0.000 description 1
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- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
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- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium(III) oxide Inorganic materials O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- OBROYCQXICMORW-UHFFFAOYSA-N tripropoxyalumane Chemical compound [Al+3].CCC[O-].CCC[O-].CCC[O-] OBROYCQXICMORW-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a lithium ion battery oxide anode material and a preparation method thereof, and a lithium ion battery, wherein the preparation method of the lithium ion battery oxide anode material comprises the following steps: adding a doping material M3, and preparing a nuclear precursor; adding a doping material M4, and preparing a shell precursor; then adding a lithium source for sintering to obtain a target product [ Li ]a(Ni1‑x‑y‑zCoxM1yM3z)O2]d·[Lis(Ni1‑m‑n‑ tComM2nM4t)O2]1‑d. The lithium ion battery oxide anode material with the core-shell structure, which is synthesized by the preparation method, has excellent cycle performance. The preparation method has simple process and controllable process, and is easy for industrial mass production.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to an oxide cathode material of a lithium ion battery and a preparation method thereof.
Background
With the popularization of new energy automobiles, the power type lithium ion battery is greatly developed, and meanwhile, the high requirements of the new energy automobiles on the endurance mileage and the energy density, the high cycle performance and the high safety performance of the new energy automobiles are also high. The oxide anode material of the lithium ion battery is one of the key materials of the lithium ion battery and is also a key factor for hindering the energy density of the lithium ion battery.
At present, most of materials produced by anode material manufacturers at home and abroad are secondary particles formed by agglomeration of fine grains. However, secondary spherical particles present some problems to be solved: (1) the structure of the secondary ball is poor in structural firmness, and the secondary ball is easy to break when being pressed by high pressure in the electrode preparation process, so that particles in the material are exposed, side reaction with electrolyte is intensified, metal ions are dissolved out, and the electrochemical performance is reduced; (2) the primary particles forming the secondary spheres have small particle size and many structural defects, and are easy to collapse under the condition of high voltage and sufficiency; (3) the interior of the secondary spherical particles is difficult to modify in structure, and interface side reaction is difficult to inhibit in the charging and discharging process; (4) the secondary spherical particles easily cause problems such as air expansion.
Researches find that the single-crystal-morphology cathode material not only has higher specific capacity and cycling stability under high voltage, but also can effectively improve the problems of the material in the aspects of high-temperature performance, gas expansion and the like compared with the traditional ternary cathode material with a secondary sphere structure, and meanwhile, the single-crystal cathode material also has the following advantages: (1) high mechanical strength, not easy to be broken in the electrode compacting process, and the compacted density can reach 3.8g/cm3～4.0g/cm3The higher compaction density can reduce the internal resistance of the material, reduce the polarization loss, prolong the cycle life of the battery and improve the energy density of the battery; (2) the special shape of primary single crystal particles has low specific surface area, and the side reaction between the material and the electrolyte is effectively reduced; (3) the surface of the single crystal particles is smooth, the single crystal particles are more fully contacted with the conductive agent, and the lithium ion transmission is facilitated. Therefore, the research on the single crystal cathode material will become a new direction for the research on the lithium ion battery material.
Disclosure of Invention
In view of this, embodiments of the present invention provide an oxide cathode material for a lithium ion battery and a method for preparing the same.
The invention provides a lithium ion battery oxide cathode material, which has a chemical formula shown in formula (I):
[Lia(Ni1-x-y-zCoxM1yM3z)O2]d·[Lis(Ni1-m-n-tComM2nM4t)O2]1-d (I)
Lia(Ni1-x-y-zCoxM1yM3z)O2is the chemical formula of the core of the oxide cathode material of the lithium ion battery, Lis(Ni1-m-n-tComM2nM4t)O2Is the chemical formula of the shell of the lithium ion battery oxide cathode material; the M1 and M2 are respectively and independently selected from Mn and/or Al; the M3 and the M4 are respectively and independently selected from one or more of alkali metal elements, alkaline earth metal elements, IIIA group elements, IVA group elements, transition metals and rare earth elements;
wherein x, y, z, m, n, a, s, t and d are mole fractions, x is more than 0, y is more than or equal to 0.01 and less than or equal to 0.10, z is more than or equal to 0 and less than or equal to 0.02, m is more than 0, n is more than or equal to 0.2 and less than or equal to 0.4, a is more than or equal to 1.01 and less than or equal to 1.07, s is more than or equal to 1.01 and less than or equal to 1.07, t is more than or equal to 0 and less than or equal to 0.02, 1-x-y-z is more than or equal to 0.80 and less than or equal to 0.96, 1-m-n-t is more than or equal to 0.30 and less than or equal to 0.70, and d is more than or equal to 0.70 and less than or equal to 1.
The second aspect of the invention provides a preparation method of the lithium ion battery oxide cathode material, which comprises the following steps:
step 1, nuclear precursor preparation: preparing a first mixed aqueous solution of a Ni source compound, a Co source compound, a M1 source compound and a M3 source compound, mixing the first mixed aqueous solution, a carbonate solution and ammonia water, and reacting under an alkaline condition to obtain a nuclear precursor Ni1-x-y-zCoxM1yM3zCO3(ii) a M3 is at least one selected from Mg, Zr, Al, Sc, Ti, W, Sr, Nb, Si, Y, La, Ta, Cs, Ce, Ga, Sn, Er, V, Sm and Mo; x, y and z are mole fractions, x>0，0.01≤y≤0.10，0≤z≤0.02，0.60≤1-x-y-z≤0.96；
And step 3, sintering: mixing and grinding the precursor with the core-shell structure obtained in the step 2, a lithium source and a water-soluble sintering aid, uniformly grinding, sintering, and cooling to room temperature after sintering to obtain a target product, wherein the chemical formula of the target product is as follows:
[Lia(Ni1-x-y-zCoxM1yM3z)O2]d·[Lis(Ni1-m-n-tComM2nM4t)O2]1-d
Lia(Ni1-x-y-zCoxM1yM3z)O2is the chemical formula of the core of the oxide cathode material of the lithium ion battery, Lis(Ni1-m-n-tComM2nM4t)O2Is the chemical formula of the shell of the lithium ion battery oxide cathode material; the M2 is selected from Mn and/or Al; the M4 is selected from one or more of alkali metal elements, alkaline earth metal elements, IIIA group elements, IVA group elements, transition metals and rare earth elements; wherein m, n, s, t and d are mole fractions, m>0，0.2≤n≤0.4，0≤t≤0.02，0.30≤1-m-n-t≤0.70，1.01≤s≤1.07，0.70≤d≤1。
In one embodiment, the present invention further comprises a second sintering step of washing the product obtained by the first sintering step, mixing the washed product with a water-soluble sintering aid and a coating material, grinding the mixture, and sintering the mixture.
The invention provides a lithium ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and an electrolyte, wherein the positive electrode comprises the lithium ion battery oxide positive electrode material.
In order to make the aforementioned and other objects, features and advantages of the invention more comprehensible, preferred embodiments accompanied with figures are described in detail below.
In one aspect, the present invention provides a lithium ion battery oxide cathode material, wherein the chemical formula of the lithium ion battery oxide cathode material is as shown in formula (I):
[Lia(Ni1-x-y-zCoxM1yM3z)O2]d·[Lis(Ni1-m-nComM2nM4t)O2]1-d (I)
in some embodiments, the chemical formula of the core of the lithium ion battery oxide cathode material is Lia(Ni1-x-y- zCoxM1yM3z)O2The chemical formula of the shell of the oxide cathode material of the lithium ion battery is Lis(Ni1-m-n-tComM2nM4t)O2. Wherein M1 and M2 are each independently selected from Mn and/or Al; the M3 and the M4 are respectively and independently selected from one or more of alkali metal elements, alkaline earth metal elements, IIIA group elements, IVA group elements, transition metals and rare earth elements.
As an embodiment, M1 is selected from Mn and Al, M2 is selected from Mn; the chemical formula of the core is Lia(Ni1-x-y-zCoxAl1- yMnyM3z)O2(ii) a The chemical formula of the shell is Lis(Ni1-m-n-tComMnnM4t)O2；
As an embodiment, M1 is selected from Mn and Al, M2 is selected from Al; the chemical formula of the core is Lia(Ni1-x-y-zCoxAl1- yMnyM3z)O2The chemical formula of the shell is Lis(Ni1-m-n-tComAlnM4t)O2；
As an embodiment, M1 is selected from Mn and Al, M2 is selected from Mn and Al; the chemical formula of the core is Lia(Ni1-x-y- zCoxAl1-yMnyM3z)O2The chemical formula of the shell is Lis(Ni1-m-n-tComAl1-nMnnM4t)O2；
In one embodiment, M1 is selected from Al, M2 is selected from Mn; the chemical formula of the core is Lia(Ni1-x-y-zCoxAlyM3z)O2The chemical formula of the shell is Lis(Ni1-m-n-tComMnnM4t)O2；
As an embodiment, M1 is selected from Al, M2 is selected from Al; the chemical formula of the core is Lia(Ni1-x-y-zCoxAlyM3z)O2The chemical formula of the shell is Lis(Ni1-m-n-tComAlnM4t)O2；
As an embodiment, M1 is selected from Al, M2 is selected from Mn and Al; the chemical formula of the core is Lia(Ni1-x-y- zCoxAlyM3z)O2The chemical formula of the shell is Lis(Ni1-m-n-tComAl1-nMnnM4t)O2；
As an embodiment, M1 is selected from Mn, M2 is selected from Mn; the chemical formula of the core is Lia(Ni1-x-y-zCoxMnyM3z)O2The chemical formula of the shell is Lis(Ni1-m-n-tComMnnM4t)O2；
As an embodiment, M1 is selected from Mn, M2 is selected from Al; the chemical formula of the core is Lia(Ni1-x-y-zCoxMnyM3z)O2The chemical formula of the shell is Lis(Ni1-m-n-tComAlnM4t)O2；
As an embodiment, M1 is selected from Mn, M2 is selected from Al and Mn; the chemical formula of the core is Lia(Ni1-x-y- zCoxMnyM3z)O2The chemical formula of the shell is Lis(Ni1-m-n-tComAl1-nMnnM4t)O2。
In some embodiments, the Mn may be derived from one or more of manganese sulfate, manganese acetate, manganese chloride, manganese nitrate; the Al may be derived from one or more of aluminum sulfate, aluminum chloride, aluminum nitrate, aluminum trichloride, aluminum acetate, aluminum isopropoxide, aluminum n-propoxide, aluminum sulfate, aluminum nitrate.
In some embodiments, the shell of the lithium ion battery oxide cathode material has a layered or spinel structure. In one embodiment, the layered lithium ion battery oxide positive electrode material comprises one or more of lithium nickel cobalt manganese oxide, lithium rich lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium cobalt oxide, lithium nickel cobalt oxide, and lithium manganese oxide. As an embodiment, the spinel lithium ion battery oxide positive electrode material includes lithium manganate and/or lithium nickel manganate.
In the embodiment of the invention, x, y, z, m, n, a, s, t and d are mole fractions, x is more than 0, y is more than or equal to 0.01 and less than or equal to 0.10, z is more than or equal to 0 and less than or equal to 0.02, m is more than 0.2 and less than or equal to 0.4, t is more than or equal to 0 and less than or equal to 0.02, a is more than or equal to 1.01 and less than or equal to 1.07, s is more than or equal to 1.01 and less than or equal to 1.07, 0.60 and less than or equal to 1-x-y-z and less than or equal to 0.96, 1-m-n-t is more than or equal to 0.30 and less than or equal to 0.70, and d is more than or equal to 0.70 and less than or equal to 1.
In some embodiments, x >0, 0.01. ltoreq. y.ltoreq.0.05, 0< z.ltoreq.0.02, m >0, 0.2. ltoreq. n.ltoreq.0.3, 0< t.ltoreq.0.02, 1.015. ltoreq. a.ltoreq.1.06, 1.015. ltoreq. s.ltoreq.1.06, 0.80. ltoreq.1-x-y-z.ltoreq.0.92, 0.34. ltoreq.1-m-n-t.ltoreq.0.60, 0.70. ltoreq. d.ltoreq.0.85.
In some embodiments, the mole fraction of Ni content in the lithium ion battery oxide cathode material (e.g., as in formula Li)a(Ni1-x-y-zCoxM1yM3z)O21-x-y-z) of (a) may be at least 0.60, at least 0.61, at least 0.62, at least 0.63, at least 0.64, at least 0.65, at least 0.66, at least 0.67, at least 0.68, at least 0.69, at least 0.70, at least 0.71, at least 0.75, at least 0.80, at least 0.81, at least 0.82, at least 0.83, at least 0.85, at least 0.86, at least 0.88, at least 0.89, at least 0.90, at least 0.91, at least 0.92, at least 0.93, at least 0.94, at least 0.95, at least 0.951. At least 0.953, at least 0.955, at least 0.957, at least 0.96, and/or not more than 0.96, not more than 0.957, not more than 0.955, not more than 0.953, not more than 0.951, not more than 0.95, not more than 0.94, not more than 0.93, not more than 0.92, not more than 0.91, not more than 0.90, not more than 0.89, not more than 0.88, not more than 0.86, not more than 0.85, not more than 0.83, not more than 0.82, not more than 0.81, not more than 0.80, not more than 0.75, not more than 0.71, not more than 0.70, not more than 0.69, not more than 0.68, not more than 0.67, not more than 0.66, not more than 0.65, not more than 0.64, not more than 0.63, not more than 0.62, not more than 0.61, not more than 0.60, and the like.
In some embodiments, the mole fraction of Li content in the lithium ion battery oxide cathode material core (e.g., as in formula Li)a(Ni1-x-y-zCoxM1yM3z)O2A) of (a) can be present in a mole fraction of at least 1.01, at least 1.02, at least 1.03, at least 1.035, at least 1.04, at least 1.045, at least 1.05, at least 1.055, at least 1.06, at least 1.065, at least 1.07, and/or not more than 1.07, not more than 1.065, not more than 1.06, not more than 1.055, not more than 1.05, not more than 1.045, not more than 1.04, not more than 1.035, not more than 1.03, not more than 1.02, not more than 1.01, and the like.
Here, when a is less than 1, the content of Li is insufficient, which may affect Li+The lithium removal or lithium insertion can reduce the charge and discharge capacity of the lithium ion battery oxide anode material, the content of Li is too high, more byproducts are generated in the preparation process, and the obtained lithium ion battery oxide anode material has LiOH and Li2CO3When alkaline substances are left, the alkaline substances on the surface are easy to attack the binder in the positive electrode glue solution, the binder forms double bonds to generate adhesion, slurry jelly is caused, the coating effect is influenced, and the performance of the battery cell is influenced. According to the embodiment of the invention, the molar fraction of the Li content is 1.01-1.07, the charge and discharge capacity is high, the byproducts are few, the improvement of the battery cell performance is facilitated, and the unexpected effect is achieved.
In some embodiments, the average of the lithium ion battery oxide cathode material structureThe particle size D50 is 3-5 μm, and the average particle size D50 of the core is 2.5-4 μm; the tap density of the oxide anode material of the lithium ion battery is 1.8-2.3g/cm3. In some embodiments, the lithium ion battery oxide cathode material is a primary particle. In some cases, secondary particles such as the lithium ion battery oxide cathode material may also be present. The oxide positive electrode material of the lithium ion battery has a core-shell structure, and can effectively inhibit the corrosion of electrolyte on a body material and the dissolution of metal ions, so that more lithium vacancies of active materials are kept, and the cycling stability of the material is improved.
In some embodiments, the tap density of the lithium ion battery oxide cathode material may be at least 1.5g/cm3At least 1.6g/cm3At least 1.7g/cm3At least 1.8g/cm3At least 1.9g/cm3At least 2.0g/cm3At least 2.1g/cm3At least 2.2g/cm3At least 2.3g/cm3And/or not more than 2.3g/cm3Not more than 2.2g/cm3Not more than 2.1g/cm3Not more than 2.0g/cm3Not more than 1.9g/cm3Not more than 1.8g/cm3Not more than 1.7g/cm3Not more than 1.6g/cm3Not more than 1.5g/cm3Etc. are present.
In some cases, the shell of the lithium ion battery oxide cathode material has a thickness of 0.05 to 1.1 μm; in some cases, the shell thickness is less than 1.1 μm, less than 1.05 μm, less than 1.0 μm, less than 0.95 μm, less than 0.9 μm, less than 0.8 μm, less than 0.7 μm, less than 0.6 μm, less than 0.5 μm, less than 0.4 μm, less than 0.3 μm, less than 0.2 μm, less than 0.1 μm, less than 0.08 μm, less than 0.06 μm, less than 0.05 μm; in some cases, the shell thickness can be at least 0.05 μm, at least 0.06 μm, at least 0.08 μm, at least 0.1 μm, at least 0.2 μm, at least 0.3 μm, at least 0.4 μm, at least 0.5 μm, at least 0.6 μm, at least 0.7 μm, at least 0.8 μm, at least 0.9 μm, at least 0.95 μm, at least 1.0 μm, at least 1.05 μm, at least 1.1 μm, and the like. In various embodiments, any combination of these is also possible; for example: the shell thickness may be between 0.05 μm and 1.1 μm. In addition, it should be understood that the shell may be uniformly or non-uniformly distributed around the core.
The thickness of the shell has a great influence on the performance of the core-shell structure composition, and if the thickness of the shell is too thin, the shell is easily corroded by electrolyte to expose the core, so that the stability of the composition is influenced; conversely, if the shell is too thick, the capacity of the composition will be reduced. The composition provided by the embodiment of the invention has proper shell thickness, can balance the stability of the composition and the capacity of the composition, and has optimal stability and capacity.
On the other hand, the embodiment of the invention also provides a preparation method of the oxide cathode material of the lithium ion battery, which comprises the following steps:
step 1, nuclear precursor preparation: preparing a first mixed aqueous solution of a Ni source compound, a Co source compound, a M1 source compound and a M3 source compound, mixing the first mixed aqueous solution, a carbonate solution and ammonia water, and reacting under an alkaline condition to obtain a nuclear precursor Ni1-x-y-zCoxM1yM3zCO3(ii) a Wherein x, y and z are mole fractions, and x is>0，0.01≤y≤0.10，0≤z≤0.02，0.60≤1-x-y-z≤0.96；
In the embodiment of the invention, M1 is selected from Mn and/or Al; m3 can be one or more of alkali metal element, alkaline earth metal element, IIIA group element, IVA group element, transition metal and rare earth element; further, M3 is at least one selected from Mg, Zr, Al, Sc, Ti, W, Sr, Nb, Si, Y, La, Ta, Cs, Ce, Ga, Sn, Er, V, Sm, and Mo. The reaction conditions include: the pH value is 9-12, the reaction temperature is 60-90 ℃, the reaction time is 3-12h under the constant temperature, and the cooling temperature is 25-30 ℃.
In one embodiment, when z is 0, the product obtained in the step 1 reaction is LiaNi1-x-yCoxM1yO2。
In the embodiment of the invention, the M2 is selected from Mn and/or Al; m4 can be one or more of alkali metal element, alkaline earth metal element, IIIA group element, IVA group element, transition metal and rare earth element; further, M4 is at least one selected from Mg, Zr, Al, Sc, Ti, W, Sr, Nb, Si, Y, La, Ta, Cs, Ce, Ga, Sn, Er, V, Sm, and Mo. The reaction conditions include: the pH value is 10-12, and the reaction temperature is 60-65 ℃.
In some embodiments, in steps 1 and 2, the reaction may be carried out in the presence of a dispersant, which may use one or more mixtures of surfactants, polyvinyl alcohols, polyglycerols. In some cases, the surfactant may be exemplified by cetyltrimethylammonium bromide (CTAB), polyvinylpyrrolidone (PVP), polyethylene glycol (PEG-400), Span-80 (Span-80), and polyoxyethylene octylphenol ether-10 (op-10), and the like.
In the present invention, the above-mentioned surfactants may be used alone or in combination of two or more, and may be used in combination with other dispersants. In the embodiment of the invention, the addition of the surfactant realizes the effect that a common surfactant such as Cetyl Trimethyl Ammonium Bromide (CTAB) is beneficial to particle dispersion and uniform particle distribution, and can regulate and control the growth direction and the dispersibility of crystals, regulate the crystal morphology, influence the layered structure of the material and enable the crystal structure to grow and have uniform particle size.
The mixed salt solution and the alkali liquor are added into the reaction kettle dispersed with the surfactant in a parallel flow manner, so that a large number of crystal nuclei are formed, when metal ions and the precipitant are continuously added, the metal ions and the precipitant are rapidly dispersed in the solution containing the surfactant under the stirring action, the concentrations of the precipitant and the metal ions in the reaction system are low, the supersaturation degree in the solution is low, new crystal nuclei are formed, the crystal particles grow gradually and the particle morphology is regulated, and the particle size of the lithium ion battery oxide anode material obtained by metal ion parallel flow feeding is relatively uniformly distributed.
In some embodiments, the Ni source compound is derived from one or more mixtures of nickel chloride, nickel sulfate, nickel acetate, nickel nitrate, or crystalline water compounds thereof; in some embodiments, the Co source compound is derived from one or more mixtures of cobalt sulfate, cobalt acetate, cobalt chloride, cobalt nitrate, or crystalline water compounds thereof.
According to the invention, a Ni source compound, a Co source compound, a Mn source compound and/or an Al source compound are prepared into a solution, nickel salt, cobalt salt, aluminum salt and manganese salt can be uniformly distributed in the solution, and the lithium ion battery oxide anode material is prepared by adopting the solution in which the nickel salt, the cobalt salt, the aluminum salt and the manganese salt are uniformly distributed. The lithium ion battery oxide anode material prepared by the method has the advantages that nickel, cobalt, aluminum and manganese are uniformly distributed in particles, the lithium ion battery oxide anode material is mixed with lithium salt, and the lithium ion battery oxide anode material is obtained by sintering, so that the crystal structure is more uniform, the framework structure is firmer, the performance of material performance is facilitated, and the capacity and the rate performance of the lithium ion battery oxide anode material are effectively improved.
And step 3, sintering: mixing and grinding the precursor with the core-shell structure prepared in the step 2, a lithium source and a water-soluble sintering aid, sintering, and cooling and annealing after sintering to obtain the lithium ion battery oxide cathode material; the chemical formula is shown as formula (I):
[Lia(Ni1-x-y-zCoxM1yM3z)O2]d·[Lis(Ni1-m-n-tComM2nM4t)O2]1-d (I)
Lia(Ni1-x-y-zCoxM1yM3z)O2is the chemical formula of the core of the oxide cathode material of the lithium ion battery, Lis(Ni1-m-n-tComM2nM4t)O2Is the chemical formula of the shell of the lithium ion battery oxide cathode material; the M4 is selected from one or more of alkali metal elements, alkaline earth metal elements, IIIA group elements, IVA group elements, transition metals and rare earth elements; m4 is at least one selected from Mg, Zr, Al, Sc, Ti, W, Sr, Nb, Si, Y, La, Ta, Cs, Ce, Ga, Sn, Er, V, Sm and Mo; wherein s, t and d are mole fractions, s is more than or equal to 1.01 and less than or equal to 1.07, t is more than or equal to 0 and less than or equal to 0.02, and d is more than or equal to 0.70 and less than or equal to 0.95.
In step 3, the sintering is carried out on the lithium source, the water-soluble auxiliary agent and the used doping material mixture for 8-20 hours at the high temperature of 780-900 ℃ in the air or oxygen atmosphere.
When the sintering temperature is less than 700 ℃, lithiation is insufficient, whereas when the sintering temperature exceeds 1000 ℃, oxidation of metal ions is inhibited, and charge-discharge cycle durability and initial capacity are reduced. The sintering temperature is preferably 780 to 900 ℃. Sintering may be performed in multiple stages.
In one embodiment, when t is 0, the product obtained in the step 3 reaction is [ Li ═ Lia(Ni1-x-y-zCoxM1yM3z)O2]d·[LisNi1-m-nComM2nO2]1-d。
As an embodiment, when z is 0 and t is 0, the product obtained from the reaction in step 3 is [ Li ═ Lia(Ni1-x- yCoxM1y)O2]d·[LisNi1-m-nComM2nO2]1-d。
As an embodiment, when z is 0, t is 0, and d is 1, the product obtained from the reaction in step 3 is Lia(Ni1-x-yCoxM1y)O2。
As the lithium source, one or more of lithium carbonate, lithium hydroxide, lithium acetate, and lithium oxalate can be used. When lithium carbonate is used as the lithium source, for example, the cost is lower than when lithium hydroxide is used. One or more of water-soluble sulfate and water-soluble chloride can be used as the water-soluble sintering aid, and the addition of the water-soluble sintering aid can further reduce the sintering temperature and avoid the influence of high-temperature sintering on the particle morphology and the performance of the high-nickel material.
In addition, in some embodiments, different temperature-reducing annealing treatments can produce different effects. Furnace cooling, staged rate cooling or rate cooling can be adopted, as an implementation mode, the cooling rate of the rate cooling is 0.01-3.0 ℃/min; as an embodiment, the cooling rate is 0.02-2.5 ℃/min; as an embodiment, the cooling rate is 0.02-1.0 deg.C/min. The composition is of a core-shell structure, and in the cooling process, if the temperature is rapidly reduced and the temperature difference change is too large, the crystallization stress of the core and the shell is inconsistent, and the stress is distorted, the shell is cracked, and the core-shell structure cannot be formed; the core-shell structure is formed by adopting rate cooling, staged rate cooling or furnace cooling, the cooling rate is slow, and the contraction ratio of the core and the shell can be effectively prevented from being inconsistent; meanwhile, the annealing process eliminates oxygen defects formed by local overburning of the material in the sintering process, so that the obtained material has higher crystallinity and better structural stability. Therefore, the high-nickel core-shell structure cathode material obtained by the preparation method has high structural stability and long cycle life.
As an embodiment, the step 3 further includes a second sintering: and (3) cleaning the sintered product obtained in the step (3), mixing and grinding the cleaned product with a water-soluble sintering aid and a coating material, and sintering the mixture in the air or oxygen atmosphere. In some cases, the sintering temperature is 500-.
In some embodiments, the cleaning means is flushed with a stream of carbon dioxide gas; in some embodiments, the washing means is washing with carbonated water. The residual alkali on the surface of the positive electrode material cleaned by carbon dioxide airflow or carbonated water is effectively reduced, the attack of alkaline substances on the surface of the positive electrode material on a binder in a positive electrode glue solution in the configuration process of the positive electrode material is reduced, double bonds formed by the binder are avoided, the coating effect is improved, and the performance of a battery cell is improved.
In some embodiments, the cladding materials M3 and M4 are each independently selected from one or more of alkali metal elements, alkaline earth metal elements, group IIIA elements, group IVA elements, transition metals, and rare earth elements.
In one embodiment, M3 and M4 are each independently selected from at least one of Mg, Zr, Al, Sc, Ti, W, Sr, Nb, Si, Y, La, Ta, Cs, Ce, Ga, Sn, Er, V, Sm, and Mo. In some cases, M3 is derived from one or more of an oxide of metal M3, a hydroxide of metal M3, a chloride of metal M3, a sulfate of metal M3, a nitrate of metal M3, a fluoride of metal M3, a sulfide of metal M3, a telluride of metal M3, a selenide of metal M3, an antimonide of metal M3, a phosphide of metal M3, and a complex oxide of metal M3. In some cases, M4 is derived from one or more of an oxide of metal M4, a hydroxide of metal M4, a chloride of metal M4, a sulfate of metal M4, a nitrate of metal M4, a fluoride of metal M4, a sulfide of metal M4, a telluride of metal M4, a selenide of metal M4, an antimonide of metal M4, a phosphide of metal M4, and a complex oxide of metal M4. In one embodiment, Mg is derived from one or more of magnesium hydroxide, magnesium chloride, magnesium sulfate, magnesium carbonate, and magnesium nitrate.
According to the technical scheme, different metal elements are coated on the surface of the core and/or the shell of the oxide anode material of the lithium ion battery, and the influence on the structure and the size of the unit cell is different, so that the influence on the multiplying power and the specific capacity of the material is different, and the alkali metal elements and the alkaline earth metal elements have structures which are beneficial to the stability of a laminated structure, so that the crystal structure is smoother, the collapse of the unit cell in the circulating process is prevented, the capacity density is improved, and the capacity and the multiplying power of the oxide anode material of the lithium ion battery are improved.
According to the method, a metal source compound and a dispersing agent are used for coprecipitation to obtain a single crystal precursor, then the single crystal precursor is mixed with a lithium source and a water-soluble auxiliary agent, the mixture is ground and sintered to obtain a single crystal anode material, wherein the single crystal precursor is of a core-shell structure, and the finally prepared anode material is single-crystal in shape and has a core-shell structure.
Drawings
Fig. 1 is a schematic structural diagram of an embodiment of the present invention.
Fig. 2 is a schematic diagram of a process for forming an oxide positive electrode material for a lithium ion battery according to one embodiment of the present invention.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description of the embodiments, structures, features and effects according to the present invention will be made with reference to the accompanying drawings and preferred embodiments.
The lithium ion battery oxide positive electrode material of the present invention will be described in detail with reference to examples.
Example 1
The lithium ion battery oxide cathode material is a primary particle, and has a structural formula as follows:
[Li1.06(Ni0.83Co0.07Al0.05Mn0.05)O2]0.95·[Li1.02(Ni0.55Co0.05Al0.4)O2]0.05
Li1.06(Ni0.83Co0.07Al0.05Mn0.05)O2is the chemical formula of the core of the oxide cathode material of the lithium ion battery, Li1.02(Ni0.55Co0.05Al0.4)CO3The chemical formula of the shell of the oxide cathode material of the lithium ion battery comprises the following steps:
step 1, preparation of Nuclear precursor
According to the molar ratio of the elements Ni: co: al: mn 0.83:0.07:0.05
Calculating and weighing soluble nickel salt, soluble cobalt salt, soluble aluminum salt and soluble manganese salt; adding the two into deionized water together to mix and prepare a first mixed aqueous solution A with the concentration of 1 mol/L;
mixing the first mixed aqueous solution A, ammonia water, carbonate solution and a dispersing agent, controlling the pH to be 9, reacting at the constant temperature of 60 ℃ for 3 hours, cooling to 30 ℃, filtering, washing and drying precipitates to obtain Ni0.83Co0.07Al0.05Mn0.05CO3；
Dissolving Ni source, Co source and Al source in deionized water in proportion to obtain a second mixed aqueous solution, mixing with Ni0.83Co0.07Al0.05Mn0.05CO3Mixing ammonia water and NaOH solution, controlling the reaction temperature of the system at 60 ℃, controlling the stirring speed at 750 rpm, adjusting the pH of the mixed solution to 10, carrying out coprecipitation reaction for 3 hours, and filtering, washing and drying the precipitate to obtain a precursor with a core-shell structure.
Step 3, preparation of lithium ion battery oxide anode material with core-shell structure
And (2) mixing the precursor obtained in the step (2), dried lithium carbonate and a water-soluble auxiliary agent in proportion, wherein the use amount of the lithium carbonate is that the molar ratio of Li in the lithium carbonate to (Ni + Co + Al) in the lithium ion battery oxide positive electrode material is 0.86, the addition amount of the water-soluble sintering auxiliary agent is that the mass ratio of the lithium ion battery oxide positive electrode material is 10%, uniformly mixing and grinding, sintering in an oxygen atmosphere, heating to 850 ℃ for reaction for 12 hours, and then cooling to room temperature along with a furnace to obtain a target product with a core-shell structure.
The structural formula of the target product is as follows:
[Li1.06(Ni0.83Co0.07Al0.05Mn0.05)O2]0.95·[Li1.02(Ni0.55Co0.05Al0.4)O2]0.05
ICP element analysis test results show that the mole percentages of Ni, Co, Al and Mn are as follows:
example 2
[Li1.05(Ni0.85Co0.08Al0.03Mn0.03Sc0.01)O2]0.93·[Li1.03(Ni0.58Co0.07Mn0.35)O2]0.07
the preparation process is similar to example 1, except that:
step 1, preparation of Nuclear precursor
According to the molar ratio of the elements Ni: co: al: mn: sc is 0.85:0.08:0.03:0.03:0.01
Calculating and weighing soluble nickel salt, soluble cobalt salt, soluble aluminum salt, soluble manganese salt and dopant Sc2O3(ii) a The first mixed aqueous solution A and the second mixed aqueous solution A are added into deionized water together and mixed to prepare 1mol/L first mixed aqueous solution A.
The structural formula of the target product in this example 2 is:
[Li1.05(Ni0.85Co0.08Al0.03Mn0.03Sc0.01)O2]0.93·[Li1.03(Ni0.58Co0.07Mn0.35)O2]0.07
ICP element analysis test results show that the mole percentages of Ni, Co, Al, Mn and Sc are as follows:
example 3
Embodiment 3 of the invention provides Zr doping and doping material V2O5The shell-doped lithium ion battery oxide cathode material has a structural formula as follows:
[Li1.07(Ni0.86Co0.08Al0.03Mn0.02Zr0.01)O2]0.9·[Li1.05(Ni0.53Co0.1Al0.1Mn0.22V0.05)O2]0.1
the preparation process is similar to example 1, except that:
step 1, preparation of Nuclear precursor
According to the molar ratio of the elements Ni: co: al: mn: zr 0.86:0.08:0.03:0.02:0.01
Calculating and weighing soluble nickel salt, soluble cobalt salt, soluble aluminum salt, soluble manganese salt and doping agent ZrO2(ii) a The first mixed aqueous solution A and the second mixed aqueous solution A are added into deionized water together and mixed to prepare 1mol/L first mixed aqueous solution A.
Dissolving a Ni source, a Co source, an Al source, a Mn source and a V source in deionized water according to a certain proportion to obtain a second mixed aqueous solution, and mixing the second mixed aqueous solution with Ni0.86Co0.08Al0.03Mn0.02Zr0.01CO3Mixing ammonia water and NaOH solution, controlling the reaction temperature of the system at 60 ℃, controlling the stirring speed at 750 rpm, adjusting the pH of the mixed solution to 10, carrying out coprecipitation reaction for 3 hours, and filtering, washing and drying the precipitate to obtain a precursor with a core-shell structure.
The target product of this example 3 has the formula:
[Li1.07(Ni0.86Co0.08Al0.03Mn0.02Zr0.01)O2]0.9·[Li1.05(Ni0.53Co0.1Al0.1Mn0.22V0.05)O2]0.1
ICP element analysis test results show that the mole percentages of Ni, Co, Al, Mn, Zr and V are as follows:
example 4
In this embodiment 4, a Ti-doped lithium ion battery oxide positive electrode material is adopted, and the structural formula is as follows:
[Li1.035(Ni0.88Co0.08Al0.04)O2]0.88·[Li1.01(Ni0.52Co0.18Al0.15Ti0.15)O2]0.12
the ICP element analysis test result shows that the mole percentages of the metals of Ni, Co, Al and Ti are as follows:
example 5
In this embodiment 5, an Sm-doped lithium ion battery oxide positive electrode material is provided, and the structural formula is:
[Li1.02(Ni0.90Co0.08Al0.01Sm0.01)O2]0.85·[Li1.015(Ni0.34Co0.26Mn0.4)O2]0.15
the ICP element analysis test result shows that the mole percentages of the metals of Ni, Co, Al, Mn and Sm are as follows:
example 6
In this embodiment 6, a Cs-doped and Mo-doped lithium ion battery oxide positive electrode material is provided, and the structural formula is:
[Li1.025(Ni0.91Co0.05Al0.03Cs0.01)O2]0.82·[Li1.03(Ni0.45Co0.15Al0.1Mn0.25Mo0.05)O2]0.18
ICP element analysis test results show that the mole percentages of Ni, Co, Al, Mn, Cs and Mo are as follows:
example 7
In this embodiment 7, a W-doped and Ta-doped lithium ion battery oxide positive electrode material is provided, and a structural formula of a target product is:
[Li1.055(Ni0.92Co0.03Mn0.04W0.01)O2]0.8·[Li1.02(Ni0.5Co0.15Al0.3Ta0.05)O2]0.2
ICP element analysis test results show that the mole percentages of Ni, Co, Al, Mn, Ta and W are as follows:
example 8
This example 8 provides an Sr-doped and Mg-doped lithium ion battery oxide cathode material, which has a structural formula:
[Li1.04(Ni0.93Co0.02Mn0.03Sr0.02)O2]0.75·[Li1.05(Ni0.6Co0.1Mn0.28Mg0.02)O2]0.25
the ICP element analysis test result shows that the mole percentage of each metal of Ni, Co, Mn, Mg and Sr is as follows:
example 9
In this embodiment 9, an Nb-doped and Al-doped lithium ion battery oxide positive electrode material is provided, and a structural formula of a target product is:
[Li1.01(Ni0.95Co0.02Mn0.02Nb0.01)O2]0.7·[Li1.03(Ni0.7Co0.08Al0.1Mn0.1Al0.02)O2]0.3
ICP element analysis test results show that the mole percentages of Ni, Co, Al, Mn and Nb are as follows:
example 10
The structural formula of the oxide positive electrode material of the lithium ion battery provided in this embodiment 10 is as follows:
[Li1.06(Ni0.61Co0.29Al0.05Mn0.05)O2]0.95·[Li1.02(Ni0.34Co0.33Mn0.33)O2]0.05
ICP element analysis test results show that the mole percentages of Ni, Co, Al and Mn are as follows:
example 11
The structural formula of the oxide positive electrode material of the lithium ion battery provided in this embodiment 11 is:
[Li1.06(Ni0.64Co0.26Al0.05Mn0.05)O2]0.95·[Li1.02(Ni0.34Co0.33Mn0.33)O2]0.05
ICP element analysis test results show that the mole percentages of Ni, Co, Al and Mn are as follows:
examples 4 to 14 are similar to the preparation methods of examples 1 to 3, except that: the reaction conditions, raw material ratios and products of each step are shown in tables 1 and 2.
Example 15
The lithium ion battery oxide cathode material is a primary particle, and has a structural formula as follows:
Li1.06(Ni0.63Co0.27Al0.05Mn0.05)O2the preparation method comprises the following steps:
step 1, precursor Ni0.63Co0.27Al0.05Mn0.05CO3Preparation of
According to the molar ratio of the elements of Ni, Co, Al and Mn being 0.63, 0.27, 0.05 and 0.05
Calculating and weighing soluble nickel salt, soluble cobalt salt, soluble aluminum salt and soluble manganese salt; adding the two into deionized water together to mix and prepare a first mixed aqueous solution A with the concentration of 1 mol/L;
mixing the first mixed aqueous solution A, ammonia water, carbonate solution and a dispersing agent, controlling the pH to be 9, reacting at the constant temperature of 60 ℃ for 3 hours, cooling to 30 ℃, filtering, washing and drying precipitates to obtain Ni0.63Co0.27Al0.05Mn0.05CO3；
And (3) sintering: drying lithium carbonate until crystal water is completely lost, and mixing with the Ni prepared in the step 10.63Co0.27Al0.05Mn0.05CO3And mixing the water-soluble sintering aid in proportion, wherein the use amount of the lithium carbonate is that the molar ratio of Li in the lithium carbonate to (Ni + Co + Al + Mn) in the composition is 0.86, the addition amount of the water-soluble sintering aid is that the mass ratio of the composition is 10%, uniformly mixing and grinding the mixture, sintering the mixture in an oxygen atmosphere, heating the mixture to 820 ℃ for reaction for 16 hours, and then cooling the mixture to room temperature at a cooling rate of 0.3 ℃/min to obtain a target product Li1.06(Ni0.63Co0.27Al0.05Mn0.05)O2。
Example 16
The lithium ion battery oxide cathode material is a primary particle, and has a structural formula as follows: li1.03(Ni0.78Co0.12Al0.10)O2The preparation process is analogous to example 15.
Example 17
The lithium ion battery oxide cathode material is a primary particle, and has a structural formula as follows: li1.05(Ni0.83Co0.07Mn0.10)O2The preparation process is analogous to example 15.
Example 18
The lithium ion battery oxide cathode material is a primary particle, and has a structural formula as follows: li1.02(Ni0.90Co0.08Al0.01Mn0.01)O2The preparation process is analogous to example 15.
Comparative example 1
Comparative example 1 provides a ternary cathode material of the formula Li1.035Ni0.815Co0.15Al0.035O2The preparation method comprises the following steps:
step (1), primary sintering: precursor Ni of ternary positive electrode material1-x-yCoxAly(OH)2+ySintering, heating to 500 ℃ and reacting for 10 hours;
step (2), sintering for the second time: and (2) drying the lithium hydroxide monohydrate until crystal water is completely lost, and mixing the lithium hydroxide monohydrate with the sintered product obtained in the step (1), wherein the dosage of the lithium hydroxide monohydrate is that the molar ratio of Li in the lithium hydroxide monohydrate to (Ni + Co + Al) in the precursor of the ternary cathode material is 1.035: 1, uniformly mixing and grinding, sintering in an oxygen atmosphere, heating to 715 ℃, reacting for 16.5 hours, and then cooling to room temperature at a cooling rate of 0.3 ℃/min;
step (3), sintering for the third time: heating the sintered product obtained in the step (2) to 650 ℃, sintering for 3.5 hours, and cooling to room temperature to obtain the comparative material Li1.035Ni0.815Co0.15Al0.035O2。
Table 1, examples 1 to 18 and comparative example 1 reaction conditions in the respective steps
Table 2, examples 1 to 18 and comparative example 1 Each step reaction conditions and products
Assembling a CR2032 button battery:
the method comprises the following steps of taking the lithium ion battery oxide positive electrode material prepared in the embodiments 1-18 and the positive electrode material prepared in the comparative example 1 as active materials of a positive electrode, taking a metal lithium sheet as a negative electrode, taking a Celgard 2500 diaphragm as the diaphragm, taking fosai LB-002 electrolyte of Suzhou Buddhist New Material Co., Ltd, assembling a CR2032 type button battery according to the prior art, wherein the assembling sequence is as follows: the positive cover is flatly placed, the spring piece is placed, the stainless steel sheet is placed, the positive plate is placed, the electrolyte is injected, the diaphragm sheet is placed, the lithium sheet is placed, the negative cap is covered, the sealing is carried out, and the assembly is completed. The cell was assembled in a dry glove box filled with argon. After the assembly was completed, the cell was subjected to performance testing, the test results of which are shown in table 3.
1. ICP elemental detection
The test method comprises the following steps: inductively coupled plasma mass spectrometry test method
Inductively coupled plasma mass spectrometer
The model is as follows: prodigy DC Arc
Test instrument manufacturers: leisha Leibos company, Rieman
2. Resistivity of powder
The test method comprises the following steps: four-probe method
The instrument name: powder resistance tester
The instrument model is as follows: MCP-T700
The instrument manufacturer: mitsubishi chemical
3. Cycle performance
Name of the test instrument: xinwei battery detection system, model: BTS-5V10mA
Test instrument manufacturers: shenzhen, New Wille electronics, Inc.;
the test method comprises the following steps: charging to 4.3V at a constant current of 1C at 25 ℃, keeping the constant voltage of 4.3V to 0.05C, then discharging to 3V at 1C, repeatedly carrying out 100 times of the charge-discharge cycles, measuring the discharge capacity at the first cycle and the discharge capacity at the 100 th cycle, and calculating the capacity retention rate after 100 cycles, wherein the formula is as follows: capacity retention after cycling ═ 100% of (discharge capacity at 100 th cycle)/(discharge capacity at first cycle).
4. Tap density
Name of the test instrument: tap density instrument
The instrument model is as follows: JZ-1
The instrument manufacturer: chengdu refined powder test equipment Co Ltd
The test method comprises the following steps: about 10 to 20g of the positive electrode material was weighed with an accuracy of 0.0001 g. And (3) putting the positive electrode material into the measuring cylinder, and then fixing the measuring cylinder on the bracket. The positive electrode material was repeated 3000 times tapping (i.e., automatically lifting and dropping the cylinder), and then the corresponding volume was measured. Tap density is the mass after tapping/volume after tapping. Three replicates were performed and the results listed in table 2 represent the average of the three experiments.
5. The surface residual alkali amount test method comprises the following steps: acid-base titration method
(1) Preparing a positive electrode material clear solution: w was weighed with an accuracy of 0.0001g1(30.0000. + -. 0.0040g) of a positive electrode material, and W was weighed with an accuracy of 0.01g2(100 +/-0.1 g) deionized water, mixing the anode material with the deionized water, and replacing the mixed solution by argonStirring the air in the container, filtering to obtain a filtrate, transferring 50mL of the filtrate, and putting the filtrate into a 100mL beaker for titration;
(2) measurement of LiOH content: using phenolphthalein as an indicator, titrating with 0.05mol/L hydrochloric acid standard solution, and measuring the volume V of the consumed hydrochloric acid standard solution at the end point1；
(3) Measurement of Li2CO3The content is as follows: replacing CO in the titrated clear liquid in the step (2) by argon2Then titrating with 0.05mol/L hydrochloric acid standard solution by using methyl red indicator, and measuring the volume V of the consumed hydrochloric acid standard solution at the end point2；
LiOH content (wt%) calculation formula: omega1＝(2V1-V2)*0.05*2.395*W2/W1/50；
Li2CO3Content (wt%) calculation formula: omega2＝(V2-V1)*0.05*7.389*W2/W1/50；
2.395: the mass of LiOH in g corresponding to the hydrochloric acid standard solution (1.000 mol/L);
7.389: li in g equivalent to hydrochloric acid standard solution (2.000mol/L)2CO3The mass of (c);
surface residual alkali content of positive electrode material omega1+ω2。
Table 3, examples 1-18 and comparative example 1 Performance test results
Referring to tables 1 to 3 together, it can be seen that:
example 1 compared with comparative example 1, in example 1, the lithium nickel cobalt manganese aluminum oxide with the core-shell structure has a capacity retention rate of 95.2% and a surface residual alkali content of 0.32% after 100 cycles, and in the cathode material of comparative example 1, the capacity retention rate of 79.7% and the surface residual alkali content of 0.83% after 100 cycles, compared with comparative example 1, the lithium nickel cobalt manganese aluminum oxide with the core-shell structure of example 1 has more stable cycle performance and reduced surface residual alkali content.
Example 2 compared with comparative example 1, example 2 is a lithium nickel cobalt manganese aluminum oxide doped with Sc core, the capacity retention rate after 100 cycles is 101.2%, the surface residual alkali weight percentage is 0.38%, the positive electrode material of comparative example 1 has the capacity retention rate after 100 cycles is 79.7%, the surface residual alkali weight percentage is 0.83%, and compared with comparative example 1, the lithium nickel cobalt manganese aluminum oxide doped with Sc core of example 2 has more stable cycle performance and reduced surface residual alkali.
Compared with the comparative example 1, the lithium nickel cobalt manganese aluminum oxide obtained by doping the Zr core and doping the V shell and cleaning the lithium nickel cobalt manganese aluminum oxide by using carbon dioxide gas flow in the embodiment 3 has the capacity retention rate of 106% after 100 cycles, the weight percentage of the surface residual alkali is 0.14%, the positive electrode material in the comparative example 1 has the capacity retention rate of 79.7% and the weight percentage of the surface residual alkali is 0.83% after 100 cycles, and compared with the comparative example 1, the lithium nickel cobalt manganese aluminum oxide obtained by doping the Zr core and doping the V shell in the embodiment 3 has more stable cycle performance; and the carbon dioxide airflow is adopted for cleaning, so that the residual alkali on the surface is effectively reduced.
Example 4 compared with comparative example 1, example 4 is a lithium nickel cobalt manganese aluminum oxide doped with a Ti shell and obtained by washing with carbonated water, the capacity retention rate after 100 cycles is 103.5%, the weight percentage of surface residual alkali is 0.12%, the capacity retention rate after 100 cycles is 79.7%, the weight percentage of surface residual alkali is 0.83% for the positive electrode material of comparative example 1, and compared with comparative example 1, the lithium nickel cobalt manganese aluminum oxide doped with a Ti shell of example 4 has more stable cycle performance; the residual alkali on the surface is effectively reduced by adopting carbonated water for cleaning.
Compared with the comparative example 1, the lithium nickel cobalt manganese aluminum oxide obtained by doping Sm core and cleaning by carbon dioxide gas flow in the example 5 has the capacity retention rate of 96.7% after 100 cycles, the weight percentage of surface residual alkali is 0.11%, the positive electrode material in the comparative example 1 has the capacity retention rate of 79.7% after 100 cycles, the weight percentage of surface residual alkali is 0.83%, and compared with the comparative example 1, the lithium nickel cobalt manganese aluminum oxide doped by Sm core in the example 5 has more stable cycle performance; and the carbon dioxide airflow is adopted for cleaning, so that the residual alkali on the surface is effectively reduced.
Compared with the comparative example 1, the lithium nickel cobalt manganese aluminum oxide obtained by doping the Cs core and the Mo shell and cleaning by carbon dioxide gas flow in the example 6 has the capacity retention rate of 102% after 100 cycles and the weight percentage of the surface residual alkali of 0.12%, the positive electrode material in the comparative example 1 has the capacity retention rate of 79.7% and the weight percentage of the surface residual alkali of 0.83% after 100 cycles, and compared with the comparative example 1, the lithium nickel cobalt manganese aluminum oxide obtained by doping the Cs core and the Mo shell in the example 6 has more stable cycle performance; and the carbon dioxide airflow is adopted for cleaning, so that the residual alkali on the surface is effectively reduced.
Compared with the comparative example 1, the lithium nickel cobalt manganese aluminum oxide obtained by doping the W core and doping the Ta shell and cleaning the lithium nickel cobalt manganese aluminum oxide by using the carbonic acid water in the example 7 has the capacity retention rate of 102.6 percent and the weight percentage of the surface residual alkali of 0.08 percent after 100 cycles, the positive electrode material in the comparative example 1 has the capacity retention rate of 79.7 percent and the weight percentage of the surface residual alkali of 0.83 percent after 100 cycles, and compared with the comparative example 1, the lithium nickel cobalt manganese aluminum oxide obtained by doping the W core and doping the Ta shell in the example 7 has more stable cycle performance; the residual alkali on the surface is effectively reduced by adopting carbonated water for cleaning.
Example 8 compared with comparative example 1, example 8 is a lithium nickel cobalt manganese aluminum oxide doped with a SrO core and a Mg shell, the capacity retention rate after 100 cycles is 101.5%, the weight percentage of surface residual alkali is 0.24%, the capacity retention rate after 100 cycles is 79.7%, the weight percentage of surface residual alkali is 0.83% for the positive electrode material of comparative example 1, and the lithium nickel cobalt manganese aluminum oxide doped with a SrO core and a Mg shell of example 8 has more stable cycle performance and reduced surface residual alkali compared with comparative example 1.
Example 9 compared with comparative example 1, example 9 is a lithium nickel cobalt manganese aluminum oxide obtained by Nb core doping, Al shell doping and washing with carbonated water, the capacity retention ratio after 100 cycles is 101.8%, the weight percentage of surface residual alkali is 0.03%, the capacity retention ratio after 100 cycles is 79.7%, the weight percentage of surface residual alkali is 0.83% of the positive electrode material of comparative example 1, and compared with comparative example 1, the lithium nickel cobalt manganese aluminum oxide obtained by Nb core doping and Al shell doping of example 9 has more stable cycle performance; the residual alkali on the surface is effectively reduced by adopting carbonated water for cleaning.
Compared with the embodiment 3, the embodiment 3 is the lithium nickel cobalt manganese aluminum oxide obtained by adopting Zr core doping, V shell doping and carbon dioxide gas flow cleaning, the capacity retention rate is 106% after 100 cycles, the weight percentage of the surface residual alkali is 0.14%, and the capacity retention rates of the embodiments 10 to 14 are 100%, 97.4%, 99.5%, 98.3% and 97% respectively after 100 cycles; compared with the examples 10-14, the lithium nickel cobalt manganese aluminum oxide doped with Zr core and V shell in the example 3 can improve the nickel content and have stable capacity retention rate.
In summary, the lithium nickel cobalt manganese aluminum oxide with the core-shell structure of the invention has at least the following advantages:
(1) the lithium nickel cobalt manganese aluminum oxide with the core-shell structure has more stable cycle performance: compared with the comparative example 1, after the cycles of the examples 1 to 9 are 100 times, the capacity retention rate of the lithium nickel cobalt manganese aluminum oxide with the core-shell structure prepared by the embodiment of the invention is higher than that of the traditional ternary cathode material in the comparative example 1; compared with the traditional ternary cathode material, the lithium nickel cobalt manganese aluminum oxide has a core-shell structure, and can effectively inhibit the corrosion of the electrolyte on the body material and the dissolution of metal ions, so that more lithium vacancies of the active material are kept, and the cycling stability of the material is improved.
(2) The lithium nickel cobalt manganese aluminum oxide prepared by core doping and shell doping has more stable cycle performance: compared with the embodiment 1, the embodiments 2 and 5 are nuclear doping, and the capacity retention rates of the embodiments 2 and 5 after 100 cycles are respectively 101.2% and 96.7%, which are higher than those of the embodiment 1: the nuclear doping can improve the cycle stability;
in example 4, the shell is doped, and the capacity retention rate after 100 cycles is 103.5%, which is obviously higher than that in example 1: shell doping is shown to improve cycling stability; similarly, in example 4, compared with examples 2 and 5, the capacity retention ratio of example 4 was 103.5% higher than that of examples 2 and 5, i.e., 101.2% and 96.7%: the shell doping is superior to the core doping in the core-shell structure for improving the cycle stability;
examples 3 and 6 to 9 are core-shell doping, and the capacity retention rates of examples 3 and 6 to 9 after 100 cycles are 106%, 102%, 102.6%, 101.5% and 101.8%, respectively, which are higher than those of example 1: the core-shell doping can improve the cycling stability.
(3) The anode material cleaned by carbon dioxide gas flow or carbonic water effectively reduces the surface residual alkali: compared with the unwashed positive electrode materials in the embodiments 1, 2 and 8 and the comparative example 1, the positive electrode materials in the embodiments 3 to 7 and 9 are washed by carbon dioxide airflow or carbonated water, and the residual alkali amount on the surface of the positive electrode material washed by the carbon dioxide airflow or the carbonated water is effectively reduced, so that the attack of alkaline substances on the surface of the positive electrode material on the binder in the positive electrode glue solution is reduced in the configuration process of the positive electrode material, the double bonds formed by the binder are avoided, the coating effect is improved, and the cell performance is improved.
(4) By using Al2O3The shell doping can effectively reduce the surface residual alkali amount of the anode material: example 9 compared with example 6, example 6 adopts Cs core doping and Mo shell doping, and the weight percentage of the surface residual alkali is 0.12%; in example 9, Nb core doping and Al shell doping are employed, the weight percentage of the surface residual alkali is 0.03%, and the surface residual alkali amount is significantly reduced. Active lithium on the surface of the anode material and CO in the air2、H2O reaction to produce LiOH and Li2CO3Using Al2O3Is coated with Al2O3Can react with active lithium on the surface of the anode material to generate LiAlO2The active lithium content on the surface of the anode material is reduced, so that LiOH and Li on the surface of the anode material are reduced2CO3The content of the residual alkali on the surface of the positive electrode material is effectively reduced, so that the attack of alkaline substances on the surface of the positive electrode material on the binder in the positive electrode glue solution can be reduced in the preparation process of the positive electrode material, the binder is prevented from forming double bonds to generate adhesion, the slurry jelly is prevented from being caused, the coating effect is improved, and the performance of a battery cell is improved.
(5) With Mg (OH)2Shell doping has more stable cycling performance and surfaceThe residual alkali amount is effectively reduced: example 8 compared with example 1, using Mg (OH)2The shell is doped, the capacity retention rate is 95.2 percent and the weight percentage of the surface residual alkali is 0.32 percent after the cycle of 100 circles in the embodiment 1; the capacity retention rate is 101.5% after the cycle of 100 cycles in the embodiment 8, the weight percentage of the surface residual alkali is 0.24%, the cycle performance is more stable, and the surface residual alkali is effectively reduced. The addition of the metal element Mg effectively improves the structural stability of the anode material, reduces the strong side reaction of the anode material and the organic electrolyte, and reduces the impedance of the battery in the charging and discharging processes, thereby improving the electrochemical performance of the anode material, and Mg (OH)2The shell-doped modified cathode material has higher capacity retention rate and more stable cycle performance.
(6) The appropriate thickness of the shell in the core-shell structure can improve the stability and the capacity of the oxide anode material of the lithium ion battery: the thickness of the oxide anode material shell of the lithium ion battery in the embodiment of the invention is 0.05-1.1 μm; if the thickness of the shell is too thin, the shell is easily corroded by electrolyte to expose the core, and the stability of the oxide cathode material of the lithium ion battery is influenced; conversely, if the shell is too thick, the capacity of the oxide positive electrode material of the lithium ion battery is reduced. The lithium ion battery oxide cathode material provided by the embodiment of the invention has proper shell thickness, can balance the stability of the lithium ion battery oxide cathode material and the capacity of the lithium ion battery oxide cathode material, and has optimal stability and capacity.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.
Claims (10)
1. The preparation method of the oxide cathode material of the lithium ion battery is characterized by comprising the following steps of:
step 1, nucleusPreparing a precursor: preparing a first mixed aqueous solution of a Ni source compound, a Co source compound, a M1 source compound and a M3 source compound, mixing the first mixed aqueous solution, a carbonate solution and ammonia water, and reacting under an alkaline condition to obtain a nuclear precursor Ni1-x-y-zCoxM1yM3zCO3(ii) a Wherein M1 is selected from Mn and/or Al; m3 is at least one selected from Mg, Zr, Al, Sc, Ti, W, Sr, Nb, Si, Y, La, Ta, Cs, Ce, Ga, Sn, Er, V, Sm and Mo; x, y and z are mole fractions, x>0，0.01≤y≤0.10，0≤z≤0.02，0.60≤1-x-y-z≤0.96；
Step 2, preparing a shell precursor: preparing a second mixed aqueous solution of a Ni source compound, a Co source compound, a M2 source compound and a M4 source compound, and mixing the second mixed aqueous solution with the nuclear precursor Ni1-x-y-zCoxM1yM3zCO3Mixing with ammonia water and NaOH solution, and precipitating a shell precursor Ni on the surface of the core precursor1-m-n-tComM2nM4t(OH)2Obtaining a precursor with a core-shell structure; wherein m, n and t are mole fractions, m>0，0.2≤n≤0.4，0≤t≤0.02，0.30≤1-m-n-t≤0.70。
And step 3, sintering: mixing and grinding the precursor with the core-shell structure obtained in the step 2, a lithium source and a water-soluble sintering aid, uniformly grinding, sintering, cooling and annealing after sintering, and cooling to room temperature to obtain a target product, wherein the chemical formula of the target product is as follows:
[Lia(Ni1-x-y-zCoxM1yM3z)O2]d·[Lis(Ni1-m-n-tComM2nM4t)O2]1-d
Lia(Ni1-x-y-zCoxM1yM3z)O2is the chemical formula of the core of the oxide cathode material of the lithium ion battery, Lis(Ni1-m-n-tComM2nM4t)O2Is the chemical formula of the shell of the lithium ion battery oxide cathode material; the M2 is selected from Mn and/or Al; the M4 is selectedOne or more selected from alkali metal elements, alkaline earth metal elements, IIIA group elements, IVA group elements, transition metals and rare earth elements; wherein m, n, a, s, t and d are mole fractions, m>0，0.2≤n≤0.4，0≤t≤0.02，0.30≤1-m-n-t≤0.70，1.01≤a≤1.07，1.01≤s≤1.07，0.70≤d≤1。
2. The method for preparing the oxide cathode material of the lithium ion battery according to claim 1, wherein the step 3 further comprises a second sintering step, wherein the product obtained by sintering in the step 3 is cleaned, mixed with a water-soluble sintering aid, ground and sintered.
3. The method for preparing the oxide cathode material of the lithium ion battery according to claim 1, wherein in the steps 1 and 2, the reaction is carried out in the presence of a dispersing agent, and the dispersing agent is one or a mixture of more of a surfactant, polyvinyl alcohol and polyglycerol.
4. The method of claim 3, wherein the surfactant is polyethylene glycol.
5. The method of claim 1, wherein the M3 and M4 are independently selected from at least one of Sc, Zr, V, Ti, Sm, Cs, Mo, W, Ta, Sr, Mg, Nb, and Al.
6. The method of claim 1, wherein z is 0, and wherein the lithium ion battery oxide cathode material has a chemical formula of [ Li ═ Li [a(Ni1-x-yCoxM1y)O2]d·[Lis(Ni1-m-n- tComM2nM4t)O2]1-dX, y, m, n, t, a, s, d are mole fractions, x>0，0.01≤y≤0.10，0.80≤1-x-y≤0.96，m>0，0.2≤n≤0.4，0≤t≤0.02，0.30≤1-m-n-t≤0.70，1.01≤a≤1.07，1.01≤s≤1.07，0.70≤d≤1。
7. The method for preparing the oxide cathode material of the lithium ion battery according to claim 6, wherein: t is 0, and the chemical formula of the lithium ion battery oxide cathode material is [ Li [ ]a(Ni1-x-yCoxM1y)O2]d·[Lis(Ni1-m-nComM2n)O2]1-dX, y, m, n, a, s, d are mole fractions, x>0，0.01≤y≤0.10，0.80≤1-x-y≤0.96，m>0，0.2≤n≤0.4，0.30≤1-m-n≤0.70，1.01≤a≤1.07，1.01≤s≤1.07，0.70≤d≤1。
8. The method for preparing the oxide cathode material of the lithium ion battery according to claim 7, wherein: d is 1, and the chemical formula of the lithium ion battery oxide cathode material is Lia(Ni1-x-yCoxM1y)O2X, y, a are mole fractions, x>0，0.01≤y≤0.10，0.80≤1-x-y≤0.96，1.01≤a≤1.07。
9. The method for preparing the oxide cathode material of the lithium ion battery according to claim 1, wherein: the surface residual alkali content of the lithium ion battery oxide cathode material is 0.03-0.38 wt%.
10. The method for preparing the oxide cathode material of the lithium ion battery according to claim 1, wherein: the capacity retention rate of a battery prepared by the lithium ion battery oxide cathode material after 100 cycles is 95-106% under the multiplying power of 1C.
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