CN103811744B - A kind of preparation method of ternary cathode material of lithium ion battery - Google Patents
A kind of preparation method of ternary cathode material of lithium ion battery Download PDFInfo
- Publication number
- CN103811744B CN103811744B CN201410050211.6A CN201410050211A CN103811744B CN 103811744 B CN103811744 B CN 103811744B CN 201410050211 A CN201410050211 A CN 201410050211A CN 103811744 B CN103811744 B CN 103811744B
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- China
- Prior art keywords
- lithium
- hours
- ion battery
- lithium ion
- preparation
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- 239000010406 cathode material Substances 0.000 title claims abstract description 33
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 205
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 38
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 239000012702 metal oxide precursor Substances 0.000 claims description 35
- 239000011777 magnesium Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 26
- 238000000498 ball milling Methods 0.000 claims description 22
- -1 ester salt Chemical class 0.000 claims description 22
- 150000004703 alkoxides Chemical class 0.000 claims description 20
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 19
- 150000004692 metal hydroxides Chemical class 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- 230000001476 alcoholic effect Effects 0.000 claims description 16
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical group [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052804 chromium Inorganic materials 0.000 claims description 15
- 229910052749 magnesium Inorganic materials 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 12
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- 229910052720 vanadium Inorganic materials 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical group [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 7
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 229910019125 CoaMnb Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 235000019359 magnesium stearate Nutrition 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical group CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical group CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- NRJQYFLFEYOYOP-UHFFFAOYSA-N C(C)(C)O.[Si] Chemical group C(C)(C)O.[Si] NRJQYFLFEYOYOP-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 150000004645 aluminates Chemical group 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical group [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005253 cladding Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- ORPJQHHQRCLVIC-UHFFFAOYSA-N magnesium;propan-2-olate Chemical group CC(C)O[Mg]OC(C)C ORPJQHHQRCLVIC-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 23
- 239000013078 crystal Substances 0.000 abstract description 12
- 239000011230 binding agent Substances 0.000 abstract description 6
- 239000006258 conductive agent Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000008187 granular material Substances 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 3
- 239000011572 manganese Substances 0.000 description 71
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 65
- 239000000126 substance Substances 0.000 description 35
- 239000010936 titanium Substances 0.000 description 21
- 239000002245 particle Substances 0.000 description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 239000011651 chromium Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 15
- 239000002994 raw material Substances 0.000 description 15
- 239000011701 zinc Substances 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 235000013495 cobalt Nutrition 0.000 description 11
- 238000003801 milling Methods 0.000 description 11
- 239000010941 cobalt Substances 0.000 description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- 229910017052 cobalt Inorganic materials 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 229910016722 Ni0.5Co0.2Mn0.3 Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- QKDGGEBMABOMMW-UHFFFAOYSA-I [OH-].[OH-].[OH-].[OH-].[OH-].[V+5] Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[V+5] QKDGGEBMABOMMW-UHFFFAOYSA-I 0.000 description 2
- LXASOGUHMSNFCR-UHFFFAOYSA-D [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O Chemical compound [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O LXASOGUHMSNFCR-UHFFFAOYSA-D 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-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
- 239000004411 aluminium Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- UHNYFORPCMZIEW-UHFFFAOYSA-N carbonic acid;vanadium Chemical compound [V].OC(O)=O UHNYFORPCMZIEW-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 2
- LXMQZGGLHVSEBA-UHFFFAOYSA-N chromium;trihydrate Chemical compound O.O.O.[Cr] LXMQZGGLHVSEBA-UHFFFAOYSA-N 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 description 2
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 2
- WCOATMADISNSBV-UHFFFAOYSA-K diacetyloxyalumanyl acetate Chemical compound [Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WCOATMADISNSBV-UHFFFAOYSA-K 0.000 description 2
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 2
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 2
- 239000011654 magnesium acetate Substances 0.000 description 2
- 235000011285 magnesium acetate Nutrition 0.000 description 2
- 229940069446 magnesium acetate Drugs 0.000 description 2
- UHNWOJJPXCYKCG-UHFFFAOYSA-L magnesium oxalate Chemical compound [Mg+2].[O-]C(=O)C([O-])=O UHNWOJJPXCYKCG-UHFFFAOYSA-L 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- 239000011656 manganese carbonate Substances 0.000 description 2
- 235000006748 manganese carbonate Nutrition 0.000 description 2
- 229940093474 manganese carbonate Drugs 0.000 description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- BBJSDUUHGVDNKL-UHFFFAOYSA-J oxalate;titanium(4+) Chemical compound [Ti+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O BBJSDUUHGVDNKL-UHFFFAOYSA-J 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- FOZHTJJTSSSURD-UHFFFAOYSA-J titanium(4+);dicarbonate Chemical compound [Ti+4].[O-]C([O-])=O.[O-]C([O-])=O FOZHTJJTSSSURD-UHFFFAOYSA-J 0.000 description 2
- OBROYCQXICMORW-UHFFFAOYSA-N tripropoxyalumane Chemical compound [Al+3].CCC[O-].CCC[O-].CCC[O-] OBROYCQXICMORW-UHFFFAOYSA-N 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 2
- 229940007718 zinc hydroxide Drugs 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229910016739 Ni0.5Co0.2Mn0.3(OH)2 Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- LREAURDORMNUIM-UHFFFAOYSA-N [Mg].[Mn].[Co].[Ni] Chemical compound [Mg].[Mn].[Co].[Ni] LREAURDORMNUIM-UHFFFAOYSA-N 0.000 description 1
- PAJORUHCTSSMSM-UHFFFAOYSA-N [Mn].[Co].[Ni].[Ti] Chemical compound [Mn].[Co].[Ni].[Ti] PAJORUHCTSSMSM-UHFFFAOYSA-N 0.000 description 1
- RYUKFAMTKSZIHB-UHFFFAOYSA-N [Ni].[Co].[Mn].[Cr] Chemical compound [Ni].[Co].[Mn].[Cr] RYUKFAMTKSZIHB-UHFFFAOYSA-N 0.000 description 1
- APIDIPGVBRXKEJ-UHFFFAOYSA-N acetic acid titanium Chemical compound [Ti].CC(O)=O.CC(O)=O APIDIPGVBRXKEJ-UHFFFAOYSA-N 0.000 description 1
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- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- YPJCVYYCWSFGRM-UHFFFAOYSA-H iron(3+);tricarbonate Chemical compound [Fe+3].[Fe+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O YPJCVYYCWSFGRM-UHFFFAOYSA-H 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- NMJKIRUDPFBRHW-UHFFFAOYSA-N titanium Chemical group [Ti].[Ti] NMJKIRUDPFBRHW-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to the preparation method of a kind of ternary cathode material of lithium ion battery.Comprise the steps: to first pass through lithium source and presoma prepares aggregate materials A, monocrystalline or class monocrystal material B is prepared the most again by lithium source and presoma, then aggregate materials A is mixed homogeneously with monocrystalline or class monocrystal material B and form material C after sintering, at one layer of coating of powder body outer wrapping of material C, i.e. obtain lithium ion tertiary cathode material.By the aggregate of different grain size and form and monocrystalline or class monocrystalline ternary material are carried out grating, single crystal grain can effectively be filled between the granule of aggregate, graded material is fully contacted with conductive agent and binding agent, the space availability ratio of material and the compacted density of material can be improved simultaneously, and then improve the volume energy density of material, be conducive to giving full play to of material electrical property, improve the effect of material heat stability simultaneously, improve the safety of battery.
Description
Technical field
The present invention relates to the preparation of anode material for lithium-ion batteries, particularly to the preparation of a kind of ternary cathode material of lithium ion battery
Method.
Background technology
Lithium ion battery as a kind of novel secondary cell, have height ratio capacity, have extended cycle life, the feature such as safety is good,
It is widely used in the driving power supply of the portable electronics such as mobile phone, notebook computer.Along with the continuous upgrading of electronic product,
And the development of electric automobile, hybrid vehicle, the requirement to battery energy density improves constantly.
Under same capacity plays premise, market demand improves constantly the volume energy density of battery, namely improves battery and lives
The unit volume loading of property material.The most commercial anode material for lithium-ion batteries is broadly divided into three classes, the phosphorus of olivine structural
Ferrous silicate lithium, specific energy is high, cheap, but himself tap density is low；The LiMn2O4 of spinel structure, produces
Technique is simple, and safety is high, but its in use capacity attenuation very fast, particularly high temperature cyclic performance is poor；Stratiform cobalt
Acid lithium, is that existing market uses widest positive electrode, but cobalt resource is rare, price is high, and toxicity is big, battery security
Difference.
Novel anode trielement composite material nickle cobalt lithium manganate, owing to cheap, good cycle, structural stability are good, jolt ramming
Density is high, becomes more satisfactory positive electrode.But the compacted density of material is little, volume energy density is low to be become restriction it should
Key factor.Chinese patent application prospectus CN101847722A points out: by micron presoma is ground to
After nanoscale, through the method that high temperature sintering prepares micron single crystal granular, the compacted density of raising ternary material, but this system
Preparation Method easily makes agglomerate grain, and particle size distribution is uneven.In Chinese patent application prospectus CN101621125A
Point out: by adding polyvinyl alcohol in process of lapping, improve particle dispersion, use multistep sintering to prepare dispersibility relatively
Good, it is compacted higher single crystal grain, but its complicated process of preparation, the production cycle is long.Chinese patent application prospectus
CN102593442A points out: use nickel, cobalt and manganese oxide and the lithium carbonate with specific median, according to certain calcining
Temperature and atmosphere prepare the lithium electricity positive electrode of high-pressure solid, but the method is narrower to raw-material median area requirement,
Make it apply and there is limitation.Chinese patent application prospectus CN102709541A points out: prepared by solvent-thermal method
Highdensity nickel-cobalt lithium manganate cathode material, but its complicated process of preparation, and it is unfavorable for large-scale production.By varigrained
Material mixing grating, can play the effect promoting tap density, such as Chinese patent application prospectus 102779976A, is situated between
Continued the grating technology of a kind of varigrained cobalt acid lithium.But, when monocrystalline or the class list of ternary material unlike cobalt acid lithium
When Jingjing grain is bigger, chemical property is very poor, so can not be by size monocrystalline different for granularity or class single crystal grain as cobalt acid lithium
It is used in mixed way, it is necessary to the method inventing other.
Summary of the invention
For solving above-mentioned technical problem, the invention discloses the preparation method of a kind of ternary cathode material of lithium ion battery, including
Following steps:
1) lithium source, metal oxide precursor or metal hydroxides presoma are mixed, in air atmosphere 800～1100 DEG C of temperature
Under degree, roasting 6～24 hours, then by the crushing material after roasting be median be the aggregate materials A of 8～25 μm,
The formula of described metal oxide precursor is Ni(1-x-y-z)CoxMnyMzOm, wherein 0 < x < 1,0 < y < 1,0 < z < 1, x+y+z < 1,1
≤ m < 2, M is one or more metallic elements；The formula of described metal hydroxides presoma is Ni(1-x-y-z)CoxMnyMz(OH)n,
Wherein 0 < x < 1,0 < y < 1,0 < z < 1, x+y+z < 1,2≤n < 3, M is one or more metallic elements；
2) lithium source, metal oxide precursor or metal hydroxides presoma are mixed, in air atmosphere 800～1100 DEG C of temperature
Under degree, roasting 6～24 hours, then by the crushing material after roasting be median be the material B of 1～7 μm, described metal
The formula of oxide precursor is Ni(1-a-b-c)CoaMnbNcOm, wherein 0 < a < 1,0 <b < 1,0 < c < 1, a+b+c < 1,1≤m < 2, N is
One or more metallic elements；The formula of described metal hydroxides presoma is Ni(1-a-b-c)CoaMnbNc(OH)n, wherein 0 < a < 1,
0 <b < 1,0 < c < 1, a+b+c < 1,2≤n < 3, N is one or more metallic elements；
3) by aggregate materials A described in step 1) and step 2) described in material B (1～4) in mass ratio: (1～4)
Proportioning ball milling 1～10 hours, then at air atmosphere 200～800 DEG C, roasting 1～5 hours, then be ground into median
It it is the material C of 5～20 μm；
4) material C described in step 3) is dissolved in ethanol, coating is dissolved in organic solution, described cladding will be dissolved with
The organic solution of thing mixes with the alcoholic solution of described material C, after stirring 10 minutes～4 hours, the temperature of 70～100 DEG C
Lower drying 1～the material after being dried for 5 hours；
5) material heat treatment 4～10 hours at air atmosphere 300～800 DEG C after drying described in step 4), i.e. obtain
Ternary cathode material of lithium ion battery.
Further, one or more during lithium source described in step 1) is lithium carbonate, Lithium hydrate and lithium oxalate.
Further, metal-oxide described in step 1) or metal hydroxides presoma include nickel source, cobalt source, manganese source,
Source of iron, zinc source, Tong Yuan, chromium source, magnesium source, aluminum source；Described nickel source include nickelous carbonate, nickel hydroxide, nickel oxalate, nickel oxide,
One or more in nickel acetate；Described cobalt source include cobalt carbonate, cobalt hydroxide, cobalt oxalate, Cobalto-cobaltic oxide, cobalt oxide and
One or more in cobalt acetate；Described manganese source includes in manganese carbonate, manganous hydroxide, manganese oxalate, manganese oxide, manganese acetate
Plant or multiple；Described source of iron includes one or more in hydrated ferric oxide., ferrum oxide, ferric oxalate, ferric acetate；Described zinc source is wrapped
Include one or more in zinc hydroxide, zinc oxide, zinc oxalate, zinc acetate；Copper source include Copper hydrate, copper oxide,
One or more in cupric oxalate, copper acetate；Described chromium source includes in chromic oxide gel, chromium oxide, chromium+oxalic acid, chromium acetate
Plant or multiple；Described magnesium source includes one or more in magnesium hydroxide, magnesium oxide, magnesium oxalate, magnesium acetate；Source of aluminium bag
Include one or more in aluminium hydroxide, aluminium oxide, oxalic acid aluminum, aluminium acetate；Described vanadium source include carbonic acid vanadium, vanadium hydroxide,
One or more in vanadium oxide, vanadium oxalate；Described titanium source includes titanium carbonate, titanium hydroxide, titanium oxide, titanium oxalate, acetic acid
One or more in titanium.
Further, step 1) described in Li atom in lithium source with in described metal-oxide or metal hydroxides presoma
The ratio of the amount of the material of all metallic atom sums is (1.0～1.2): 1.0.
Further, the element M in metal oxide precursor formula described in step 1) be Zr, Zn, Cu, Cr, Mg,
One or more elements in Al, Fe, V, Ti；Element M in metal hydroxides precursor formula described in step 1)
For one or more elements in Zr, Zn, Cu, Cr, Mg, Al, Fe, V, Ti.
Further, step 2) described in lithium source include the one in lithium carbonate, Lithium hydrate, lithium acetate and lithium oxalate or many
Kind.
Further, step 2) described in metal-oxide or metal hydroxides presoma include nickel source, cobalt source, manganese source,
Source of iron, zinc source, Tong Yuan, chromium source, magnesium source, aluminum source, vanadium source and titanium source；Described nickel source includes nickelous carbonate, nickel hydroxide, grass
One or more in acid nickel, nickel oxide, nickel acetate；Described cobalt source includes cobalt carbonate, cobalt hydroxide, cobalt oxalate, four oxidations
One or more in three cobalts, cobalt oxide and cobalt acetate；Described manganese source include manganese carbonate, manganous hydroxide, manganese oxalate, manganese oxide,
One or more in manganese acetate；Described source of iron includes in ferric carbonate, hydrated ferric oxide., ferrum oxide, ferric oxalate, ferric acetate
Plant or multiple；Described zinc source includes one or more in zinc carbonate, zinc hydroxide, zinc oxide, zinc oxalate, zinc acetate；Institute
State copper source and include one or more in curpic carbonate, Copper hydrate, copper oxide, cupric oxalate, copper acetate；Described chromium source includes carbon
One or more in acid chromium, chromic oxide gel, chromium oxide, chromium+oxalic acid, chromium acetate；Described magnesium source includes magnesium carbonate, hydroxide
One or more in magnesium, magnesium oxide, magnesium oxalate, magnesium acetate；Source of aluminium include aluminium carbonate, aluminium hydroxide, aluminium oxide,
One or more in oxalic acid aluminum, aluminium acetate；Described vanadium source includes in carbonic acid vanadium, vanadium hydroxide, vanadium oxide, vanadium oxalate
Plant or multiple；Described titanium source includes one or more in titanium carbonate, titanium hydroxide, titanium oxide, titanium oxalate, acetic acid titanium.
Further, step 2) Li atom in described lithium source and institute in described metal-oxide or metal hydroxides presoma
The ratio having the amount of the material of metallic atom is (1.0～1.2): 1.0.
Further, step 2) described in element N in metal oxide precursor formula be Zr, Zn, Cu, Cr, Mg,
One or more elements in Al, Fe, V, Ti；Step 2) described in element N in metal hydroxides precursor formula
For one or more elements in Zr, Zn, Cu, Cr, Mg, Al, Fe, V, Ti.
Further, step 2) described in material B be monocrystal material or class monocrystal material.
Further, step 4) described in the concentration of alcoholic solution of material C be 1%～85%.Described cladding material organic molten
The concentration of the solution of agent is 0.2%～1%
Further, coating described in step 4) includes Mg element ester salt, Mg element alkoxide, Ti element ester salt, Ti unit
Element alkoxide, Si element ester salt, Si element alkoxide, Al element ester salt, Al element alkoxide, Sn element ester salt, Sn element alkoxide.
Further, above-mentioned Mg element ester salt is magnesium stearate；Above-mentioned Mg element alkoxide is magnesium isopropoxide；Above-mentioned Ti element
Ester salt is butyl titanate；Above-mentioned Ti element alkoxide is isopropyl titanate；Above-mentioned Si element ester salt is butyl silicate；Above-mentioned Si
Element alkoxide is isopropanol silicon；Above-mentioned Al element ester salt is Aluminate；Above-mentioned Al element alkoxide is aluminum isopropylate.；Above-mentioned Sn
Element ester salt is stannic acid ester；Above-mentioned Sn element alkoxide is tin spirit.
Further, above-mentioned steps 4) in dissolve described coating organic solvent be the one in ethanol, acetone and isopropanol
Or it is multiple.
Further, above-mentioned steps 4) described in all metallic atoms and material C described in step 4) in coating organic solution
The ratio of the amount of the material of all metallic element atoms in alcoholic solution is (0.001～0.5): 1.
Further, aggregate materials A described in step 1) and step 2) described in material B chemical formula possibility identical, also
May be different, depend primarily on lithium source, metal oxide precursor or the chemical composition of metal hydroxides presoma.
The feature of the present invention and advantage be:
(1) ternary cathode material of lithium ion battery that the present invention provides is by by the aggregate of different grain size and form and monocrystalline or class
Monocrystalline ternary material carries out grating, and single crystal grain can effectively be filled between the granule of aggregate so that graded material and conduction
Agent and binding agent are fully contacted, and can improve the space availability ratio of material and the compacted density of material simultaneously, and then improve material
Volume energy density, beneficially the giving full play to of material electrical property；
(2) ternary cathode material of lithium ion battery that the present invention provides is by by varigrained aggregate and monocrystalline or class monocrystalline three
Unit's material carries out grating, and single crystal grain can effectively be filled between the granule of aggregate, and the specific surface area of material can be made to adjust
To preferable scope, improve the effect of material heat stability simultaneously, improve the safety of battery.
(3) ternary cathode material of lithium ion battery that the present invention provides is by by varigrained aggregate and monocrystalline or class monocrystalline three
Unit's material carries out grating, and the material after grating carries out secondary Surface coating process, and material so can be made to reduce and the connecing of electrolyte
Contacting surface is amassed, and reduces the material dissolving at electrolyte, and the surface texture making material is more stable, thus improves following of lithium ion battery
Ring performance.100 high temperature circulation volume conservation rates of gained lithium ion battery are more than 90%.
In actual battery, the internal particle of secondary agglomeration body is difficult to directly contact with electrolyte and conductive agent, binding agent, causes
Electronics, ion transmission the most difficult, be unfavorable for giving full play to of material electrical property, and single crystal grain and conductive agent and binding agent
(as shown in Figure 1) can be fully contacted；The monocrystalline of small grain size or class monocrystal material, its specific surface area is relatively big, and therefore specific capacity is relatively
Height, but specific surface area the most also makes its electrochemical stability poor, is not suitable for being used alone, and the specific surface area of aggregate is less,
So by small grain size monocrystalline or class single crystal grain being mixed with the secondary agglomeration body of big granularity, the specific surface area of material can be made to adjust
Whole to preferable scope.It addition, the heat stability of secondary agglomeration body material is poor, and monocrystalline or the heat stability of class single crystal grain
Good, it mixes with secondary agglomeration body, can play the effect improving material heat stability, thus improves the safety of battery.
In sum, secondary agglomeration body and monocrystalline or class single crystal grain bi-material are carried out grating, improve material tap density
Meanwhile, also improve material and binding agent, the contacting of conductive agent, optimize the specific surface area of material, thus further improve
The chemical property of material and heat stability, resulting materials either circulates or high rate performance is better than single monocrystalline or reunion
Body.Finally the material after grating is carried out secondary Surface coating process, material so can be made to reduce the contact area with electrolyte,
In reduction material, manganese is in the dissolving of electrolyte, and the surface texture making material is more stable, thus improves the cyclicity of lithium ion battery
Energy.
Accompanying drawing explanation
Fig. 1 is single crystal grain and conductive agent and the position relationship schematic diagram of binding agent
Fig. 2 is the tertiary cathode material scanning electron microscope diagram (SEM) of specific embodiment 3 preparation
Fig. 3 is the tertiary cathode material scanning electron microscope diagram (SEM) of specific embodiment 6 preparation
Fig. 4 is the tertiary cathode material scanning electron microscope diagram (SEM) of comparative example 1 preparation
Fig. 5 is the tertiary cathode material scanning electron microscope diagram (SEM) of comparative example 2 preparation
Fig. 6 be embodiment three, embodiment six and comparative example one, comparative example two preparation tertiary cathode material 3.0～4.3V, 45
Cycle performance figure under the conditions of DEG C.
Fig. 7 be embodiment three, embodiment six and comparative example one, comparative example two preparation tertiary cathode material 3.0～4.3V, 25
High rate performance comparison diagram under the conditions of DEG C.
Detailed description of the invention
The method present invention being described in further detail below by embodiment, but this is not limitation of the present invention, this area skill
Art personnel are according to the basic thought of invention, and various modifications may be made or improves, without departing from the basic thought of the present invention, all
Within the scope of the present invention.
Specific embodiment 1
By lithium carbonate (lithium source) and a kind of nickel cobalt manganese aluminium hydroxide presoma, (chemical formula is Ni0.5Co0.1Mn0.3Al0.1(OH)2.1Press
According to Li:(Ni+Co+Mn+Al) atomic ratio be 1.20:1.0 ball milling mix 4 hours；Mixed raw material is placed in roasting
In stove, 800 DEG C of roastings 24 hours in air atmosphere；After product after roasting is first passed through coarse crushing, re-use airflow milling and enter
Row essence is broken obtains mean particle size D50For the aggregate materials A of 25um, its chemical formula formula is Li1.2Ni0.5Co0.1Mn0.3Al0.1O2；
By Lithium hydrate (lithium source) and another kind of nickel cobalt manganese hydroxide precursor, (chemical formula is Ni0.5Co0.2Mn0.3(OH)2According to
Li:(Ni+Co+Mn) atomic ratio is that 1.20:1.0 ball milling mixes 4 hours；Mixed raw material is placed in roaster,
1100 DEG C of roastings 6 hours in air atmosphere；After product after roasting is first passed through coarse crushing, re-use airflow milling and carry out smart broken
Broken obtain mean particle size D50For monocrystalline or the class monocrystal material B of 1um, its chemical formula formula is Li1.2Ni0.5Co0.2Mn0.3O2；
It is that 1:1 ball milling mixes 10 hours by aggregate materials A and material B according to mass ratio；Mixed material is placed in roasting
Burn in stove, 200 DEG C of roastings 5 hours in air atmosphere, then be ground into the material C that median is 5 μm；
The material C obtained is placed in equipped with in the stir mixing tank of industrial alcohol, the now alcoholic solution of material C in agitator tank
Concentration is 85%；After stirring 30 minutes, adding the concentration being dissolved in isopropanol is 0.2% aluminum isopropylate. solution, now, different
The ratio of the amount of the material of all metallic atom sums is 0.001:1 to aluminum atom in Aluminum tripropoxide with material C alcoholic solution；Stirring
Mix to be dried in 100 DEG C of water-baths under state and obtain dried material in 1 hour；Dried material is placed in push pedal tunnel cave,
At 300 DEG C, heat treatment 10 hours, sieve after cooling, i.e. obtain the ternary cathode material of lithium ion battery with Al clad.
Specific embodiment 2
According to Li:(Ni+Co+Mn+Mg) atomic ratio be 1.03:1.0, by lithium carbonate (lithium source) and a kind of nickel cobalt manganese magnesium
(chemical formula is Ni to hydroxide precursor0.4Co0.2Mn0.3Mg0.1(OH)2, ball milling mixes 4 hours；Mixed raw material is placed in
In roaster, 1100 DEG C of roastings 6 hours in air atmosphere；After product after roasting is first passed through coarse crushing, re-use air-flow
It is broken that mill carries out essence, the mean particle size D of powder50For the aggregate materials A of 8um, its chemical formula formula is Li1.03Ni0.4Co0.2Mn0.3
Mg0.1O2；
According to Li:(Ni+Co+Mn+Al) atomic ratio be 1.01:1.0, by Lithium hydrate (lithium source) and another kind of nickel cobalt
(chemical formula is Ni to manganese aluminium hydroxide presoma0.5Co0.1Mn0.3Al0.1(OH)2.1, ball milling mixes 4 hours；Mixed raw material is put
In roaster, 800 DEG C of roastings 24 hours in air atmosphere；After product after roasting is first passed through coarse crushing, re-use gas
It is broken that stream mill carries out essence, the mean particle size D of powder50For monocrystalline or the class monocrystal material B of 1um, its chemical formula formula is
Li1.01Ni0.5Co0.1Mn0.3Al0.1O2；
Aggregate materials A and material B being weighed according to the ratio that weight ratio is 1:4, ball milling mixes 1 hour；By mixed
Material is placed in roaster, 800 DEG C of roastings 1 hour in air atmosphere, then is ground into the material C that median is 5 μm.
The material C obtained is placed in equipped with in the stir mixing tank of industrial alcohol, the now alcoholic solution of material C in agitator tank
During concentration 31.84%, after stirring 4 hours, adding the concentration being dissolved in isopropanol is 0.6% aluminum isopropylate. solution, now,
The ratio of the amount of the material of all metallic atom sums is 0.01:1 to aluminum atom in aluminum isopropylate. with material C alcoholic solution；?
It is dried 5 hours in 70 DEG C of water-baths under stirring, obtains dried material；Dried material is placed in push pedal tunnel cave
In, at 800 DEG C, heat treatment 4 hours, sieve after cooling, i.e. obtain the lithium ion battery tertiary cathode material with Al clad
Material.
Specific embodiment 3
According to Li:(Ni+Co+Mn) atomic ratio be 1.06:1.0, by lithium carbonate (lithium source) and a kind of nickel cobalt manganese hydroxide
(chemical formula is Ni to thing presoma0.5Co0.2Mn0.3(OH)2, ball milling mixes 4 hours；Mixed raw material is placed in roaster,
960 DEG C of roastings 10 hours in air atmosphere；After product after roasting is first passed through coarse crushing, re-use airflow milling and carry out smart broken
Broken, the aggregate materials A that mean particle size D 50 is 10um of powder, its chemical formula is Li1.06Ni0.5Co0.2Mn0.3O2。
According to Li:(Ni+Co+Mn) atomic ratio be 1.06:1.0, by lithium carbonate (lithium source) and another kind of nickel cobalt manganese hydrogen-oxygen
(chemical formula is Ni to compound presoma0.5Co0.2Mn0.3(OH)2, ball milling mixes 4 hours；Mixed raw material is placed in roaster,
960 DEG C of roastings 10 hours in air atmosphere；After product after roasting is first passed through coarse crushing, re-use airflow milling and carry out smart broken
Broken, the monocrystalline that mean particle size D 50 is 3um of powder or class monocrystal material B, its chemistry is Li1.06Ni0.5Co0.2Mn0.3O2。
Aggregate materials A and material B being weighed according to weight ratio 1:2, ball milling mixes 6 hours；Mixed material is placed in
In roaster, 400 DEG C of roastings 2 hours in air atmosphere, then it is ground into the material C that median is 9 μm.
The mixed-powder obtained is placed in equipped with in the stir mixing tank of industrial alcohol, the now alcoholic solution of material C in agitator tank
Concentration time 8.5%, after stirring 10 minutes, adding the concentration that is dissolved in isopropanol is 0.9% aluminum isopropylate. solution, the most different
Aluminum atom in Aluminum tripropoxide is 0.05:1 with the ratio of the amount of the material of all metallic atom sums in material C alcoholic solution；?
It is dried 2 hours in 100 DEG C of water-baths under stirring；Dried material is placed in push pedal tunnel cave, at 750 DEG C at heat
Manage 5 hours, sieve after cooling, i.e. obtain the ternary cathode material of lithium ion battery with Al clad.
Material is carried out compacted density, high temperature cyclic performance and high rate performance test.
Compacted density uses dry powder compacted density, uses the sample of 5g to join in the mould of Φ 10, uses 100Mpa's
Pressure carries out dry powder compacting, and pressurize retreats mould in 1 minute, measures thickness, can be calculated according to ρ=m/v, in suitable granularity
Under, material dry powder compacted density prepared by the inventive method is 3.91g/cm3, compacted density is improved significantly.
Cycle performance and high rate performance test use 2032 type button cell tests, and in button cell, the ratio of positive electrode is:
Active substance: SP: PVDF=90: 5: 5, uses Clgard2300 type barrier film, and negative pole uses metal lithium sheet, charge and discharge
Piezoelectric voltage is 3.0～4.3V.After grating, the chemical property of material realizes bigger raising, sees Fig. 6 and Fig. 7.
Specific embodiment 4
According to Li:(Ni+Co+Mn+Cr) atomic ratio be 1.06:1.0, by lithium carbonate (lithium source) and a kind of nickel cobalt manganese chromium
(chemical formula is Ni to hydroxide precursor0.5Co0.1Mn0.3Cr0.1(OH)2.1, ball milling mixes 4 hours；Mixed raw material is placed in roasting
Burn in stove, 960 DEG C of roastings 10 hours in air atmosphere；After product after roasting is first passed through coarse crushing, re-use airflow milling
Carry out essence broken, the mean particle size D of powder50For the aggregate materials A of 10um, its chemical formula is Li1.06Ni0.5Co0.1Mn0.3
Cr0.1O2。
According to Li:(Ni+Co+Mn) atomic ratio be 1.06:1.0, by lithium acetate (lithium source) and another kind of nickel cobalt manganese hydrogen-oxygen
(chemical formula is Ni to compound presoma0.5Co0.2Mn0.3(OH)2, ball milling mixes 4 hours；Mixed raw material is placed in roaster,
960 DEG C of roastings 10 hours in air atmosphere；After product after roasting is first passed through coarse crushing, re-use airflow milling and carry out smart broken
Broken, the mean particle size D of powder50For monocrystalline or the class monocrystal material B of 3um, its chemical formula is Li1.06Ni0.5Co0.2Mn0.3O2。
Being weighed according to the ratio that weight ratio is 1:1 by the powder of aggregate materials A and material B, ball milling mixes 6 hours；Will be mixed
Material after conjunction is placed in roaster, 400 DEG C of roastings 2 hours in air atmosphere, then is ground into the material that median is 8 μm
Material C.
The material C obtained being placed in equipped with in the stir mixing tank of industrial alcohol, now the concentration of material C is 5.52%, stirring
After 10 minutes, add and be dissolved in the aluminum isopropylate. solution that concentration in isopropanol is 0.93%, now the aluminum atom in aluminum isopropylate. with
In material C alcoholic solution, the ratio of the amount of the material of all metallic atoms is 0.08:1；Under stirring in 100 DEG C of water-baths
It is dried 3 hours；Being placed in push pedal tunnel cave by dried material, at 750 DEG C, heat treatment 5 hours, sieve after cooling,
I.e. obtain the ternary cathode material of lithium ion battery with Al clad.
This material is carried out compacted density and electrochemical property test, and method is with embodiment three, and dry powder compacted density is 3.89g/cm3,
As can be seen from Figures 6 and 7, after grating, the chemical property of material realizes bigger raising.
Specific embodiment 5
According to Li:(Ni+Co+Mn+Ti) atomic ratio be 1.06:1.0, by Lithium hydrate (lithium source) and a kind of nickel cobalt manganese
(chemical formula is Ni to titanium hydroxide precursor0.5Co0.2Mn0.2Ti0.1(OH)2.2, ball milling mixes 4 hours；Mixed raw material is placed in
In roaster, 960 DEG C of roastings 10 hours in air atmosphere；After product after roasting is first passed through coarse crushing, re-use air-flow
It is broken that mill carries out essence, and the aggregate materials A that mean particle size D 50 is 10um of powder, its chemical formula is Li1.06Ni0.5Co0.2Mn0.2
Ti0.1O2。
According to Li:(Ni+Co+Mn+Ti) atomic ratio be 1.06:1.0, by lithium oxalate (lithium source) and nickel cobalt manganese titanium hydrogen-oxygen
(chemical formula is Ni to compound presoma0.5Co0.2Mn0.2Ti0.1(OH)2.2, ball milling mixes 4 hours；Mixed raw material is placed in roaster
In, 960 DEG C of roastings 10 hours in air atmosphere；After product after roasting is first passed through coarse crushing, re-use airflow milling and carry out
Essence is broken, and the monocrystalline that mean particle size D 50 is 7um of powder or class monocrystal material B, its chemical formula is
Li1.06Ni0.5Co0.2Mn0.2Ti0.1O2。
Being weighed according to the ratio that weight ratio is 1:2 by the powder of aggregate materials A and material B, ball milling mixes 6 hours；Will be mixed
Material after conjunction is placed in roaster, 400 DEG C of roastings 2 hours in air atmosphere, then to be ground into median be 7 μm
Material C.
Being placed in the material C obtained equipped with in the stir mixing tank of industrial alcohol, now the concentration of the alcoholic solution of material C is
1%, after stirring 10 minutes, add the aluminum isopropylate. solution that concentration is 0.98% dissolved in acetone, now in aluminum isopropylate.
Aluminum atom be 0.5:1 with the ratio of the amount of the material of all metallic atoms in material C alcoholic solution；In 100 under stirring
DEG C water-bath is dried 4 hours；Dried material is placed in push pedal tunnel cave, heat treatment 5 hours at 750 DEG C, cooling
After sieve, i.e. obtain the ternary cathode material of lithium ion battery with Al clad.
Specific embodiment 6
According to Li:(Ni+Co+Mn) atomic ratio be 1.06:1.0, by lithium oxalate (lithium source) and a kind of nickel cobalt manganese hydroxide
(chemical formula is Ni to thing presoma0.5Co0.2Mn0.3(OH)2, ball milling mixes 4 hours；Mixed raw material is placed in roaster,
960 DEG C of roastings 10 hours in air atmosphere；After product after roasting is first passed through coarse crushing, re-use airflow milling and carry out smart broken,
The aggregate materials A that mean particle size D 50 is 10um of powder, its chemical formula is Li1.06Ni0.5Co0.2Mn0.3O2。
According to Li:(Ni+Co+Mn) atomic ratio be 1.06:1.0, before Quilonorm (SKB) (lithium source) and nickel cobalt manganese hydroxide
(chemical formula is Ni to drive body0.5Co0.2Mn0.3(OH)2, ball milling mixes 4 hours；Mixed raw material is placed in roaster, at air
960 DEG C of roastings 10 hours in atmosphere；After product after roasting is first passed through coarse crushing, re-use airflow milling and carry out smart broken, powder
The monocrystalline that mean particle size D 50 is 3um at end or class monocrystal material B, its chemical formula is Li1.06Ni0.5Co0.2Mn0.3O2。
Being weighed according to weight ratio 1:1 by the powder of aggregate materials A and material B, ball milling mixes 6 hours；By mixed thing
Material is placed in roaster, 400 DEG C of roastings 2 hours in air atmosphere, then is ground into the material C that median is 6 μm.
Being placed in the material C obtained equipped with in the stir mixing tank of industrial alcohol, now the concentration of material C alcoholic solution is
48.3%, after stirring 10 minutes, add the butyl titanate solution that concentration is 0.51% being dissolved in isopropanol, now, titanium
Titanium atom in acid four butyl esters is 0.005:1 with the ratio of the amount of the material of all metallic atoms in material C alcoholic solution；In stirring
It is dried 1 hour in 100 DEG C of water-baths under state；Dried material is placed in push pedal tunnel cave, heat treatment 5 at 850 DEG C
Hour, sieve after cooling, i.e. obtain the ternary cathode material of lithium ion battery with Ti clad.
Material is carried out compacted density, high temperature cyclic performance and high rate performance test.Method is with embodiment three, dry powder compacted density
For 3.91g/cm3。
Specific embodiment 7
Roughly the same with specific embodiment 1, differ only in:
1, preparing metal hydroxides presoma used by aggregate materials A is Ni0.5Co0.2Mn0.2Zr0.1(OH)2.9；
2, preparing metal oxide precursor used by material B is Ni0.4Co0.2Mn0.3Mg0.1O1.2；
3, the powder of aggregate materials A and material B is weighed according to the ratio that weight ratio is 4:1.
Specific embodiment 8
Roughly the same with specific embodiment 1, differ only in:
1, preparing metal hydroxides presoma used by aggregate materials A is Ni0.4Co0.2Mn0.3Zn0.1(OH)2；
2, preparing metal oxide precursor used by material B is Ni0.4Co0.2Mn0.3Cr0.1O1.2。
Specific embodiment 9
Roughly the same with specific embodiment 1, differ only in:
1, preparing metal hydroxides presoma used by aggregate materials A is Ni0.4Co0.2Mn0.3Cu0.1(OH)2；
2, preparing metal oxide precursor used by material B is Ni0.5Co0.2Mn0.2Al0.1O1.1；
Specific embodiment 10
Roughly the same with specific embodiment 1, differ only in:
1, preparing metal hydroxides presoma used by aggregate materials A is Ni0.4Co0.2Mn0.3Fe0.1(OH)2；
2, preparing metal oxide precursor used by material B is Ni0.5Co0.2Mn0.2Ti0.1O1.1。
Specific embodiment 11
Roughly the same with specific embodiment 1, differ only in:
1, preparing metal hydroxides presoma used by aggregate materials A is Ni0.5Co0.1Mn0.3V0.1(OH)2.1；
2, preparing metal oxide precursor used by material B is Ni0.5Co0.2Mn0.2Zr0.1O1.1。
Specific embodiment 12
Roughly the same with specific embodiment 1, differ only in:
1, preparing metal oxide precursor used by aggregate materials A is Ni0.5Co0.1Mn0.3V0.1O1.9；
2, preparing metal oxide precursor used by material B is Ni0.4Co0.2Mn0.3Zn0.1O1.1；
3, in step 4), coating is magnesium stearate, and magnesium stearate is dissolved in ethanol solution.
Specific embodiment 13
Roughly the same with specific embodiment 1, differ only in:
1, preparing metal oxide precursor used by aggregate materials A is Ni0.4Co0.2Mn0.3Fe0.1O1.5；
2, preparing metal oxide precursor used by material B is Ni0.4Co0.2Mn0.3Cu0.1O1.2；
3, in step 4), coating is isopropyl titanate, and isopropyl titanate is dissolved in acetone soln.
Specific embodiment 14
Roughly the same with specific embodiment 1, differ only in:
1, preparing metal oxide precursor used by aggregate materials A is Ni0.4Co0.2Mn0.3Cu0.1O1.1；
2, preparing metal oxide precursor used by material B is Ni0.5Co0.1Mn0.3V0.1O1.9；
3, in step 4), coating is butyl silicate, and butyl silicate is dissolved in acetone soln.
Specific embodiment 15
Roughly the same with specific embodiment 1, differ only in:
1, preparing metal oxide precursor used by aggregate materials A is Ni0.4Co0.2Mn0.3Zn0.1O；
2, preparing metal oxide precursor used by material B is Ni0.4Co0.2Mn0.3Fe0.1O1.5；
2, in step 4), coating is isopropanol silicon.
Specific embodiment 16
Roughly the same with specific embodiment 1, differ only in:
1, preparing metal oxide precursor used by aggregate materials A is Ni0.5Co0.2Mn0.2Zr0.1O1.1；
2, preparing metal oxide precursor used by material B is Ni0.4Co0.2Mn0.3Mg0.1(OH)2；
3, in step 4), coating is Aluminate.
Specific embodiment 17
Roughly the same with specific embodiment 1, differ only in:
1, preparing metal oxide precursor used by aggregate materials A is Ni0.5Co0.2Mn0.2Ti0.1O1.1；
2, preparing metal oxide precursor used by material B is Ni0.5Co0.1Mn0.3Cr0.1(OH)2.1；
3, in step 4), coating is aluminum isopropylate..
Specific embodiment 18
Roughly the same with specific embodiment 1, differ only in:
1, preparing metal oxide precursor used by aggregate materials A is Ni0.5Co0.2Mn0.2Al0.1O1.2；
2, preparing metal oxide precursor used by material B is Ni0.5Co0.2Mn0.2Zr0.1(OH)2.9；
3, in step 4), coating is stannic acid ester.
Specific embodiment 19
Roughly the same with specific embodiment 1, differ only in:
1, preparing metal oxide precursor used by aggregate materials A is Ni0.4Co0.2Mn0.3Cr0.1O1.1；
2, preparing metal oxide precursor used by material B is Ni0.4Co0.2Mn0.3Zn0.1(OH)2；
3, in step 4), coating is tin spirit.
Specific embodiment 20
Roughly the same with specific embodiment 1, differ only in:
1, preparing metal oxide precursor used by aggregate materials A is Ni0.4Co0.2Mn0.3Mg0.1O1.1；
2, preparing metal oxide precursor used by material B is Ni0.4Co0.2Mn0.3Cu0.1(OH)2
3, in step 4), coating is magnesium isopropoxide.
Specific embodiment 21
Roughly the same with specific embodiment 1, differ only in and prepare metal oxide precursor used by material B and be
Ni0.4Co0.2Mn0.3Fe0.1(OH)2。
Specific embodiment 22
Roughly the same with specific embodiment 1, differ only in: preparing metal oxide precursor used by material B is
Ni0.4Co0.2Mn0.3V0.1(OH)2。
Comparative example 1
According to Li:(Ni+Co+Mn) atomic ratio be 1.06:1.0, by lithium carbonate (lithium source) and a kind of nickel cobalt manganese hydroxide
(chemical formula is Ni to thing presoma0.5Co0.2Mn0.3(OH)2, ball milling mixes 4 hours；Mixed raw material is placed in roaster,
960 DEG C of roastings 10 hours in air atmosphere；After product after roasting is first passed through coarse crushing, re-use airflow milling and carry out smart broken,
The aggregate materials A that mean particle size D 50 is 10um of powder, its chemical formula is Li1.06Ni0.5Co0.2Mn0.3O2。。
By the aggregate materials A that obtains equipped with in the stir mixing tank of industrial alcohol, after stirring 10 minutes, add be dissolved in different
Aluminum isopropylate. solution (the aluminum atom in aluminum isopropylate. and the amount of the material of all metal units atom in aggregate materials A in propanol
Ratio be 0.005:1)；It is dried in 100 DEG C of water-baths under stirring；Dried material is placed in push pedal tunnel cave,
At 750 DEG C, heat treatment 5 hours, sieve after cooling, i.e. obtain the aggregate tertiary cathode material with Al clad.
This material is carried out compacted density and electrochemical property test, and method is with embodiment three, and dry powder compacted density is 3.85g/cm3,
Compacted density significantly lower than graded material.As can be seen from Figures 6 and 7, by the electricity of the ternary material of size particles grating
Chemical property is better than single particle.
Comparative example 2
According to Li:(Ni+Co+Mn) atomic ratio be 1.06:1.0, by lithium carbonate (lithium source) and a kind of nickel cobalt manganese hydroxide
(chemical formula is Ni to thing presoma0.5Co0.2Mn0.3(OH)2, ball milling mixes 4 hours；Mixed raw material is placed in roaster,
960 DEG C of roastings 10 hours in air atmosphere；After product after roasting is first passed through coarse crushing, re-use airflow milling and carry out smart broken,
The monocrystalline that mean particle size D 50 is 3um of powder or class monocrystal material B, its chemical formula is Li1.06Ni0.5Co0.2Mn0.3O2。
The aggregate materials A obtained is placed in equipped with in the stir mixing tank of industrial alcohol, after stirring 10 minutes, adds and dissolve
Aluminum isopropylate. solution (the aluminum atom in aluminum isopropylate. and the material of all metallic atoms in aggregate materials A in isopropanol
The ratio of amount is 0.005:1) it is dried in 100 DEG C of water-baths under stirring；Dried material is placed in push pedal tunnel cave,
At 750 DEG C, heat treatment 5 hours, sieve after cooling, i.e. obtain the single crystal grain tertiary cathode material with Al clad.
This material is carried out electrochemical property test, and method is with embodiment three, as can be seen from Figures 6 and 7, by size
The ternary material chemical property that grade is joined is better than single particle.
Claims (7)
1. a preparation method for ternary cathode material of lithium ion battery, comprises the steps:
1) lithium source, metal oxide precursor or metal hydroxides presoma are mixed, in air atmosphere 800～1100 DEG C of temperature
Under degree, roasting 6～24 hours, then by the crushing material after roasting be median be the aggregate materials A of 8～25 μm,
The formula of described metal oxide precursor is Ni(1-x-y-z)CoxMnyMzOm, wherein 0 < x < 1,0 < y < 1,0 < z < 1, x+y+z < 1,1
≤ m < 2, M is one or more elements in Zr, Zn, Cu, Cr, Mg, Al, Fe, V, Ti；Described metallic hydrogen aoxidizes
The formula of thing presoma is Ni(1-x-y-z)CoxMnyMz(OH)n, wherein 0 < x < 1,0 < y < 1,0 < z < 1, x+y+z < 1,2≤n < 3, M
For one or more elements in Zr, Zn, Cu, Cr, Mg, Al, Fe, V, Ti；
2) lithium source, metal oxide precursor or metal hydroxides presoma are mixed, in air atmosphere 800～1100 DEG C of temperature
Under degree, roasting 6～24 hours, then by the crushing material after roasting be median be monocrystalline or the class monocrystal material of 1～7 μm
B, the formula of described metal oxide precursor is Ni(1-a-b-c)CoaMnbNcOm, wherein 0 < a < 1,0 <b < 1,0 < c < 1, a+b+c < 1,1
≤ m < 2, N is one or more elements in Zr, Zn, Cu, Cr, Mg, Al, Fe, V, Ti；Described metal hydrogen-oxygen
The formula of compound presoma is Ni(1-a-b-c)CoaMnbNc(OH)n, wherein 0 < a < 1,0 <b < 1,0 < c < 1, a+b+c < 1,2≤n < 3, N
For one or more elements in Zr, Zn, Cu, Cr, Mg, Al, Fe, V, Ti；
3) by step 1) described in aggregate materials A and step 2) described in monocrystalline or class monocrystal material B in mass ratio (1～
4): the proportioning ball milling 1 of (1～4)～10 hours, then at air atmosphere 200～800 DEG C, roasting 1～5 hours, then pulverize
The material C becoming median to be 5～20 μm；
4) by step 3) described material C is dissolved in ethanol, is dissolved in organic solution by coating, will be dissolved with described cladding
The organic solution of thing mixes with the alcoholic solution of described material C, after stirring 10 minutes～4 hours, the temperature of 70～100 DEG C
Lower drying 1～the material after being dried for 5 hours, described coating includes Mg element ester salt, Mg element alkoxide, Ti element
Ester salt, Ti element alkoxide, Si element ester salt, Si element alkoxide, Al element ester salt, Al element alkoxide, Sn element ester salt,
Sn element alkoxide；
5) by step 4) described in dry after material heat treatment 4～10 hours at air atmosphere 300～800 DEG C, i.e. obtain
Ternary cathode material of lithium ion battery.
2. the preparation method of ternary cathode material of lithium ion battery as claimed in claim 1, it is characterised in that step 1) in
Described lithium source is one or more in lithium carbonate, Lithium hydrate and lithium oxalate.
3. the preparation method of ternary cathode material of lithium ion battery as claimed in claim 1, it is characterised in that step 1) in
Li atom in described lithium source and the material of all metallic atom sums in described metal-oxide or metal hydroxides presoma
The ratio of amount be (1.0～1.2): 1.0.
4. the preparation method of ternary cathode material of lithium ion battery as claimed in claim 1, it is characterised in that step 2) in
Described lithium source is one or more in lithium carbonate, Lithium hydrate, lithium acetate and lithium oxalate.
5. the preparation method of ternary cathode material of lithium ion battery as claimed in claim 1, it is characterised in that described Mg unit
Element ester salt is magnesium stearate；Described Mg element alkoxide is magnesium isopropoxide；Described Ti element ester salt is butyl titanate；Described Ti
Element alkoxide is isopropyl titanate；Described Si element ester salt is butyl silicate；Described Si element alkoxide is isopropanol silicon；Described
Al element ester salt is Aluminate；Described Al element alkoxide is aluminum isopropylate.；Described Sn element ester salt is stannic acid ester；Described Sn
Element alkoxide is tin spirit.
6. the preparation method of ternary cathode material of lithium ion battery as claimed in claim 1, it is characterised in that step 4) in
The organic solvent dissolving described coating is one or more in ethanol, acetone and isopropanol.
7. the preparation method of ternary cathode material of lithium ion battery as claimed in claim 1, it is characterised in that step 4) in
All metallic atoms in described coating organic solution and step 4) described in all metallic atoms in material C alcoholic solution
The ratio of the amount of material is (0.001～0.5): 1.
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