CN113764670A - 导电聚合物修饰改性无钴单晶三元正极材料及其制备方法 - Google Patents
导电聚合物修饰改性无钴单晶三元正极材料及其制备方法 Download PDFInfo
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- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 55
- 239000013078 crystal Substances 0.000 title claims abstract description 48
- 239000010406 cathode material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000011572 manganese Substances 0.000 claims abstract description 60
- 239000007774 positive electrode material Substances 0.000 claims abstract description 43
- 229910010881 LiInO2 Inorganic materials 0.000 claims abstract description 36
- 238000001354 calcination Methods 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 13
- 229910013100 LiNix Inorganic materials 0.000 claims abstract description 11
- 238000000975 co-precipitation Methods 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 229910052738 indium Inorganic materials 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910013716 LiNi Inorganic materials 0.000 claims description 19
- 229920000128 polypyrrole Polymers 0.000 claims description 15
- MLUWDMSBBKQRCG-UHFFFAOYSA-N manganese nickel zirconium Chemical compound [Mn].[Ni].[Zr] MLUWDMSBBKQRCG-UHFFFAOYSA-N 0.000 claims description 12
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
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- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 5
- 229940099596 manganese sulfate Drugs 0.000 claims description 5
- 239000011702 manganese sulphate Substances 0.000 claims description 5
- 235000007079 manganese sulphate Nutrition 0.000 claims description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- -1 polyphenylene Polymers 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 claims description 3
- 229920001197 polyacetylene Polymers 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 229920000123 polythiophene Polymers 0.000 claims description 3
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- AMNSWIGOPDBSIE-UHFFFAOYSA-H indium(3+);tricarbonate Chemical compound [In+3].[In+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O AMNSWIGOPDBSIE-UHFFFAOYSA-H 0.000 claims description 2
- 229910000337 indium(III) sulfate Inorganic materials 0.000 claims description 2
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000003980 solgel method Methods 0.000 claims description 2
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 claims description 2
- 239000010405 anode material Substances 0.000 abstract description 31
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 229910017052 cobalt Inorganic materials 0.000 description 11
- 239000010941 cobalt Substances 0.000 description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 11
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
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- 239000012300 argon atmosphere Substances 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 239000008139 complexing agent Substances 0.000 description 4
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- 239000011777 magnesium Substances 0.000 description 4
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- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
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- 150000001875 compounds Chemical class 0.000 description 2
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- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
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- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- 239000011780 sodium chloride Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910011854 Li4Mn2O5 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910012463 LiTaO3 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910003684 NixCoyMnz Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910010252 TiO3 Inorganic materials 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
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- 239000007772 electrode material Substances 0.000 description 1
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- 230000002401 inhibitory effect Effects 0.000 description 1
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- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
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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
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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Abstract
导电聚合物修饰改性无钴单晶三元正极材料及其制备方法，所述导电聚合物修饰改性无钴单晶三元正极材料为LiNixMnyZrzO2@LiInO2@EAP，其制备方法包括下列步骤：(1)将镍源、锰源和锆源加入去离子水中，进行共沉淀法反应，得三元正极材料前驱体；(2)将所述三元正极材料前驱体与锂源混合，进行煅烧，得无钴三元正极材料；(3)将所述无钴三元正极材料与铟源、锂源混合，进行煅烧，得锂化物包覆的无钴三元正极材料；(4)将所述锂化物包覆的无钴三元正极材料与导电聚合物混合，然后进行热处理，即成。本发明正极材料制备方法简单，电化学性能好。
Description
技术领域
本发明涉及一种锂离子电池正极材料及其制备方法，尤其是涉及一种导电聚合物修饰改性无钴单晶三元正极材料及其制备方法。
背景技术
近年来，锂离子电池被广泛应用于电子产品和新能源汽车领域。锂离子电池正极材料是锂离子电池的重要组成部分，常用的锂离子电池正极材料有钴酸锂、镍钴锰三元正极材料(NCM)和镍钴铝三元正极材料(NCA)，其中钴是必不可少的重要元素之一。然而，随着钴资源的不断开发，钴资源越来越少，钴的价格也逐步增长。制作含钴的锂离子电池正极材料的成本也不断增加。随着电动汽车行业的迅猛发展，钴资源将面临供不应求的难题。因此，迫切需要降低传统锂离子电池正极材料中钴元素的含量，以利于可持续发展。
CN107516731A公开了一种改性锂离子电池正极材料及其制备方法，其中改性锂离子电池正极材料包括正极材料内核及包覆于正极材料内核表面的复合包覆层，所述复合包覆层由含有Li0.5La0.5TiO3的第一包覆层和含有LiTaO3的第二包覆层组成，所述正极材料内核结构式为Li1±εNixCoyMnzM1-x-y-zO2，其中，-0.1＜ε＜0.1，0＜x，y，z＜1，M为Mg、Sr、Ba、Al、In、Ti、V、Mn、Co、Ni、Y、Zr、Nb、Mo、W、La、Ce、Nd、Sm等元素中的一种。但该方法所得正极材料仍含有钴元素，并且还含有La元素，生产成本高。
CN108682843A公开了一种岩盐型锂离子电池正极材料的制备方法，包括以下步骤：(1)将锂源、高价态锰源、低价态锰源经研磨混合均匀后于惰性气氛下煅烧，随炉冷却研磨得到LiMnO2前驱体；(2)将步骤(1)中得到的LiMnO2前驱体与过氧化锂经研磨混合均匀后于惰性气氛下煅烧并退火处理，随炉冷却即得到上述岩盐型锂离子电池正极材料Li4Mn2O5。该方法所得正极材料虽然不含钴元素，但是该正极材料电化学性能欠佳。
发明内容
本发明要解决的技术问题是，克服现有技术存在的上述缺陷，提供一种制备方法简单，生产成本低，电化学性能好的导电聚合物修饰改性无钴单晶三元正极材料。
本发明进一步要解决的技术问题是，提供一种操作简便的导电聚合物修饰改性无钴单晶三元正极材料的制备方法。
本发明解决其技术问题采用的技术方案是，一种导电聚合物修饰改性无钴单晶三元正极材料，所述导电聚合物修饰改性无钴单晶三元正极材料为LiNixMnyZrzO2@LiInO2@EAP，其中0.8≤x<1，0<y≤0.1，0<z≤0.1，x+y+z＝1，EAP为导电聚合物。
进一步，所述导电聚合物为聚乙炔(PA)、聚噻吩(PTh)、聚吡咯(PPy)、聚苯胺(PAn)、聚苯撑(PPP)和聚苯撑乙烯(PPVs)中的一种或多种。
本发明进一步解决其技术问题采用的技术方案是，一种导电聚合物修饰改性无钴单晶三元正极材料的制备方法，包括下列步骤：
(1)将镍源、锰源和锆源加入去离子水中，搅拌均匀，然后进行共沉淀法反应，得镍锰锆三元正极材料前驱体；
(2)将步骤(1)所得的镍锰锆三元正极材料前驱体与锂源混合，进行煅烧，得无钴三元正极材料LiNixMnyZrzO2；
(3)将步骤(2)所得的无钴三元正极材料LiNixMnyZrzO2与铟源、锂源通过溶胶凝胶法混合，蒸发溶剂，干燥，得混合物；然后将所述混合物进行煅烧，得无钴单晶三元正极材料LiNixMnyZrzO2@LiInO2；
(4)将步骤(3)所得的无钴单晶三元正极材料LiNixMnyZrzO2@LiInO2与导电聚合物混合，球磨均匀，然后进行热处理，得导电聚合物修饰改性无钴单晶三元正极材料LiNixMnyZrzO2@LiInO2@EAP。
进一步，步骤(1)中，所述镍源为乙酸镍、硝酸镍和硫酸镍中的一种或多种；所述锰源为乙酸锰、硝酸锰和硫酸锰中的一种或多种；所述锆源为乙酸锆、硝酸锆、硫酸锆和碳酸锆中的一种或多种。
进一步，步骤(1)中，进行共沉淀反应时，加入沉淀剂NaOH溶液和络合剂NH3·H2O溶液，沉淀剂NaOH溶液的浓度为4～8mol/L，NH3·H2O溶液的浓度为4～10mol/L，优选5～8mol/L。
进一步，步骤(1)中，所述共沉淀反应的时间为10～16h。
进一步，步骤(2)中，所述镍锰锆三元正极材料前驱体与锂源的摩尔比为1:1.03～1.09。
进一步，步骤(2)中，所述煅烧分为两段烧结，第一段烧结的煅烧温度为400～600℃，煅烧的时间为4～6h，第二段煅烧的煅烧温度为700～850℃，煅烧的时间为10～15h。
进一步，步骤(3)中，所述铟源为乙酸铟、硝酸铟、硫酸铟和碳酸铟中的一种或多种；所述锂源为氢氧化锂、碳酸锂和硝酸锂中的一种或多种。
进一步，步骤(3)中，所述溶剂为乙醇、乙二醇和异丙醇中的一种或多种；所述蒸发的温度为65～100℃；所述干燥的温度为110～150℃，所述干燥的时间为10-15h。
进一步，步骤(3)中，所述煅烧的温度为400～650℃；所述煅烧的时间为8～12h；所述煅烧的气氛为氩气、氧气或空气。
进一步，步骤(4)中，所述热处理的温度为100～300℃，优选200～250℃；所述热处理的时间为2～8h，优选5～6h；所述热处理的气氛是氩气或氮气。
与现有技术相比，本发明具有以下有益效果：
(1)本发明用含锂化合物LiInO2与导电聚合物对无钴三元正极材料LiNixMnyZrzO2进行双重改性，LiInO2和导电聚合物的双重改性结合了LiInO2优异的离子导电性和导电聚合物良好的电子导电性，不仅减缓了充放电过程中电解液对三元正极材料LiNixMnyZrzO2的腐蚀速度，而且提高了三元正极材料LiNixMnyZrzO2的结构稳定性，导电性和离子传输速率；
(2)研究表明，在正极材料中Zr元素的化合价稳定，不会发生化学反应，能有效维持三元层状正极材料结构的稳定，Zr元素还具有优异的金属强度和热稳定性，能增强正极材料的机械强度和热稳定性，含Zr元素的化合物的价格比钴资源便宜，用Zr元素取代正极材料中的钴元素降低了正极材料的生产成本；
(3)研究表明，除Zr元素外，用其他元素(如镁)替代Co元素制得的正极材料组装的锂离子电池的电化学性能不如Zr元素，且本发明导电聚合物修饰的无钴单晶三元正极材料中掺杂的Zr元素、包覆层LiInO2和导电聚合物之间具有协同作用，通过其协同作用，不仅有利于提高锂离子的传输性能，抑制HF的形成，还能减少无钴单晶三元正极材料内部裂纹的产生，提高无钴单晶三元正极材料的循环稳定性；
(4)使用本发明导电聚合物修饰改性无钴单晶三元正极材料LiNixMnyZrzO2@LiInO2@EAP制作的正极组装的锂离子电池放电容量高，循环性能好，制备方法简单，生产成本低。
附图说明
图1是本发明实施例1中所得镍锰锆三元正极材料前驱体Ni0.88Mn0.06Zr0.06(OH)2的SEM图。
图2是本发明实施例1导电聚合物修饰改性无钴单晶三元正极材料LiNi0.88Mn0.06Zr0.06O2@LiInO2@PPy的SEM图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步说明。
实施例1
本实施例导电聚合物修饰改性无钴单晶三元正极材料为LiNi0.88Mn0.06Zr0.06O2@LiInO2@PPy。
本实施例导电聚合物修饰改性无钴单晶三元正极材料的制备方法，包括下列步骤：
(1)将硫酸镍、硫酸锰和硫酸锆按摩尔比0.88:0.06:0.06加入去离子水中，搅拌均匀，配制成4mol/L的混合盐溶液；将所述混合盐溶液与4mol/L的沉淀剂NaOH溶液和5mol/L的络合剂NH3·H2O混合，共沉淀法反应16h，得镍锰锆三元正极材料前驱体Ni0.88Mn0.06Zr0.06(OH)2；
(2)将步骤(1)所得的1mol镍锰锆三元正极材料前驱体与1.1mol硝酸锂混合，在纯氧气氛中先在480℃煅烧6h，再升温至850℃煅烧18h，得无钴三元正极材料LiNi0.88Mn0.06Zr0.06O2；
(3)将步骤(2)所得的无钴三元正极材料LiNi0.88Mn0.06Zr0.06O2与0.01mol硝酸铟、0.01mol硝酸锂分散在100ml无水乙醇中，90℃蒸发4h，110℃真空干燥12h，得混合物；然后将所述混合物在氮气气氛下650℃煅烧10h，得锂化物包覆的无钴单晶三元正极材料LiNi0.88Mn0.06Zr0.06O2@LiInO2；
(4)将步骤(3)所得的LiNi0.88Mn0.06Zr0.06O2@LiInO2与1g导电聚合物PPy混合，球磨均匀，然后在氩气气氛中200℃热处理5h，即得导电聚合物修饰改性无钴单晶三元正极材料LiNi0.88Mn0.06Zr0.06O2@LiInO2@PPy。
如图1所示，本实施例无钴三元正极材料前驱体Ni0.88Mn0.06Zr0.06(OH)2为球形颗粒，分布均匀，颗粒粒径大小为2-4μm；如图2所示，本实施例导电聚合物PPy修饰无钴单晶三元正极材料LiNi0.88Mn0.06Zr0.06O2@LiInO2粒径很小，明显为单晶颗粒。
采用本实施例导电聚合物修饰改性无钴单晶三元正极材料LiNi0.88Mn0.06Zr0.06O2@LiInO2@PPy制成的正极组装成纽扣电池，进行电化学测试，本实施例导电聚合物修饰改性无钴单晶三元正极材料LiNi0.88Mn0.06Zr0.06O2@LiInO2@PPy在3～4.3V电压范围内，0.1C(1C＝200mA/g)下的首次放电克容量达218.7mAh/g，1C下放电比容量为195.2mAh/g，循环100圈后容量保持率达95.7％。
实施例2
本实施例导电聚合物修饰改性无钴单晶三元正极材料为LiNi0.83Mn0.10Zr0.07O2@LiInO2@PPVs。
本实施例导电聚合物修饰改性无钴单晶三元正极材料的制备方法，包括下列步骤：
(1)将硫酸镍、硫酸锰和硫酸锆按摩尔比0.83:0.10:0.07加入去离子水中，搅拌均匀，配制成4mol/L的混合盐溶液；将所述混合盐溶液与4mol/L的沉淀剂NaOH溶液和8mol/L的络合剂NH3·H2O混合，共沉淀法反应14h，得镍锰锆三元正极材料前驱体；
(2)将步骤(1)所得的1mol镍锰锆三元正极材料前驱体与1.05mol氢氧化锂混合，在纯氧气氛中先在450℃煅烧6h，再升温至800℃煅烧21h，得无钴三元正极材料LiNi0.83Mn0.10Zr0.07O2；
(3)将步骤(2)所得的无钴三元正极材料LiNi0.83Mn0.10Zr0.07O2与0.01mol硝酸铟、0.01mol硝酸锂分散在100ml无水乙醇中，90℃蒸发4h，120℃真空干燥12h，得混合物；然后将所述混合物在氮气气氛下650℃煅烧10h，得无钴单晶三元正极材料LiNi0.83Mn0.10Zr0.07O2@LiInO2；
(4)将步骤(3)所得的LiNi0.83Mn0.10Zr0.07O2@LiInO2与1g导电聚合物PPVs混合，球磨均匀，然后在氩气气氛中250℃热处理5h，即得导电聚合物PPVs修饰改性无钴单晶三元正极材料LiNi0.83Mn0.10Zr0.07O2@LiInO2。
采用本实施例导电聚合物修饰改性无钴单晶三元正极材料LiNi0.83Mn0.10Zr0.07O2@LiInO2@PPVs制成的正极组装成纽扣电池，进行电化学测试，本实施例导电聚合物修饰改性无钴单晶三元正极材料LiNi0.83Mn0.10Zr0.07O2@LiInO2@PPVs在3～4.3V电压范围内，0.1C(1C＝200mA/g)下的首次放电克容量达210.4mAh/g，1C下放电比容量为189.3mAh/g，循环100圈后容量保持率达96.2％。
实施例3
本实施例导电聚合物修饰改性无钴单晶三元正极材料为LiNi0.90Mn0.06Zr0.04O2@LiInO2@PAN。
本实施例导电聚合物修饰改性无钴单晶三元正极材料的制备方法，包括下列步骤：
(1)将硫酸镍、硫酸锰和硫酸锆按摩尔比0.90:0.06:0.04加入去离子水中，搅拌均匀，配制成4mol/L的混合盐溶液；将所述混合盐溶液与4mol/L的沉淀剂NaOH溶液和5mol/L的络合剂NH3·H2O混合，共沉淀法反应16h，得镍锰锆三元正极材料前驱体；
(2)将步骤(1)所得的1mol镍锰锆三元正极材料前驱体与1.03mol碳酸锂混合，在纯氧气氛中先在480℃煅烧6h，再升温至850℃煅烧18h，得无钴三元正极材料LiNi0.90Mn0.06Zr0.04O2；
(3)将步骤(2)所得的无钴三元正极材料LiNi0.90Mn0.06Zr0.04O2与0.01mol乙酸铟，0.005mol碳酸锂分散在100ml无水乙醇中，85℃蒸发6h，100℃真空干燥10h，得混合物；然后将所述混合物在氩气气氛下500℃煅烧12h，得无钴单晶三元正极材料LiNi0.90Mn0.06Zr0.04@LiInO2；
(4)将步骤(3)所得的LiNi0.90Mn0.06Zr0.04@LiInO2与1g导电聚合物PAN混合，球磨均匀，然后在氩气气氛中300℃热处理6h，即得LiNi0.90Mn0.06Zr0.04O2@LiInO2@PAN。
采用本实施例导电聚合物修饰改性无钴单晶三元正极材料LiNi0.90Mn0.06Zr0.04O2@LiInO2@PAN制成的正极组装成纽扣电池，进行电化学测试，本实施例导电聚合物修饰改性无钴单晶三元正极材料LiNi0.90Mn0.06Zr0.04O2@LiInO2@PAN在3～4.3V电压范围内，0.1C(1C＝200mA/g)下的首次放电克容量达225.7mAh/g，1C下放电比容量为199.5mAh/g，循环100圈后容量保持率达90.8％。
对比例1
对比例1与实施例1相比较，区别在于将硫酸镁替换了硫酸锆，其他反应原料和制备条件不变。
使用对比例1的导电聚合物修饰的无钴三元正极材料LiNi0.88Mn0.06Mg0.06O2@LiInO2@PPy制成锂离子电池正极材料组装成纽扣电池，进行电化学测试，对比例1导电聚合物修饰的无钴三元正极材料LiNi0.88Mn0.06Mg0.06O2@LiInO2@PPy在3～4.3V电压范围内，0.1C(1C＝200mA/g)下的首次放电克容量达216.3mAh/g，1C下放电比容量为190.7mAh/g，循环100圈后容量保持率达88.2％。
对比例2
对比例2与实施例1相比较，区别在于没有进行LiInO2包覆，其他反应原料和制备条件不变。
使用对比例2的无钴三元正极材料LiNi0.88Mn0.06Zr0.06O2@PPy制成锂离子电池正极材料组装成纽扣电池，进行电化学测试，对比例2无钴三元正极材料LiNi0.88Mn0.06Zr0.06O2@PPy在3～4.3V电压范围内，0.1C(1C＝200mA/g)下的首次放电克容量达215.7mAh/g，1C下放电比容量为189.3mAh/g，循环100圈后容量保持率达87.4％。
对比例3
对比例3与实施例1相比较，区别在于没有进行PPy包覆，其他反应原料和制备条件不变。
使用对比例3的无钴三元正极材料LiNi0.88Mn0.06Zr0.06O2@LiInO2制成锂离子电池正极材料组装成纽扣电池，进行电化学测试，对比例3无钴三元正极材料LiNi0.88Mn0.06Zr0.06O2@LiInO2在3～4.3V电压范围内，0.1C(1C＝200mA/g)下的首次放电克容量达216.4mAh/g，1C下放电比容量为191.7mAh/g，循环100圈后容量保持率达88.9％。
Claims (10)
1.导电聚合物修饰改性无钴单晶三元正极材料，其特征在于，所述导电聚合物修饰改性无钴单晶三元正极材料为LiNixMnyZrzO2@LiInO2@EAP，其中0.8≤x<1，0<y≤0.1，0<z≤0.1，x+y+z＝1，EAP为导电聚合物。
2.根据权利要求1所述的导电聚合物修饰改性无钴单晶三元正极材料，其特征在于，所述导电聚合物为聚乙炔、聚噻吩、聚吡咯、聚苯胺、聚苯撑和聚苯撑乙烯中的一种或多种。
3.一种如权利要求1或2所述的导电聚合物修饰改性无钴单晶三元正极材料的制备方法，其特征在于，包括下列步骤：
(1)将镍源、锰源和锆源加入去离子水中，搅拌均匀，然后进行共沉淀法反应，得镍锰锆三元正极材料前驱体；
(2)将步骤(1)所得的镍锰锆三元正极材料前驱体与锂源混合，进行煅烧，得无钴三元正极材料LiNixMnyZrzO2；
(3)将步骤(2)所得的无钴三元正极材料LiNixMnyZrzO2与铟源、锂源通过溶胶凝胶法混合，蒸发溶剂，干燥，得混合物；然后将所述混合物进行煅烧，得无钴单晶三元正极材料LiNixMnyZrzO2@LiInO2；
(4)将步骤(3)所得的无钴单晶三元正极材料LiNixMnyZrzO2@LiInO2与导电聚合物混合，球磨均匀，然后进行热处理，得导电聚合物修饰改性无钴单晶三元正极材料LiNixMnyZrzO2@LiInO2@EAP。
4.根据权利要求3所述的导电聚合物修饰改性无钴单晶三元正极材料的制备方法，其特征在于，步骤(1)中，所述镍源为乙酸镍、硝酸镍和硫酸镍中的一种或多种；所述锰源为乙酸锰、硝酸锰和硫酸锰中的一种或多种；所述锆源为乙酸锆、硝酸锆、硫酸锆和碳酸锆中的一种或多种。
5.根据权利要求3或4所述的导电聚合物修饰改性无钴单晶三元正极材料的制备方法，其特征在于，步骤(2)中，所述镍锰锆三元正极材料前驱体与锂源的摩尔比为1:1.03～1.09。
6.根据权利要求3或4所述的导电聚合物修饰改性无钴单晶三元正极材料的制备方法，其特征在于，步骤(2)中，所述煅烧分为两段烧结，第一段烧结的煅烧温度为400～600℃，煅烧的时间为4～6h，第二段煅烧的煅烧温度为700～850℃，煅烧的时间为10～15h。
7.根据权利要求3或4所述的导电聚合物修饰改性无钴单晶三元正极材料的制备方法，其特征在于，步骤(3)中，所述铟源为乙酸铟、硝酸铟、硫酸铟和碳酸铟中的一种或多种；所述锂源为氢氧化锂、碳酸锂和硝酸锂中的一种或多种。
8.根据权利要求3或4所述的导电聚合物修饰改性无钴单晶三元正极材料的制备方法，其特征在于，步骤(3)中，所述溶剂为乙醇、乙二醇和异丙醇中的一种或多种；所述蒸发的温度为65～100℃；所述干燥的温度为110～150℃，所述干燥的时间为10～15h。
9.根据权利要求3或4所述的导电聚合物修饰改性无钴单晶三元正极材料的制备方法，其特征在于，步骤(3)中，所述煅烧的温度为400～650℃；所述煅烧的时间为8～12h；所述煅烧的气氛为氩气、氧气或空气。
10.根据权利要求3或4所述的导电聚合物修饰改性无钴单晶三元正极材料的制备方法，其特征在于，步骤(4)中，所述热处理的温度为100～300℃；所述热处理的时间为2～8h；所述热处理的气氛是氩气或氮气。
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