CN110071278A - 一种含活性氧去除剂的高镍三元正极材料及其制备方法 - Google Patents
一种含活性氧去除剂的高镍三元正极材料及其制备方法 Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000001301 oxygen Substances 0.000 title claims abstract description 45
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 45
- 239000010406 cathode material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000006213 oxygenation reaction Methods 0.000 title claims description 4
- 239000000463 material Substances 0.000 claims abstract description 24
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 9
- 238000005253 cladding Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 6
- -1 nickel cobalt manganese (aluminium) Chemical compound 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910014330 LiNi1-x-yCoxAlyO2 Inorganic materials 0.000 claims description 2
- 229910014336 LiNi1-x-yCoxMnyO2 Inorganic materials 0.000 claims description 2
- 229910014446 LiNi1−x-yCoxMnyO2 Inorganic materials 0.000 claims description 2
- 229910014360 LiNi1−x−yCoxAlyO2 Inorganic materials 0.000 claims description 2
- 229910014825 LiNi1−x−yCoxMnyO2 Inorganic materials 0.000 claims description 2
- 229910020042 NbS2 Inorganic materials 0.000 claims description 2
- 229910003092 TiS2 Inorganic materials 0.000 claims description 2
- FYWUVDVZWURZJH-UHFFFAOYSA-E [OH-].[Al+3].[Mn+2].[Co+2].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-] Chemical compound [OH-].[Al+3].[Mn+2].[Co+2].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-] FYWUVDVZWURZJH-UHFFFAOYSA-E 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052960 marcasite Inorganic materials 0.000 claims description 2
- 239000000320 mechanical mixture Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052961 molybdenite Inorganic materials 0.000 claims description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 229910052683 pyrite Inorganic materials 0.000 claims description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical group 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 22
- 238000000034 method Methods 0.000 abstract description 12
- 238000003860 storage Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 230000006641 stabilisation Effects 0.000 abstract description 2
- 238000011105 stabilization Methods 0.000 abstract description 2
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 14
- 230000014759 maintenance of location Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical class CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 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 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 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 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
Abstract
本发明公开的一种含活性氧去除剂的高镍三元正极材料,包括活性氧去除剂及高镍三元材料,所述活性氧去除剂包覆在所述高镍三元正极材料表面,本发明还提供一种活性氧去除剂包覆的高镍三元正极材料的制备方法,是将高镍三元正极材料与活性氧去除剂按照一定质量比溶解在无水乙醇中进行超声分散,过滤后将样品在100℃下真空干燥12~24h而得到,既可以消除高镍三元正极材料在循环或存储过程中形成的活性氧,抑制电解液氧化分解产气,还可以消除高镍三元正极材料表面残锂,降低表面残碱,保持电解液中碳酸盐溶剂的化学稳定性,从而提高循环性能及稳定性,有效抑制电池循环存储产气和阻抗增加,并且包覆工艺简单,易于操作。
Description
技术领域
本发明涉及锂离子电池技术领域,尤其涉及一种含活性氧去除剂的高镍三元正极材料及其制备方法。
背景技术
近年来,随着电动汽车市场的飞速发展,人们对锂离子电池的续航能力、安全性能提出了更高的要求,高镍三元正极材料因成本低廉、能量密度高、电压平台高等优势备受青睐,然而高镍三元正极材料热稳定性差、易产气等问题仍然无法得到有效的改善。
众所周知,在循环或存储过程中,特别是高脱锂状态下,高镍三元正极材料表面会发生不可逆的相变反应,从层状结构到尖晶结构再到岩盐结构,并伴随着活性氧的释放。活性氧的氧化活性非常强,极易氧化电解液,导致电池阻抗增加和电池鼓胀,破坏正负极界面,有可能触发电池内部热失控,进而引起锂离子电池的容量衰退,目前针对上述技术问题也公开了多种解决方案,如中国专利CN106207128A公开了一种Zr(OH)4包覆镍钴铝正极材料的制备方法,该包覆方法采用低温干法包覆,可有效降低循环过程中界面的电阻、抑制副反应发生,提高循环稳定性。现有技术总解决这一技术问题的方法要么是对高镍三元材料表面进行包覆,如中国专利CN108899531A公开了一种磷酸盐包覆镍钴锰三元正极材料的制备方法,包覆后的正极材料有更高的离子迁移和电子传递能力,能有效抑制正极材料与电解液之间的副反应,提高材料的循环性能,但是,包覆材料的用量有限,并不可能完全隔离电解液,长期循环过后包覆材料也会受到电解液中HF的侵蚀而遭到破坏,更无法避免高镍三元正极材料在相变过程中因活性氧的释放而造成危害。现有技术在解决这一问题时,要么是在电解液中添加添加剂,促进正极成膜,如中国专利CN109390631A公开了一种高镍三元正极材料电解液及所述电解液在锂离子电池中的应用,其实采用正极成膜添加剂4,4,4-三氟丁酸乙酯促进正极表面形成均匀致密的SEI膜,改善电解液与正负极界面相容性,提高锂离子电池高温循环性能。CN109301309A公开了一种高压镍钴锰三元正极材料的电解液及所述电解液在锂离子电池中的应用,是采取双功能添加剂1,1,1-三甲基-N-(三苯基正膦亚基)硅烷胺在正极成膜,保护正极,减小正极与电解液的副反应,且形成的CEI膜热稳定性好,有效提高锂离子电池高电压性能和高压下的存储性能。在电解液中添加添加剂,促进正极成膜的方法能够改善正极、电解液的界面反应,并且成本低廉操作简单,然而,高镍三元正极材料的热稳定性差、易释放活性氧是其材料本身的特性所决定的,且活性氧的释放对电池性能破坏极大,成膜添加剂在正极成膜后固然能够降低正极、电解液的副反应,但是并不能完全避免高镍三元正极材料活性氧释放而快速消耗电解液的问题。
发明内容
为了解决上述技术问题,本发明公开一种含活性氧去除剂的高镍三元正极材料及其制备方法,旨在消除高镍三元材料在相变过程中形成的活性氧,避免因活性氧氧化电解液导致阻抗增加以及严重产气等问题,避免电解液氧化分解,从而提高材料的热稳定性和循环稳定性。
本发明公开的一种含活性氧去除剂的高镍三元正极材料,包括活性氧去除剂及高镍三元材料,所述活性氧去除剂包覆在所述高镍三元正极材料上,所述高镍三元材料的通式为LiNi1-x-yCoxMnyO2或LiNi1-x-yCoxAlyO2,其中0≤x≤0.2,0≤y≤0.2,所述活性氧去除剂为过渡金属二硫化物MS2;
本发明的又一目的是提供一种含活性氧去除剂的高镍三元正极材料及其制备方法,包括如下步骤:
(1)采用共沉淀法,在惰性气氛下制备镍钴锰(铝)前驱体;
(2)将步骤(1)中所述前驱体和锂源机械混合并研磨;
(3)将步骤(2)中的混合物在通氧管式炉中经过煅烧工艺制得镍钴锰(铝)三元正极材料;
(4)将步骤(3)中所述镍钴锰(铝)三元正极材料与活性氧去除剂按照一定质量比溶解在无水乙醇中进行超声分散10~15min,过滤后将样品在100℃下真空干燥12~24h得到烘干产物;
(5)将步骤(4)中所述烘干产物置于马弗炉中在无氧气氛下,600℃~800℃保温3~7h,冷却至室温,过筛即可得到MS2包覆高镍三元材料。
进一步的,步骤(1)中,所述镍钴锰(铝)前驱体为镍钴锰(铝)氢氧化物、镍钴锰(铝)碳酸盐中的至少一种;
进一步的,步骤(1)中,所述惰性气体气氛为氮气、氩气中的至少一种;
进一步的,步骤(4)中,所述活性氧去除剂MS2,包括CoS2,FeS2,MoS2,TiS2,WS2,NbS2中的至少一种;
进一步的,步骤(4)中,活性氧去除剂MS2占镍钴锰(铝)三元正极材料质量的0.1%~10%。
有益效果
本发明提供的一种活性氧去除剂包覆的高镍三元材料及其制备方法,是在高镍三元正极材料表面包覆活性氧去除剂MS2,既可以消除高镍三元正极材料在循环或存储过程中形成的活性氧,抑制电解液氧化分解产气,还可以形成稳定的包覆层阻止其与电解液接触,另外,还可以消除高镍三元正极材料表面的残锂,降低表面残碱,保持电解液中碳酸盐溶剂的化学稳定性,从而提高循环性能及稳定性,有效抑制电池循环存储产气和阻抗增加,并且包覆工艺简单,易于操作。
附图说明
图1为本发明实施例2所制备的正极材料的SEM图。
具体实施方式
为了使本发明的目的、技术方案和效果更加清晰,以下结合附图对本发明作进一步说明。另外,本说明书中描述的实施例仅仅是为了解释本发明,并非为了限制本发明。对比例1:
(1)将Ni(NO3)2、Co(NO3)2和Mn(NO3)2按摩尔比n(Ni):n(Co):n(Mn)=8:1:1溶解在去离子水中配制成金属离子总浓度为2mol/L的混合盐溶液加入到连续搅拌的反应釜中,同时将浓度为4mol/L的NaOH和2mol/L的氨水的混合溶液也加入反应釜中,设定搅拌速度为300r/min,PH值控制在11左右,以氮气作为保护气,控制反应温度在50℃下反应1h,然后陈化12h、洗涤过滤、在80℃下真空干燥24h,研磨过筛得到镍钴锰氢氧化物前驱体;
(2)将步骤(1)中所述前驱体和LiOH•H2O按照Li:M(金属阳离子,Ni,Co,Mn)=1.05:1机械混合并研磨均匀,然后置于通氧管式炉中,以5℃/min的升温速率升至500℃下预烧5h,再以5℃/min的升温速率升至750℃焙烧15h,然后冷却至室温,经粉碎过筛后得到LiNi0.8Co0.1Mn0.1O2;
(3)将NCM811、导电剂乙炔黑、粘结剂PVDF按一定质量比进行搅拌,搅拌完成后滴加NMP(氮甲基吡咯烷铜)调粘度,将浆料转移至涂布机,使正极浆料均匀涂覆在铝箔上,真空烘干后辊压,制得正极片;以石墨作为负极,电解液为含有LiPF6(1mol/L)的EC/PC/DEC体系,制作成的软包电芯型号为383450(3.8mm厚,34mm宽,50mm长)。
测试对比例1制备的高镍三元正极材料表面杂质残锂含量及PH值、室温下1C循环1000圈的容量保持率(电压范围为2.8V-4.3V)和60℃存储120天体积膨胀率(满电状态4.3V),其测试结果如表1所示。
实施例1:
(1)制备高镍三元正极材料LiNi0.8Co0.1Mn0.1O2,其制备方法与对比例1类似。
(2)将步骤(1)中所述LiNi0.8Co0.1Mn0.1O2与活性氧去除剂CoS2按照质量比100:1溶解在无水乙醇中,超声分散10min,过滤后将样品在100℃下真空干燥12h,然后置于马弗炉中在无氧气氛下700℃煅烧5h,然后冷却至室温,过筛即可得到质量分数为1%的CoS2包覆LiNi0.8Co0.1Mn0.1O2。
(3)将步骤(2)中所制备的质量分数为1%的CoS2包覆LiNi0.8Co0.1Mn0.1O2材料作正极,石墨作负极,制备软包电池,其制备方法与对比例1类似。
测试实施例1制备含1%含量CoS2包覆高镍三元正极材料表面杂质残锂含量及PH值、室温下1C循环1000圈的容量保持率(电压范围为2.8V-4.3V)和60℃存储120天体积膨胀率(满电状态4.3V),其测试结果如表1所示。
实施例2:
(1)制备高镍三元正极材料LiNi0.8Co0.1Mn0.1O2,其制备方法与对比例1类似;
(2)将步骤(1)中所述LiNi0.8Co0.1Mn0.1O2与活性氧去除剂CoS2按照质量比50:1溶解在无水乙醇中,超声分散10min,过滤后将样品在100℃下真空干燥12h,然后置于马弗炉中在无氧气氛下700℃煅烧5h,然后冷却至室温,过筛即可得到质量分数为2%的CoS2包覆LiNi0.8Co0.1Mn0.1O2。
(3)将步骤(2)中所制备的质量分数为2%的CoS2包覆LiNi0.8Co0.1Mn0.1O2材料作正极,石墨作负极,制备软包电池,其制备方法与对比例1类似。
测试实施例2制备含2%含量CoS2包覆的高镍三元正极材料表面杂质残锂含量及PH值、室温下1C循环1000圈的容量保持率(电压范围为2.8V-4.3V)和60℃存储120天体积膨胀率(满电状态4.3V),其测试结果如表1所示。
实施例3:
(1)制备高镍三元正极材料LiNi0.8Co0.1Mn0.1O2,其制备方法与对比例1类似;
(2)将步骤(1)中所述LiNi0.8Co0.1Mn0.1O2与活性氧去除剂CoS2按照质量比20:1溶解在无水乙醇中,超声分散10min,过滤后将样品在100℃下真空干燥12h,然后置于马弗炉中在无氧气氛下700℃煅烧5h,然后冷却至室温,过筛即可得到质量分数为5%的CoS2包覆LiNi0.8Co0.1Mn0.1O2。
(3)将步骤(2)中所制备的质量分数为5%的CoS2包覆LiNi0.8Co0.1Mn0.1O2材料作正极,石墨作负极,制备软包电池,其制备方法与对比例1类似。
测试实施例3制备的含5%含量CoS2包覆的高镍三元正极材料表面杂质残锂含量及PH值、室温下1C循环1000圈的容量保持率(电压范围为2.8V-4.3V)和60℃存储120天体积膨胀率(满电态4.3V),其测试结果如表1所示。
表1是对比例1与实施例1、实施例2和实施例3制备的高镍三元正极材料的电性能测试结果。
分组 | 残余总锂量(%) | PH值 | 1C循环1000圈容量保持率(%) | 60℃存储120天体积膨胀率(%) |
对比例1 | 0.2021% | 11.92 | 88.30% | 52% |
实施例1 | 0.1568% | 11.69 | 90.09% | 30% |
实施例2 | 0.1455% | 11.51 | 92.00% | 28% |
实施例3 | 0.1823% | 11.82 | 89.33% | 39% |
由表1可知,与对比例1中采用常规方法制备的高镍三元正极材料相比,本发明实施例1、实施例2和实施例3制备CoS2包覆LiNi0.8Co0.1Mn0.1O2正极材料表面残锂和PH值明显降低,有利于电解液中碳酸盐溶剂的化学稳定。另外,实施例1、实施例2和实施例3采用CoS2作为包覆物,在循环或存储过程中与高镍三元正极材料释放的活性氧反应,消耗大量活性氧,可避免其氧化电解液导致电池性能恶化,因此,存储产气明显较小,循环性能也具有明显优势,提高了高镍三元材料的热稳定性,能减缓充电态下正极材料对电解液的氧化,极大改善了正极材料的循环性能以及高温存储性能。然而,活性氧去除剂用量也应适量,过多不仅会影响正极材料克容量发挥,包覆层较厚影响Li+迁移增大电池内阻造成温升,反过来又会加剧电池内部副反应,影响电池性能。
上述具体实施例并非限制本发明,本发明也并不局限于上述实施例。另外,在本发明的实质范围内做出的变化,添加或替换,都应该属于本发明的保护范围。
Claims (6)
1.一种含活性氧去除剂的高镍三元正极材料,其特征在于,包括活性氧去除剂及高镍三元材料,所述活性氧去除剂包覆在所述高镍三元正极材料表面,所述高镍三元材料的通式为LiNi1-x-yCoxMnyO2或LiNi1-x-yCoxAlyO2,其中0≤x≤0.2,0≤y≤0.2,所述活性氧去除剂为过渡金属二硫化物MS2。
2.一种含活性氧去除剂的高镍三元正极材料及其制备方法,包括如下步骤:
(1)采用共沉淀法,在惰性气氛下制备镍钴锰(铝)前驱体;
(2)将步骤(1)中所述的前驱体和锂源机械混合并研磨;
(3)将步骤(2)中的混合物在通氧管式炉中经过煅烧工艺制得镍钴锰(铝)三元正极材料;
(4)将步骤(3)中所述镍钴锰(铝)三元正极材料与活性氧去除剂按照一定质量比溶解在无水乙醇中进行超声分散10~15min,过滤后将样品在100℃下真空干燥12~24h得到烘干产物;
(5)将步骤(4)中所述烘干产物置于马弗炉中在无氧气氛下,600℃~800℃保温3~7h,冷却至室温,过筛即可得到MS2包覆的高镍三元材料。
3.如权利要求2所述的一种含活性氧去除剂的高镍三元正极材料的制备方法,其特征在于,所述镍钴锰(铝)前驱体为镍钴锰(铝)氢氧化物、镍钴锰(铝)碳酸盐中的至少一种。
4.如权利要求2所述的一种含活性氧去除剂的高镍三元正极材料的制备方法,其特征在于,所述惰性气体气氛为氮气、氩气中的至少一种。
5.如权利要求2所述的一种含活性氧去除剂的高镍三元正极材料的制备方法,其特征在于,所述活性氧去除剂MS2,包括CoS2,FeS2,MoS2,TiS2,WS2,NbS2中的至少一种。
6.如权利要求2所述的一种含活性氧去除剂的高镍三元正极材料的制备方法,其特征在于,活性氧去除剂MS2占镍钴锰(铝)三元正极材料质量的0.1%~10%。
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103825001A (zh) * | 2014-01-14 | 2014-05-28 | 深圳市振华新材料股份有限公司 | 安全性高的锂离子二次电池用正极材料、制法和电池应用 |
CN104134795A (zh) * | 2014-07-25 | 2014-11-05 | 江南大学 | 一种球形层状结构锂离子电池正极材料外包覆纳米金属氧化物制备方法 |
CN104810521A (zh) * | 2015-05-11 | 2015-07-29 | 田东 | 一种镍钴锰酸锂三元正极材料的制备方法 |
CN106384815A (zh) * | 2016-10-25 | 2017-02-08 | 成都新柯力化工科技有限公司 | 一种高温稳定性镍钴锰酸锂复合电极及其制备方法与应用 |
CN108832089A (zh) * | 2018-06-08 | 2018-11-16 | 中南大学 | 一种二硫化钼包覆镍钴锰酸锂复合材料及其制备方法和应用 |
CN108899531A (zh) * | 2018-08-10 | 2018-11-27 | 合肥工业大学 | 一种磷酸盐包覆镍钴铝三元正极材料的制备方法 |
-
2019
- 2019-04-26 CN CN201910344798.4A patent/CN110071278A/zh active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103825001A (zh) * | 2014-01-14 | 2014-05-28 | 深圳市振华新材料股份有限公司 | 安全性高的锂离子二次电池用正极材料、制法和电池应用 |
CN104134795A (zh) * | 2014-07-25 | 2014-11-05 | 江南大学 | 一种球形层状结构锂离子电池正极材料外包覆纳米金属氧化物制备方法 |
CN104810521A (zh) * | 2015-05-11 | 2015-07-29 | 田东 | 一种镍钴锰酸锂三元正极材料的制备方法 |
CN106384815A (zh) * | 2016-10-25 | 2017-02-08 | 成都新柯力化工科技有限公司 | 一种高温稳定性镍钴锰酸锂复合电极及其制备方法与应用 |
CN108832089A (zh) * | 2018-06-08 | 2018-11-16 | 中南大学 | 一种二硫化钼包覆镍钴锰酸锂复合材料及其制备方法和应用 |
CN108899531A (zh) * | 2018-08-10 | 2018-11-27 | 合肥工业大学 | 一种磷酸盐包覆镍钴铝三元正极材料的制备方法 |
Non-Patent Citations (1)
Title |
---|
SHENG S. ZHANG ET AL.: ""Pyrite FeS2 as an in-situ oxygen remover for rechargeable batteries with layered cathode materials"", 《JOURNAL OF POWER SOURCES》, pages 167 - 172 * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111446450A (zh) * | 2020-03-31 | 2020-07-24 | 珠海冠宇电池股份有限公司 | 一种功能材料、含有该功能材料的正极片及锂离子电池 |
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