CN1245773C - 一种锂离子电池锂钴锰镍氧化物正极材料的制备方法 - Google Patents

一种锂离子电池锂钴锰镍氧化物正极材料的制备方法 Download PDF

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CN1245773C
CN1245773C CNB031262554A CN03126255A CN1245773C CN 1245773 C CN1245773 C CN 1245773C CN B031262554 A CNB031262554 A CN B031262554A CN 03126255 A CN03126255 A CN 03126255A CN 1245773 C CN1245773 C CN 1245773C
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manganese
nickel
lithium
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CN1514502A (zh
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崔成伟
杨书廷
张希平
张彦航
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Xinxiang City Kai Hong Trading Co ltd
Xinxiang Zhongke Science&technology Co ltd
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Xinxiang Green New Energy Material Co Ltd
OXYGEN-FREE COPPER MATERIAL GENERAL FACTORY XINXIANG
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection 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
    • CCHEMISTRY; METALLURGY
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    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00Compounds of nickel
    • C01G53/40Nickelates
    • C01G53/42Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1391Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
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    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection 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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    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2006/40Electric properties
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/04Processes of manufacture in general
    • H01M4/0471Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • YGENERAL 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
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    • Y02E60/10Energy storage using batteries

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Abstract

本发明公开了一种锂离子电池锂钴锰镍氧化物正极材料的制备方法,包括有固相合成和高温灼烧工序,工序(1)按锂∶(钴+锰+镍)原子比为1-1.1∶1,且钴∶锰∶镍原子比为1∶1∶1,将锂源、钴源、锰源和镍源料混匀后,加入聚丙烯酰胺和氧化钕搅拌均匀成胶状料。工序(2)将上述胶状料在150℃下烘干30小时,在球磨机内球磨并过300目筛,形成粉料。工序(3)将上述粉料在300-450℃条件下预烧10小时后,自然冷却至室温,工序(4)将预烧的粉料再次进行球磨研细,过300目筛,在650-850℃条件下灼烧3小时,过300目筛即成。本发明由于在固相合成工序中加入了聚丙烯酰胺和氧化钕,增加了预烧工序,因而与现有技术比,具有比容量高、循环性能好且无污染的优点。

Description

一种锂离子电池锂钴锰镍氧化物正极材料的制备方法
技术领域:
本发明涉及一种电池,特别是一种锂离子电池锂钴锰镍氧化物正极材料的制备方法。
背景技术:
已商品化生产锂离子电池用的正极材料为锂钻氧化物,由于钴资源缺乏,价格高,不利于锂离子电池的大规模推广使用。目前以锰、镍取代钴是降低材料成本的有效途径之一,有许多文献报道了Li-Cox-Mny-Nil-yO2的制备方法和性能,其制备方法多在氧气下进行,设备复杂,工艺成本高。
发明内容:
本发明需要解决的技术问题是设计一种锂离子电池锂钴锰镍氧化物正极材料的制备方法,所制备的正极材料具有较高的可逆比容量和良好的循环性能,且工艺成本较低。本发明的技术方案是,一种锂离子电池锂钴锰镍氧化物正极材料的制备方法,包括有固相合成和高温灼烧工序,其特征在于:工序(1)按锂∶(钴+锰+镍)原子比为1-1.1∶1,且钴∶锰∶镍的原子比为1∶1∶1,将锂源、钴源、锰源和镍源料混匀后,按上述锂、钴、锰、镍混合料重量的6-10%加入聚丙烯酰胺,加入氧化钕的钕原子数为(钴+锰+镍)原子数的5-8%,形成胶状料,工序(2)将上述胶状料在150℃下烘干30小时,在球磨机内球磨并过300目筛,形成粉料,工序(3)将上述粉料在300-450℃条件下预烧10小时后,自然冷却至室温,工序(4)将预烧的粉料再次进行球磨研细,过300目筛,在650-850℃条件下灼烧3小时,过300目筛即成。由于在固相合成中加入了高分子网络剂(聚丙烯酰胺)和稳定剂(氧化钕)有成球的作用,使灼烧出的锂钴锰镍氧化物成球形,使其比重增大,改善了充放电过程中的循环寿命,增加了预热处理,使锂源充分分解、氧与锂和钴离子结合,锂与钴在原子级水平混合,在850℃下灼烧出结晶性好的层状正极材料。因而本发明与现有技术比既具有比容量高、放电电位高、耐过充性和循环性能及热稳定性能较好,稳定的循环使用寿命,而且还具有工艺成本低的显著优点。
具体实施方式:
实施例1
工序(1)将锂与(钴+锰+镍)的原子比为1且钴∶锰∶镍的原子比为1的锂源和钴源、锰源、镍源的混料混匀,按此混料重量比的6%加入聚丙烯酰胺,加入氧化钕的钕原子数为(钴+锰+镍)原子数的5%,搅拌均匀成胶状料。
工序(2)将在上述工序(1)得到的胶状物经干燥箱在150℃下烘干30小时后,再称一定量烘干料球磨5小时,过300目振动筛,形成粉料。
工序(3)将上述工序(2)得到的粉末物料在300℃条件下预烧10小时自然冷却。
工序(4)将在上述工序(3)预烧的粉末物再经求磨、研细、过筛,再在700℃条件下灼烧3小时,过300目筛即成。
实施例2
工序(1)将锂与(钴+锰+镍)的原子比为1.02且钴∶锰∶镍的原子比为1的锂源和钴源、锰源、镍源的混料混匀,按此混料重量比的6%加入聚丙烯酰胺,加入氧化钕的钕原子数为(钴+锰+镍)原子数的5%,搅拌均匀成胶状料。
工序(2)将在上述工序(1)得到的胶状物经干燥箱在150℃下烘干30小时后,再称一定量烘干料球磨5小时,过300目振动筛,形成粉料。
工序(3)将上述工序(2)得到的粉末物料在300℃条件下预烧10小时自然冷却。
工序(4)将在上述工序(3)预烧的粉末物再经求磨、研细、过筛,再在750℃条件下灼烧3小时,过300目筛待用。
实施例3
工序(1)将锂与(钴+锰+镍)的原子比为1.05且钴∶锰∶镍的原子比为1的锂源和钻源、锰源、镍源的混料混匀,按此混料重量比的8%加入聚丙烯酰胺,加入氧化钕的钕原子数为(钴+锰+镍)原子数的5%,搅拌均匀成胶状料。
工序(2)将在上述工序(1)得到的胶状物经干燥箱在150℃下烘干30小时后,再称一定量烘干料球磨5小时,过300目振动筛,形成粉料。
工序(3)将在上述工序(2)得到的粉末物料在400℃预烧10小时自然冷却。
工序(4)将在上述工序(3)预烧的粉末物料再经球磨、研细、过筛,再在650℃灼烧3小时,过300目筛待用。
实施例4
工序(1)将锂与(钴+锰+镍)的原子比为1.05且钴∶锰∶镍的原子比为1的锂源和钴源、锰源、镍源的混料混匀,按此混料重量比的6%加入聚丙烯酰胺,加入氧化钕的钕原子数为(钴+锰+镍)原子数的5%,搅拌均匀成胶状料。
工序(2)将在上述工序(1)得到的胶状物经干燥箱在150℃下烘干30小时后,再称一定量烘干料球磨5小时,过300目振动筛,形成粉料。
工序(3)将在上述工序(2)得到的粉末物料在400℃预烧10小时自然冷却。
工序(4)将在上述工序(3)预烧的粉末物料再经球磨、研细、过筛,再在700℃灼烧3小时,过300目筛待用。
实施例5
工序(1)将锂与(钴+锰+镍)的原子比为1.08且钴∶锰∶镍的原子比为1的锂源和钴源、锰源、镍源的混料混匀,按此混料重量比的8%加入聚丙烯酰胺,加入氧化钕的钕原子数为(钴+锰+镍)原子数的5%,搅拌均匀成胶状料。
工序(2)将在上述工序(1)得到的胶状物经干燥箱在150℃下烘干30小时后,再称一定量烘干料球磨5小时,过300目振动筛,形成粉料。
工序(3)将在上述工序(2)得到的粉末物料在450℃预烧10小时自然冷却。
工序(4)将在上述工序(3)预烧的粉末物再经球磨、研细、过筛,再在800℃灼烧3小时,过300目筛待用。
实施例6
工序(1)将锂与(钴+锰+镍)的原子比为1.08且钴∶锰∶镍的原子比为1的锂源和钻源、锰源、镍源的混料混匀,按此混料重量比的8%加入聚丙烯酰胺,加入氧化钕的钕原子数为(钴+锰+镍)原子数的5%,搅拌均匀成胶状料。
工序(2)将在上述工序(1)得到的胶状物经干燥箱在150℃下烘干30小时后,再称一定量烘干料球磨5小时,过300目振动筛,形成粉料。
工序(3)将在上述工序(2)得到的粉末物料在450℃预烧10小时自然冷却。
工序(4)将在上述工序(3)预烧的粉末物再经球磨、研细、过筛,再在850℃灼烧3小时,过300目筛待用。
实施例7
工序(1)将锂与(钴+锰+镍)的原子比为1.08且钴∶锰∶镍的原子比为1的锂源和钴源、锰源、镍源的混料混匀,按此混料重量比的6%加入聚丙烯酰胺,加入氧化钕的钕原子数为(钴+锰+镍)原子数的5%,搅拌均匀成胶状料。
工序(2)将在上述工序(1)得到的胶状物经干燥箱在150℃下烘干30小时后,再称一定量烘干料球磨5小时,过300目振动筛,形成粉料。
工序(3)将在上述工序(2)得到的粉末物料在450℃预烧10小时自然冷却。
工序(4)将在上述工序(3)预烧的粉末物再经球磨、研细、过筛,再在850℃灼烧3小时,过300目筛待用。
实施例8
工序(1)将锂与(钴+锰+镍)的原子比为1.1且钴∶锰∶镍的原子比为1的锂源和钴源、锰源、镍源的混料混匀,按此混料重量比的10%加入聚丙烯酰胺,加入氧化钕的钕原子数为(钴+锰+镍)原子数的5%,搅拌均匀成胶状料。
工序(2)将在上述工序(1)得到的胶状物经干燥箱在150℃下烘干30小时后,再称一定量烘干料球磨5小时,过300目振动筛,形成粉料。
工序(3)将在上述工序(2)得到的粉末物料在400℃预烧10小时自然冷却。
工序(4)将在上述第三处理步骤预烧的粉末物再经球磨、研细、过筛,再在800℃灼烧3小时,过300目筛待用。
将上述方法制备的锂离子电池正极材料与锂离子电池负极材料石墨,以偏氟乙烯为极板粘结剂,分别制成锂离子电池的正极片与负极片,以聚丙烯微孔膜为电极隔膜,以体积比为碳酸二甲酯∶碳酸二乙酯∶碳酸乙烯酯=1∶1∶1的1M六氟磷酸锂为电解液组装成锂离子电池。
                 各实施例制备的锂离子电池的性能表
Figure C0312625500061

Claims (1)

1.一种锂离子电池锂钴锰镍氧化物正极材料的制备方法,包括有固相合成和高温灼烧工序,其特征在于:工序(1)按锂∶(钴+锰+镍)原子比为1-1.1∶1,且钴∶锰∶镍的原子比为1∶1∶1,将锂源、钴源、锰源和镍源料混匀后,按上述锂、钴、锰、镍混合料的重量6-10%加入聚丙烯酰胺,加入氧化钕的钕原子数为(钴+锰+镍)原子数的5-8%,形成胶状料,工序(2)将上述胶状料在150℃下烘干30小时,在球磨机内球磨并过300目筛,形成粉料,工序(3)将上述粉料在300-450℃条件下预烧10小时后,自然冷却至室温,工序(4)将预烧的粉料再次进行球磨研细,过300目筛,在650-850℃条件下灼烧3小时,过300目筛即成。
CNB031262554A 2003-07-15 2003-07-15 一种锂离子电池锂钴锰镍氧化物正极材料的制备方法 Expired - Fee Related CN1245773C (zh)

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CN101139108B (zh) * 2006-09-06 2010-09-29 北京有色金属研究总院 锂离子电池用的层状锂镍钴锰氧化物正极材料的制备方法
CN101626080B (zh) * 2008-10-17 2011-02-09 成都晶元新材料技术有限公司 一种镍钴锰多元掺杂锂离子电池正极材料及其制备方法
CN101621125B (zh) 2009-02-13 2011-03-30 成都晶元新材料技术有限公司 一种镍钴锰多元掺杂锂离子电池正极材料及其制备方法
CN101582497B (zh) * 2009-06-18 2012-07-11 中南大学 一种高容量锂离子电池复合正极材料的制备方法

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