CN1180499C - 锂离子电池正极材料的制造方法 - Google Patents

锂离子电池正极材料的制造方法 Download PDF

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CN1180499C
CN1180499C CNB021004412A CN02100441A CN1180499C CN 1180499 C CN1180499 C CN 1180499C CN B021004412 A CNB021004412 A CN B021004412A CN 02100441 A CN02100441 A CN 02100441A CN 1180499 C CN1180499 C CN 1180499C
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杨书廷
朱善福
崔成伟
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Beijing Universal Amperex Technology Ltd
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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
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131Electrodes 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
    • H01M4/02Electrodes composed of, or comprising, active material
    • 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
    • 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
    • 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
    • H01M4/52Selection 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M2004/026Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028Positive electrodes
    • 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

本发明公开了一种锂离子电池正极材料的制造方法,其中包括工业级Li2CO3 2~19重量份,电解MnO2 15~100重量份,将工业级Li2CO3和电解MnO2混合搅拌均匀,混合搅拌时间0.1~10小时,将工业级Li2CO3和电解MnO2的混合物输入加热设备中,进行分阶段加热,在第一阶段的加热温度300~720℃,保温时间1~5小时,在第二阶段的加热温度870~950℃,保温时间3~9小时,将经过焙烧的工业级Li2CO3和电解MnO2的混合物冷却,达到温度15~30℃,进行粉碎,然后通过100~450目筛网进行筛选。

Description

锂离子电池正极材料的制造方法
技术领域
本发明涉及一种锂离子电池正极材料的制造方法。
背景技术
锂离子电池是以嵌锂化和物作为正极材料高比能量蓄电池,其具有电池电压高,比能量大,循环寿命长,自放电量小,以及有利于环保等优点,因此越来越引起本专业技术人员的注意。在锂离子电池的广泛应用过程中,电池的性能和价格是决定性的因素,然而,制备性能价格比优良的关键因素之一是提供理想的嵌锂化合物正极材料。
在现有技术中,专业人员进行了多方面的努力。采用锂锰氧化物作为原材料,可以降低成本,而且锂锰氧化物的资源丰富,采用这种锂锰氧化物制成的电极,具有电压高、耐过充放电性能好,以及无毒性等显著优点,采用这种锂锰氧化物,制造锂离子电池的正极材料,能够获得令人满意的效果。但是,这种锂离子电池的正极材料的制造方法还需要进一步改进。在2001年5月出版的《无机材料学报》刊登了一篇文章名称是“锂离子电池正极材料LiMn2CO4制备新工艺”的文章,其中记载采用Li2CO3和MnO2按照摩尔比=1∶2进行配比,在第一加热阶段的温度是600℃,加热时间为5小时,在第二加热阶段的温度时800℃,加热时间为20小时,这种生产方法生产周期过长,不利于工业化生产。本发明在此基础上进行了改进,通过提高第二加热阶段的温度,同时缩短该阶段加热温度的时间,由此缩短了锂离子电池正极材料制造方法的生产周期,从而提高了生产率。
发明内容
本发明的目的是提供一种锂离子电池正极材料的制造方法,其步骤包括:
将工业级Li2CO32~19重量份,电解MnO215~100重量份混合搅拌均匀,混合搅拌时间0.1~10小时;
将工业级Li2CO3和电解MnO2的混合物输入加热设备中,进行分阶段加热,在第一阶段的加热温度300~720℃,保温时间1~5小时,在第二阶段的加热温度870~950℃,保温时间3~9小时;
将经过焙烧的工业级Li2CO3和电解MnO2的混合物冷却,达到温度10~50℃;
对经过冷却的工业级Li2CO3和电解MnO2的混合物进行粉碎;
然后通过100~450目筛网,进行筛选。
按照本发明提供的另一种锂离子电池正极材料的制造方法,在其制造步骤中:
包括工业级Li2CO33~13重量份,电解MnO219~72重量份,将工业级Li2CO3和电解MnO2混合搅拌均匀的时间1~7小时;
在将工业级Li2CO3和电解MnO2的混合物分阶段加热的第一阶段,加热温度350~710℃,保温时间2~3.5小时,在第二阶段的加热温度870~910℃,保温时间4~7小时;
将经过焙烧的工业级Li2CO3和电解MnO2的混合物冷却到温度17~40℃;
粉碎后,采用300目筛网进行筛选。
按照本发明提供的又一种锂离子电池正极材料的制造方法,在其制造步骤中:
包括工业级Li2CO313重量份,电解MnO256重量份,将工业级Li2CO3和电解MnO2混合搅拌2小时,使它们混合搅拌均匀;
在第一阶段的加热温度560℃,保温时间3小时,在第二阶段的加热温度870℃,保温时间5小时;
将经过焙烧的工业级Li2CO3和电解MnO2的混合物冷却,达到温度24℃,然后进行粉碎。
采用本发明提供的锂离子电池正极材料的制造方法,能够获得较高比能量的蓄电池,这种蓄电池的自放电量小,使用寿命长。在自然界中由于锰的贮藏量比钴的贮藏量大的多,故锰酸锂比钴酸锂价格便宜的多,更由于其无毒性,而有利于环境保护。
而且,在本发明中通过提高第二加热阶段的温度,同时缩短该阶段加热温度的时间,由此缩短了锂离子电池正极材料制造方法的生产周期,从而有效提高了生产率。
具体实施方式
在本发明的一个优选实施例中,提供了一种锂离子电池正极材料的制造方法,其步骤包括:
将工业级Li2CO32~19重量份,电解MnO215~100重量份混合搅拌均匀,混合搅拌时间0.1~10小时;
将工业级Li2CO3和电解MnO2的混合物输入加热设备中,进行分阶段加热,在第一阶段的加热温度300~720℃,保温时间1~5小时,在第二阶段的加热温度870~950℃,保温时间3~9小时;
将经过焙烧的工业级Li2CO3和电解MnO2的混合物冷却,达到温度10~50℃;
对经过冷却的工业级Li2CO3和电解MnO2的混合物进行粉碎;
然后通过100~450目筛网,进行筛选。
按照本发明的另一个制造锂离子电池正极材料的方法,其中包括工业级Li2CO33~13重量份,电解MnO219~72重量份,将工业级Li2CO3和电解MnO2混合搅拌均匀的时间1~7小时;
在将工业级Li2CO3和电解MnO2的混合物分阶段加热的第一阶段,加热温度350~710℃,保温时间2~3.5小时,在第二阶段的加热温度870~910℃,保温时间4~7小时;
将经过焙烧的工业级Li2CO3和电解MnO2的混合物冷却到温度17~40℃;
粉碎后,采用300目筛网进行筛选。
按照本发明的另一个制造锂离子电池正极材料的方法,其中包括工业级Li2CO313重量份,电解MnO256重量份,将工业级Li2CO3和电解MnO2混合搅拌2小时,使它们混合搅拌均匀;
在第一阶段的加热温度560℃,保温时间3小时,在第二阶段的加热温度870℃,保温时间5小时;
将经过焙烧的工业级Li2CO3和电解MnO2的混合物冷却,达到温度24℃,然后进行粉碎。
上述实施例仅仅是对本发明进行说明,并非对本发明进行限定。本发明请求保护的范围和构思,都记载在权利要求书中。

Claims (3)

1.一种锂离子电池正极材料的制造方法,其步骤包括:
将工业级Li2CO32~19重量份,电解MnO215~100重量份混合搅拌均匀,混合搅拌时间0.1~10小时;
将工业级Li2CO3和电解MnO2的混合物输入加热设备中,进行分阶段加热,在第一阶段的加热温度300~720℃,保温时间1~5小时,在第二阶段的加热温度870~950℃,保温时间3~9小时;
将经过焙烧的工业级Li2CO3和电解MnO2的混合物冷却,达到温度10~50℃;
对经过冷却的工业级Li2CO3和电解MnO2的混合物进行粉碎;
然后通过100~450目筛网,进行筛选。
2.按照权利要求1所述的锂离子电池正极材料的制造方法,其特征是:
其中包括工业级Li2CO33~13重量份,电解MnO219~72重量份,将工业级Li2CO3和电解MnO2混合搅拌均匀的时间1~7小时;
在将工业级Li2CO3和电解MnO2的混合物分阶段加热的第一阶段,加热温度350~710℃,保温时间2~3.5小时,在第二阶段的加热温度870~910℃,保温时间4~7小时;
将经过焙烧的工业级Li2CO3和电解MnO2的混合物冷却到温度17~40℃;
粉碎后,采用300目筛网进行筛选。
3.按照权利要求2所述的锂离子电池正极材料的制造方法,其特征是:
其中包括工业级Li2CO313重量份,电解MnO256重量份,将工业级Li2CO3和电解MnO2混合搅拌2小时,使它们混合搅拌均匀;
在第一阶段的加热温度560℃,保温时间3小时,在第二阶段的加热温度870℃,保温时间5小时;
将经过焙烧的工业级Li2CO3和电解MnO2的混合物冷却,达到温度24℃,然后进行粉碎。
CNB021004412A 2002-01-30 2002-01-30 锂离子电池正极材料的制造方法 Expired - Fee Related CN1180499C (zh)

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CN1233058C (zh) 2003-07-30 2005-12-21 黑龙江中强能源科技有限公司 聚合物锂离子电池及其制造方法
CN100339310C (zh) * 2006-02-27 2007-09-26 新乡市中科科技有限公司 尖晶石结构锂锰氧化物的制备方法
CN103078106B (zh) * 2013-02-07 2015-05-13 湖南信达新材料有限公司 锂离子电池锰酸锂正极材料的制备方法

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