CN1455466A - 锂离子电池用结构稳定的尖晶石锰酸锂及其制备方法 - Google Patents

锂离子电池用结构稳定的尖晶石锰酸锂及其制备方法 Download PDF

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CN1455466A
CN1455466A CN03117801A CN03117801A CN1455466A CN 1455466 A CN1455466 A CN 1455466A CN 03117801 A CN03117801 A CN 03117801A CN 03117801 A CN03117801 A CN 03117801A CN 1455466 A CN1455466 A CN 1455466A
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lithium
temperature
lithium ion
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杨永平
陈宝荣
何鵾曙
肖扬
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Yunnan Nengtou Huilong Technology Co ltd
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H01M4/1315—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx containing halogen atoms, e.g. 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M4/13915—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx containing halogen atoms, e.g. LiCoOxFy
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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
    • H01M4/50—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
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Abstract

一种锂离子电池用结构稳定的尖晶石锰酸锂及其制备方法，将粒径10～20μm的电解二氧化锰、粒径5～10μm的碳酸锂和粒径5～10μm的氧化钴混合均匀，经多元掺杂、高温固相烧结而成，按质量百分比为：含量大于92％的电解二氧化锰MnO270～72％、含量大于99.9％的碳酸锂Li2CO315～17％、含量大于70％的氧化钴CoO10～20％以及由镍Ni、铬Cr、铁Fe、锰Mg、硒Si、氟F组成的多元掺杂体1～3％。

Description

锂离子电池用结构稳定的尖晶石锰酸锂及其制备方法
技术领域
本发明涉及电池制造技术，尤其是一种锂离子电池用结构稳定的尖晶石锰酸锂及其制备方法。
背景技术
随着能源的日趋缺乏和生态环境的日益恶化，电动交通工具取代内燃机是必然的选择，世界发达国家如美国，法国、德国、日本等都投入了大量人力、物力、财力从事电动车的研制开发。我国政府对电动车项目非常重视，在“八五”期间就把电动车技术的研制开发列为国家科技攻关重点项目，“九五”期间被列为国家重大科技产业工程项，“十五”期间电动汽车产业化被国家科技部列为重大科技专项。
目前电动车存在的主要问题如价格、续驶里程、动力性能等都与电池技术密切相关。作为电动车用蓄电池应具有以下特点：①高的质量比能量和体积比能量：②具有快速充电和大电流放电能力；③良好的循环寿命性能；④价格低，使用维护方便；⑤无污染，安全性能好。
锂离子电池由于具有高的比能量和良好的循环寿命性能而成为电动车用动力源的首选，但锂离子动力电池的性能关键取决于其正极材料。目前，已广泛应用和正在进行开发研究的锂离子电池正极材料主要是锂钴氧LiCoO2、锂镍氧LiNiO2和锂锰氧LiMn2O4三种，LiCoO2具有良好的电化学性能和3.6伏的工作电压，技术较为成熟，是当前市场的主流产品，但钴的储量有限，价格昂贵，存在一定的安全隐患，面临被其它产品替代的趋势。LiNiO2具有价格和储量上的优势，其实际容量190mAh.g-1～210mAh.g-1已接近理论容量的70～80％，但工作电压低、制备难度大。尖晶石结构的锰酸锂LiMn2O4具有较好的正极材料特性，具有价格低廉、工作电压高、自放电小、安全无污染、性价比高等特点，是锂离子动力电池首选正极材料，但随着电池充放电循环的进行，出现容量衰减的现象，从而导致循环性能差。
发明内容
本发明的目的就在于克服上述现有技术中存在的不足，提出一种锂离子电池用结构稳定的尖晶石锰酸锂及其制备方法，它是以碳酸锂和电解二氧化锰为原料、经过掺杂改性，以多元掺杂的方式，经高温固相烧结而成电容量高的产品，能有效改善产品的循环性能；制备方法简单易控制、生产工艺流程短，适合规模化工业生产。
本发明提出的锰酸锂按质量百分比为：含量大于92％的电解二氧化锰MnO2 70～72％、含量大于99.9％的碳酸锂Li2CO3 15～17％、含量大于70％的氧化钴CoO 10～20％以及由镍Ni、铬Cr、铁Fe、锰Mg、硒Si、氟F组成的多元掺杂体1～3％。
其制作方法为：将粒径10～20μm的电解二氧化锰、粒径5～10μm的碳酸锂、粒径5～10μm的氧化钴和多元掺杂体按上述比例充分混合在一起，将混合均匀的上述原料置入连续式烧结炉中，先在110～130℃的温度下恒温加热12～15h，接着在550～750℃温度下恒温加热18～20h，最后在800～850℃温度下加热12～15h。焙烧反应完后在连续式烧结炉中自然冷却10小时，分级检验即得到产品。
本发明与现有技术相比有以下优点：
1、本发明提出的制备方法工艺简单易控制，缩短了流程，节省反应时间，可降低生产成本，增加经济效益，并能够保证合成锰酸锂为尖晶石结构，并可大规模工业化生产，日产可达1100公斤。
2、本发明在制备中采用多元掺杂的方式，使LiMn2O4的尖晶石结构的晶格结构移固并可在表面形成保护膜，加入的钴、镍、铬、铁、镁、硒、氟元素不是进入尖晶石八面体中心位置取代锰而是在尖晶石晶胞间存在，起稳定尖晶石作用，防止被破坏；这些元素对尖晶石胞体稳定影响不大，在充放电过程中，锂离子能在尖晶石晶胞中自由出入。
3、本发明获得的产品容量高，循环性能好，该产品在EC∶DMC(1∶1)+1mol/1LiPF6电解液中表现出较好的充放电性能和良好的循环性能，并且产品结构稳定，首次放电容量达130mAh.g-1，500次循环后容量持有率可达73.41％。

Claims (2)

1、锂离子电池用结构稳定的尖晶石锰酸锂，其特征在于锰酸锂组成按质量百分比为：含量大于92％的电解二氧化锰MnO2 70～72％、含量大于99.9％的碳酸锂Li2CO3 15～17％、含量大于70％的氧化钴CoO 10～20％以及由镍Ni、铬Cr、铁Fe、锰Mg、硒Si、氟F组成的多元掺杂体1～3％。
2、如权利要求1所述锂离子电池用结构稳定的尖晶石锰酸锂的制备方法，其特征在于：将粒径10～20μm的电解二氧化锰、粒径5～10μm的碳酸锂、粒径5～10μm的氧化钴和多元掺杂体按比例混合均匀，上述原料置入连续式烧结炉中，先在110～130℃的温度下恒温加热12～15h，接着在550～750℃温度下恒温加热18～20h，最后在800～850℃温度下加热12～15h，焙烧反应完后，在连续式烧结炉中自然冷却10小时，分级检验即得到产品。
CNB031178014A 2003-04-30 2003-04-30 锂离子电池用结构稳定的尖晶石锰酸锂的制备方法 Expired - Lifetime CN1300868C (zh)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101117234B (zh) * 2006-08-04 2010-05-12 比亚迪股份有限公司 一种掺杂的富锂的尖晶石型锂锰氧的制备方法
CN101964416A (zh) * 2010-10-25 2011-02-02 湖南长远锂科有限公司 锂离子电池正极材料锰酸锂的制备方法及车用锂离子电池
WO2012159253A1 (zh) 2011-05-23 2012-11-29 中国科学院宁波材料技术与工程研究所 锂离子电池正极材料、其制备方法及锂离子电池

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102195042A (zh) * 2010-03-09 2011-09-21 中国科学院过程工程研究所 一种高性能锂离子电池正极材料锰酸锂及其制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11180717A (ja) * 1997-12-22 1999-07-06 Ishihara Sangyo Kaisha Ltd マンガン酸リチウム及びその製造方法ならびにそれを用いてなるリチウム電池
KR100544541B1 (ko) * 1998-02-09 2006-01-24 하.체. 스타르크 게엠베하 리튬-전이 금속 혼합물의 제조 방법
CN1175509C (zh) * 2001-04-11 2004-11-10 中南大学 一种锰酸锂的制备方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101117234B (zh) * 2006-08-04 2010-05-12 比亚迪股份有限公司 一种掺杂的富锂的尖晶石型锂锰氧的制备方法
CN101964416A (zh) * 2010-10-25 2011-02-02 湖南长远锂科有限公司 锂离子电池正极材料锰酸锂的制备方法及车用锂离子电池
CN101964416B (zh) * 2010-10-25 2012-06-27 湖南长远锂科有限公司 锂离子电池正极材料锰酸锂的制备方法及车用锂离子电池
WO2012159253A1 (zh) 2011-05-23 2012-11-29 中国科学院宁波材料技术与工程研究所 锂离子电池正极材料、其制备方法及锂离子电池

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