CN1055793C - 锂锰电池中锂锰复合氧化物的制造方法 - Google Patents

锂锰电池中锂锰复合氧化物的制造方法 Download PDF

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Publication number
CN1055793C
CN1055793C CN95101589A CN95101589A CN1055793C CN 1055793 C CN1055793 C CN 1055793C CN 95101589 A CN95101589 A CN 95101589A CN 95101589 A CN95101589 A CN 95101589A CN 1055793 C CN1055793 C CN 1055793C
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lithium
manganese dioxide
manganese
cobalt oxide
spinel
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CN1129855A (zh
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刘昌炎
李桂芳
马巍
王艳乔
邸振文
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Institute of Chemistry CAS
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Institute of Chemistry CAS
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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
    • H01M4/36—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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

一种锂锰复合氧化物的制造方法，它是涉及锂电池中正极活性材料制造方法，二氧化锰与氢氧化锂或碳酸锂混合后加入氧化钴，三者比例为1∶0.5～1∶0～0.15经热处理后形成掺杂尖晶石，是二次锂电池正极活性物质材料，由于氧化钴使尖晶石晶格形成空隙，从而使比容量由100mAh/g提高至160mAh/g。

Description

锂锰电池中锂锰复合氧化物的制造方法
本发明涉及一种锂电池中正极活性材料的制造方法。
在锂电池中，以二氧化锰(MnO2)作正极活性材料，具有价格低廉，保存性能好等优点，日本专利Jp02054865以MnO2为主体加入适量的LiOH或Li2CO3混合均匀后进行热处理，反应后得到具有尖晶石结构的活性材料。
在二次锂电池中应用这种正极材料时，在充放电过程中，锂离子在尖晶石中进行“嵌入”和“脱嵌”循环，而正极材料结构不发生变化，因此制得的电池可以深度充放电，具有长的充放电循环寿命。但是，这种尖晶石材料活性低，比容量大约在100mAh/g左右，无法制备成高容量的二次电池。
本发明的目的是为了克服比容量低的缺点而提供一种高比容量的尖晶石正极活性材料的制造方法。
本发明是在LiOH或Li2CO3与MnO2的混合物中加入少量过渡元素氧化物，如V2O5，NiO2，Co2O3，进行热处理，反应后的产物称为掺杂的尖晶石。Co2O3使尖晶石晶格形成空隙便于锂离子深入尖晶石晶格内“嵌入”和“脱嵌”，从而提高正极材料的活性，增大比容量，掺杂尖晶石正极活性材料的制备包括以下步骤：将纯度为85％的MnO2经水洗至中性，烘干。在1摩尔MnO2中加入0.5～1摩尔的LiOH，再加入0～0.15摩尔的Co2O3，混合研磨，以350-470℃热处理10-24小时，最佳热处理条件为380-470℃，18-21小时，然后水洗至中性，以除去未反应的LiOH烘干备用。
用常规方法将正极材料压片，以塑料薄膜为隔膜，用1摩尔的LiClO4溶解在碳酸丙烯酯中和乙二醇二甲醚混合溶剂中作为电解质，制成扣式电池。
表I为以掺杂和未掺杂尖晶石为正极材料所制得的锂电池电池容量的比较：电池           E0(伏)  放电制式        终止电压(伏)  比容量(mAh/g)1号(掺)        3.4      0.2mA恒流       2.0           1672号(未)        3.4      0.2mA恒流       2.0           106
图1表示出1，2号电池的放电曲线，图2表示出掺杂尖晶正极材料的循环伏安特性。用掺杂的尖晶石作正极材料，制成AA型园柱电池，总重量为20g，容量可达1000mAh。
实施例1、
将纯度为85％的MnO2水洗至中性，烘干，取其10克加入2.8克的LiOH和1克Co2O3研磨混合，在400℃反应20小时，将产物放入清水中洗至中性过滤，烘干得掺杂尖晶石10克，以该尖晶石作锂电池正极活性材料，放电容量为143mAh/g。实施例2、
将纯度为85％的MnO2水洗至中性，烘干取其10克，LiOH5.5克，Co2O32.9克，研磨混合均匀，在470℃反应18小时，后处理条件同实施例1，得掺杂尖晶石11.5克制成锂电池的放电容量为141mAh/g。实施例3、
将纯度为85％的MnO2水洗至中性，烘干，取其10克加入LiOH1.2克在380℃下反应21小时，后处理条件同实施例1，得掺杂尖晶石9克，制成的锂电池放电容量为115mAh/g。

Claims (3)

1、一种锂锰氧化物的制备方法，它由二氧化锰，和锂化合物经加热制成，其特征在于在二氧化锰和氢氧化锂或碳酸锂混合物中还加入氧化钴，其中二氧化锰∶锂化合物∶氧化钴按摩尔比为1∶0.5～1∶0～0.15，三者经混合研磨后在350～470℃，热处理10-24小时。
2、根据权利要求1所述的锂锰氧化物的制备方法，其特征在于热处理条件为380-470℃，时间为18-21小时。
3、根据权利要求1所述的锂锰氧化物的制备方法，其特征在于所述的二氧化锰经水洗至中性。
CN95101589A 1995-02-22 1995-02-22 锂锰电池中锂锰复合氧化物的制造方法 Expired - Fee Related CN1055793C (zh)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1894822B (zh) * 2003-12-15 2010-06-02 日本电气株式会社 二次电池

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1100355C (zh) * 1999-07-28 2003-01-29 北京大陆太极电池有限公司 固态法制备锂二次电池正极材料LiCrxMn2－x04的新方法
CN110676450A (zh) * 2019-10-16 2020-01-10 南昌工程学院 一种二次电池正极材料及其电池

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04123762A (ja) * 1990-09-14 1992-04-23 Honda Motor Co Ltd アルカリ金属二次電池用正極活物質およびこれを用いた正極の製造方法
JPH076763A (ja) * 1993-06-15 1995-01-10 Toray Ind Inc 非水溶媒系二次電池

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04123762A (ja) * 1990-09-14 1992-04-23 Honda Motor Co Ltd アルカリ金属二次電池用正極活物質およびこれを用いた正極の製造方法
JPH076763A (ja) * 1993-06-15 1995-01-10 Toray Ind Inc 非水溶媒系二次電池

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1894822B (zh) * 2003-12-15 2010-06-02 日本电气株式会社 二次电池

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