CN1288772C - 锂离子电池正极材料LiMn2O4乳胶干燥熔融制备方法 - Google Patents

锂离子电池正极材料LiMn2O4乳胶干燥熔融制备方法 Download PDF

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CN1288772C
CN1288772C CNB021168989A CN02116898A CN1288772C CN 1288772 C CN1288772 C CN 1288772C CN B021168989 A CNB021168989 A CN B021168989A CN 02116898 A CN02116898 A CN 02116898A CN 1288772 C CN1288772 C CN 1288772C
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沈涛
唐琛明
董辉
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Jiangsu Highstar Battery Manufacturing 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
    • H01M4/04—Processes of manufacture in general
    • 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
    • H01M4/139—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
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

采用乳胶干燥熔融法制备LiMn2O4适用于制成动力型锂离子电池正极膜。本发明公开了LiMn2O4正极粉是以MnCO3和LiCH3COO为原料，按比例混合，掺杂少部分离子，与PVDF及聚乙烯醇混合成乳胶液，干燥后在850℃温度下成熔融态后经粉化处理制得。制得的LiMn2O4正极粉组装成电池，工作电位在3.7-4.15V，比容量为135mAh/g(正极粉)以上，5C放电容量在128mAh/g以上。

Description

锂离子电池正极材料LiMn2O4乳胶干燥熔融制备方法
(一)技术领域
本发明涉及一种适用动力型锂离子电池正极材料LiMn2O4的制备方法，它属于电化学、无机合成和电子产品技术领域。
(二)背景技术
随着社会的发展，充电电池被家电、交通等领域广泛使用，而锂离子电池以其重量轻、功率大、寿命长、无记忆效应、无污染等多项优点被公认为是未来最具发展潜力的电力能源供应品之一。但目前普通锂离子电池，其成本很高，大电流、高低温性能差，不易在电动车辆推广使用，正极材料制备是关键技术之一，许多公司和研究机构研究各种正极材料及制备方法，有一些材料已是成熟产品，文献报道，已发展的合成方法有：①高温固相法(TARASCON JM，MCKINNOM W R，COOWAR F，et al.Synthesis condition and oxygenstoichiometry effects on Li insertion into spinel LiMn2O4[J].JElectrochem Soc，1994，141(6)：1421.)②溶胶-凝胶法(BACH S，HENRY M，BAFFIER N，etal.SOL-gel synthesis of manganese oxides[J].State Chem，1990，88：325.)③水热合成法(HUANG Haitao.BRUCE Peter G.A 4 V lithium manganese oxidecathode for rocking-chair lithium-ion cells[J].J ElectrochemSoc，1994，141(9)：L 106.)④Rechini方法(LIU W，KOWALK，FARRINGTONK G C.Synthesisand electrochemical studies of spine phase LiMn2O4 cathode materialprepared by the pechini process[J].J Electrochem Soc，1996，143(3)：879.)等，目前常法制备的LiMn2O4(锰酸锂)由于其循环寿命短及容量低，大电流放电性能差，限制使用。需寻找一种更适合动力型锂电用的LiMn2O4的制备方法。
(三)发明内容
本发明的目的在于提供一种LiMn2O4的制备方法，该法是采用乳胶干燥熔融法制备LiMn2O4，能适用于制造成动力型锂离子电池正极膜。具有原料易得、生产成本较低、工艺简单稳定、适于规模化生产的特点。
(四)具体实施方式
为实现本发明的目的所采取的技术措施是：
1、材料制备原理
合成LiMn2O4是以碳酸锰(MnCO3)和醋酸锂(LiCH3COO)为原料，基本合成反应为
Figure C0211689800031
2、合成材料配方
按投料原料的正确成分和含量锂/锰摩尔比为0.5的比例混合，添加总重量比为1％的含Ni2+、Co3+、Mg2+离子和由聚偏二氟乙烯(PVDF)及聚乙烯醇(PVA)组成、其中聚偏二氟乙烯(PVDF)重量占胶总重量15～20％的混合胶。
3、合成工艺
按上述配方，将原料混合成乳胶状在200℃温度下干燥5～7小时，然后在850℃温度下成熔融态反应10小时，冷却后取出，经过粉化处理制得LiMn2O4正极粉。
与已有技术相比，本发明已达到的效果
本发明制备的LiMn2O4具有以下显著特点
1、制备的LiMn2O4材料晶相均匀，放电性能达到135mAh/g比容量，工作电位在3.7～4.15V。
2、制备的材料大电流放电性能较好，5C放电容量在128mAh/g。
3、工艺简单稳定，适于规模化生产。
4、原料易得，生产成本较低。
附图说明：
图1是用本发明方法制得的LiMn2O4材料制成正极膜在0.2C倍率充放电及5C倍率放电下的曲线。
图注：①充电曲线
      ②0.2C放电曲线
      ③5C放电曲线

Claims (5)

1、一种可以达135mAh/g高比容量、能5C倍率放电的的锂离子电池正极材料LiMn2O4乳胶干燥熔融制备方法，其特征在于该方法是以碳酸锰(MnCO3)和醋酸锂(LiCH3COO)为原料，按比例配合，添加占总重比1％的Ni2+、Co3+、Mg2+离子和含聚偏二氟乙烯(PVDF)的聚乙烯醇混合胶，将原料混合成乳胶状后在200℃温度下先干燥5～7小时，然后在850℃温度下成熔融、冷却，经过粉化处理制得产品。
2、按权利要求1所述的制备方法，其特征在于原料采用碳酸锰(MnCO3)和醋酸锂(LiCH3COO)，其中锂/锰摩尔比为0.5。
3、按权利要求1所述的制备方法，其特征是制备时添加的混合胶作为胶粘剂，混合胶由聚偏二氟乙烯(PVDF)及聚乙烯醉(PVA)组成，其中聚偏二氟乙烯(PVDF)重量占胶总重量15～20％。
4、按权利要求1所述的制备方法，其特征是制备成乳胶状浆料混合后有一干燥过程，其干燥温度200℃。
5、按权利要求1所述的制备方法，其特征是制成的LiMn2O4具有放电性能达到135mAh/g比容量，工作电位在3.7～4.15V，5C放电容量大于128mAh/g。
CNB021168989A 2002-04-26 2002-04-26 锂离子电池正极材料LiMn2O4乳胶干燥熔融制备方法 Expired - Fee Related CN1288772C (zh)

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