CN104733732A - F取代523三元材料的制备方法 - Google Patents

F取代523三元材料的制备方法 Download PDF

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CN104733732A
CN104733732A CN201510072336.3A CN201510072336A CN104733732A CN 104733732 A CN104733732 A CN 104733732A CN 201510072336 A CN201510072336 A CN 201510072336A CN 104733732 A CN104733732 A CN 104733732A
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牛翱翔
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JIANGSU KING LITHIUM CELL CO Ltd
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JIANGSU KING LITHIUM CELL 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
    • H01M4/36—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
    • 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
    • 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
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M2004/028—Positive electrodes
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

本发明涉及锂离子电池正极材料的制备方法，具体是一种F取代523三元材料的制备方法。该方法是:将NH4F于玛瑙研钵中研细后，以0.5%-2%的质量比与已制备好并破碎的523三元材料在三维锥混机内混合均匀；将混合物在400-700℃进行烧结；冷却后使用万能破碎机进行破碎制得F取代三元正极材料LiNi0.5Co0.2Mn0.3O2-zFz。本发明通过F取代523三元材料，能够获得循环性能、倍率性能及高温储存性能良好的锂离子电池正极材料。

Description

F取代523三元材料的制备方法
技术领域
本发明涉及锂离子电池正极材料的制备方法，具体是一种F取代523三元材料的制备方法。
背景技术
523三元材料(LiNi0.5Co0.2Mn0.3O2)是一种已知的锂离子电池的正极材料，该材料存在着循环性能较低的缺陷，不能满足高性能锂离子电池的使用要求。
发明内容
本发明所要解决的技术问题是，通过对常规523三元材料的成份进行调整，提供一种具有较好循环性能的F取代523三元材料的制备方法。
本发明的F取代523三元材料的制备方法是:
将NH4F于玛瑙研钵中研细后，以0.5％-2％的质量比与已制备好并破碎的523三元材料在三维锥混机内混合均匀；将混合物在400-700℃进行烧结；冷却后使用万能破碎机进行破碎制得F取代三元正极材料LiNi0.5Co0.2Mn0.3O2-zFz。
优选地，所述NH4F与523三元材料的质量比为1％，烧结温度为600℃。
上述步骤中作为原料的523三元材料的制备方法是：按1.01-1.10摩尔比将电池级碳酸锂和523三元前驱体分别于玛瑙研钵中研细后，放入三维锥混机内混合均匀，在90-100℃真空干燥箱中干燥12-15h；再将其研磨3-4h。
本发明通过F取代523三元材料，能够获得循环性能、倍率性能及高温储存性能良好的锂离子电池正极材料。
附图说明
图1是本发明实施例样品与普通523三元材料的的放电容量随循环周数变化对比曲线图。
具体实施方式
本发明实施例步骤如下：
1、制备523三元材料LiNi0.5Co0.2Mn0.3O2：按1.05的摩尔比将电池级碳酸锂与523三元前驱体分别于玛瑙研钵中研细后，放入三维锥混机内混合均匀，在95℃真空干燥箱中干燥15h；再将其研磨4h；
2、制备F取代三元正极材料LiNi0.5Co0.2Mn0.3O2-zFz：将NH4F于玛瑙研钵中研细后，以1％的质量比与已制备好并破碎的523三元材料在三维锥混机内混合均匀；将混合物在600℃进行烧结，气流量为40L/min；冷却后使用万能破碎机进行破碎制得成品。
制得的正极材料样品检测指标如表1、表2：
表1 LiNi0.5Co0.2Mn0.3O2-zFz样品物化指标
测试压实密度所使用的辊直径为800mm
表2 LiNi0.5Co0.2Mn0.3O2-zFz样品克容量及倍率性能
本发明实施例制得的样品在60度烘烤7天的放电容量随循环周数变化图如图1所示，可以看出本发明的样品较未取代的523三元材料样品具有良好的循环性能。

Claims (3)

1.一种F取代523三元材料的制备方法，其特征是:
将NH4F于玛瑙研钵中研细后，以0.5%-2%的质量比与已制备好并破碎的523三元材料在三维锥混机内混合均匀；将混合物在400-700℃进行烧结；冷却后使用万能破碎机进行破碎制得F取代三元正极材料LiNi0.5Co0.2Mn0.3O2-zFz。
2.根据权利要求1所述的F取代523三元材料的制备方法，其特征是:所述NH4F与523三元材料的质量比为1%，烧结温度为600℃。
3.根据权利要求1所述的F取代523三元材料的制备方法，其特征是:
作为原料的523三元材料的制备方法是：按1.01-1.10摩尔比将电池级碳酸锂和523三元前驱体分别于玛瑙研钵中研细后，放入三维锥混机内混合均匀，在90-100℃真空干燥箱中干燥12-15 h；再将其研磨3-4 h。
CN201510072336.3A 2015-02-11 2015-02-11 F取代523三元材料的制备方法 Pending CN104733732A (zh)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102403494A (zh) * 2011-10-17 2012-04-04 江苏科捷锂电池有限公司 锰基层状晶体结构锂电池正极材料及其制备方法
CN102903904A (zh) * 2012-10-09 2013-01-30 江苏科捷锂电池有限公司 LiAlO2包覆尖晶石锰酸锂正极材料的制备方法
CN103117380A (zh) * 2013-01-31 2013-05-22 中信大锰矿业有限责任公司 锂离子电池用锰系镍钴锰酸锂三元材料的制备方法
CN103500824A (zh) * 2013-09-24 2014-01-08 上海空间电源研究所 一种表面阴离子改性的富锂锰基正极材料及其制备方法
CN103943863A (zh) * 2013-01-23 2014-07-23 江南大学 阴离子掺杂改性的过锂(5:3:2)型三元锂离子电池正极材料

Patent Citations (5)

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CN102403494A (zh) * 2011-10-17 2012-04-04 江苏科捷锂电池有限公司 锰基层状晶体结构锂电池正极材料及其制备方法
CN102903904A (zh) * 2012-10-09 2013-01-30 江苏科捷锂电池有限公司 LiAlO2包覆尖晶石锰酸锂正极材料的制备方法
CN103943863A (zh) * 2013-01-23 2014-07-23 江南大学 阴离子掺杂改性的过锂(5:3:2)型三元锂离子电池正极材料
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CN103500824A (zh) * 2013-09-24 2014-01-08 上海空间电源研究所 一种表面阴离子改性的富锂锰基正极材料及其制备方法

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