CN1147951C - 一种提高钴酸锂的中位径和振实密度的方法 - Google Patents

一种提高钴酸锂的中位径和振实密度的方法

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Publication number
CN1147951C
CN1147951C CNB011234318A CN01123431A CN1147951C CN 1147951 C CN1147951 C CN 1147951C CN B011234318 A CNB011234318 A CN B011234318A CN 01123431 A CN01123431 A CN 01123431A CN 1147951 C CN1147951 C CN 1147951C
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position radius
tap density
licoo
meso
licoo2
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CN1328351A (zh
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周恒辉
杨正
任献举
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Xianxing Science-Technology-Industry Co., Ltd., Beijing Univ
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Xianxing Science-Technology-Industry Co Ltd Beijing Univ
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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
    • H01M4/52—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
    • 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
    • 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)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

一种提高钴酸锂的中位径和振实密度的方法。将Li2CO3、LiOH或两者的混合物、CoCO3、Co3O4或两者的混合物、LiCoO2，三种物料按比例混合均匀；在300～1000℃下合成2～20小时；将合成物料中的团聚物破碎。用这种方法所制备的LiCoO2的中位径和振实密度大，并克服了一次烧成LiCoO2大粒子所造成的可能粒子内部反应不完全和晶型不完整，避免了为提高LiCoO2中位径和振实密度而将LiCoO2多次烧结造成的锂的过度挥发，和对粒子表面的破坏，以及能耗巨大。可用于高能电源特别是锂离子电池的制造领域。

Description

一种提高钴酸锂的中位径和振实密度的方法
技术领域：本发明属于高能电源的技术领域，尤其设计一种提高钴酸锂(LiCoO2)的中位径和振实密度的方法。
背景技术：LiCoO2作为锂离子电池的正极材料，因其比容量高，性能稳定和制备工艺简单而已被广泛地商业化生产。当LiCoO2的粒度分布的中位径D50＜10微米(μm)时，LiCoO2的表面活性较大而使锂离子电池的安全性较差；并且振实密度较小(＜2.5克/立方厘米(g/cm3))，难以提高锂离子电池的体积比容量。为了改善这两方面的性能，即D50＞10微米和振实密度＞2.5g/cm3，人们往往采用提高锂钴比(Li/Co)(＞1.00)比例和温度(＞900℃)或多次烧结等方法来实现，如参考文献：1.T.Nakamura，A.Kajiyama，Solid State Ionics 123(1999)95～101；2.N.Imanishi，M.Fujii，A.Hirano，et al.，Solid State Ionics 140(2001)45～53；3.Glenn G.Amatucci，Jean-Marie Tarascon，US005693435A Dec.2，1997。
但这将造成LiCoO2的比容量和平均电压较低，并且工业化生产的能耗大。
发明内容：本发明的目的在于在保持已有的性能的情况下，如放电比容量＞140mAh/g(毫安小时/克)，合成出振实密度和中位径大的LiCoO2。
本发明的一种提高钴酸锂的中位径和振实密度的方法，其步骤包括
1.将碳酸锂(Li2CO3)、氢氧化锂(LiOH)之一或两者的混合物，碳酸钴(CoCO3)、氧化钴(Co3O4)之一或两者的混合物，钴酸锂(LiCoO2)三种物料混合均匀，其中前两种物料的Li/Co比例为0.95～1.10；
2.在300～1000℃下合成2～20小时；
3.将合成后物料中的团聚物破碎。
上述物料中LiCoO2占整个物料的重量比为大于0％而小于100％。
上述所用物料料LiCoO2的中位径＜10微米，振实密度＜2.5g/cm3。
用上述方法所制备的LiCoO2的中位径D50＞10μm，振实密度＞2.5g/cm3，放电比容量＞140mAh/g，其它性能不亚于其它方法合成的LiCoO2；本发明的优点还在于：以LiCoO2为晶核，含钴物料和含锂物料在其表面反应所形成的LiCoO2大粒子，克服了一次烧成LiCoO2大粒子所造成的可能粒子内部反应不完全和晶型不完整；并且避免了为提高LiCoO2中位径和振实密度而将LiCoO2多次烧结造成的锂的过度挥发，和对粒子表面的破坏，以及能耗巨大。采用本发明方法制成的LiCoO2可用于锂离子电池。锂离子电池作为高能电源，广泛应用于手提电话，笔记本电脑，摄象机，电动自行车及电动汽车等。
具体实施方式：
实例1
Li2CO3和Co3O4的Li/Co比例为1.02；LiCoO2的重量占整个物料的10％，三种物料混合均匀；混合物料在500℃下合成，烧结时间为5小时；降温后将LiCoO2破碎。LiCoO2的中位径D50：10.5μm，振实密度：2.6g/cm3，放电比容量：144mAh/g。
实例2
Li2CO3和Co3O4的Li/Co比例为1.03；LiCoO2的重量占整个物料的30％，三种物料混合均匀；混合物料在700℃下合成，烧结时间为8小时；降温后将LiCoO2破碎。LiCoO2的中位径D50：11.2μm，振实密度：2.65g/cm3，放电比容量：143mAh/g。
实例3
Li2CO3和Co3O4的Li/Co比例为1.05；LiCoO2的重量占整个物料的50％，三种物料混合均匀；混合物料在800℃下合成，烧结时间为4小时；降温后将LiCoO2破碎。LiCoO2的中位径D50：12.0μm，振实密度：2.7g/cm3，放电比容量：145mAh/g。
实例4
Li2CO3和Co3O4与CoCO3(两钴盐的重量比为8∶2)的Li/Co比例为1.08；LiCoO2的重量占整个物料的60％，三种物料混合均匀；混合物料在900℃下合成，烧结时间为10小时；降温后将LiCoO2破碎。LiCoO2的中位径D50：13.2μm，振实密度：2.75g/cm3，放电比容量：145mAh/g。
实例5
Li2CO3和LiOH的重量比为3∶7，和Co3O4的Li/Co比例为1.03；LiCoO2的重量占整个物料的90％，三种物料混合均匀；混合物料在400℃下合成，烧结时间为15小时；降温后将LiCoO2破碎。LiCoO2的中位径D50：11.8μm，振实密度：2.55g/cm3，放电比容量：142mAh/g。

Claims (3)

1.一种提高钴酸锂的中位径和振实密度的方法，其步骤包括
1)将Li2CO3、LiOH之一或两者的混合物、CoCO3、Co3O4之一或两者的混合物、LiCoO2三种物料混合均匀，其中前两种物料的Li/Co比例为0.95～1.10；
2)在300～1000℃下合成2～20小时；
3)将合成后物料中的团聚物破碎。
2.如权利要求1所述的一种提高钴酸锂的中位径和振实密度的方法，其特征在于LiCoO2占整个物料的重量比为大于0％而小于100％。
3.如权利要求1所述的一种提高钴酸锂的中位径和振实密度的方法，其特征在于所用原料LiCoO2的中位径＜10微米，振实密度＜2.5g/cm3。
CNB011234318A 2001-07-23 2001-07-23 一种提高钴酸锂的中位径和振实密度的方法 Expired - Lifetime CN1147951C (zh)

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ATE333149T1 (de) * 2002-05-30 2006-08-15 Sulzer Hexis Ag Verfahren zum präparieren einer beschichtungspaste
CN100385248C (zh) * 2004-06-01 2008-04-30 肇庆市风华锂电池有限公司 电池电极材料填充性能测试方法
CN102169990B (zh) * 2011-04-07 2013-06-26 先进储能材料国家工程研究中心有限责任公司 一种三元正极材料及其生产方法
CN102779976B (zh) * 2011-10-10 2015-05-20 北大先行泰安科技产业有限公司 一种钴酸锂基锂离子电池正极材料的制备方法

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