CN1244045A - 溶胶－凝胶法制备锂二次电池正极材料LiCr XMn2-X04的新方法 - Google Patents

溶胶－凝胶法制备锂二次电池正极材料LiCr XMn2-X04的新方法 Download PDF

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CN1244045A
CN1244045A CN99111152A CN99111152A CN1244045A CN 1244045 A CN1244045 A CN 1244045A CN 99111152 A CN99111152 A CN 99111152A CN 99111152 A CN99111152 A CN 99111152A CN 1244045 A CN1244045 A CN 1244045A
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positive electrode
sol
electrode material
lithium battery
licr
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CN1102805C (zh
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唐致远
杨冬平
郭鹤桐
李建纲
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DALU TAIJI BATTERY Co Ltd BEIJING
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M4/36—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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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

本发明涉及溶胶－凝胶法制备锂二次电池正极材料LiCrxMn2－xO4(0< x< 0.3)的新方法,用于锂二次电池的正极材料及制备方法,这种材料为掺铬锂锰复合氧化物LiCrxMn2－xO4(0< x< 0.3)。溶胶－凝胶三步合成法制备这种材料的步骤是:将所用金属的硝酸盐按Li∶Mn∶Cr(原子比)=1～1.05∶2－X∶X的比溶于柠檬酸的乙二醇溶液中制成胶体,再经60～180℃真空干燥、200～300℃热分解后于500～800℃热处理6～12小时。该产物用于锂二次电池的正极材料,具有比容量高、循环性能优良等特点,其充放电循环前十次放电的平均比容量高达128mAh/g,完全可以和LiCoO2相媲美,但成本非常低。

Description

溶胶-凝胶法制备锂二次电池正极材料 LiCrxMn2-xO4的新方法
本发明属于能源技术领域，特别涉及锂二次电池正极材料掺铬锂锰复合氧化物LiCrxMn2-xO4(0＜x＜0.3)的制备方法，利用此法制得的电极材料具有容量高、循环性能好等特点。
锂二次电池正极材料LiMn2O4具有高容量、低成本、低污染等显著的优点，被认为是继LiCoO2之后首选的正极材料，但其较差的循环性限制了其应用。Li Guohua等(J.Electrochem.Soc.，143(1)，178，1996)采用掺杂Co、Cr、Ni改善了LiMn2O4的循环性能。他们以LiCO3、Mn(CHCOO)2·4H2O及Cr2O3为原料，在600℃下预处理6小时后，于750℃合成3天制得了LiCrxMn2-xO4(0＜x＜0.33)。Robertson等(J.Electrochem.Soc.，144(10)，3500，1997)用混合的计量氧化物、碳酸盐或氢氧化物直接在控制气氛下于800℃煅烧20～45小时制得了循环可逆容量达110mAh/g的低掺杂正极材料LiCr0.02Mn1.98O4。最近，D.Zhang等(J.Power Sources 76，81，1998)采用高压固态反应制备了LiCrxMn2-xO4，其比容量也超过了110mAh/g。虽然这些文献中合成的LiCrxMn2-xO4都具有较高比容量与优良的循环性能，但由于都采用固态反应，原料混合不均匀，热合成温度过高，合成时间过长，易造成产物缺陷，影响其比容量与循环性能。
本发明的目的是克服现有技术中的缺点，采用能在原子水平上混合的溶胶-凝胶法制备出高容量、优良循环性能的正极材料LiCrxMn2-xO4(0＜x＜0.3)。
本发明中正极材料LiCrxMn2-xO4(0＜x＜0.3)化合物的制备方法为：将所用金属的硝酸盐按Li∶Mn∶Cr(原子比)＝1～1.05∶2-X∶X的比溶于柠檬酸的乙二醇溶液中制成胶体，再经60～180℃真空干燥、200～300℃热分解、500～800℃热处理6～12小时。
采用双电极式Swagelock模拟电池对LiCoO2、LiMn2O4、LiCrxMn2-xO4(固态法)以及本发明的掺铬锂锰复合氧化物进行性能测试，电池的正极材料组成加下：75～90％正极活性材料，10～15％导电剂乙炔黑，5～10％的粘结剂聚四氟乙烯乳液。电池的负极为锂片，电解液为1MLiPF6的1∶1碳酸乙烯酯(EC)-碳酸二乙酯(DEC)溶液，隔膜为Cellgard2500微孔隔膜。
下面通过实例对比显示本发明专利的有利效果。
           例1
将日本进口LiCoO2正极材料按前述制成薄片进行性能测试，典型极片重量为15～20mg，直径1cm，在4.25～2.75V电压范围内以0.2mA/cm2的电流恒流充放。测试结果如图1所示，该图显示了Li/LiCoO2电池的循环性能。
           例2
将LiCO3与MnCO3按Li∶Mn(原子比)＝1∶2的比例充分混合，置于瓷坩埚内，在空气中于600℃预处理6小时，然后于750℃下加热48小时。所得产物按前述制成正极薄片进行充放电测试，典型极片重量15～20mg，直径1cm以0.2mA/cm2的电流恒流充放，电压范围4.3～3.35V。测试结果如图2所示，该图显示了Li/LiMn2O4电池的循环性能。
            例3
按Li Guohua等(J.Electrochem.Soc.，143(1)，178，1996)的固态法合成LiCrxMn2-xO4。所得产物按前述制成正极薄片进行充放电测试，典型极片重量15～20mg直径1cm，以0.2mA/cm2的电流恒流充放，电压范围4.3～3.35V。测试结果如图3所示，该图显示了Li/LiCr0.1Mn1.9O4(固态法)电池的循环性能。
          例4
将硝酸锂、硝酸锰与硝酸铬按Li∶Mn∶Cr(原子比)＝1∶2-X∶X的比溶于柠檬酸的乙二醇溶液中制成胶体，于140℃蒸除过量溶剂后经180℃真空干燥制成前体物，将前体物研磨后置于瓷坩埚内，在空气中于300℃热分解，然后于600℃热处理8小时。所得产物按前述制成正极薄片进行充放电测试，条件同例2。测试结果如图4所示，该图显示了Li/LiCr0.03Mn1.97O4(溶胶-凝胶法)电池的循环性能。
上述各实例的测试结果对比在下表中示出。从表中可以看出，采用本发明[例4]制备的掺铬锂锰复合氧化物与LiCoO2相比具有相近的比容量；与LiCrxMn2-xO4(固态法)相比，其比容量明显提高，且循环性能优良。因此，用本发明制备的掺铬锂锰复合氧化物完全可以取代LiCoO2作为锂二次电池的正极材料。
     表1各种材料前十次的充放电性能对照表
  实例编号     正极材料   平均比容量(mAh/g) 平均容量衰减(mAh/循环)
    1     LiCoO2     120     3
    2     LiMn2O4     97     5
    3   LiCr0.1Mn1.9O4     116     1
    4  LiCr0.03Mn1.97O4     128     0.5
本发明的有益效果：
采用本发明溶胶-凝胶法能制备的新材料其充放电循环性能优良，其前上次放电平均比容量达128mAh/g，可以与LiCoO2材料相比美，但其成本相对却便宜的多。
附图说明：
图1为Li/LiCoO2电池的循环性能曲线。
图2为Li/LiMn2O4电池的循环性能曲线。
图3为Li/LiCr0.1Mn1.9O4(固态法)电池的循环性能曲线。
图4为Li/LiCr0.03Mn1.97O4(溶胶-凝胶法)电池的循环性能曲线。

Claims (4)

  1. 一种溶胶-凝胶法制备锂二次电池正极材料LiCrxMn2-xO4的新方法，其特征是：
    (1)将金属硝酸盐按Li∶Mn∶Cr(原子比)＝1～1.05∶2-X∶X的比例溶于柠檬酸的乙二醇溶液中制成胶体；
  2. (2)经60～180℃真空干燥；
  3. (3)200～300℃热分解；
  4. (4)500～800℃热处理6～12小时制得。
CN99111152A 1999-07-28 1999-07-28 溶胶－凝胶法制备锂二次电池正极材料LiCrxMn2－xO4的新方法 Expired - Fee Related CN1102805C (zh)

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Cited By (1)

* Cited by examiner, † Cited by third party
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CN103715408A (zh) * 2013-12-13 2014-04-09 天津大学 锂离子电池负极材料钛酸锌锂的溶胶凝胶制备方法

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DE4025208A1 (de) * 1990-08-09 1992-02-13 Varta Batterie Elektrochemisches sekundaerelement
US5783333A (en) * 1996-11-27 1998-07-21 Polystor Corporation Lithium nickel cobalt oxides for positive electrodes

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* Cited by examiner, † Cited by third party
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CN103715408A (zh) * 2013-12-13 2014-04-09 天津大学 锂离子电池负极材料钛酸锌锂的溶胶凝胶制备方法

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