CN1339835A - 一种高性能锂离子二次电池正极材料的合成方法 - Google Patents

一种高性能锂离子二次电池正极材料的合成方法 Download PDF

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CN1339835A
CN1339835A CN00123843A CN00123843A CN1339835A CN 1339835 A CN1339835 A CN 1339835A CN 00123843 A CN00123843 A CN 00123843A CN 00123843 A CN00123843 A CN 00123843A CN 1339835 A CN1339835 A CN 1339835A
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positive electrode
nanoscale
secondary cell
high performance
lithium iron
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潘树明
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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
    • H01M4/13—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
    • 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
    • H01M4/13—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
    • H01M4/485—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
    • 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
    • H01M4/52—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
    • 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)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

本发明涉及一种高性能锂离子二次电池正极材料的合成方法。它是以Li、Mn、Co、Ni、Cr、P的相应氧化物或相应的碳酸盐,硝酸盐、氢氧化物为原料，按LiNixCo1－xO2(X=01－0.99)、LiMnxQ2－xO4(X=0.1～2,Q为Cr、V、P、Co)比例混合,研磨至纳米级或接近纳米级,装入微波炉中通入氧气,进行加热,保温取出后再研磨到纳米级或接近纳米级。即可得到性能良好的正极材料产品。

Description

一种高性能锂离子二次电池正极材料的合成方法
本发明涉及电极的活性材料的制作方法，更确切地，便是用于锂离子二次电池的正极材料的制作方法。
目前用于锂离子电池正极材料：LiCoO2、LiNiO2、LiMn2O4常规方法是固相反应法，即以锂的盐或其氢氧化物和Ni、Co、Mn、的盐或金属的氢氧化物在600-900℃高温下较长时间煅烧，经数次重复，所得材料其电化学可逆容量均在110-140mAh/g；其缺点是：消耗大量电能，周期长，混合的均匀性差，锂盐大量挥发，难以控制成份，因而产品稳定性差。制出电池均匀性、一致性差。
本发明的目的在于克服上述制作技术的缺点，能有效地控制成份，得到正极材料稳定性好，制出电池均匀性、一致性良好的产品。并节省电能，降低成本。
本发明的目的是这样实现的：合成正极材料使用的设备是用微波0.1-500GH2频率的微波炉，合成过程中通以氧气使反应进行加快而且反应完成的好，之后再粉碎到纳米级粒度。首先将原料按组成配方如LiNixCo1-xO2(x为0.1-0.99)、LiCoO2、LiMnxQ2-xO4(x＝0.1～2，Q为Cr、V、P、Co)混合均匀，放在耐高温材料容器中，然后置入0.1-500GH2频率的微波炉中，合成温度是450～1000℃之间，保温时间0.5～1.5小时，通入少量氧气，保温之后，停电随炉冷，合成的正极材料组成是：
LixM1-yQyO2，其中x＝0.1～1，y＝0～1，M＝Ni、Co、MnQ＝Ni、Co、Mn、V、Cr、P等的锂离子电池用的正极材料。本发明特点之一是使原材料和最终合成的正极材料粒度是纳米级，或接近纳米级，合成的正极材料粉碎到纳米级或接近纳米级，使其本身的放电容量大大提高。
本发明使用0.1～500GH2范围的微波炉除具有频率高波长短，穿透能力优外，反应中有电磁搅拌加快反应，通入氧气加快合成速度，故不仅效率高而且节省电能，减少Li离子挥发，使成份准确。
以下用非限定实例具体详细地描述发明将有助于对本发明及其优点的理解，本发明的保护范围不受这些实例的限定，本发明保护范围由权利要求书来决定。
实例1：正极材料LiNi0.55Co0.45O2的合成。
原料：LiOH、Ni2O3、Co2O3(均为分析纯)
配比：Li∶Co∶Ni＝1∶0.45∶0.55，将配好的料放入球磨机中磨研，充分混合，而且磨到纳粒级或接近纳米级，置入玻璃容器中，装入频率为6.25GH2的微波炉中置入少量氧气进行合成，合成温度为860℃，保温15分钟，然后随炉冷却。冷到室温后取出，再磨到纳米级或接近纳米级，测其比容量达162mAh/g。循环寿命达到使用要求。
实例2：正极材料LiMn1.9Cr0.1O4的合成，原料：LiOH、MnO2、Cr2O3(均为化学纯)，配比Li∶Mn∶Cr＝1∶1.9∶0.1将配好的料放入球磨机中磨研，充分混合，而且磨到纳米级或接近纳米级，置入玻璃容器中，装入频率为5.5GH2的微波炉中，置入少量氧气进行合成。合成温度为620℃，保温20分钟，然后随炉冷却。冷到室温后取出，再磨到纳米级或接近纳米级，测其比容量达155mAh/g，循环性能达到用户要求。

Claims (3)

1.一种合成锂离子二次电池中正极材料的方法，其特征在于该方法是以LiOH，Li2CO3或LiNO3，MnO2，Co2O3，Cr2O3和Mn，Co，Cr的硝酸、碳酸盐为原料，按比例混合，磨研至纳米级或接近纳米级装入的耐高温材料容器中，置入微波炉中，合成过程中，通氧气，加温、保温冷却取出，球磨到纳米级或接近纳米级，即得到产品。
2.按权利要求1所述的合成电池正级材料方法，其特征在于微波炉频率为0.1～500GH2。
3.按权利要求1所述的合成正极材料方法，其特征在于加温温度为450℃-1000℃，保温0.5-1.5小时。
CN00123843A 2000-08-22 2000-08-22 一种高性能锂离子二次电池正极材料的合成方法 Pending CN1339835A (zh)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1321471C (zh) * 2004-03-31 2007-06-13 潘树明 锂离子电池的纳米正极材料LiCoO2三步合成制备方法
CN1324731C (zh) * 2003-07-15 2007-07-04 新乡无氧铜材总厂 一种锂离子电池用锂锰氧化物正极材料的制备工艺
CN101800309A (zh) * 2010-04-16 2010-08-11 中国科学院新疆理化技术研究所 锂离子电池正极材料多元掺杂锰酸锂的微波合成方法
CN102779974A (zh) * 2011-05-09 2012-11-14 凌春喜 纳米电池及加工该纳米电池制造方法
CN113651364A (zh) * 2021-08-20 2021-11-16 中南大学 一种微波加热快速合成纳米多孔LiMnO2的方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1324731C (zh) * 2003-07-15 2007-07-04 新乡无氧铜材总厂 一种锂离子电池用锂锰氧化物正极材料的制备工艺
CN1321471C (zh) * 2004-03-31 2007-06-13 潘树明 锂离子电池的纳米正极材料LiCoO2三步合成制备方法
CN101800309A (zh) * 2010-04-16 2010-08-11 中国科学院新疆理化技术研究所 锂离子电池正极材料多元掺杂锰酸锂的微波合成方法
CN102779974A (zh) * 2011-05-09 2012-11-14 凌春喜 纳米电池及加工该纳米电池制造方法
CN102779974B (zh) * 2011-05-09 2015-09-30 凌春喜 纳米电池及加工该纳米电池制造方法
CN113651364A (zh) * 2021-08-20 2021-11-16 中南大学 一种微波加热快速合成纳米多孔LiMnO2的方法

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