锂电池正极材料Li_3MnO_4的优化制备工艺与改性研究
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摘要
锂离子电池由于其电压高、能量密度大、可逆性好等优势在电子器件、电动车、军事和航天等多个领域具有广阔的应用前景。人们一致认为电池中的正极活性材料是控制锂离子电池性能的关键。常见的正极材料LiCoO2、LiNiO2、LiMn2O4、LiFePO4各有各的优势同时又存在一些不尽人意的缺点。新型锂电池正极材料Li3MnO4由于具有非常可观的理论容量而被认为是极具潜力的正极材料。但目前国内外对其优化制备工艺和改性的研究尚属空白。本文选择Li3MnO4正极材料体系作为研究对象,采用离子交换技术首先合成了制备+5价Li3MnO4的原料——+7价的LiMnO4-3H2O,并采用低温固相烧结技术成功合成了目标产物Li3MnO4正极材料。同时结合TG/DSC、XRD、FESEM、电化学性能测试等多种测试手段研究了制备Li3MnO4的优化工艺参数。考察了制备过程中锂盐原料种类、间歇性碾磨、退火温度、退火时间等对Li3MnO4正极材料结构、形貌以及电化学性能的影响。实验结果表明：采用LiOH·H2O作为锂盐原料与LiMnO4·3H2O按2：1的化学计量比混合退火,在70℃～125℃之间采用间歇性碾磨,在170℃下保温2.5h,得到的正极材料具有最佳的综合性能,其初始容量为116.3mAh/g。另外,在以上优化工艺参数的基础上,针对Li3MnO4存在导电性不佳导致活性材料利用率低以及结构不稳定影响循环性能等问题采取了一系列的改性措施,以改善其结构和电性能。研究表明：采用湿法预混合原料和导电剂的改性工艺,有助于导电剂更好的分散于正极材料中,同时促进了反应物的充分混合,使得材料电性能达到了138.8 mAh/g。该条件下的正极涂敷厚度也对材料电性能发挥有明显影响,当涂覆厚度为2.7mg/cm2时,正极材料容量达到了198.9mAh/g。同时掺杂PO43-对稳定材料结构和改善循环性能有明显的作用。另外,针对导电性不佳的问题探讨了石墨、乙炔黑、碳纳米管复合导电剂的使用对Li3MnO4正极材料颗粒间形成良好的导电网络,从而改善其导电性的作用。
Lithium-ion batteries have great application prospect in electronic devices, electric vehicles, military, aerospace and many other fields because of its high voltage and energy density, as well as its excellent reversibility. It is believed that the properties of lithium-ion batteries greatly depend on the electrode materials, specially the cathode materials. Common cathode materials like LiCoO2, LiNiO2, LiMn2O4, LiFePO4, etc. all have their own advantages as well as their undesirable drawbacks. Recently, a study suggested that a generally new system Li3MnO4 can be used as a promising cathode material which has great potential because of its considerable theoretical capacities. However, there is still not any report about its optimized preparation process and modifications.
In this work, the remarkable cathode Li3MnO4 was chosen as a major subject. The reactant LiMnO4·3H2O (Mn:+7) powders were synthesized by ion exchange technology and the target cathode material Li3MnO4 was successfully synthesized by solid-state reaction at a low temperature. The thermal decomposition behavior of the precursor powder was examined by TG/DSC to determine the temperature of heat-treatment. XRD and FESEM were used to characterize the structures, phase composition and morphology of the prepared powders. The electrochemical properties of Li3MnO4 were also investigated using galvanostatic charge/discharge cycling. The influences of raw materials, intermittent grinding, annealing temperature and time on the quality of Li3MnO4 cathode were explored. The results showed that the best raw material is LiOH·H2O and the best comprehensive behavior is obtained from a sample annealed at 170℃for 2.5h using intermittent grinding among 70℃～125℃, which has an initial discharge capacity of 116.3 mAh/g.
What's more, on the basis of the optimized process parameters above, some modification measures were utilized in order to improve the conductivity and structure stability of Li3MnO4. The results showed that:pre-mixing the reactants and graphite in solution can improve the conductive agent dispersed in the cathode materials much better while promoting the mixing of the reactants at the same time. The initial capacity of the Li3MnO4 sample used pre-mixed method reached 138.8 mAh/g. Under these conditions, it's found that the coating amount of the cathode material plays a significant role in its electrochemical properties. The capacity reaches 198.9mAh/g when the cathode coating amount is 2.7mg/cm2.The influences of PO43- doping on structure stability and cycling performance were also studied in this thesis. Conductive agent which is composed of graphite, acetylene black and carbon nanotube was also used to form an excellent conductive network and it's useful to improve the conductivity of the cathode materials.
Lithium-ion batteries have great application prospect in electronic devices, electric vehicles, military, aerospace and many other fields because of its high voltage and energy density, as well as its excellent reversibility. It is believed that the properties of lithium-ion batteries greatly depend on the electrode materials, specially the cathode materials. Common cathode materials like LiCoO2, LiNiO2, LiMn2O4, LiFePO4, etc. all have their own advantages as well as their undesirable drawbacks. Recently, a study suggested that a generally new system Li3MnO4 can be used as a promising cathode material which has great potential because of its considerable theoretical capacities. However, there is still not any report about its optimized preparation process and modifications.
In this work, the remarkable cathode Li3MnO4 was chosen as a major subject. The reactant LiMnO4·3H2O (Mn:+7) powders were synthesized by ion exchange technology and the target cathode material Li3MnO4 was successfully synthesized by solid-state reaction at a low temperature. The thermal decomposition behavior of the precursor powder was examined by TG/DSC to determine the temperature of heat-treatment. XRD and FESEM were used to characterize the structures, phase composition and morphology of the prepared powders. The electrochemical properties of Li3MnO4 were also investigated using galvanostatic charge/discharge cycling. The influences of raw materials, intermittent grinding, annealing temperature and time on the quality of Li3MnO4 cathode were explored. The results showed that the best raw material is LiOH·H2O and the best comprehensive behavior is obtained from a sample annealed at 170℃for 2.5h using intermittent grinding among 70℃～125℃, which has an initial discharge capacity of 116.3 mAh/g.
What's more, on the basis of the optimized process parameters above, some modification measures were utilized in order to improve the conductivity and structure stability of Li3MnO4. The results showed that:pre-mixing the reactants and graphite in solution can improve the conductive agent dispersed in the cathode materials much better while promoting the mixing of the reactants at the same time. The initial capacity of the Li3MnO4 sample used pre-mixed method reached 138.8 mAh/g. Under these conditions, it's found that the coating amount of the cathode material plays a significant role in its electrochemical properties. The capacity reaches 198.9mAh/g when the cathode coating amount is 2.7mg/cm2.The influences of PO43- doping on structure stability and cycling performance were also studied in this thesis. Conductive agent which is composed of graphite, acetylene black and carbon nanotube was also used to form an excellent conductive network and it's useful to improve the conductivity of the cathode materials.
引文
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