尖晶石型LiCr0.04Mn1.96O4正极材料的简易合成及其高倍率与长循环性能研究

Study on the simple synthesis and high-rate and long-cycle performance of spinel-type LiCr0.04Mn1.96O4 cathode materials

  • 摘要: 采用固相燃烧法制备了一种Cr掺杂的LiCr0.04Mn1.96O4正极材料,利用X射线衍射、X射线光电子能谱及扫描电子显微镜对材料的晶体结构、结晶性、元素组成和形貌进行表征,并且通过循环伏安(CV)、恒电流充放电循环、电化学阻抗(EIS)对正极材料的电化学性能进行测试. 结果表明,Cr掺杂改性的LiCr0.04Mn1.96O4正极材料的晶体结构与尖晶石型LiMn2O4相一致,且具有高结晶性和良好的颗粒分散;LiCr0.04Mn1.96O4正极材料在1 C倍率的首次放电比容量为100.3 mA·h·g−1,200次循环后容量保持率是83.3%;5 C倍率的初始放电比容量为90.4 mA·h·g−1,充放电循环1000次后的容量保持率为66.2%. 适量的Cr掺杂能降低Jahn-Teller效应,提高了材料的结构稳定性,LiCr0.04Mn1.96O4材料还具有更大的锂离子扩散系数(1.18×10−16 cm2·s−1)与更小的表观活化能(30.10 kJ·mol−1),因此提升了尖晶石型LiMn2O4正极材料的循环寿命和倍率容量.

     

    Abstract: A Cr-doped LiCr0.04Mn1.96O4 cathode material was synthesized via solid-state combustion method. The crystal structure, crystallinity, elemental composition and morphology of the material were characterized by X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy. The electrochemical performance of the cathode material was tested by cyclic voltammetry (CV), galvanostatic charge/discharge cycling and electrochemical impedance spectroscopy (EIS). The results show that the crystal structure of the Cr-doped modified LiCr0.04Mn1.96O4 cathode material is consistent with the spinel LiMn2O4, and it has high crystallinity and good particle dispersion. The LiCr0.04Mn1.96O4 cathode material delivered an initial discharge capacity of 100.3 mA·h·g-1 at 1 C, and the capacity retention rate after 200 cycles is 83.3%. At 5 C the LiCr0.04Mn1.96O4 cathode material showed a high initial discharge capacity of 90.4 mA·h·g-1, with the capacity retention rate of 66.2% after 1000 cycles. Appropriate Cr doping can reduce the Jahn-Teller effect, and improve the structural stability of the material. The LiCr0.04Mn1.96O4 material also has a larger lithium ion diffusion coefficient (1.18×10-16 cm2·s-1) and a smaller apparent activation energy (30.10 kJ·mol-1), thus improving the cycle life and rate capacity of spinel LiMn2O4 cathode materials.

     

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