Understanding the Effect of Al Doping on the Electrochemical Performance Improvement of the LiMn₂O₄ Cathode Material

It is well known that the electrochemical performance of spinel LiMn₂O₄ can be improved by Al doping. Herein, combining X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, and spherical aberration-corrected scanning transmission electron microscopy (Cs-STEM) with in situ electron-beam (E-beam) irradiation techniques, the influence of Al doping on the structural evolution and stability improvement of the LiMn₂O₄ cathode material is revealed. It is revealed that an appropriate concentration of Al³⁺ ions could dope into the spinel structure to form a more stable LiAl_xMn_2-xO₄ phase framework, which can effectively stabilize the surface and bulk structure by inhibiting the dissolution of Mn ions during cycling. The optimized LiAl_0.05Mn_1.95O₄ sample exhibits a superior capacity retention ratio of 80% after 1000 cycles at 10 C (1 C = 148 mA h g^-1) in the voltage range of 3.0-4.5 V, which possesses an initial discharge capacity of 90.3 mA h g^-1. Compared with the undoped LiMn₂O₄ sample, the Al-doped sample also shows superior rate performance, especially the capacity recovery performance.