Building Ultrathin Li₄Mn₅O₁₂ Shell for Enhancing the Stability of Cobalt-Free Lithium-Rich Manganese Cathode Materials

Abstract

Spinel Li4Mn5O12 was successfully prepared by the wet chemical method to modify the surface of Li1.2Ni0.2Mn0.6O2. The results showed that an ultrathin spinel Li4Mn5O12 surface-modified layer with a thickness of approximately 10 nm was successfully constructed on the raw material surface, and that the cationic order was improved. In addition, the lithium ion diffusion coefficients (DLi+) of the raw materials and the modified materials were calculated using the EIS test and impedance fitting. The results indicated that the ultrathin Li4Mn5O12 surface modification shell can increase the lithium ion diffusion rate of the material and improve the rate capability of the material. So, the surface modification layer of spinel Li4Mn5O12 can reduce the oxygen loss of the first cycle and improve the cationic order of the material. Therefore, the first coulombic efficiency of Li4Mn5O12/Li1.2Ni0.2Mn0.6O2 material at the current density of 12.5 mA·g−1 reaches 80.46%, and the capacity retention rate reaches 91.74% after 50 cycles, which are 3.36% and 21.23% higher than those of the raw materials, respectively. It showed better electrochemical reversibility and cyclic stability. This study provides a straightforward and convenient modification method for improving the stability of cobalt-free lithium-rich manganese cathode materials and has a favorable application prospect.

Keywords

• lithium-ion battery
• positive electrode
• cobalt-free lithium-rich manganese oxide
• Li₄Mn₅O₁₂-coated