Architecture and performance of anion-doped Co-free lithium-rich cathode material with nano-micron combined morphology

Co-free cathode materials are gradually attracted wide attention due to the low budget and environmental friendliness, but their application is still prevented by the poor rate performance and cyclic stability. Herein, the Co-free lithium-rich cathode materials (Li1.2Ni0.2Mn0.6O2, LRNMO) with a nano-micron combined morphology is prepared by a simple oxalate co-precipitation route and further modified by an anion doping strategy. It has been found that the F− anion doping can increase the content of Mn4+ in LRNMO, reduce the influence of the Jahn-Teller effect, and further impede the transition from layered phase to spinel phase. As a result, the as-obtained Li1.2Ni0.2Mn0.6O2-xFx (x = 0.04, named as F4-LRNMO) shows an optimal electrochemical performance, for instance, high discharge capacity (243 mAh g−1) with a satisfactory initial coulombic efficiency of 84.37% at 0.1C. Meanwhile, the F4-LRNMO sample also can display high capacity retention of 92.2% after 200 cycles at 1C, and a remarkably high discharge capacity of 151 mAh g−1 with capacity retention of 95.4% after 100 cycles even at high rate of 5C. In consequence, this work can not only ameliorate the defects of poor stability and low initial coulomb efficiency, but also offer a meaningful exploration for the development of Co-free lithium-rich cathode materials with high capacity and high performance-price ratio.