Understanding the mechanism of performance difference when substituting Al for different transition metal ions in Li-rich Mn-based cathode materials

The Al-doped modification strategy by substituting Al for different transition metal ions (TMs, TM = Mn, Ni, Co) has achieved excellent results in improving the cyclic performance of Li-rich Mn-based cathode materials (LRMs). However, the traditional explanation known as "pegging effect" is hard to distinguish how Al works in different TM substitutions. Herein, the electrochemical performances of Li1.2Mn0.52Ni0.13Co0.13Al0.02O2 (LRM-Mn), Li1.2Mn0.54Ni0.11Co0.13Al0.02O2 (LRM-Ni) and Li1.2Mn0.54Ni0.13Co0.11Al0.02O2 (LRM-Co) are studied, and LRM-Mn shows the superior long-term cycling stability, especially at the high temperature of 55 °C. Density functional theory (DFT) reveals that LRM-Mn crystal structure has higher thermodynamic stability than any other sample, which is advantageous for inhibiting the transition of LRMs to low-energy stable phases during cycling (e.g., spinel phase and rock salt phase). Combined with density of states and Bader charge analyses, we think that the increased thermodynamic stability of LRM-Mn results from the reduction of the charge transfer of Mn and Co ions in a single delithiation process, which lowers the reactivity of TMs, alleviates the Li/TM mixing and inhibits the irreversible oxygen release. In addition, the biggest volume change during the delithiation process was observed when Al was substituted for Co, which results in the materials' premature production of fatigue stresses and intergranular cracking. This work comprehensively explains the modification mechanism of Al-doped in LRMs. It demonstrates practical significance for both the rational design of materials and the electrode electrochemical performance prediction.