Lithium-rich manganese-based cathode materials (LRMs, Li1.2Mn0.54Ni0.13Co0.13O2) are promising prospects for subsequent-generation lithium-ion batteries owing to their elevated operating voltage, large specific capacity, and affordability. Nonetheless, their actual implementation is significantly impeded by irreversible lattice-oxygen redox reactions, surface structural disorder, and interfacial phase collapse, leading to low initial Coulombic efficiency (ICE), inadequate rate capability, and sluggish Li+ transport. Herein, we report a simple and mild glycolic acid-assisted surface-engineering strategy to enhance the electrochemical performance of LRM. Glycolic acid treatment induces controlled H+/Li+ ion exchange at the particle surface and anchors surface transition metals through the formation of transition metals (TM)–OH and TM–O–C=O bonds. Subsequent calcination constructs an in situ carbon layer-spinel-layered heterostructure, accompanied by the generation of coupled anionic and cationic vacancies. This reconstructed surface provides fast Li+ diffusion pathways and stabilized ion-transport channels, while the dual-vacancy configuration enhances lattice-oxygen reversibility and suppresses structural disorder. Consequently, the modified LRM delivers a high initial discharge capacity of 285.3 mAh⋅g−1 with an ICE of 89.9%, while maintaining 81% capacity retention after 100 cycles. Notably, it exhibits a significantly suppressed voltage decay of only 1.7 mV/cycle at 3C, markedly outperforming the pristine LRM. Density Functional Theory (DFT) calculations reveal that the surface-modified sample possesses enhanced electronic conductivity, as evidenced by the improved Density of States (DOS), and achieves superior structural stability through increased binding energies. This environmentally benign surface-engineering strategy offers a practical and efficient route toward the industrial application of LRM.
Yang et al. (Sun,) studied this question.