• • Li-rich layered oxides (LLOs) can achieve energy densities up to 1000 Wh kg−1, positioning them as high-energy cathode materials for advanced lithium-ion batteries.
• • The LiMn6 hexatomic-ring, featuring π-type hybridization between Mn 3d(t2g) and O 2p orbitals, acts as a distributed redox center, contributing to enhanced capacity, voltage, and structural stability.
• • Substituting Mn within LiMn6 rings breaks the symmetry of the π-bond ring, altering redox behavior and reversibility, which is a critical factor in material design.
• • Ordering LiMn6 functional units into specific spatial configurations can mitigate structural instability, addressing challenges like limited cycle life and voltage decay in LLOs.