From Oxygen Redox to Sulfur Redox: A Paradigm for Li-Rich Layered Cathodes

The utilization of anionic redox chemistry provides an opportunity to further improve the energy density of Li-ion batteries, particularly for Li-rich layered oxides. However, oxygen-based hosts still suffer from unfavorable structural rearrangement, including the oxygen release and transition metal (TM)-ion migration, in association with the tenuous framework rooted in the ionicity of the TM-O bonding. An intrinsic solution, by using a sulfur-based host with strong TM-S covalency, is proposed here to buffer the lattice distortion upon the highly activating sulfur redox process, and it achieves howling success in stabilizing the host frameworks. Experimental results demonstrate the prolonged preservation of the layered sulfur lattice, especially the honeycomb superlattice, during the Li⁺ extraction/insertion process in contrast to the large structural degeneration in Li-rich oxides. Moreover, the Li-rich sulfide cathodes exhibited a negligible overpotential of 0.08 V and a voltage drop of 0.13 mV/cycle, while maintaining a substantial reversible capacity upon cycling. These superior electrochemical performances can be unambiguously ascribed to the much shorter trajectories of sulfur in comparison to those of oxygen revealed by molecular dynamics simulations at a large scale (∼30 nm) and a long time scale (∼300 ps) via high-dimensional neural network potentials during the delithiation process. Our findings highlight the importance of stabilizing host frameworks and establish general guidance for designing Li-rich cathodes with durable anionic redox chemistry.