Expandable Li Percolation Network: The Effects of Site Distortion in Cation-Disordered Rock-Salt Cathode Material

Cation-disordered rock-salt (DRX) materials receive intensive attention as a new class of cathode candidates for high-capacity lithium-ion batteries (LIBs). Unlike traditional layered cathode materials, DRX materials have a three-dimensional (3D) percolation network for Li⁺ transportation. The disordered structure poses a grand challenge to a thorough understanding of the percolation network due to its multiscale complexity. In this work, we introduce the large supercell modeling for DRX material Li_1.16Ti_0.37Ni_0.37Nb_0.10O₂ (LTNNO) via the reverse Monte Carlo (RMC) method combined with neutron total scattering. Through a quantitative statistical analysis of the material's local atomic environment, we experimentally verified the existence of short-range ordering (SRO) and uncovered an element-dependent behavior of transition metal (TM) site distortion. A displacement from the original octahedral site for Ti⁴⁺ cations is pervasive throughout the DRX lattice. Density functional theory (DFT) calculations revealed that site distortions quantified by the centroid offsets could alter the migration barrier for Li⁺ diffusion through the tetrahedral channels, which can expand the previously proposed theoretical percolating network of Li. The estimated accessible Li content is highly consistent with the observed charging capacity. The newly developed characterization method here uncovers the expandable nature of the Li percolation network in DRX materials, which may provide valuable guidelines for the design of superior DRX materials.