Activate 1‐TM Channel of Disordered Rock Salts via Electrostatic Repulsion Regulation for Enhanced Lithium Storage

Cation-disordered rock-salt (DRX) has emerged as a promising high-capacity cathode material for next-generation high-energy-density Li-ion batteries. However, its practical deployment is hindered by intrinsic Li⁺ diffusion mechanism, where only 0-transition metal (0-TM) channels permit feasible Li⁺ migration while 1-TM and 2/3/4-TM channels exhibit prohibitively high Li⁺ diffusion energy barriers. Here, we leverage electrostatic repulsion regulation to activate the 1-TM channel, which holds the highest potential for activation while constrained by restrictive tetrahedral site geometries, thereby introducing more Li⁺ diffusion pathways and establishing a well-connected percolating 3D Li⁺ diffusion network within the DRX lattice to fundamentally addressing the kinetic limitations of DRX. Systematic investigations reveal that in the optimized sample, the tetrahedral height of 1-TM channels increased significantly from 2.525 to 2.613 Å, concomitant with a volumetric expansion from 3.254 to 4.010 ų, along with the Li⁺ migration energy barrier significantly reduced from 1.48 to 0.26 eV. The enhanced Li⁺ transport kinetics yield enhanced capacity (306 mAh g^-1 at 10 mA g^-1), alongside superior rate capability (∼200 mAh g^-1 at 100 mA g^-1). This work establishes a material design paradigm overcome transport bottlenecks in disordered cathode architectures.