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

Abstract

Abstract 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 Å 3 , 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.