Emphasizing a ‐parameter Expansion in Lattice Distortions of Disordered Rock Salt Li 3 V 2 O 5 : From Crystallographic Design to Feasible Large‐Scale Chemical Lithiation

Abstract Disordered rock‐salt Li 3 V 2 O 5 (DRX‐LVO) anode exhibits distinctive 3D Li + percolation transport networks, which offers the unique advantage for ultra‐charging. However, the existing chemical lithiation preparation routes not only pose safety risks due to the use of highly reactive reagents but also inevitably result in products with poor crystallinity. Investigating the origin, impact, and strategies for crystallinity degradation is pivotal for advancing the industrialization of chemical lithiation. To address the safety issue, different lithiation reagents were evaluated from the perspective of lone electron activity, and lithium naphthalene was identified as an ideal reagent balancing safety and efficiency. Through DFT calculations, the mechanism underlying different types of distortions in the DRX system was decoupled while the distinct effects of a / b / c ‐axis variations on migration energy barriers were elucidated. Guided by theoretical insights, the a ‐axis was nominated as the critical parameter for enhancing electrochemical performance, leading to the development of Li 3 V 2 O 5 with elongated a ‐axis dimensions that exhibit significantly improved rate capabilities (80 mAh g −1 at 20 A g −1 ). This study elucidates the distortion mechanisms via exploring the correlation among chemical lithiation feasibility, lattice tuning and kernel parameter confirmation, as well as fast‐charging behavior, shedding light on precise crystallographic design on high‐performance fast‐charging anode.