Disorder‐Induced Targeted Formation of Amorphous Lithium Sulfide for Ah‐Level Lithium–Sulfur Batteries

Abstract Efficient bidirectional conversion of lithium sulfide (Li 2 S) is of paramount importance for constructing high‐energy‐density lithium–sulfur (Li–S) batteries, but the sluggish reaction kinetics stemming from its intrinsic insulation and anisotropically planar proliferation remains a formidable challenge. Herein, a crystallographic regulation strategy is demonstrated for bidirectional Li 2 S conversion, striving to optimize the reaction kinetics and improve the active sulfur utilization. Specifically, by leveraging the tunable geometric structures of spinel oxides, Li‐rich Li 1.2 Mn 1.8 O 4 is elaborately designed as an effective electrocatalyst for Li–S batteries. The pertinently incorporated Li atoms at octahedral Mn sites endow Li 1.2 Mn 1.8 O 4 with disordered geometric and electronic arrangements, leading to a relatively mismatched geometric coherence with sulfur species and thus driving the precipitation of amorphous Li 2 S instead of crystalline counterpart. The pre‐formed amorphous Li 2 S nucleus regulators are beneficial to their isotropically epitaxial growth and interfacial charge and mass transfer, achieving splendid bidirectional conversion kinetics of Li 2 S. Accordingly, the assembled Ah‐level Li–S pouch cell delivers a prominent specific energy of 309 Wh kg total −1 at 0.2 C and a remarkable capacity retention of 98.3% after 30 cycles. The proposed strategy surmounts the intrinsic limitations of crystalline Li 2 S and pilots an innovative electrocatalyst design avenue for practical Li–S batteries.