Freestanding Mo3N2 nanotubes for long‐term stabilized 2e− intermediate‐based high energy efficiency Li–CO2 batteries

Abstract

AbstractLi–CO2 batteries are considered one of the promising power sources owing to ultrahigh energy density and carbon fixation. Nevertheless, the sluggish reaction kinetics of 4e− discharged process (Li2CO3) impede its potential application. One of the efficient strategies for developing cathode catalysts is to stabilize 2e− intermediate Li2C2O4 and improve reaction reversibility. However, long‐term catalysts of stabilized Li2C2O4 are barely achieved, whereas cycle stability is far from satisfactory level. Herein, non‐noble metal–based Mo3N2 is synthesized and employed as freestanding cathodes for Li–CO2 batteries. Owing to rich delocalized electrons of Mo2+ and reversible electron localization structure, freestanding Mo3N2 cathodes exhibit a low charge potential (3.28 V) with an ultralow potential gap (0.64 V), high energy efficiency of up to 80.46%, fast rate capability, and outstanding cycle stability (>910 h). In situ experiments and theoretical calculation verify that Mo3N2 stabilizes 2e− Li2C2O4 intermediate by the interaction of Mo2+ as active sites where Mo2+ promotes the transfer of outer electrons to O, prevents its disproportionation to Li2CO3, and promotes reaction kinetics, contributing to high energy efficiency and outstanding cycle reversibility. In addition, the pouch‐cells deliver ultrahigh energy density of up to 6350.7 W h kg−1 based on the mass of cathode materials.