KCrS2 Cathode with Considerable Cyclability and High Rate Performance: The First K+ Stoichiometric Layered Compound for Potassium‐Ion Batteries

KCrS2 is presented as a stable and high‐rate layered material that can be used as a cathode in potassium‐ion batteries. As far as it is known, KCrS2 is the only layered material with stoichiometric amounts of K+, which enables coupling with a graphite anode for full‐cell construction. Cr(III)/Cr(IV) redox in KCrS2 is also unique, because LiCrS2 and NaCrS2 are known to experience S2−/S2 2− redox. O3‐KCrS2 is first charged to P3‐K0.39CrS2 and subsequently discharged to O′3‐K0.8CrS2, delivering an initial discharge capacity of 71 mAh g−1. The following charge/discharge (C/D) shows excellent reversibility between O′3‐K0.8CrS2 and P3‐K0.39CrS2, retaining ≈90% of the initial capacity during 1000 continuous cycles. The rate performance is also noteworthy. A C/D rate increase of 100‐fold (0.05 to 5 C) reduces the reversible capacity only by 39% (71 to 43 mAh g−1). The excellent cyclic stability and high rate performance are ascribed to the soft sulfide framework, which can effectively buffer the stress caused by K+ deinsertion/insertion. During the transformation between P3‐K0.39CrS2 and O′3‐K0.8CrS2, the material resides mostly in the P3 phase, which minimizes the abrupt dimension change and allows facile K+ diffusion through spacious prismatic sites. Structural analysis and density functional theory calculations firmly support this reasoning. KCrS2 is proposed as a new cathode material with considerable stability and high rate performance in potassium‐ion batteries. When fully charged to 3.0 V versus K/K+, O3‐KCrS2 can be reversibly charged/discharged between P3‐K0.39CrS2 and O′3‐K0.80CrS2, while maintaining its P3‐type within an almost entire range of potential. This feature provides KCrS2 with excellent cyclic stability during 1000 charge/discharge cycles and facile K+ diffusion.