Discovering the Order‐Disorder Transition in Quinoline Intercalated Vanadium Oxide with Superior Calcium Storage via Polyhedral Distortion

Abstract Calcium‐ion batteries (CIBs) are considered as potential next‐generation energy storage systems due to their abundant reserves and relatively low cost. However, irreversible structural changes and weak conductivity still hinder in current CIBs cathode materials. Herein, an organic molecular intercalation strategy is proposed, in which V 2 O 5 regulated with quinoline, pyridine, and water molecules are studied as cathode material to provide fast ion diffusion channels, large storage host, and high conductivity for Ca ions. Among them, V 2 O 5 ‐quinoline (QVO) owns the largest interplanar spacing of 1.25 nm and the V‐O chains are connected with organic molecular by hydrogen bond, which stabilizes the crystal structure. As a result, QVO exhibits a specific capacity of 168 mAh g −1 at 1 A g −1 and capacity retention of 80% after 500 cycles at 5 A g −1 than the other materials. Furthermore, X‐Ray diffraction and X‐ray absorption spectroscopy results reveal a reversible order‐disorder transformation mechanism of Ca 2+ for QVO, which can make full use of the abundant active sites for high capacity and simultaneously achieve fast reaction kinetics for excellent rate performance. These results demonstrate that QVO is a promising cathode material for CIBs, providing more choices for the development of high‐performance CIBs.