Operando XAFS on Hydrated Calcium Vanadium Bronze Cathode for Aqueous Zn‐ion Storage

Abstract Multivalent ion storage and aqueous electrochemical systems continue to build interest for energy application. The Zn‐ion system with 2 electron transfer and an ideal metal anode is a strong candidate but is still at the early stage of development. Using both in situ near‐edge (XANES) and X‐ray absorption fine structure spectroscopy, EXAFS, a nanostructured cathode material, Ca x V 2 O 5 ‐H 2 O (CVO), was probed at the V‐ K absorption edge. This operando study reveals the local electronic and geometric structure changes for CVO during galvanostatic cycling as the active material in an aqueous Zn‐ion cell. The XANES data provides a fine resolution to track the evolution of the vanadium oxidative state and near‐neighbor coordination sphere showing subtle shifts and delocalized charge. The Zn‐ion influence on the V‐ K absorption edge is visualized using a difference technique called Δμ. Coupled with theoretical calculations and modelling, the extended region extracted local bonding information further confirms excellent electronic and structural reversibility of this vanadium oxide bronze in an aqueous Zn‐ion electrochemical cell.