Operando Synchrotron X-Ray Absorption Spectroscopy: A Key Tool for Cathode Material Studies in Next-Generation Batteries.

Abstract

Rechargeable batteries are central to modern energy storage systems, from portable electronics to electric vehicles. The cathode material, a critical component, largely dictates a battery's energy density, capacity, and overall performance. This review focuses on the application of operando X-ray absorption spectroscopy (XAS) to study cathode materials in Li-ion, Na-ion, Li-S, and Na-S batteries. Operando XAS provides real-time insights into the local electronic structure, oxidation states, and coordination environments, which are crucial for understanding complex electrochemical processes, such as redox reactions, phase transitions, and structural degradation. The review highlights the strengths of hard and soft XAS techniques in probing transition metal (TM) and anionic redox processes, particularly in layered oxide cathodes, where reversible oxygen redox and TM behavior are pivotal. The role of operando XAS is also explored in analyzing conversion-type S-based cathodes, where it helps unravel the intricate reaction mechanisms. Furthermore, the review addresses the challenges of in situ cell design for operando XAS, especially under ultrahigh vacuum conditions for soft XAS. By discussing recent advancements and future directions, this review underscores the critical role of operando XAS in driving innovation and improving the design and performance of next-generation battery technologies.