Designing Advanced Vanadium‐Based Materials to Achieve Electrochemically Active Multielectron Reactions in Sodium/Potassium‐Ion Batteries

Abstract Next‐generation sodium‐ion batteries (SIBs) and potassium‐ion batteries (PIBs) are considered to be promising alternatives to replace current lithium‐ion batteries due to the high abundance of sodium and potassium resources. New energetic vanadium‐based compounds that undergoes multielectron reactions and demonstrate good sodium/potassium storage capability, provide new solutions for high‐performance SIBs/PIBs in terms of high energy/power density and long‐time cyclability. So far, desirable rich redox centers (V 2+ ‐V 5+ ), consolidated frameworks, and the high theoretical capacities of vanadium‐based compounds have been widely explored for practical applications. Rational materials design utilizing vanadium multiredox centers and the fundamental understanding of their charge‐transfer processes and mechanisms are critical in the development of high‐performance battery systems. The scientific importance and basic design strategies for high performance V‐based anode/cathode materials, structure‐function properties and state‐of‐the‐art understanding of V‐based electrode materials are herein classified and highlighted alongside their design strategies. The important role of the valence electron layer of vanadium, and the scientific advances of vanadium partitions in other electrochemical behaviors are also summarized in detail. Finally, relevant strategies and perspectives discussed in this review provide practical guidance to explore the undiscovered potentials of multi‐electron reaction relationships of not only V‐based composites, but also other types of electrode materials.