Organic Molecular Intercalation Enabled Anionic Redox Chemistry with Fast Kinetics for High Performance Magnesium Storage

Abstract Rechargeable magnesium‐ion batteries possess desirable characteristics in large‐scale energy storage applications. However, severe polarization, sluggish kinetics and structural instability caused by high charge density Mg²⁺ hinder the development of high‐performance cathode materials. Herein, the anionic redox chemistry in VS₄ is successfully activated by inducing cations reduction and introducing anionic vacancies via polyacrylonitrile (PAN) intercalation. Increased interlayer spacing and structural vacancies can promote the electrolyte ions migration and accelerate the reaction kinetics. Thanks to this “three birds with one stone” strategy, PAN intercalated VS₄ exhibits an outstanding electrochemical performance: high discharge specific capacity of 187.2 mAh g⁻¹ at 200 mA g⁻¹ after stabilization and a long lifespan of 5000 cycles at 2 A g⁻¹ are achieved, outperforming other reported VS₄‐based materials to date for magnesium storage under the APC electrolyte. Theoretical calculations confirm that the intercalated PAN can indeed induce cations reduction and generate anionic vacancies by promoting electron transfer, which can accelerate the electrochemical reaction kinetics and activate the anionic redox chemistry, thus improving the magnesium storage performance. This approach of organic molecular intercalation represents a promising guideline for electrode material design on the development of advanced multivalent‐ion batteries.