Manganese‐Based Materials for Rechargeable Batteries beyond Lithium‐Ion

Abstract The newly emerging rechargeable batteries beyond lithium‐ion, including aqueous and nonaqueous Na‐/K‐/Zn‐/Mg‐/Ca‐/Al‐ion batteries, are rapidly developing toward large‐scale energy storage application. The properties of electrode materials are determinant for electrochemical performance of the batteries. By virtue of the prominent features of low cost, non‐toxicity, high voltage, and rich valence states, Mn‐based electrode materials have attracted increasing attention. The big family of Mn‐based materials with rich composition and polymorphs, provides great possibilities for exploring and designing advanced electrode materials for these emerging rechargeable batteries. In this review, three main categories of Mn‐based materials, including oxides, Prussian blue analogous, and polyanion type materials, are systematically introduced to offer a comprehensive overview about the development and applications of Mn‐based materials in various emerging rechargeable battery systems. Their crystal structure, electrochemical performance, and reaction mechanism are highlighted. In addition, the key issues encountered by many Mn‐based materials, including Jahn–Teller distortion, Mn dissolution, crystal water, impact of electrolyte, etc., are also discussed. Finally, challenges and perspectives on the future development of manganese‐based materials are provided as well. It is believed this review is timely and important to further promote exploration and applications of Mn‐based materials in both aqueous and nonaqueous rechargeable battery systems beyond lithium‐ion.