Sodium and Manganese Stoichiometry of P2‐Type Na2/3MnO2. (15th September 2016)

• Record Type: Journal Article
• Authors: Kumakura, Shinichi; Tahara, Yoshiyuki; Kubota, Kei; Chihara, Kuniko; Komaba, Shinichi
• Is Part Of: Angewandte Chemie. Volume 128:Number 41(2016)
• Page Start: 12952
• Page End: 12955
• Publication Date: 2016-09-15
• Subjects: Elektrodenmaterialien -- Jahn-Teller-Verzerrung -- Natriumionenbatterien -- Polymorphie -- Schichtverbindungen; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201606415
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: To realize a reversible solid‐state Mn III/IV redox couple in layered oxides, co‐operative Jahn–Teller distortion (CJTD) of six‐coordinate Mn III (t2g 3 –eg 1 ) is a key factor in terms of structural and physical properties. We develop a single‐phase synthesis route for two polymorphs, namely distorted and undistorted P2‐type Na2/3 MnO2 having different Mn stoichiometry, and investigate how the structural and stoichiometric difference influences electrochemical reaction. The distorted Na2/3 MnO2 delivers 216 mAh g −1 as a 3 V class positive electrode, reaching 590 Wh (kg oxide) −1 with excellent cycle stability in a non‐aqueous Na cell and demonstrates better electrochemical behavior compared to undistorted Na2/3 MnO2 . Furthermore, reversible phase transitions correlated with CJTD are found upon (de)sodiation for distorted Na2/3 MnO2, providing a new insight into utilization of the Mn III/IV redox couple for positive electrodes of Na‐ion batteries.