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Manganese‐Based Na‐Rich Materials Boost Anionic Redox in High‐Performance Layered Cathodes for Sodium‐Ion Batteries
Author(s) -
Zhang Xiaoyu,
Qiao Yu,
Guo Shaohua,
Jiang Kezhu,
Xu Sheng,
Xu Hang,
Wang Peng,
He Ping,
Zhou Haoshen
Publication year - 2019
Publication title -
advanced materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 10.707
H-Index - 527
eISSN - 1521-4095
pISSN - 0935-9648
DOI - 10.1002/adma.201807770
Subject(s) - redox , materials science , manganese , x ray photoelectron spectroscopy , raman spectroscopy , electrochemistry , cationic polymerization , ion , cathode , chemical engineering , inorganic chemistry , chemistry , electrode , polymer chemistry , organic chemistry , physics , optics , engineering , metallurgy
To improve the energy and power density of Na‐ion batteries, an increasing number of researchers have focused their attention on activation of the anionic redox process. Although several materials have been proposed, few studies have focused on the Na‐rich materials compared with Li‐rich materials. A key aspect is sufficient utilization of anionic species. Herein, a comprehensive study of Mn‐based Na 1.2 Mn 0.4 Ir 0.4 O 2 (NMI) O3‐type Na‐rich materials is presented, which involves both cationic and anionic contributions during the redox process. The single‐cation redox step relies on the Mn 3+ /Mn 4+ , whereas Ir atoms build a strong covalent bond with O and effectively suppress the O 2 release. In situ Raman, ex situ X‐ray photoelectron spectroscopy, and soft‐X‐ray absorption spectroscopy are employed to unequivocally confirm the reversibility of O 2 2− species formation and suggest a high degree of anionic reaction in this NMI Na‐rich material. In operando X‐ray diffraction study discloses the asymmetric structure evolution between the initial and subsequent cycles, which also explains the effect of the charge compensation mechanism on the electrochemical performance. The research provides a novel insight on Na‐rich materials and a new perspective in materials design towards future applications.