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High-entropy layered oxide materials containing various metals that exhibit smooth voltage curves and excellent electrochemical performances have attracted attention in the development of positive electrode materials for sodium-ion batteries. However, the smooth voltage curve can be obtained by suppression of the Na+-vacancy ordering, and therefore, it is not necessary to use a greater variety of metals than necessary. In this study, the Na+-vacancy ordering is found to be disturbed by dual substitution of TiIV for MnIV and ZnII for NiII in P2-Na2/3[Ni1/3Mn2/3]O2. Dual-substituted Na2/3[Ni1/4Mn1/2Ti1/6Zn1/12]O2 demonstrates almost non-step voltage curves with a reversible capacity of 114 mAh g-1 and less structural changes with maintaining a high crystalline structure during charging and discharging. Synchrotron X-ray, neutron, and electron diffraction measurements reveal that dual-substitution with TiIV and ZnII uniquely promotes in-plane NiII-MnIV ordering, which is quite different from the disordered mixing in conventional multiple metal substitution.

権利情報:

• Creative Commons BY-NC-ND Attribution-NonCommercial-NoDerivs 4.0 International
  

キーワード: Cathode materials, Intercalation, Layered oxides, Sodium batteries, Structural analysis, Substitution, Superstructure

刊行年月日: 2023-05-13

出版者: Wiley

掲載誌:

• Advanced Materials (ISSN: 15214095) vol. 35 issue. 26 2300714

研究助成金:

• Japan Science and Technology Agency AS2614056L
• Japan Science and Technology Agency JPMJSC17C1
• Japan Science and Technology Agency JPMJCR21O6
• Ministry of Education Culture, Sports, Science and Technology JPMXP0112101003

原稿種別: 出版者版 (Version of record)

MDR DOI:

公開URL: https://doi.org/10.1002/adma.202300714

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更新時刻: 2025-01-08 16:30:44 +0900

MDRでの公開時刻: 2025-01-08 16:30:44 +0900