Correlation between the Cation Disorders of Fe 3+ and Li + in P3-Type Na 0.67 [Li 0.1 (Fe 0.5 Mn 0.5 ) 0.9 ]O 2 for Sodium Ion Batteries

• Published in: ACS applied materials & interfaces 2022-07, Vol.14 (29), p.33120-33129
• Main Authors: Lim, Shin Gwon, Kwon, Mi-Sook, Kim, Taehun, Kim, Hyeongi, Lee, Suyeon, Lim, Jungwoo, Kim, Hanseul, Lee, Kyu Tae
• Format: Article
• Language: English
• ISSN: 1944-8244; 1944-8252
• DOI: 10.1021/acsami.2c05784

Various Fe-based layered oxide materials have received attention as promising cathode materials for sodium ion batteries because of their low cost and high specific capacity. Only a few P3-type Fe-based oxide materials, however, have been examined as cathodes because the synthesis of highly crystalline P3-type Fe-based oxides is not facile. For this reason, the structural merits of the P3 structure are not yet fully understood. Herein, highly crystalline P3-type Na [Li (Fe Mn ) ]O heated at 900 °C is introduced to improve the electrochemical performance of Fe-based layered oxides. The structures, reaction mechanisms, and electrochemical performances of P3 Na [Li (Fe Mn ) ]O , P2 Na [Li (Fe Mn ) ]O , and P2 Na [Fe Mn ]O are compared to demonstrate the roles of Li doping in the improved electrochemical performance of P3 Na [Li (Fe Mn ) ]O , such as stable capacity retention over 100 cycles. P3 Na [Li (Fe Mn ) ]O significantly suppresses the migration of Fe ions to tetrahedral sites in the Na layer during cycling because the cation disorder of Li is more favorable than that of Fe . As a result, P3 Na [Li (Fe Mn ) ]O shows better cycle performance than P2 Na [Fe Mn ]O . P3 Na [Li (Fe Mn ) ]O also exhibits an improved rate performance compared to P2 Na [Fe Mn ]O . This finding provides fundamental insights to improve the electrochemical performance of layered oxide cathode materials for sodium ion batteries.