Metal Substitution versus Oxygen-Storage Modifier to Regulate the Oxygen Redox Reactions in Sodium-Deficient Three-Layered Oxides

Authors: Mariya Kalapsazova, Rositsa Kukeva, Ekaterina Zhecheva, and Radostina Stoyanova


Open Access

Abstract: Sodium-deficient nickel-manganese oxides with three-layered stacking exhibit the unique property of dual nickel-oxygen redox activity, which allows them to achieve enormous specific capacity. The challenge is how to stabilize the oxygen redox activity during cycling. This study demonstrates that oxygen redox activity of P3-Na2/3Ni1/2Mn1/2O2 during both Na+ and Li+ intercalation can be regulated by the design of oxide architecture that includes target metal substituents (such as Mg2+ and Ti4+) and oxygen storage modifiers (such as CeO2). Although the substitution for nickel with Ti4+ amplifies the oxygen redox activity and intensifies the interaction of oxides with NaPF6– and LiPF6-based electrolytes, the Mg2+ substituents influence mainly the nickel redox activity and suppress the deposition of electrolyte decomposed products (such as MnF2). The CeO2-modifier has a much stronger effect on the oxygen redox activity than that of metal substituents; thus, the highest specific capacity is attained. In addition, the CeO2-modifier tunes the electrode–electrode interaction by eliminating the deposition of MnF2. As a result, the Mg-substituted oxide modified with CeO2 displays high capacity, excellent cycling stability and exceptional rate capability when used as cathode in Na-ion cell, while in Li-ion cell, the best performance is achieved for Ti-substituted oxide modified by CeO2.

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