High-Performance P2-Phase Na2/3Mn0.8Fe0.1Ti0.1O2 Cathode Material for Ambient-Temperature Sodium-Ion Batteries

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• 作者：Man Huon Han ; Elena Gonzalo ; Neeraj Sharma ; Juan Miguel López del Amo ; Michel Armand ; Maxim Avdeev ; Jose Javier Saiz Garitaonandia ; Teófilo Rojo
• 刊名：Chemistry of Materials
• 出版年：2016
• 出版时间：January 12, 2016
• 年：2016
• 卷：28
• 期：1
• 页码：106-116
• 全文大小：644K
• ISSN：1520-5002

文摘

High-performance Mn-rich P2-phase Na_2/3Mn_0.8Fe_0.1Ti_0.1O₂ is synthesized by a ceramic method, and its stable electrochemical performance is demonstrated. ²³Na solid-state NMR confirms the substitution of Ti⁴⁺ ions in the transition metal oxide layer and very fast Na⁺ mobility in the interlayer space. The pristine electrode delivers a second charge/discharge capacity of 146.57/144.16 mA·h·g^–1 and retains 95.09% of discharge capacity at the 50th cycle within the voltage range 4.0–2.0 V at C/10. At 1C, the reversible specific capacity still reaches 99.40 mA·h·g^–1, and capacity retention of 87.70% is achieved from second to 300th cycle. In addition, the moisture-exposed electrode reaches reversible capacities of more than 130 and 80 mA·h·g^–1 for C/10 and 1C, respectively, with excellent capacity retention. The correlation between overall electrochemical performance of both electrodes and crystal structural characteristics are investigated by neutron powder diffraction. The stability of pristine electrode’s crystallographic structure during the charge/discharge process has been investigated by in situ X-ray diffraction, where only a solid solution reaction occurs within the given voltage range except for a small biphasic mechanism occurring at or below 2.2 V during the discharge process. The relatively small substitution (20%) at the transition metal site leads to stable electrochemical performance, which is in part derived from the structural stability during electrochemical cycling. Therefore, the small cosubstitution (e.g., with Ti and Fe) route suggests a possible new scope for the design of sodium-ion battery electrodes that are suitable for long-term cycling.