Switching Redox-Active Sites by Valence Tautomerism in Prussian Blue Analogues AxMny[Fe(CN)6]•nH2O (A: K, Rb): Robust Frameworks for Reversible Li Storage
Switching Redox-Active Sites by Valence Tautomerism in Prussian Blue Analogues AxMny[Fe(CN)6]•nH2O (A: K, Rb): Robust Frameworks for Reversible Li Storage
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DOI：
10.1021/jz100708b
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发表时间：
2010-07-15
影响因子：
5.7
通讯作者：
Honma, I.
中科院分区：
文献类型：
--
作者：
Okubo, M.;Asakura, D.;Honma, I.
提供可逆Li离子插入/提取反应的新电极材料的发现对于Li离子电池具有首要重要性。本文研究了价态互变异构普鲁士蓝类似物A（x）Mn（y）[Fe（CN）（6）]（A：K，Rb）的电化学锂离子嵌入/引出。非原位X-射线衍射实验表明，不存在价态互变异构现象的K盐表现出Li离子的插入/脱出过程是Fe离子的氧化还原过程，而存在价态互变异构现象的Rb盐表现出Mn离子的氧化还原过程。无论氧化还原活性的金属离子，实现了高度可逆的Li离子存储。XPS实验证实了锂离子嵌入/脱出过程中电子结构的变化。
The discovery of a new electrode material that provides a reversible Li ion insertion/extraction reaction is of primary importance for Li ion batteries. In this report, electrochemical Li ion insertion/extraction in valence tautomeric Prussian blue analogues A(x)Mn(y)[Fe(CN)(6)] (A: K, Rb) was investigated. Ex situ X-ray diffraction experiments revealed that the K salt without the valence tautomerism exhibits the Li ion insertion/extraction with a redox process of an Fe ion, while the Rb salt with the valence tautomerism exhibits that with a redox process of a Mn ion. Regardless of the redox-active metal ions, highly reversible Li ion storage was achieved. The electronic structure changes during the Li ion insertion/extraction are confirmed by XPS experiments.