普鲁士蓝
阴极
化学
离子
电解质
无机化学
二价
分析化学(期刊)
电化学
物理化学
电极
有机化学
作者
Chong‐Yu Du,Zi-Hao Zhang,Xun‐Lu Li,Rong Luo,Chao Ma,Jian Bao,Jie Zeng,Xuan Xu,Fei Wang,Yong‐Ning Zhou
标识
DOI:10.1016/j.cej.2022.138650
摘要
Calcium-ion batteries (CIBs) have been of interest for rechargeable batteries due to their high energy density and fast ion diffusion in liquid electrolyte originated from the divalence and low charge/radius ratio of Ca ion. However, exploring high performance cathode materials for CIBs is very challenging. In this work, divalent Fe ions are introduced into copper hexacyanoferrate (CuHCF) to construct a new Prussian blue cathode material rich of Fe2+ by using K4Fe(CN)6 as the precursor instead of K3Fe(CN)6. The Fe2+ ions at low-spin state can improve the structural stability of CuHCF during Ca ions extraction and insertion processes effectively. It is found that the lattice parameter change of CuHCF is only 0.13 % during charge and discharge, much less than the CuHCF with Fe3+. X-ray absorption spectroscopy indicates that the charge compensation of CuHCF(Fe2+) is mainly contributed by Fe2+/Fe3+ redox couple. The octahedral distortion in CuHCF is also suppressed effectively. As a result, the CuHCF(Fe2+) cathode can deliver a reversible capacity of 54.5 mAh/g at 20 mA g−1 with a high capacity retention of 90.43 % after 1000 cycles.
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