不同温度下制备的CoHCF和NiHCF薄膜中组成、结晶度与化学结构的相互作用

中文摘要 AI 辅助

理解生长条件如何控制普鲁士蓝类似物（PBAs）薄膜中的结构有序性和离子传输，对于优化其电化学性能至关重要。在此，通过恒电位电沉积在20至60摄氏度之间的温度下制备了钴和镍六氰合铁酸盐（CoHCF和NiHCF）薄膜。采用循环伏安法、扫描电子显微镜、X射线衍射和拉曼光谱相结合的方法，阐明了组成、结晶度和化学结构之间的相互作用。在相同条件下，CoHCF的最大电流密度约为NiHCF的2.2倍，表明其电化学动力学显著更快。X射线衍射揭示了与温度相关的晶格膨胀，无相变发生，在40摄氏度附近达到最大值，这与结构弛豫和组成变化有关。拉曼光谱进一步揭示了与温度相关的局部结构演变，其中中间温度下氰化物谱带的变窄表明短程有序性改善，而较高温度下谱带的展宽则反映了缺陷密度的增加。这些发现表明，温度控制的缺陷再分布同时调控了PBA薄膜中的短程和长程结构有序性，直接影响离子传输和电化学响应。这项工作为PBAs中的结构-性能关系提供了新的见解，并将沉积温度确立为调节六氰合铁酸盐基电极电化学功能的关键参数。

英文摘要

Understanding how growth conditions govern structural order and ion transport in Prussian blue analogues (PBAs) thin films is essential for optimizing their electrochemical performance. Here, cobalt and nickel hexacyanoferrate (CoHCF and NiHCF) thin films were electrodeposited potentiostatically at temperatures between 20 and 60 degrees C. A combination of cyclic voltammetry, scanning electron microscopy, X-ray diffraction, and Raman spectroscopy was employed to elucidate the interplay between composition, crystallinity, and chemical structure. Under identical conditions, CoHCF exhibits a maximum current density approximately 2.2 times higher than NiHCF, indicating significantly faster electrochemical kinetics. X-ray diffraction reveals temperature-dependent lattice expansion without phase transitions, with a maximum near 40 degrees C, associated with structural relaxation and compositional variations. Raman spectroscopy further reveals temperature-dependent local structural evolution, where cyanide band narrowing at intermediate temperatures indicates improved short-range order, while band broadening at higher temperatures reflects increased defect density. These findings demonstrate that temperature-controlled defect redistribution governs both short- and long-range structural order in PBA thin films, directly influencing ion transport and electrochemical response. This work provides new insights into structure-property relationships in PBAs and establishes deposition temperature as a key parameter for tuning electrochemical functionality in hexacyanoferrate-based electrodes.

发表机构

• Faculty of Physical Engineering/Computer Sciences, University of Applied Sciences Zwickau（茨维考应用科学大学物理工程/计算机科学系）
• Leibniz Institute for Solid State and Materials Research Dresden (IFW Dresden)（德累斯顿莱布尼兹固体与材料研究所）

机构由 AI 辅助整理，请以论文原文为准。