发表机构
University of Applied Sciences Zwickau; Leibniz Institute for Solid State and Materials Research Dresden (IFW Dresden)（茨维考应用技术大学; 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。AI 中文总结
本研究揭示电解质种类通过调控普鲁士蓝类似物薄膜的晶格缺陷与结构无序，直接影响离子-电子耦合输运及电化学性能，为优化储能材料提供关键依据。
AI 中文摘要
理解电解质组成如何影响普鲁士蓝类似物（PBAs）中的电荷存储，需要阐明结构无序与离子输运之间的耦合效应。本文在相同的电化学条件下，研究了从KCl、NaCl、NH4Cl和LiCl电解质中电沉积的Fe基、Co基和Ni基六氰合铁酸盐薄膜。尽管所有薄膜均保持立方PBA结构，但电解质种类导致晶格参数、缺陷浓度和局部配位环境出现显著差异。Na+促进晶格膨胀，同时伴随空位形成增加、微应变增大和结构异质性增强，而K+和NH4+则产生结构更连贯的框架。拉曼光谱表明，结构无序度的增加拓宽了局部配位环境的分布，并与日益分散的电化学行为相关。电化学阻抗谱进一步揭示了离子-电子耦合输运，从FeHCF到NiHCF，阻抗增加超过一个数量级。值得注意的是，CPE指数随拉曼谱带展宽而系统性降低，建立了结构无序与输运分散之间的直接关联。这些结果表明，电解质种类不仅控制晶格尺寸，还控制缺陷网络的组织和连通性，凸显了结构连贯性和可及输运路径是决定PBA薄膜电化学性能的关键因素。
英文摘要
Understanding how electrolyte composition influences charge storage in Prussian blue analogues (PBAs) requires clarifying the coupled effects of structural disorder and ion transport. Here, we investigate Fe-, Co-, and Ni-based hexacyanoferrate thin films electrodeposited from KCl, NaCl, NH4Cl, and LiCl electrolytes under identical electrochemical conditions. Although all films retain the cubic PBA structure, electrolyte identity produces pronounced differences in lattice parameters, defect concentration, and local coordination environments. Na+ promotes lattice expansion accompanied by increased vacancy formation, microstrain, and structural heterogeneity, whereas K+ and NH4+ yield more structurally coherent frameworks. Raman spectroscopy shows that increasing structural disorder broadens the distribution of local coordination environments and correlates with increasingly dispersed electrochemical behavior. Electrochemical impedance spectroscopy further reveals coupled ion-electron transport, with impedance increasing by more than one order of magnitude from FeHCF to NiHCF. Notably, the CPE exponent decreases systematically with Raman band broadening, establishing a direct correlation between structural disorder and transport dispersion. These results demonstrate that electrolyte identity controls not only lattice dimensions but also the organization and connectivity of defect networks, highlighting structural coherence and accessible transport pathways as key factors governing electrochemical performance in PBA thin films.
