Electrolyte Dependent Structure Transport Relationships in Electrodeposited Prussian Blue Analogue Thin Films
Abstract
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.
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BibTeX
@misc{garcia2026electrolyte,
title = {{Electrolyte Dependent Structure Transport Relationships in Electrodeposited Prussian Blue Analogue Thin Films}},
author = {Larissa de O. Garcia and Michael Pohlitz and Mohammed F. Kalady and Christian K. Muller},
howpublished = {arXiv},
year = {2026},
month = sep,
doi = {10.48550/arxiv.2609.26008},
eprint = {2609.26008},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2609.26008},
}
RIS
TY - UNPB
TI - Electrolyte Dependent Structure Transport Relationships in Electrodeposited Prussian Blue Analogue Thin Films
AU - Larissa de O. Garcia
AU - Michael Pohlitz
AU - Mohammed F. Kalady
AU - Christian K. Muller
PY - 2026
DA - 2026/09/22
PB - arXiv
DO - 10.48550/arxiv.2609.26008
UR - https://arxiv.org/abs/2609.26008
AB - 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.
ER -