Uncovering the Interplay of Competing Distortions in the Prussian Blue Analogue K2Cu[Fe(CN)6

Uncovering the Interplay of Competing Distortions in the Prussian Blue Analogue K2Cu[Fe(CN)6

© 2022 The Authors. Published by American Chemical Society.

Bibliographische Detailangaben
Veröffentlicht in:Chemistry of materials : a publication of the American Chemical Society. - 1998. - 34(2022), 11 vom: 14. Juni, Seite 5000-5008
1. Verfasser: Cattermull, John (VerfasserIn)
Weitere Verfasser: Sada, Krishnakanth, Hurlbutt, Kevin, Cassidy, Simon J, Pasta, Mauro, Goodwin, Andrew L
Format: Online-Aufsatz
Sprache:English
Veröffentlicht: 2022
Zugriff auf das übergeordnete Werk:Chemistry of materials : a publication of the American Chemical Society
Schlagworte:Journal Article
Beschreibung
Zusammenfassung:© 2022 The Authors. Published by American Chemical Society.
We report the synthesis, crystal structure, thermal response, and electrochemical behavior of the Prussian blue analogue (PBA) K2Cu[Fe(CN)6]. From a structural perspective, this is the most complex PBA yet characterized: its triclinic crystal structure results from an interplay of cooperative Jahn-Teller order, octahedral tilts, and a collective "slide" distortion involving K-ion displacements. These different distortions give rise to two crystallographically distinct K-ion channels with different mobilities. Variable-temperature X-ray powder diffraction measurements show that K-ion slides are the lowest-energy distortion mechanism at play, as they are the only distortion to be switched off with increasing temperature. Electrochemically, the material operates as a K-ion cathode with a high operating voltage and an improved initial capacity relative to higher-vacancy PBA alternatives. On charging, K+ ions are selectively removed from a single K-ion channel type, and the slide distortions are again switched on and off accordingly. We discuss the functional importance of various aspects of structural complexity in this system, placing our discussion in the context of other related PBAs
Beschreibung:Date Revised 30.08.2024
published: Print-Electronic
Citation Status PubMed-not-MEDLINE
ISSN:0897-4756
DOI:10.1021/acs.chemmater.2c00288