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Structural and Dynamical Behaviors of Fast Ionic Conducting Potassium nido-(Carba)borates
Interdisciplinary Nanoscience Center (iNANO) and Department of Chemistry;Aarhus University;NIST Center for Neutron Research;National Institute of Standards and Technology.ORCID iD: 0000-0003-2663-8988
NIST Center for Neutron Research;National Institute of Standards and Technology.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.ORCID iD: 0000-0002-7119-0951
NIST Center for Neutron Research;National Institute of Standards and Technology;National Renewable Energy Laboratory;Transport at Nanoscale Interfaces Laboratory, Swiss Federal Laboratories for Material Science and Technology (EMPA), Ueberlandstrasse 129, 8600 Duebendorf, Switzerland.ORCID iD: 0000-0002-9439-1019
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2025 (English)In: Chemistry of Materials, ISSN 0897-4756, E-ISSN 1520-5002, Vol. 37, no 17, p. 6450-6461Article in journal (Refereed) Published
Abstract [en]

Solid-state batteries are one of the most recent iterations of electrochemical energy storage, and the technology can potentially provide safer and more-energy-dense batteries. The metal closo- and nido-(carba)borates show promise as versatile solid electrolytes and have been shown to have some of the highest ionic conductivities as well as wide electrochemical stability windows. In the present study, we investigate the four potassium nido-(carba)borates KB11H14, K-7-CB10H13, K-7,8-C2B9H12, and K-7,9-C2B9H12, and a total of eight new crystal structures were solved. All four compounds transition from a low-temperature, ordered phase to a high-temperature, disordered phase with the space group Fm-3m. In the high-temperature polymorphs, the anions are disordered and undergo rapid reorientational dynamics, which is confirmed by quasielastic neutron scattering experiments. Reorientational activation energies of 0.151(2), 0.146(32), and 0.143(3) eV were determined for K-7-CB10H13, K-7,8-C2B9H12, and K-7,9-C2B9H12, respectively. Additionally, such rotationally fluid anions are concomitant with fast potassium-ion conductivity. The highest ionic conductivity is observed for K-7,8-C2B9H12 with 1.7·10–2 S cm–1 at 500 K and an activation energy of 0.28 eV in the disordered state. The differences in phase transition temperatures, reorientational dynamics, and ionic conductivities among the potassium nido-(carba)borates illustrate a strong correlation between the K+ cationic mobility and the local cation–anion interactions, anion dynamics, and the specific positions of the carbon atoms in the nido-(carba)borate anion cages.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2025. Vol. 37, no 17, p. 6450-6461
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Condensed Matter Physics Inorganic Chemistry Materials Chemistry
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URN: urn:nbn:se:uu:diva-573224DOI: 10.1021/acs.chemmater.5c00151ISI: 001554819700001Scopus ID: 2-s2.0-105015963957OAI: oai:DiVA.org:uu-573224DiVA, id: diva2:2021033
Funder
Göran Gustafsson Foundation for Research in Natural Sciences and MedicineÅForsk (Ångpanneföreningen's Foundation for Research and Development), 21-453Available from: 2025-12-12 Created: 2025-12-12 Last updated: 2026-01-29Bibliographically approved

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Andersson, Mikael

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