Anomalous Impact of Mechanochemical Treatment on the Na-ion Conductivity of Sodium Closo-Carbadodecaborate Probed by X-Ray Raman Scattering Spectroscopy

Valerio Gulino*, Alessandro Longo*, Laura M. de Kort, Hendrik P. Rodenburg, Fabrizio Murgia, Matteo Brighi, Radovan Černý, Christoph J. Sahle, Martin Sundermann, Hlynur Gretarsson, Frank de Groot, Peter Ngene*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

Abstract

Solid-state sodium ion conductors are crucial for the next generation of all-solid-state sodium batteries with high capacity, low cost, and improved safety. Sodium closo-carbadodecaborate (NaCB11H12) is an attractive Na-ion conductor owing to its high thermal, electrochemical, and interfacial stability. Mechanical milling has recently been shown to increase conductivity by five orders of magnitude at room temperature, making it appealing for application in all-solid-state sodium batteries. Intriguingly, milling longer than 2 h led to a significant decrease in conductivity. In this study, X-ray Raman scattering (XRS) spectroscopy is used to probe the origin of the anomalous impact of mechanical treatment on the ionic conductivity of NaCB11H12. The B, C, and Na K-edge XRS spectra are successfully measured for the first time, and ab initio calculations are employed to interpret the results. The experimental and computational results reveal that the decrease in ionic conductivity upon prolonged milling is due to the increased proximity of Na to the CB11H12 cage, caused by severe distortion of the long-range structure. Overall, this work demonstrates how the XRS technique, allowing investigation of low Z elements such as C and B in the bulk, can be used to acquire valuable information on the electronic structure of solid electrolytes and battery materials in general.

Original languageEnglish
Article number2300833
Number of pages9
JournalSmall Methods
Volume8
Issue number1
Early online date8 Oct 2023
DOIs
Publication statusPublished - 19 Jan 2024

Bibliographical note

Publisher Copyright:
© 2023 The Authors. Small Methods published by Wiley-VCH GmbH.

Funding

Financial support from The Netherlands Organization for Scientific Research (NWO‐ECHO and NWO‐RELEASE) was gratefully acknowledged. The authors kindly acknowledge Marcel Van Asselen and Sander Deelen for the design of the cell, and Masoud Lazemi for the support in the laboratory activities, all from Utrecht University. We acknowledge the European Synchrotron Radiation Facility (ESRF) for provision of synchrotron radiation facilities under proposal number CH‐6019 as well as computing resources and we would like to thank F. Gerbon for assistance and support in using beamline ID20. Part of the research presented in this document was carried out at PETRA III synchrotron (DESY) beamline P01, Hamburg, Germany. Financial support from The Netherlands Organization for Scientific Research (NWO-ECHO and NWO-RELEASE) was gratefully acknowledged. The authors kindly acknowledge Marcel Van Asselen and Sander Deelen for the design of the cell, and Masoud Lazemi for the support in the laboratory activities, all from Utrecht University. We acknowledge the European Synchrotron Radiation Facility (ESRF) for provision of synchrotron radiation facilities under proposal number CH-6019 as well as computing resources and we would like to thank F. Gerbon for assistance and support in using beamline ID20. Part of the research presented in this document was carried out at PETRA III synchrotron (DESY) beamline P01, Hamburg, Germany.

FundersFunder number
Masoud Lazemi
NWO-ECHO
NWO-RELEASE
NWO‐ECHO
NWO‐RELEASE
European Synchrotron Radiation FacilityCH-6019
Universiteit Utrecht
Nederlandse Organisatie voor Wetenschappelijk Onderzoek

    Keywords

    • all-solid-state batteries
    • closo-carbadodecaborate
    • complex hydrides electrolytes
    • sodium-ion conductors
    • solid-state electrolytes
    • X-ray Raman scattering (XRS)

    Fingerprint

    Dive into the research topics of 'Anomalous Impact of Mechanochemical Treatment on the Na-ion Conductivity of Sodium Closo-Carbadodecaborate Probed by X-Ray Raman Scattering Spectroscopy'. Together they form a unique fingerprint.

    Cite this