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 language | English |
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Article number | 2300833 |
Number of pages | 9 |
Journal | Small Methods |
Volume | 8 |
Issue number | 1 |
Early online date | 8 Oct 2023 |
DOIs | |
Publication status | Published - 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.
Funders | Funder number |
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Masoud Lazemi | |
NWO-ECHO | |
NWO-RELEASE | |
NWO‐ECHO | |
NWO‐RELEASE | |
European Synchrotron Radiation Facility | CH-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)