Anomalous Impact ofMechanochemical Treatment on the Na-ion Conductivity ofSodium Closo-Carbadodecaborate Probed by X-Ray Raman Scattering Spectroscopy

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Main Authors: Gulino, Valerio, Alessandro, Longo, de Kort, Laura, Rodenburg, Henrik, Murgia, Fabrizio, Brighi, Matteo, Černý, Radovan, Sahle, Christoph, Sundermann, Martin, Gretarsson, Hlynur, de Groot, Frank, Ngene, Peter
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Published: Zenodo 2023
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author Gulino, Valerio
Alessandro, Longo
de Kort, Laura
Rodenburg, Henrik
Murgia, Fabrizio
Brighi, Matteo
Černý, Radovan
Sahle, Christoph
Sundermann, Martin
Gretarsson, Hlynur
de Groot, Frank
Ngene, Peter
author_facet Gulino, Valerio
Alessandro, Longo
de Kort, Laura
Rodenburg, Henrik
Murgia, Fabrizio
Brighi, Matteo
Černý, Radovan
Sahle, Christoph
Sundermann, Martin
Gretarsson, Hlynur
de Groot, Frank
Ngene, Peter
contents <p>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 (NaCB<sub>11</sub>H<sub>12</sub>) 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 NaCB<sub>11</sub>H<sub>12</sub>. 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 CB<sub>11</sub>H<sub>12</sub> 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.</p>
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institution Zenodo
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publishDate 2023
publisher Zenodo
record_format zenodo
spellingShingle Anomalous Impact ofMechanochemical Treatment on the Na-ion Conductivity ofSodium Closo-Carbadodecaborate Probed by X-Ray Raman Scattering Spectroscopy
Gulino, Valerio
Alessandro, Longo
de Kort, Laura
Rodenburg, Henrik
Murgia, Fabrizio
Brighi, Matteo
Černý, Radovan
Sahle, Christoph
Sundermann, Martin
Gretarsson, Hlynur
de Groot, Frank
Ngene, Peter
<p>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 (NaCB<sub>11</sub>H<sub>12</sub>) 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 NaCB<sub>11</sub>H<sub>12</sub>. 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 CB<sub>11</sub>H<sub>12</sub> 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.</p>
title Anomalous Impact ofMechanochemical Treatment on the Na-ion Conductivity ofSodium Closo-Carbadodecaborate Probed by X-Ray Raman Scattering Spectroscopy
url https://doi.org/10.1002/smtd.202300833