Electrochemical Sodium Storage in Hard Carbon Powder Electrodes Implemented in an Improved Cell Assembly: Insights from In‐Situ and Ex‐Situ Solid‐State NMR

In this work, we report on an improved cell assembly of cylindrical electrochemical cells for ²³Na in‐situ solid‐state NMR (ssNMR) investigations. The cell set‐up is suitable for using powder electrode materials. Reproducibility of our cell assembly is analyzed by preparing two cells containing hard carbon (HC) powder as working electrode and sodium metal as reference electrode. Electrochemical storage properties of HC powder electrode derived from carbonization of sustainable cellulose are studied by ssNMR. ²³Na in‐situ ssNMR monitors the sodiation/desodiation of a Na|NaPF₆|HC cell (cell 1) over a period of 22 days, showing high cell stability. After the galvanostatic process, the HC powder material is investigated by high resolution ²³Na ex‐situ MAS NMR. The formation of ionic sodium species in different chemical environments is obtained. Subsequently, a second Na|NaPF₆|HC cell (cell 2) is sodiated for 11 days achieving a capacity of 220 mAh/g. ²³Na ex‐situ MAS NMR measurements of the HC powder material extracted from this cell clearly indicate the presence of quasi‐metallic sodium species next to ionic sodium species. This observation of quasi‐metallic sodium species is discussed in terms of the achieved capacity of the cell as well as of side reactions of sodium in this electrode material.

An improved cell assembly for preparation of stable Na/Na⁺ electrochemical cell systems is presented which is appropriate for investigation of powder electrodes applying in-situ solid-state NMR studies. Insights into the electrochemical storage of Hard Carbon powder electrodes are provided combining in-situ and ex-situ solid-state ²³Na NMR techniques.