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Batteries 2022, 8, 127 11 of 13 References The improvement observed in most cases in the presence of the SO2-based additives is attributed to both the favorable interaction of the additive molecules with the sodium ions and the specific adsorption of the sulfur-containing molecule on the metal surface, which promote sodium deposition. In addition, the formation of an SEI on the sodium surface should be considered. In the case of SO2 as an additive, Na2S2O4 (Equation (5)) is expected to be the main component of the SEI, while RSO3Na and Na2SO3 would be present when sulfolane is added (Equation (6)). Further investigation is underway to confirm some of these hypotheses. Finally, it is remarkable that both sulfur-based additives could be employed in the formulation of new organic electrolytes for sodium metal batteries, using either a sodium metal anode or an anode-free configuration. The additive mole fractions needed are relatively low, thus avoiding the main drawbacks of these compounds when used as solvents: corrosivity and high volatility (in the case of SO2) and high viscosity (in the case of sulfolane). From a practical perspective, it should also be considered that sulfolane can be handled more easily than SO2, which is a gas under normal conditions. In addition, the partial pressure of the additive in equilibrium with the electrolyte is much lower for sulfolane, favoring the stability of the solution under a wider range of conditions (relatively high temperatures). Supplementary Materials: The following supporting information can be downloaded at: https:// www.mdpi.com/article/10.3390/batteries8090127/s1, Figure S1: CVs for Na-on-Na deposition/ stripping in: (a,b) 2M NaTf /DOL:DME without and with 0.02 SO2 mole fraction. (c,d) 1.6 M NaTf /DOL:DME with 0.05 and 0.1 SO2 mole fraction; Figure S2: CVs for Na-on-Na deposition/stripping in 2 M NaSCN/DOL:DME containing SO2 mole fractions of (a) 0, (b) 0.02, (c) 0.05, (d) 0.10 and (e) 0.20; Figure S3. Cyclic voltammograms for Na-on-Na deposition/stripping in 1 M NaClO4/PC containing SO2 mole fractions of (a) 0, (b) 0.05, (c) 0.10 and (d) 0.20. Author Contributions: Conceptualization, D.R.-M. and R.G.; Methodology, D.R.-M. and R.G.; Valida- tion, D.R.-M. and R.G.; Formal Analysis, R.G.; Investigation, D.R.-M.; Resources, R.G.; Data Curation, D.R.-M.; Writing—Original Draft Preparation, D.R.-M.; Writing—Review & Editing, D.R.-M. and R.G.; Visualization, D.R.-M.; Supervision, D.R.-M. and R.G.; Project Administration, R.G.; Funding Acquisition, R.G. All authors have read and agreed to the published version of the manuscript. Funding: This research was partially funded by the Ministerio de Ciencia e Innovación/Agencia Estatal de Investigación/Fondos FEDER through project RTI2018-102061-B-I00 and by the Generalitat Valenciana through project PROMETEO/2020/089. Institutional Review Board Statement: Not applicable. Informed Consent Statement: Not applicable. Data Availability Statement: The data presented in this study are available in the article. Acknowledgments: We are grateful to Andras Kovacs from BROADBIT for fruitful discussions and to the funding agencies supporting our work. Conflicts of Interest: The authors declare no conflict of interest. 1. Coetzer, J. A New High Energy Density Battery System. J. Power Sources 1986, 18, 377–380. [CrossRef] 2. Dustmann, C.-H. Advances in ZEBRA Batteries. J. Power Sources 2004, 127, 85–92. [CrossRef] 3. Kim, B.-R.; Jeong, G.; Kim, A.; Kim, Y.; Kim, M.G.; Kim, H.; Kim, Y.-J. High Performance Na-CuCl2 Rechargeable Battery toward Room Temperature ZEBRA-Type Battery. Adv. Energy Mater. 2016, 6, 1600862. [CrossRef] 4. Zheng, X.; Bommier, C.; Luo, W.; Jiang, L.; Hao, Y.; Huang, Y. Sodium Metal Anodes for Room-Temperature Sodium-Ion Batteries: Applications, Challenges and Solutions. Energy Storage Mater. 2019, 16, 6–23. [CrossRef] 5. Lee, J.; Kim, J.; Kim, S.; Jo, C.; Lee, J. A Review on Recent Approaches for Designing the SEI Layer on Sodium Metal Anodes. Mater. Adv. 2020, 1, 3143–3166. [CrossRef] 6. Liu, W.; Liu, P.; Mitlin, D. Review of Emerging Concepts in SEI Analysis and Artificial SEI Membranes for Lithium, Sodium, and Potassium Metal Battery Anodes. Adv. Energy Mater. 2020, 10, 2002297. [CrossRef]PDF Image | Sulfur Dioxide and Sulfolane Sodium Batteries
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