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Batteries 2022, 8, x FOR PEER REVIEW Batteries 2022, 8, x FOR PEER REVIEW Batteries 2022, 8, 127 9 of 13 9 of 13 Figure 6. CVs at 20 mVs for the plating/stripping of Na on Cu in 1 M NaClO /PC with different −1 4 Figure 6. CVs at 20 mVs for the plating/stripping of Na on Cu in 1 M NaClO4/PC with different mole fractions of sulfolane: (a) 0; (b) 0.02 and (c) 0.10. (d) Picture showing the aspect of a 1 M mole fractions of sulfolane: (a) 0; (b) 0.02 and (c) 0.10. (d) Picture showing the aspect of a 1 M mole fractions of sulfolane: (a) 0; (b) 0.02 and (c) 0.10. (d) Picture showing the aspect of a 1 M NaClO4/PC solution with a 0.20 mole fraction of sulfolane. NaClO /PC solution with a 0.20 mole fraction of sulfolane. NaClO4/PC sol4ution with a 0.20 mole fraction of sulfolane. 9 of 13 −1 Figure 6. CVs at 20 mVs −1for the plating/stripping of Na on Cu in 1 M NaClO4/PC with different The improvement induced in the Na deposition process by the presence of sulfolane The improvement induced in the Na deposition process by the presence of sulfolane The improvement induced in the Na deposition process by the presence of sulfolane is related to the adsorption of the additive molecules on both copper and sodium, which is related to the adsorption of the additive molecules on both copper and sodium, which is is related to the adsorption of the additive molecules on both copper and sodium, which is likely followed by their spontaneous reduction. Such an adsorption is probably favored likely followed by their spontaneous reduction. Such an adsorption is probably favored at is likely followed by their spontaneous reduction. Such an adsorption is probably favored at negative potentials because of the expected strong interaction of the additive molecules negative potentials because of the expected strong interaction of the additive molecules at negative potentials because of the expected strong interaction of the additive molecules with the sodium ions. According to the literature, SO2 is adsorbed perpendicularly to the with the sodium ions. According to the literature, SO2 is adsorbed perpendicularly to the with the sodium ions. According to the literature, SO2 is adsorbed perpendicularly to the surface of Cu and the interaction between adsorbate and adsorbent can occur either surface of Cu and the interaction between adsorbate and adsorbent can occur either through surface of Cu and the interaction between adsorbate and adsorbent can occur either through the S atom, or through the S atom and at least one of the O atoms (Figure 7a) [21– the S atom, or through the S atom and at least one of the O atoms (Figure 7a) [21–34]. The through the S atom, or through the S atom and at least one of the O atoms (Figure 7a) [21– ++ 3f4o]r.mThaetiofonrmofathioisnaodfltahyiesrasdhlaoyuelrdsfhuoruthlderfufarvthoerrbfoatvhorthbeoathppthreoacphporofatchhe oNfatheioNnas tioonthse 34]. The formation of this adlayer should further favor both the approach of the Na+ ions ++ tomtehtealmsuetrafalcseurafnadcethaenidrrtehdeiurcrteiodnu,cftaiocinli,tfaatcinilgitathtiengNtahe/Nap/Nlaatipnlgatpinrogcepsrsoc[3e5ss–3[385].–38]. to the metal surface and their reduction, facilitating the Na+/Na plating process [35–38]. substrate. Figure 7. (a) Schematic representations for the interaction of (a) SO2 and (b) sulfolane with the Cu Figure 7. (a) Schematic representations for the interaction of (a) SO2 and (b) sulfolane with the Figure 7. (a) Schematic representations for the interaction of (a) SO2 and (b) sulfolane with the Cu substrate. Cu substrate. The results shown in Figure 6 for the 1 M NaClO4/PC electrolyte with sulfolane as an additive suggest a modification of the electrode-solution interface due to the adsorption of the sulfolane molecules on Cu (Figure 7b), which improves the Na+/Na process. Fur- thermore, sulfolane can also be involved in the formation of a stable SEI on the workingPDF Image | Sulfur Dioxide and Sulfolane Sodium Batteries
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