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- - a e - - - - c d - y t s o - s - s - - % Batteries 2022, 8, 127 of the 1 M NaClO4/PC electrolyte for which Rps decreases as the SO2 mole fraction in creases. In this particular case, for an SO2 mole fraction of 0.20, the current density in creases notably, becoming similar to that obtained in the absence of additive, but with much higher stability as the plating-stripping resistance does not significantly chang ing amounts of SO2 plays a role in the performance and kinetics of the Na+/Na process slowing it down and making it more robust. In contrast, a synergetic effect seems to hap upon repeated cycling. Likely, the enhanced growth of the SEI in the presence of increas pen in the NaClO4-based electrolyte, for which the current density increases as the con becoming similar to that obtained in the absence of additive, but with a much higher centration of additive does. stability as the plating-stripping resistance does not significantly change upon repeated As observed in Table 1, the highest values for the resistance were obtained for rela 5 of 13 In this particular case, for an SO2 mole fraction of 0.20, the current density increases notably, cycling. Likely, the enhanced growth of the SEI in the presence of increasing amounts tively high contents of SO2 in 1.6 M NaTf/DOL:DME. This is likely related to a drasti of SO2 plays a role in the performance and kinetics of the Na+/Na process, slowing it chadnogweninanthdemealekcintrgoiltymteo’rsenraotburset.,Iwnhcoicnhtrbasetc,oamsyensearggeetilc. Aeffcetcutasleleym, tshteoshoalpupteionninwthaes dilute NaClO -based electrolyte, for which the current density increases as the concentration of by 20% w4ith respect to that employed in the absence of SO2 as to facilitate the measure high contents of SO2 in 1.6 M NaTf/DOL:DME. This is likely related to a drastic change in additive does. ments, and a SO2 mole fraction of 0.2 was not studied because the electrolyte was full gelled. As observed in Table 1, the highest values for the resistance were obtained for relatively On the other hand, the development of anode-free batteries may represent importan the electrolyte’s nature, which becomes a gel. Actually, the solution was diluted by 20% practical advantages as it may allow mounting SMBs in a fully discharged state, thu with respect to that employed in the absence of SO2 as to facilitate the measurements, and avoaidSOingmthole hfranctdiolinnogf o0.f2swodasiunmot smtuedtaield. Ibnectahuiserethsepelcetc,tsroldytieumwaps lfautlilyng/esllterdip. ping was als 2 On the other hand, the development of anode-free batteries may represent important performed on a copper foil substrate. As with the sodium metal electrodes, CVs were ac practical advantages as it may allow mounting SMBs in a fully discharged state, thus quired in both the presence and the absence of SO2. Figure 2 shows the corresponding CV avoiding the handling of sodium metal. In this respect, sodium plating/stripping was in the case of the NaTf/DOL:DME electrolyte. Without additive, the electrolyte concentra also performed on a copper foil substrate. As with the sodium metal electrodes, CVs were tion was 2 M, while with SO2 it was slightly lowered to 1.6 M (as explained previously) acquired in both the presence and the absence of SO2. Figure 2 shows the corresponding As observed in the red curve of Figure 2a, in the absence of SO2, there are no clear sign CVs in the case of the NaTf/DOL:DME electrolyte. Without additive, the electrolyte + ofscodnicuenmtrdateiopnoswitaison2Mon,wChui,levweinthrSeOachiitnwgaaspsloigtehntltyialolwaserleodwtoas1.−60M.2V(asvesx.pNlain/eNda.How 2 previously). As observed in the red curve of Figure 2a, in the absence of SO , there are ever, low mole fractions of SO2 favor the plating process, which occurs n2ow at a low over no clear signs of sodium deposition on Cu, even reaching a potential as low as −0.2 V vs. voltage and with significant reversibility. The Coulombic efficiency attains a value of 70 Na+/Na. However, low mole fractions of SO2 favor the plating process, which occurs now after adding a 0.02 SO2 mole fraction. at a low overvoltage and with significant reversibility. The Coulombic efficiency attains a value of 70% after adding a 0.02 SO2 mole fraction. Figure 2. (a) CVs for the deposition of Na on Cu in 2 M or 1.6 M (in the presence of SO2) NaTf/DOL:DME at 20 mV·s−1 for different mole fractions of SO2. Pictures showing the sodium Figure 2. (a) CVs for the deposition of Na on Cu in 2 M or 1.6 M (in the presence of SO2 deposit morphology on Cu before (b) and after (c) adding a SO2 mole fraction of 0.02. Pictures (b,c) NaTf/DOL:DME at 20 mV·s−1 for different mole fraction+s of SO2. Pictures showing the sodium deposi were obtained after applying a potential of −0.2 V vs. Na /Na for 500 s. morphology on Cu before (b) and after (c) adding a SO2 mole fraction of 0.02. Pictures (b,c) were ob The pictures in Figure 2b,c show the aspect of the sodium deposits on the Cu substrate tained after applying a potential of −0.2 V vs. Na+/Na for 500 s. obtained after applying a potential of −0.2 V vs. Na+/Na for 500 s in the absence of and in the presence of the additive, respectively. It should be emphasized that the morphol- ogy of the sodium deposit dramatically changes upon the introduction of the additive, from one formed by particles that easily detach from the substrate to a continuous and homogeneous sodium deposit on the entire Cu surface in contact with the electrolyte. It is worth mentioning that this type of experimental result is not commonly reported in batteryPDF Image | Sulfur Dioxide and Sulfolane Sodium Batteries
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