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        IV-SFG studies on the effect of Li<sup>+</sup> in extending the electrochemical window at the Pt|[C<sub>2</sub>mim][FSA] interface

        Iwahashi, Takashi,Miwa, Yujiro,Zhou, Wei,Sakai, Yasunari,Yamagata, Masaki,Ishikawa, Masashi,Kim, Doseok,Ouchi, Yukio Elsevier 2016 Electrochemistry Communications Vol.72 No.-

        <P><B>Abstract</B></P> <P>The effect of Li<SUP>+</SUP> addition at the interface of a 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)amide ([C<SUB>2</SUB>mim][FSA]) room-temperature ionic liquid (RTIL) and a Pt electrode is investigated by infrared-visible sum-frequency generation (IV-SFG) vibrational spectroscopy. Addition of Li<SUP>+</SUP> to the Pt|[C<SUB>2</SUB>mim][FSA] system results in the extension of the electrochemical window (EW) by >1.0V at its negative edge. The potential dependence of the SF signal reveals that the [FSA]<SUP>−</SUP> anion of neat [C<SUB>2</SUB>mim][FSA] is desorbed at −1.5V while it remains in place even at −2.0V when Li<SUP>+</SUP> is added. The SFG spectra indicate that the [FSA]<SUP>−</SUP> anion at the Pt|[C<SUB>2</SUB>mim][FSA] interface interacts with Li<SUP>+</SUP> at the interface with the negatively-charged Pt electrode. This [FSA]<SUP>−</SUP> anion layer anchored through Li<SUP>+</SUP> suppresses [C<SUB>2</SUB>mim]<SUP>+</SUP> cation adsorption on the negatively-charged Pt electrode, resulting in a wider electrochemical window.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Li<SUP>+</SUP> addition to Pt|[C<SUB>2</SUB>mim][FSA] extends EW by >1V at the negative edge. </LI> <LI> IV-SFG directly probes the presence of [FSA]<SUP>−</SUP> on Pt. </LI> <LI> Without Li<SUP>+</SUP>, [FSA]<SUP>−</SUP> desorbs from Pt at −1.0V. </LI> <LI> Li<SUP>+</SUP> is adsorbed on Pt to anchor [FSA]<SUP>−</SUP> to suppress [C2mim]<SUP>+</SUP> adsorption at −2.0V. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

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