NMR and Raman studies of a novel fast-ion-conducting polymer-in-salt electrolyte based on LiCF3SO3 and PAN

We report spectroscopic results from investigations of a novel solid polymeric fast-ion-conductor based on poly(acrylonitrile), (PAN, of repeat unit [CH₂CH(CN)]_<i>n</i>), and the salt LiCF₃SO<b>3</b> . From NMR studies of the temperature and concentration dependencies of ⁷Li- and ^lH-NMR linewidths, we conclude that significant ionic motion occurs at temperatures close to the glass transition temperature of these <i>polymer-in-salt</i> electrolytes, in accordance with a recent report on the ionic conductivity. In the dilute <i>salt-in-polymer</i> regime, however, ionic motion appears mainly to be confined to local salt-rich domains, as determined from the dramatic composition dependence of the ionic conductivity. FT-Raman spectroscopy is used to directly probe the local chemical anionic environment, as well as the Li⁺–PAN interaction. The characteristic δ_s(CF₃) mode of the CF₃SO₃⁻ anion at _~750–780 cm^−l shows that the ionic substructure is highly complex. Notably, no spectroscopic evidence of free anions is found even at relatively salt-depleted compositions (e.g. N:Li_~60–10:1). A strong Li⁺–PAN interaction is manifested as a pronounced shift of the characteristic polymer C=N stretching mode, found at _~2244 cm^−lin pure PAN, to _~2275 cm^−l for Li⁺-coordinated C=N moieties. Our proton-NMR data suggest that upon complexation of PAN with LiCF<b>3</b> SO₃, the glass transition occurs at progressively lower temperatures.<br />