Structures of crystalline and amorphous phases of the poly(ethylene oxide)/lithium trifluoromethanesulfonate complexes as studied by solid-state high-resolution 13C nuclear magnetic resonance

Abstract

Solid-state high-resolution 13C NMR studies are carried out on a series of PEO/LiCF3SO3 complexes with different EO/Li molar ratios at room temperature. The obtained spectra clearly show that there are four phases, namely the crystalline PEO, the amorphous PEO, the PEO3:LiCF3SO3 crystalline complex and the PEO3:LiCF3SO3 amorphous complex, coexisting in the samples with EO/Li molar ratios larger than 3. The solid-state 13C NMR spectrum of the PEO3:LiCF3SO3 crystalline complex exhibits six peaks with high resolution at room temperature, while the previously reported 13C NMR spectra showed only one peak. These six peaks are assigned with the combination of the 13C dipolar-INADEQUATE and the two-dimensional exchange spectra. Moreover, remarkable helical jumps of PEO segments are demonstrated to exist in the crystalline complex. Our study paves the way towards a better understanding of the phase structures and subsequently the conduction mechanism of PEO-based solid polymer electrolytes.