The phase structure, chain diffusion motion and local reorientation motion: ¹³C Solid-state NMR study on the highly-crystalline solid polymer electrolytes

In our previous paper, we investigated the influence of the phase structure on the polymeric chain diffusion in the complexed crystals of solid polymer electrolytes of PEO:LiAsF₆ and PEO:LiCF₃SO₃. We observed that with the increase of the crystallinity, the chain diffusion rate decreases dramatically. In this work, by employing the ¹³C CODEX NMR spectroscopy, we demonstrate that opposite to the behavior of the chain diffusion motion, the local reorientation motion of polymeric chains within the complexed crystals are greatly increased with the increase of the crystallinity, which is accompanied by the change of the phase structure. The relationship between the different molecular motions within the complexed crystals and the phase structure are discussed therefore.