Transport Mechanisms of Ions in Graft-Copolymer Based Salt-in-Polymer Electrolytes

Salt-in-polymer electrolytes based on graft copolymers with oligoether side chains and added LiCF3SO3 (LiTf) are investigated concerning the transport and dynamics of the ionic species with respect to applications as Li ion conductors. Polymer architectures are based on polysiloxane or polyphosphazene backbones with one or two side chains per monomer, respectively. NMR methods provide information about molecular dynamics on different length scales: The mechanisms governing local dynamics and long range mass transport are studied on the basis of temperature dependent spin-lattice relaxation rates and pulsed field gradient diffusion measurements for Li-7, F-19 and H-1, respectively. The correlation times characterizing local ion dynamics reflect the complexation of the cations by the oligoether side chains of the polymer. Li-7 and F-19 diffusion coefficients and their activation energies are rather similar, suggesting the formation of ion pairs and clusters with similar activation barriers for cation and/or anion long-range transport. Activation energies of local reorientations are generally significantly smaller than activation energies of long range diffusion. Long range transport is affected by (1) the coupling of conformational side chain reorientations to the cation movement, and (2) the correlated diffusion of cations and anions within ion pairs. Ion pairs and their dissociation play a major role in controlling the resulting conductivity of the material. Guidelines for material optimization in terms of a maximized conductivity can thus be derived by identifying a compromise between high ionic mobility and good Li complexation by the coordinating side chains.