Polymer gel electrolytes (PGEs) have been prepared using lithium tetrafluoroborate (LiBF4), propylene carbonate (PC) and poly (vinylidene fluoride) (PVDF). Self diffusion coefficients have been measured using pulse field gradient nuclear magnetic resonance (PFG-NMR) for the lithium cation, BF4 anion and solvent molecules using Li-7, F-19 and H-1 nuclei, respectively. It was found that lithium ion diffusion was slow compared to the much larger fluorinated BF4 anion, which is attributed to a large solvation shell around the lithium ions. The Li-7 and H-1 diffusion measurements also exhibited two unique environments for the diffusive species. The measurement of NMR transverse relaxation times has confirmed the presence of lithium ions in multiple phases as shown by the diffusion measurements. (C) 2016 Published by Elsevier Ltd.