Conduction Mechanisms in Crystalline LiPF₆·PEO₆ Doped with SiF₆²⁻ and SF₆

Molecular dynamics (MD) simulations have been made under imposed electric fields for crystalline LiPF 6 ·PEO 6, (LiPF 6 ) 1 - x (Li 2 SiF 6 ) x ·PEO 6, and (LiPF 6 ) 1 - x (SF 6 ) x ·PEO 6 for x = 0.01 under standard pressure and temperature conditions with the aim of identifying the conduction mechanisms in the systems. Contrary to the results of earlier experimental investigations where only cation mobility was observed, ionic transport is here found to occur in regions between the polymer hemi-helices, with a high transference number (0.9−1.0) for the PF 6 - anions .