Solid ionic conductors with good conductivity at room temperature and mechanical flexibility are very attractive candidates for application as electrolytes for secondary lithium batteries. Plastic crystal electrolytes formed by doping succinonitrile with lithium salts can potentially meet these requirements. In this study, succinonitrile doped with various lithium salts were characterized by differential scanning calorimetry, powder X-ray diffraction, conductivity measurements and in electrochemical studies. The much better conductivities and electrochemical performance of certain lithium salts in comparison to the others studied has been found to be correlated to their propensity to form crystalline adducts with succinonitrile at low molar concentrations. Of the lithium salts studied, only two which did not form crystalline adducts at low concentrations: lithium bistrifluoromethanesulphonylimide (Li[CF3SO2](2)N) and lithium tetrafluorborate (LiBF4) had high enough conductivities at ambient temperature for evaluation in lithium cells. Contrary to prior predictions, both showed reasonable capacities, high coulombic efficiencies, and good capacity retention even with metallic lithium as the anode. Crown Copyright (c) 2007 Published by Elsevier B.V. All rights reserved.