Three ionic plastic crystalline solids were synthesized and analyzed to evaluate their suitability for use as electrolytes in Li-ion batteries: N-propyl-N-methylpiperidinium hexafluorophosphate (PP13PF₆), N-propyl-N-methylpiperidinium tetrafluoroborate (PP13BF₄) and piperidinium perchlorate (PPClO₄). The physical and electro(chemical) properties will be discussed.Voltammetric analysis of the plastic crystals alone showed very wide electrochemical windows (>7.5 V) for PP13PF₆ and PP13BF₄, and a relatively wide window for PPClO₄ (4V). Addition of the analogous lithium salts to each of these species (LiPF₆, LiBF₄ and LiClO₄) in a 50:50 wt% ratio showed sluggish Li⁺ transport at room temperature, but improved when heated to temperatures greater than 45 °C. However, addition of 20 wt% of EC/DEC solvent increased Li⁺ transport dramatically, particularly for PP13PF₆ and PP13BF₄. Overall, a mixture containing LiBF₄, PP13BF₄ and EC/DEC displayed a stable wide electrochemical window of activity for several cycles and good Li⁺transport through the electrolyte rendering it a promising mixture for future use in Li-ion batteries.