Acid-Base Chemistry Provides a Simple and Cost-Effective Route to New Redox-Active Ionic Liquids.

Redox-active ionic liquids (RAILs) hold great promise as high density electrochemical energy storage materials, but are hampered by high costs and low bulk conductivities. In this work, we introduce and electrochemically characterise novel redox-active protic ionic liquids (RAPILs) formed by acid-base neutralisation from cheap and plentiful starting materials. We also demonstrate a novel RAIL-in-IL solvent system for electrochemical characterisation of RAPILs, which enables efficient and cost-effective determination of redox potentials and screening for electrochemical reversibility. Of the redox-active ionic liquids tested in this work, only propylammonium 4-nitrophenylacetate demonstrates completely reversible electrochemistry and preservation of ionic character upon redox cycling under acidic or neutral conditions. Propylammonium 2,5-dihydroxyphenyl-carboxylate also demonstrates two reversible redox processes, but is unstable to oxidation at 0.27 V vs Ag (-0.14 V vs Fc), most likely forming an uncharged benzoquinone species. Using the lessons learned from this prototypical set of RAPILs, we propose design criteria to guide future experimental and computational work.