Oxygen Reduction Reactions in Ionic Liquids and the Formulation of a General ORR Mechanism for Li-Air Batteries

Oxygen reduction and evolution reactions (ORRs and OERs) have been studied in ionic liquids containing singly charged cations having a range of ionic radii, or charge densities. Specifically, ORR and OER mechanisms were studied using cyclic and rotating disk electrode voltammetry in the neat ionic liquids (ILs), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMITFSI) and 1-methyl-1-butyl-pyrrolidinium bis-(triflouromethanesulfonyl)imide (PYR14TFSI), and in their solutions containing LiTFSI, NaPF6, KPF6, and tetrabutylammonium hexafluorophosphate (TBAPF(6)). A strong correlation was found between the ORR products and the ionic charge density, including those of the ionic liquids. The observed trend is explained in terms of the Lewis acidity of the cation present in the electrolyte using an acidity scale created from C-13 NMR chemical shifts and spin-attice relaxation (T-1) times of C-13=O in solutions of these charged ions in propylene carbonate (PC). The ionic liquids lie in a continuum of a cascading Lewis acidity scale with respect to the charge density of alkali. metal, IL, and TBA cations with the result that the ORR products in ionic liquids and in organic electrolytes containing any conducting cations can be predicted on the basis of a general theory based on the hard soft acid base (HSAB) concept.