The Role of Air-Electrode Structure on the Incorporation of Immiscible PFCs in Nonaqueous Li-O₂ Battery

Perfluorocarbons (PFCs) are considered advantageous additives to nonaqueous Li-O₂ battery due to their superior oxygen solubility and diffusivity compared to common battery electrolytes. Up to now, the main focus was concentrated on PFCs-electrolyte investigation; however, no special attention was granted to the role of carbon structure in the PFCs-Li-O₂ system. In our current research, immiscible PFCs, rather than miscible fluorinated ethers, were added to activated carbon class air electrode due to their higher susceptibility toward O₂^•- attack and to their ability to shift the reaction from two-phase to an artificial three-phase reaction zone. The results showed superior battery performance upon PFCs addition at lower current density (0.05 mA cm^-2) but unexpectedly failed to do so at higher current density (0.1 and 0.2 mA cm^-2), where oxygen transport limitation is best illustrated. The last was a direct result of liquid-liquid displacement phenomenon occurring when the two immiscible liquids were introduced into the porous carbon medium. The investigation and role of carbon structure on the mechanism upon PFCs addition to Li-O₂ system are suggested based on electrochemical characterization, wettability behavior studies, and the physical adsorption technique. Finally, we suggest an optimum air-electrode structure enabling the incorporation of immiscible PFCs in a nonaqueous Li-O₂ battery.