Use of Polarization Curves and Impedance Analyses to Optimize the “Triple-Phase Boundary” in K–O₂ Batteries

K–O2 superoxide batteries have shown great potential for energy-storage applications due to the unique single-electron redox processes in the oxygen or gas-diffusion electrode. Optimization of the ‘triple-phase boundary’, the region of the cathode where the O2, electrolyte, and electrode surface are in immediate contact, is crucial for maximizing their power performance, but one that has not been explored. Herein, we demonstrate an efficient method for maximizing the power capabilities of the K–O2 battery system by optimizing the interface using polarization and impedance analyses. At the one extreme, an electrolyte volume-deficient state decreases access to the electrochemically active surface area resulting in a limitation of the maximum power output of the K–O2 battery, whereas an excess electrolyte volume state increases the diffusion path to the active surface area for the dissolved O2 inducing mass-transfer limitations sooner, which results in a decrease in the current and power output. Finally, we show that the optimal electrolyte volume closely matches the void volume of the internal cell materials (separators, cathode) resulting in a maximization of the electrochemically accessible surface area while minimizing the O2 diffusion path.