Positive Feedback Mechanism to Increase the Charging Voltage of Li–O<sub>2</sub> Batteries
Yoko Hase, Takeshi Uyama, Kiho Nishioka, Juntaro Seki, Kota Morimoto, Nobuhiro Ogihara, Yoshiharu Mukouyama, Shuji Nakanishi
Abstract
The large overpotential of nonaqueous Li–O 2 batteries when charging causes low round-trip efficiency and decomposition of the electrode materials and electrolyte. The origins of this overpotential have been enthusiastically explored to date; however, a full understanding has not yet been reached because of the complexity of multistep reaction mechanisms. Here, we applied structural and electrochemical analysis techniques to investigate the reaction step that results in the increase of the overpotential when charging. Rietveld refinement of ex situ powder X-ray diffraction showed that a Li-deficient phase of Li 2 O 2, Li 2– x O 2, formed when discharging and was present over the course of charging. The galvanostatic intermittent titration technique revealed that the rate-determining process in the first step of charging was a solid–solution type of delithiation. The chemical diffusion coefficient of Li + ions in Li 2– x O 2, D Li, decreases as the cell voltage increases, which in turn leads to a decrease in the oxidation rate of Li 2– x O 2 . Under galvanostatic conditions, the deceleration of oxidation induces further increase of the cell voltage; therefore, an intrinsic mechanism of positive feedback to increase the cell voltage occurs in the first step. The results demonstrate that the continuity of the first step can be extended by the suppression of changes in any of the elements of the positive feedback loop, i.e., the oxidation rate, cell voltage, or D Li .