Direct Observations of the Formation and Redox-Mediator-Assisted Decomposition of Li<sub>2</sub> O<sub>2</sub> in a Liquid-Cell Li-O<sub>2</sub> Microbattery by Scanning Transmission Electron Microscopy.

Yang, Chuchu; Han, Jiuhui; Liu, Pan; Hou, Chen; Huang, Gang; Fujita, Takeshi; Hirata, Akihiko; Chen, Mingwei · Adv Mater · 2017

basic_science · Level V

Where this comes from

Abstract

Operando scanning transmission electron microscopy observations of cathodic reactions in a liquid-cell Li-O<sub>2</sub> microbattery in the presence of the redox mediator tetrathiafulvalene (TTF) in 1.0 m LiClO<sub>4</sub> dissolved dimethyl sulfoxide electrolyte are reported. It is found that the TTF addition does not obviously affect the discharge reaction for the formation of a solid Li<sub>2</sub> O<sub>2</sub> phase. The coarsening of Li<sub>2</sub> O<sub>2</sub> nanoparticles occurs via both conventional Ostwald ripening and nonclassical crystallization by particle attachment. During charging, the oxidation reaction at significantly reduced charge potentials mainly takes place at Li<sub>2</sub> O<sub>2</sub> /electrolyte interfaces and has obvious correspondence with the oxidized TTF<sup>+</sup> distributions in the electric fields of the charged electrode. This study provides direct evidence that TTF truly plays a role in promoting the decomposition of Li<sub>2</sub> O<sub>2</sub> as a soluble charge-transfer agent between the electrode and the Li<sub>2</sub> O<sub>2</sub> .