3 years ago

Li Salt Anion Effect on O2 Solubility in an Li–O2 Battery

Li Salt Anion Effect on O2 Solubility in
an Li–O2 Battery
Ann Cornell, Patrik Johansson, Gustav Åvall, Jonas Lindberg, Göran Lindbergh, Balázs Endrődi
For the promising Li–O2 battery to be commercialized, further understanding of its constituents is needed. This study deals with the role of O2 in Li–O2 batteries, both its influence on electrochemical performance and its solubility in lithium-salt-containing dimethyl sulfoxide (DMSO) electrolytes. Experimentally, the electrochemical performance was evaluated using cylindrical ultramicroelectrodes. Two independent techniques, using a mass spectrometer and an optical sensor, were used to evaluate the O2 solubility, expressed as Henry’s constant. Furthermore, the ionic conductivity, dynamic viscosity, and density were also measured. Density functional theory calculations were made of the interaction energy between O2 and the different species in the electrolytes. When varying O2 partial pressure, the current was larger at high pressures confirming that the O2 concentration is of key importance when studying the kinetics of this system. Compared with neat DMSO, the O2 solubility increased with addition of LiTFSI and decreased with addition of LiClO4, indicating that the salt influences the solubility. This solubility trend is best explained in terms of apparent molar volume and interaction energy between O2 and the salt anion. In conclusion, this study shows the importance of O2 concentration, not just its partial pressure, and that the choice of Li salt can make this concentration increase or decrease.

Publisher URL: http://dx.doi.org/10.1021/acs.jpcc.7b09218

DOI: 10.1021/acs.jpcc.7b09218

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