Solvent Critical Role in Nonaqueous Lithium-Oxygen Battery Electrochemistry

Bryan D. McCloskey, Donald S. Bethune, Ronald M. Shelby, Girish Girishkumar, Alan C. Luntz
Year of publication: 
The Journal of Physical Chemistry Letters

Among the many important challenges facing the development of Li–air batteries, understanding the electrolyte’s role in producing the appropriate reversible electrochemistry (i.e., 2Li+ + O2 + 2e– ↔ Li2O2) is critical. Quantitative differential electrochemical mass spectrometry (DEMS), coupled with isotopic labeling of oxygen gas, was used to study Li–O2 electrochemistry in various solvents, including carbonates (typical Li ion battery solvents) and dimethoxyethane (DME). In conjunction with the gas-phase DEMS analysis, electrodeposits formed during discharge on Li–O2 cell cathodes were characterized using ex situ analytical techniques, such as X-ray diffraction and Raman spectroscopy. Carbonate-based solvents were found to irreversibly decompose upon cell discharge. DME-based cells, however, produced mainly lithium peroxide on discharge. Upon cell charge, the lithium peroxide both decomposed to evolve oxygen and oxidized DME at high potentials. Our results lead to two conclusions; (1) coulometry has to b...