A high-energy-density lithium-oxygen battery based on a reversible four-electron conversion to lithium oxide

An elevated lithium battery Batteries based on lithium metal and oxygen could offer energy densities an order of magnitude larger than that of lithium ion cells. But, under normal operation conditions, the lithium oxidizes to form peroxide or superoxide. Xia et al. show that, at increased temperatures, the formation of lithium oxide is favored, through a process in which four electrons are transferred for each oxygen molecule (see the Perspective by Feng et al.). Reversible cycling is achieved through the use of a thermally stable inorganic electrolyte and a bifunctional catalyst for both oxygen reduction and evolution reactions. Science, this issue p. 777; see also p. 758 At elevated temperatures, lithium can reversibly cycle to form dilithium oxide through a four-electron transfer process. Lithium-oxygen (Li-O2) batteries have attracted much attention owing to the high theoretical energy density afforded by the two-electron reduction of O2 to lithium peroxide (Li2O2). We report an inorganic-electrolyte Li-O2 cell that cycles at an elevated temperature via highly reversible four-electron redox to form crystalline lithium oxide (Li2O). It relies on a bifunctional metal oxide host that catalyzes O–O bond cleavage on discharge, yielding a high capacity of 11 milliampere-hours per square centimeter, and O2 evolution on charge with very low overpotential. Online mass spectrometry and chemical quantification confirm that oxidation of Li2O involves transfer of exactly 4 e–/O2. This work shows that Li-O2 electrochemistry is not intrinsically limited once problems of electrolyte, superoxide, and cathode host are overcome and that coulombic efficiency close to 100% can be achieved.