A major challenge for lithium‐containing electrochemical systems is the formation of lithium carbonates. Solid‐state electrolytes circumvent the use of organic liquids that can generate these species, but they are still susceptible to Li2CO3 formation from exposure to water vapor and carbon dioxide. It is reported here that trace quantities of Li2CO3, which are re‐formed following standard mitigation and handling procedures, can decompose at high charging potentials and degrade the electrolyte–cathode interface. Operando electrochemical mass spectrometry (EC–MS) is employed to monitor the outgassing of solid‐state batteries containing the garnet electrolyte Li7La3Zr2O12 (LLZO) and using appropriate controls CO2 and O2 are identified to emanate from the electrolyte–cathode interface at charging potentials > 3.8 V (vs Li/Li+). The gas evolution is correlated with a large increase in cathode interfacial resistance observed by potential‐resolved impedance spectroscopy. This is the first evidence of electrochemical decomposition of interfacial Li2CO3 in garnet cells and suggests a need to report “time‐to‐assembly” for cell preparation methods.

Li-O2 batteries are mainly limited by the poor conductivity of their discharge products as well as parasitic reactions with carbon-containing electrodes and electrolytes. Here, Li-O2 cells utilizing inorganic solid-state electrolytes are investigated as a means to operate at elevated temperature, thereby increasing the conductivity of discharge products. Growth of dense, conductive Li x O y products further removes the need for high-surface area support structures commonly made of carbon. Patterned Au electrodes, evaporated onto Li7La3Zr2O12 (LLZO) solid electrolyte, are used to create a triple-phase boundary for the nucleation of the discharge product, with growth outward into the cell headspace with gaseous O2. Through capacity measurements and imaging, discharge product growths are estimated to reach a critical dimension of approximately 10 μm, far exceeding what would be possible for a conformal film based on its room temperature electronic conductivity. Raman spectroscopy and electrochemical mass spectrometry are used to characterize the discharge chemistry and reveal a mixed lithium oxide character, with evidence of trace lithium hydroxides and initial carbonate contamination. These results showcase that thermal enhancement of Li-O2 batteries could be a viable strategy to increase capacity when paired with solid electrolytes.

Li-O2 batteries are mainly limited by the poor conductivity of their discharge products as well as parasitic reactions with carbon-containing electrodes and electrolytes. Here, Li-O2 cells utilizing inorganic solid state electrolytes are investigated as a means to operate at elevated temperature, thereby increasing the conductivity of discharge products. Growth of dense, conductive LixOy products further removes the need for high surface area support structures commonly made of carbon. Patterned Au electrodes, evaporated onto Li7La3Zr2O12 (LLZO) solid electrolyte, are used to create a triple phase boundary for the nucleation of discharge product, with growth outward into the cell headspace with gaseous O2. Through capacity measurements and imaging, discharge product growths are estimated to reach a critical dimension of approximately 10 microns, far exceeding what would be possible for a conformal film based on its room temperature electronic conductivity. Raman spectroscopy and electrochemical mass spectrometry (EC-MS) are used to characterize the discharge chemistry and reveal a mixed lithium oxide character, with evidence of trace lithium hydroxides and initial carbonate contamination. These results showcase that thermal enhancement of Li-O2 batteries could be a viable strategy to increase capacity when paired with solid electrolytes.