Journal of Power Sources, Vol.390, 297-312, 2018
Present understanding of the stability of Li-stuffed garnets with moisture, carbon dioxide, and metallic lithium
Fast lithium-ion conducting garnet-type metal oxides are promising membranes for next-generation all-solid-state Li batteries and beyond Li-ion batteries, including Li-air and Li-S batteries, due to their high total Li-ion conductivity and excellent chemical stability against reaction with elemental Li. Several studies have been reported on structure-chemical composition-ionic conductivity property in Li-stuffed garnet-type metal oxides. Here, an overview of the chemical and electrochemical stability of lithium-based garnets against moisture/humidity, aqueous solutions, carbon dioxide, sulfur, and metallic lithium are analyzed. Moisture and aqueous stability studies focus on understanding the crystal structure stability, the proton exchange capacity as a function of Li content in Li-stuffed garnets, and how the protonated species affect the crystal structure and mass transport properties. H+/Li+ exchange was found to be in the range of 2-100%. Stability concerning Li-ion conductivity and morphology under carbon dioxide are discussed. Interfacial chemical stability with lithium metal characterized by electrochemical stability window, Li dendrite formation and area specific resistance (ASR) for the reaction Li reversible arrow Li+ + e(-) are presented. Recent attempts to suppress dendrite formation and to reduce ASR via surface modification are also highlighted. Li and Li-stuffed garnet interface ASR values are shown to be as high as > 2000 Omega cm(2) and as low as 1 Omega cm(2) at room temperature for surface modified Li-stuffed samples. Furthermore, recent studies on Li-S battery utilizing chemically stable Li - garnet electrolyte are also discussed.
Keywords:Lithium garnet;Li7La3Zr2O12 (LLZO);Chemical stability;Interfacial resistance;Li cycling;Chemical reactivity