Invited Presentation: Highly Reversible Hybrid Lithium-Air Batteries

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Lithium-air batteries have become attractive due to their extremely high theoretical energy density. However, conventional lithium-air cells operating with nonaqueous electrolytes suffer from poor cycle life due to the clogging of the porous air cathodes by insoluble discharge products, contamination of the organic electrolyte by moist air, and decomposition of the electrolyte during cycling. Attempts to overcome these problems by developing compatible electrolyte/catalyst combinations have invariably been disappointing. These difficulties could be overcome by adopting a new cell configuration consisting of a lithium metal anode in the conventional organic electrolyte separated by a lithium-ion conducting solid electrolyte from the air electrode in an aqueous catholyte. Accordingly, this presentation will focus on the development of catholytes that can avoid corrosion of the solid electrolyte as well as efficient, inexpensive electroctalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER).A buffer catholyte solution with a moderate pH, consisting of phosphoric acid and a supporting salt, has been developed to keep the solid electrolyte stable and reduce the internal resistance and overpotential. With a high operating voltage and the utilization of all three protons of phosphoric acid, the buffer catholyte enables a rechargeable lithium-air cell with high energy density. Further increase in power density has been realized by increasing the solid-electrolyte conductivity and the operating temperature to 40 oC.The biggest challenge with lithium-air cells is the large overpotentials associated with the ORR and OER. Nanocrystalline iridium oxide has been the best OER catalyst, but it is expensive. In this regard, the low-temperature form of lithium cobalt oxide (designated as LT-lithium cobalt oxide) that adopts a lithiated spinel structure has been developed as an inexpensive, efficient electrocatalyst for OER. Its OER activity is much higher than that of the high-temperature form of lithium cobalt oxide (designated as HT-lithium cobalt oxide), which has a layered structure and is used as a cathode in lithium-ion batteries, and even slightly higher than that of iridium oxide. Although the ORR activity of LT-lithium cobalt oxide is low, a combination of high ORR and OER activity could be realized by chemically extracting lithium from the LT-lithium cobalt oxide, demonstrating the lithium-deficient, spinel-type LT-lithium cobalt oxide as a bifunctional catalyst for rechargeable metal-air batteries. The high OER and ORR activities of spinel-type LT-lithium cobalt oxides are attributed to cubane-like subunits and a pinning of the cobalt-3d energy with the top of the oxygen-2p band. Furthermore, a novel 3-D O- and N-doped carbon nanoweb (ON-CNW) has been developed as an inexpensive, metal-free catalyst for ORR. The 3-D nanoweb structure provides an ideal backbone support for catalytically active sites due to the fast electron and mass transport properties compared to 1-D or 2-D structures. Also, the synergistic effect between the O and N groups creates highly active pyridone groups all over the nanoweb surface that significantly improves the ORR activity. With a hybrid lithium-air cell, the ON-CNW exhibits performance close to that of commercial Pt/C. In addition, a novel hybrid lithium-air cell configuration with decoupled ORR and OER electrodes has been developed. With the conventional bifunctional air cathode that supports ORR during discharge and OER during charge, the ORR catalyst and carbon support suffer from degradation under the highly oxidizing conditions during the charge process, resulting in rapid increase in overpotential upon cycling and limiting the cycle life. In contrast, the hybrid lithium-air cell with decoupled ORR and OER electrodes eliminates the degradation problems and leads to high efficiency with good cycle life.