Reactions in the rechargeable lithium-O2 battery with alkyl carbonate electrolytes.

The nonaqueous rechargeable lithium-O(2) battery containing an alkyl carbonate electrolyte discharges by formation of C(3)H(6)(OCO(2)Li)(2), Li(2)CO(3), HCO(2)Li, CH(3)CO(2)Li, CO(2), and H(2)O at the cathode, due to electrolyte decomposition. Charging involves oxidation of C(3)H(6)(OCO(2)Li)(2), Li(2)CO(3), HCO(2)Li, CH(3)CO(2)Li accompanied by CO(2) and H(2)O evolution. Mechanisms are proposed for the reactions on discharge and charge. The different pathways for discharge and charge are consistent with the widely observed voltage gap in Li-O(2) cells. Oxidation of C(3)H(6)(OCO(2)Li)(2) involves terminal carbonate groups leaving behind the OC(3)H(6)O moiety that reacts to form a thick gel on the Li anode. Li(2)CO(3), HCO(2)Li, CH(3)CO(2)Li, and C(3)H(6)(OCO(2)Li)(2) accumulate in the cathode on cycling correlating with capacity fading and cell failure. The latter is compounded by continuous consumption of the electrolyte on each discharge.

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