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Lithium-Air Batteries

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A New Piece in the Puzzle of Lithium/Air Batteries: Computational Study on the Chemical Stability of Propylene Carbonate in the Presence of Lithium Peroxide

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Laino Teodoro and Alessandro Curioni,

Chemistry: A European Journal, 18 (12), 3510-3520, 2012




The electrolyte role in non-aqueous lithium/air batteries is attracting a lot of attention in several research groups, because of its fundamental importance in producing the appropriate reversible electrochemical reduction. While recent published works identify the lithium superoxide as the main degrading agent for propylene carbonate (PC), there is no clear experimental evidence that the oxygen at the cathode interface layer does not reduce further to peroxide before reacting with PC. Here, we investigate the reactivity of lithium peroxide versus propylene carbonate and find that Li2O2 irreversibly decomposes the carbonate solvent, leading to alkyl carbonates. We also show that, compared with a single Li2O2 unit in PC, a crystalline surface of Li2O2 exhibits an enhanced reactivity. Our findings support the possibility that in lithium/air cells, oxygen may still be reduced to peroxide, with the formation of solid Li2O2, which degrades by decomposing PC.

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