We report a significant difference in the growth mechanism of Li 2 O 2 in Li-O 2 batteries for toroidal and thin-film morphologies which is dependent on the current rate that governs the electrochemical pathway. Evidence from diffraction, electrochemical, FESEM and STEM measurements shows that slower current densities favor aggregation of lithium peroxide nanocrystallites nucleated via solution dismutase on the surface of the electrode; whereas fast rates deposit quasi-amorphous thin films. The latter provide a lower overpotential on charge due to their nature and close contact with the conductive electrode surface, albeit at the expense of lower discharge capacity.

Recently, there has been a transition from fully carbonaceous positive electrodes for the aprotic lithium oxygen battery to alternative materials and the use of redox mediator additives, in an attempt to lower the large electrochemical overpotentials associated with the charge reaction. However, the stabilizing or catalytic effect of these materials can become complicated due to the presence of major side-reactions observed during dis(charge). Here, we isolate the charge reaction from the discharge by utilizing electrodes prefilled with commercial lithium peroxide with a crystallite size of about 200-800 nm. Using a combination of S/TEM, online mass spectrometry, XPS, and electrochemical methods to probe the nature of surface films on carbon and conductive Ti-based nanoparticles, we show that oxygen evolution from lithium peroxide is strongly dependent on their surface properties. Insulating TiO2 surface layers on TiC and TiN - even as thin as 3 nm-can completely inhibit the charge reaction under these conditions. On the other hand, TiC, which lacks this oxide film, readily facilitates oxidation of the bulk Li2O2 crystallites, at a much lower overpotential relative to carbon. Since oxidation of lithium oxygen battery cathodes is inevitable in these systems, precise control of the surface chemistry at the nanoscale becomes of upmost importance.

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