  Compact solid discharge products enable energy storage devices with high
gravimetric and volumetric energy densities, but solid deposits on active
surfaces can disturb charge transport and induce mechanical stress. In this
Letter we develop a nanoscale continuum model for the growth of Li2O2 crystals
in lithium-oxygen batteries with organic electrolytes, based on a theory of
electrochemical non-equilibrium thermodynamics originally applied to Li-ion
batteries. As in the case of lithium insertion in phase-separating LiFePO4
nanoparticles, the theory predicts a transition from complex to uniform
morphologies of Li2O2 with increasing current. Discrete particle growth at low
discharge rates becomes suppressed at high rates, resulting in a film of
electronically insulating Li2O2 that limits cell performance. We predict that
the transition between these surface growth modes occurs at current densities
close to the exchange current density of the cathode reaction, consistent with
experimental observations.
