ABSTRACT
A surface coating that simultaneously suppressed Li dendrite growth and polysulfide shuttling on a lithium anode was successfully developed using a polymer blend composed of Nafion® and polyvinylidene difluoride (PVDF). This hierarchically nanostructured composite coating efficiently alleviated the swelling and dissolution problems of cation-selective Nafion® in the electrolyte and provided sufficient mechanical strength to accommodate large volumetric variations in the Li anode during charge-discharge cycles. The Nafion®/PVDF-coated Li anode exhibited substantially enhanced rate performance and cyclability as well as improved Coulombic efficiency for Li-S prototype batteries with a high-S-content cathode.
ABSTRACT
The discharge products of ether-based Li-O2 cells were grown directly on common carbon-coated TEM grids and observed by oxidation-state-sensitive full field transmission soft X-ray microscopy (TXM). The acquired data have permitted to quantify and localize with spatial resolution the distribution of the oxygen discharge products in these samples (i.e., lithium superoxide, peroxide, and carbonates) and appreciate several compositional, structural, and morphological aspects. Most of the peroxide particles had a toroidal shape, often with a central hole usually open on only one side, and which included significant amounts of superoxide-like phases (LiO2/Li2O2 ratio between 0.2 and 0.5). Smaller particles had smaller or no superoxide content, from which we infer that abundance of soluble LiO2 may have a role in toroid formation. Significant amount of carbonates were found irregularly distributed on the electrode surface, occasionally appearing as small particles and aggregates, and mostly coating lithium peroxide particles. This suggests the formation of a barrier that, similar to the solid electrolyte interface (SEI) critical in Li-ion batteries, requires an appropriate management for a reversible operation.
Subject(s)
Electric Power Supplies , Lithium/chemistry , Microscopy, Electron/methods , Oxygen/chemistry , SynchrotronsABSTRACT
By comparing carbon electrodes with varying porosity in Li-O2 cells, we show that the effect of electrolyte stirring at a given current density can result in a change from 2D to 3D growth of discharged deposits. The change of morphology is evident using electron microscopy and by analyzing electrode pore size distribution with respect to discharge capacity. As a consequence, carbon electrodes with different textural properties exhibit different capacity enhancements in stirred-electrolyte cells. We demonstrate that mass transport can directly control the discharge mechanism, similar to the electrolyte composition and current density, which have already been recognized as determining factors.
