Mechanistic modeling of capacity loss and polysulfide shuttle in lithium-sulfur batteries

02/10/2013 17:27:53

Lithium-sulfur (Li/S) cells are promising candidates for a next generation of safe and cost-effective high energy density batteries for mobile and stationary applications. At present, Li/S cells still suffer from poor cyclability, capacity loss under moderate current densities and self-discharge. Furthermore, the underlying chemical mechanisms of the general discharge/charge behavior as well as Li/S-specific phenomena like the polysulfide shuttle are not yet fully understood. Here we present a thermodynamically consistent, fully reversible continuum model of a Li/S cell with simplified four-step electrochemistry, including a simple description of the polysulfide shuttle effect. The model is parameterized using experimental discharge curves obtained from literature and reproduces behavior at various current densities with fairly high accuracy. While being instructively simple, the presented model can still reproduce distinct macroscopic Li/S-cell features caused by the shuttle effect, e.g., seemingly infinite charging at low charge current densities, and low coulombic efficiency. The irreversible transport of active material from the cathode to the anode results in a voltage drop and capacity loss during cycling, which can also be observed experimentally.

Autors: Andreas F. Hofmann, David N. Fronczek, Wolfgang G. Bessler

Magazine: Submitted to Journal of Power Sources