Comparing Cycling Characteristics of Symmetric Lithium-Polymer-Lithium Cells with Theoretical Predictions

We develop a model based on concentrated solution theory for predicting the cycling characteristics of a lithium-polymer-lithium symmetric cell containing an electrolyte with known transport properties. The electrolytes used in this study are mixtures of polyethylene oxide (PEO) and lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) salt, prepared over a wide range of salt concentrations. The transport properties of PEO/LiTFSI previously reported in the literature are used as inputs for our model. We calculate salt concentration and potential profiles, which develop in these electrolytes under a constant dc polarization, as a function of current density, electrolyte thickness, and salt concentration. These profiles are nonlinear at steady-state due to the strong concentration dependence of the transport properties of this electrolyte. The effect of this nonlinearity on limiting current is demonstrated. Cycling characteristics of a series of lithium symmetric cells were measured to test the validity of our model, without resorting to any adjustable parameters. The time-dependence and steady-state value of the potential measured during cycling experiments were in excellent agreement with model predictions.