Li-S batteries exhibit poor rate capability under lean electrolyte conditions required for achieving high practical energy densities. In this contribution, we argue that the rate capability of commercially-viable Li-S batteries is mainly limited by mass transfer rather than charge transfer during discharge. We first present experimental evidence showing that the charge-transfer resistance of Li-S batteries and hence the cathode surface covered by Li2S are proportional to the state-of-charge (SoC) and not to the current, directly contradicting previous theories. We further demonstrate that the observed Li-S behaviors for different discharge rates are qualitatively captured by a zero-dimensional Li-S model with transport-limited reaction currents. This is the first Li-S model to also reproduce the characteristic overshoot in voltage at the beginning of charge, suggesting its cause is the increase in charge transfer resistance brought by Li2S precipitation.
Zhang, T., Marinescu, M., Walus, S., Kovacik, P., & Offer, G. J. (2018). What Limits the Rate Capability of Li-S Batteries during Discharge: Charge Transfer or Mass Transfer? Journal of The Electrochemical Society, 165(1), A6001–A6004. https://doi.org/10.1149/2.0011801jes