Modulating Electron Conducting Properties at Lithium Anode Interfaces for Durable Lithium–Sulfur Batteries

The lithium (Li) ion and electron diffusion behaviors across the actual solid electrolyte interphase (SEI) play a critical role in regulating the Li nucleation and growth and improving the performance of lithium-sulfur (Li-S) batteries. To date, a number of researchers have pursued an SEI with high Li-ion conductivity while ignoring the Li dendrite growth caused by electron tunneling in the SEI. Herein, an artificial anti-electron tunneling layer with enriched lithium fluoride (LiF) and sodium fluoride (NaF) nanocrystals is constructed using a facile solution-soaking method. As evidenced theoretically and experimentally, the LiF/NaF artificial SEI exhibits an outstanding electron-blocking capability that can reduce electron tunneling, resulting in dendrite-free and dense Li deposition beneath the SEI, even with an ultrahigh areal capacity. In addition, the artificial anti-electron tunneling layer exhibits improved ionic conductivity and mechanical strength, compared to those of routine SEI. The symmetric cells with protected Li electrodes achieve a stable cycling of 1500 h. The LiF/NaF artificial SEI endows the Li-S full cells with long-term cyclability under conditions of high sulfur loading, lean electrolyte, and limited Li excess. This study provides a perspective on the design of the SEI for highly safe and practical Li-S batteries.