Surface Chemistry of LLZO Garnet Electrolytes with Sulfur in Electron Pair Donor Solvents.

Conventional Li-S batteries rely on liquid electrolytes based on LiNO3/DOL/DME mixtures that produce a quasistable interface with the lithium anode. Electron pair donor (EPD) solvents, also known as high donor number solvents, provide much higher polysulfide solubility and close-to-ideal sulfur utilization, making them solvents of choice for lean electrolyte Li-S cells. However, their instability to reduction requires incorporation of an ion-conductive membrane that is stable with Li-such as garnet LLZO and also stable with sulfur/polysulfides. We report that even trace amounts of LiOH on a LLTZO surface trigger a complex reaction with sulfur dissolved in typical EPD solvents (i.e., N,N-dimethylacetamide, DMA) to produce a highly resistive impedance layer that quickly grows with time from 1000 to 10,000 Ω cm2 over a few hours, thus impeding Li+ transport across the interface. Decorating the LLZO with protective phosphate groups to produce a modified surface provides a very low charge-transfer resistance of 40 Ω cm2 that is maintained over time and inhibits the reaction of LiOH and dissolved sulfur. Hybrid liquid-solid electrolyte cells constructed on this concept result in a high sulfur utilization of 1400 mAh g-1 which is 85% of theoretical and remains constant over cycling even with conventional, unoptimized carbon/sulfur cathodes.

Stabilizing Lithium Plating by a Biphasic Surface Layer Formed In†Situ.

The dendritic growth of Li metal leads to electrode degradation and safety concerns, impeding its application in building high energy density batteries. Forming a protective layer on the Li surface that is electron-insulating, ion-conducting, and maintains an intimate interface is critical. We herein demonstrate that Li plating is stabilized by a biphasic surface layer composed of a lithium-indium alloy and a lithium halide, formed in situ by the reaction of an electrolyte additive with Li metal. This stabilization is attributed to the fast lithium migration though the alloy bulk and lithium halide surface, which is enabled by the electric field across the layer that is established owing to the electron-insulating halide phase. A greatly stabilized Li-electrolyte interface and dendrite-free plating over 400 hours in Li|Li symmetric cells using an alkyl carbonate electrolyte is demonstrated. High energy efficiency operation of the Li4 Ti5 O12 (LTO)|Li cell over 1000 cycles is achieved.