High plating currents without dendrites at the interface between a lithium anode and solid electrolyte

Abstract

Avoiding lithium dendrites at the lithium/ceramic electrolyte interface and, as a result, avoiding cell short circuit when plating at practical current densities remains a significant challenge for all-solid-state batteries. Typically, values are limited to around 1 mA cm−2, even, for example, for garnets with a relative density of >99%. It is not obvious that simply densifying ceramic electrolytes will deliver high plating currents. Here we show that plating currents of 9 mA cm−2 can be achieved without dendrite formation, by densifying argyrodite, Li6PS5Cl, to 99%. Changes in the microstructure of Li6PS5Cl on densification from 83 to 99% were determined by focused ion beam-scanning electron microscopy tomography and used to calculate their effect on the critical current density (CCD). Modelling shows that not all changes in microstructure with densification act to increase CCD. Whereas smaller pores and shorter cracks increase CCD, lower pore population and narrower cracks act to decrease CCD. Calculations show that the former changes dominate over the latter, predicating an overall increase in CCD, as observed experimentally. High plating currents are achieved in solid-state batteries without dendrites by densifying Li6PS5Cl, with modelling showing how specific microstructural changes increase the critical current density.