Investigating the Cyclability and Stability at the Interfaces of Composite Solid Electrolytes in Li Metal Batteries

Despite the fact that much work has been dedicated to finding the ideal additive for composite solid electrolytes (CSEs) for lithium-based solid-state batteries, little is known about the properties of a CSE that enable stable cycling with a lithium metal anode. In this work, we use three CSEs based on lithium nitride (Li₃N), a fast lithium-ion conductor, and lithium hydroxide (LiOH) to investigate the properties and interfacial interactions that impact the cyclability of CSEs. We present a method for stabilizing Li₃N with a shell of LiOH, and we incorporate Li₃N, core-shell particles, and LiOH into CSEs using polyethylene oxide (PEO) and lithium bis(trifluoromethanesulfonyl)imide. Through improved interfacial chemistry, CSEs with core-shell particles have superior electrochemical cycling performance compared to those with unprotected Li₃N in symmetric Li-Li cells. This CSE features a high ionic conductivity of 0.66 mS cm^-1 at 60 °C, a high critical current density of 1.2 mA cm^-2, and a wide voltage window of 0-5.1 V. Full cells with the core-shell CSE and lithium iron phosphate cathodes exhibit stable cycling and high reversible specific capacities in cells as high as 2.5 mAh cm^-2. We report that the improved ionic conductivity and amorphous PEO content have a limited effect on the solid-state electrolyte performance, while improving the electrolyte-Li metal anode interface is key to cycling longevity.