Understanding Interfaces at the Positive and Negative Electrodes on Sulfide-Based Solid-State Batteries

[Image: see text] Despite the high ionic conductivity and attractive mechanical properties of sulfide-based solid-state batteries, this chemistry still faces key challenges to encompass fast rate and long cycling performance, mainly arising from dynamic and complex solid–solid interfaces. This work provides a comprehensive assessment of the cell performance-determining factors ascribed to the multiple sources of impedance from the individual processes taking place at the composite cathode with high-voltage LiNi(0.6)Mn(0.2)Co(0.2)O(2), the sulfide argyrodite Li(6)PS(5)Cl separator, and the Li metal anode. From a multiconfigurational approach and an advanced deconvolution of electrochemical impedance signals into distribution of relaxation times, we disentangle intricate underlying interfacial processes taking place at the battery components that play a major role on the overall performance. For the Li metal solid-state batteries, the cycling performance is highly sensitive to the chemomechanical properties of the cathode active material, formation of the SEI, and processes ascribed to Li diffusion in the cathode composite and in the space-charge layer. The outcomes of this work aim to facilitate the design of sulfide solid-state batteries and provide methodological inputs for battery aging assessment.