All-solid-state batteries (ASSBs) present a promising route towards safe and high power battery systems in order to meet the future demands in the consumer and automotive market. Composite cathodes are one way to boost the energy density of ASSBs compared to thin-film configurations. In this manuscript we investigate composites consisting of β-Li 3 PS 4 (β-LPS) solid electrolyte and high energy Li( Ni 0.6 Mn 0.2 Co 0.2 )O 2 (NMC622). The fabricated cells show a good cycle life with a satisfactory capacity retention. Still, the cathode utilization is below the values reported in the literature for systems with liquid electrolytes. Common understanding is that interface processes between the active material and solid electrolyte are responsible for the reduced performance. In order to throw some light on this topic, we perform 3D microstructureresolved simulations on virtual samples obtained via X-ray tomography. Through this approach we are able to correlate the composite microstructure with electrode performance and impedance. We identify the low electronic conductivity in the fully lithiated NMC622 as material inherent restriction preventing high cathode utilization. Moreover, we find that geometrical properties and morphological changes of the microstructure interact with the internal and external interfaces, significantly affecting the capacity retention at higher currents.

All-solid-state batteries promise to enable lithium metal anodes and outperform state-of-the-art lithium-ion battery technology. To achieve high battery capacity, utilization of the active material in the cathode must be maximized. Carbon-based conductive additives are known to improve the capacity and rate performance of electrode composites. However, their influence on cathode composites in all-solid-state batteries is yet not fully understood. Here, we study the influence of several carbon additives with different morphologies and surface areas on the performance of an all-solid-state battery cell Li|β-Li 3 PS 4 | Li(Ni 0.6 Co 0.2 Mn 0.2 )O 2 /β-Li 3 PS 4 /carbon. Cycling tests and microstructure-resolved simulations show that higher utilization of the cathode active material can be achieved using fiber-shaped vapor-grown carbon additives, whereas particle-shaped carbons show a minor influence. Unfortunately, carbon additives generally lead to an accelerated capacity loss during cycling and an enhanced formation of solid electrolyte decomposition products. The latter was studied in more detail using cyclic voltammetry, X-ray photoelectron spectroscopy, and cycling experiments. The results show that carbon additives with a small surface area and a fiber-like morphology result in the lowest degree of decomposition. To completely overcome electrolyte degradation caused by the use of carbon additives, a protection concept is developed. A thin alumina coating with a few nanometers thickness was deposited on the carbon fibers by atomic layer deposition, which successfully prevents decomposition reactions, reduces long-term capacity fading, and leads to an enhanced overall all-solid-state battery performance.

Lithium metal anodes are vital enablers for high-energy all-solid-state batteries (ASSBs). To promote ASSBs in practical applications, performance limitations such as the high lithium interface resistance and the grain boundary resistance in the solid electrolyte (SE) need to be understood and reduced by optimization of the cell design. In this work, we use our 3D microstructure-resolved simulation approach combined with a modified grain boundary transport model for the SE to shed some light on the aforementioned limitations in garnet ASSBs. Using high-resolution volume images of the SE electrode sample, we are able to reconstruct the SE microstructure. Using a grain segmentation algorithm, we further distinguish individual grains and account for the influence of the SE grain size and grain boundaries. We focus our simulation work on the trilayer cell architecture, consisting of two porous SE electrodes separated by a dense layer. Even though the highly porous SE electrodes reduce the lithium interface resistance by providing a higher active surface area, the increased electrode tortuosity also reduces the effective ionic conductivity in the SE. We confirm via impedance simulation studies and validation against experimental results that with increasing SE electrode porosity, the lithium transport becomes limited by grain boundaries. We also correlate the area-specific resistance to different lithium infiltration stages in the trilayer cell by spatially resolving the current density distribution. This analysis allows us to suggest a plausible deposition mechanism, and moreover, we identify current density hot spots in the proximity of the dense layer. These hot spots might lead to dendrite formation and long-term cell failure. The joint theoretical and experimental study gives guidelines for cell design and optimization which allow further improvement of the trilayer architecture.