Electrolyte-electrode interface plays a critical role in the electrochemical performance of all-solid-state Li-ion batteries. In this work, a mesoscale study is presented to investigate lithium transport and stress in the solid electrolyte based positive electrode during discharge. It is found that increasing electrolyte-electrode interface contact facilitates Li intercalation into the electrode and alleviates the stresses in both the electrode and the electrolyte. Using small electrode particles helps to improve rate capability and avoid interfacial failures due to the volume change of electrode particles. Interface stress strongly depends on the mechanical properties of the two components. In addition, this study demonstrates the importance of electrolyte network through the porous active particle backbone. Li-ion batteries have attracted intensive research interest because of the emerging demand for energy storage devices, and energy density has primarily driven the technological advance of lithium-ion batteries.1,2 Recently, increasing efforts are directed to developing allsolid-state Li-ion batteries, which possess prominent advantages over liquid electrolyte based Li-ion batteries.3-5 Replacing the flammable organic electrolyte with solid electrolyte can improve battery safety by reducing the risk of fire and explosion. For all-solid-state batteries, the mitigation of dendritic growth enables the batteries to use Li metal anode over extended cycling, resulting in high specific capacities and operating voltages. In the literature, various solid electrolytes are used as Li-ion conductors. An electronically insulating electrolyte should have high Liion permeability to enhance Li transport kinetics, as well as the high stiffness to resist the dendritic propagation through electrolyte. The widely investigated electrolytes include polymer polyethylene oxide (PEO), NASICON-type electrolytes, garnet-type electrolytes, and sulfides. [7][8][9] In general, the sulfide electrolytes have high ionic conductivities but low chemical stabilities, which are sensitive to moisture. In contrast, garnet-type electrolytes present the most stable interface with Li metal anodes, which are anticipated to be promising electrolytes to achieve high energy densities.
10Despite the remarkable progress, all-solid-state batteries still face key challenges. Among them, the solid electrolyte-electrode interface is the bottleneck for Li transport. 11,12 The high interfacial resistance between the solid electrolyte and electrode render the charge transfer and Li transport very slow, and thus, it limits the electrochemical performance of all-solid-state Li-ion batteries. Using nuclear magnetic resonance spectroscopy, Yu et al. reported that the electrolyteelectrode Li 6 PS 5 Cl-Li 2 S interface is the dominant factor responsible for the restricted power performance. 13 To improve the interfacial transfer, in addition to interlayer coatings, 14 Sharafi et al. found that the interfacial resistance of Li-Li 7 La 3 Zr 2 O 12 can be dramatically re...