Heteroionic Interfaces in Hybrid Solid-State Batteries─Current Constriction at the Interface between Different Solid Electrolytes

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The requirements for suitable electrolyte materials in solid-state batteries are diverse and vary greatly depending on their role as separator or as part of the composite cathode. Hybrid cell concepts that incorporate different types of solid electrolytes are considered a promising solution to overcome the limitations of single material classes. However, the kinetics at the heteroionic interface (i.e., charge transfer) substantially affects the cell performance. Moreover, non-ideal physical contacts hinder detailed electrochemical characterization of the interface properties. Thus, we use microstructure-resolved electric network computations to explore how the impedance response of a homogeneous bilayer system is influenced by the interface morphology and the material parameters of the single solid electrolyte layers. Porous interfaces and the resulting current constriction effects give rise to signatures in the impedance spectrum that resemble that of actual migration processes. This hinders unequivocal identification of the origin of the impedance contributions. The resistance and capacitance of this geometric interface signal depend strongly on the contact area and its spatial distribution, the pore capacitance, and the local conductivities around the interface. An experimental case study of an oxide-sulfide multilayer is considered to highlight the challenges in impedance analysis and the assessment of reliable material parameters. These findings are universal and apply to any heterojunction.