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

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.

Nanostructured 2D WS2@PANI nanohybrids for electrochemical energy storage.

2D materials are interesting flat nanoplatforms for the implementation of different electrochemical processes, due to the high surface area and tunable electronic properties. 2D transition metal dichalcogenides (TMDs) can be produced through convenient top-down liquid-phase exfoliation (LPE) methods and present capacitive behaviour that can be exploited for energy storage applications. However, in their thermodynamically stable 2H crystalline phase, they present poor electrical conductivity, being this phase a purely semiconducting one. Combination with conducting polymers like polyaniline (PANI), into nanohybrids, can provide better properties for the scope. In this work, we report on the preparation of 2D WS2@PANI hybrid materials in which we exploit the LPE TMD nanoflakes as scaffolds, onto which induce the in-situ aniline polymerization and thus achieve porous architectures, with the help of surfactants and sodium chloride acting as templating agents. We characterize these species for their capacitive behaviour in neutral pH, achieving maximum specific capacitance of 160 F/g at a current density of 1 A/g, demonstrating the attractiveness of similar nanohybrids for future use in low-cost, easy-to-make supercapacitor devices.