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.

Influence of Microstructure on the Material Properties of LLZO Ceramics Derived by Impedance Spectroscopy and Brick Layer Model Analysis.

Variants of garnet-type Li7La3Zr2O12 are being intensively studied as separator materials in solid-state battery research. The material-specific transport properties, such as bulk and grain boundary conductivity, are of prime interest and are mostly investigated by impedance spectroscopy. Data evaluation is usually based on the one-dimensional (1D) brick layer model, which assumes a homogeneous microstructure of identical grains. Real samples show microstructural inhomogeneities in grain size and porosity due to the complex behavior of grain growth in garnets that is very sensitive to the sintering protocol. However, the true microstructure is often omitted in impedance data analysis, hindering the interlaboratory reproducibility and comparability of results reported in the literature. Here, we use a combinatorial approach of structural analysis and three-dimensional (3D) transport modeling to explore the effects of microstructure on the derived material-specific properties of garnet-type ceramics. For this purpose, Al-doped Li7La3Zr2O12 pellets with different microstructures are fabricated and electrochemically characterized. A machine learning-assisted image segmentation approach is used for statistical analysis and quantification of the microstructural changes during sintering. A detailed analysis of transport through statistically modeled twin microstructures demonstrates that the transport parameters derived from a 1D brick layer model approach show uncertainties up to 150%, only due to variations in grain size. These uncertainties can be even larger in the presence of porosity. This study helps to better understand the role of the microstructure of polycrystalline electroceramics and its influence on experimental results.

Understanding the Impedance of Mesoporous Oxides: Reliable Determination of the Material-Specific Conductivity.

The unique architecture of ordered mesoporous oxides makes them a promising class of materials for various electrochemical applications, such as gas sensing or energy storage and conversion. The high accessibility of the internal surface allows tailoring of their electrochemical properties, e.g., by adjusting the pore size or surface functionalization, resulting in superior device performance compared to nanoparticles or disordered mesoporous counterparts. However, optimization of the mesoporous architecture requires reliable electrochemical characterization of the system. Unfortunately, the interplay between nanocrystalline grains, grain boundaries, and the open pore framework hinders a simple estimation of material-specific transport quantities by using impedance spectroscopy. Here, we use a 3D electric network model to elucidate the impact of the pore structure on the electrical transport properties of mesoporous thin films. It is demonstrated that the impedance response is dominated only by the geometric current constriction effect arising from the regular pore network. Estimating the effective conductivity from the total resistance and the electrode geometry, thus, differs by more than 1 order of magnitude from the material-specific conductivity of the solid mesoporous framework. A detailed analysis of computed impedances for varying pore size allows for the correlation of the effective conductivity with the material-specific conductivity. We derive an empirical expression that accounts for the porous structure of the thin films and allows a reliable determination of the material-specific conductivity with an error of less than 8%.

3D Impedance Modeling of Metal Anodes in Solid-State Batteries-Incompatibility of Pore Formation and Constriction Effect in Physical-Based 1D Circuit Models.

A non-ideal contact at the electrode/solid electrolyte interface of a solid-state battery arising due to pores (voids) or inclusions results in a geometric constriction effect that severely deteriorates the electric transport properties of the battery cell. The lack of understanding of this phenomenon hinders the optimization process of novel components, such as reversible and high-rate metal anodes. Deeper insight into the constriction phenomenon is necessary to correctly monitor interface degradation and to accelerate the successful use of metal anodes in solid-state batteries. Here, we use a 3D electric network model to study the fundamentals of the constriction effect. Our findings suggest that dynamic constriction as a non-local effect cannot be captured by conventional 1D equivalent circuit models and that its electric behavior is not ad hoc predictable. It strongly depends on the interplay of the geometry of the interface causing the constriction and the microscopic transport processes in the adjacent phases. In the presence of constriction, the contribution from the non-ideal electrode/solid electrolyte interface to the impedance spectrum may exhibit two signals that cannot be explained when the porous interface is described by a physical-based (effective medium theory) 1D equivalent circuit model. In consequence, the widespread assumption of a single interface contribution to the experimental impedance spectrum may be entirely misleading and can cause serious misinterpretation.

Interplay of Dynamic Constriction and Interface Morphology between Reversible Metal Anode and Solid Electrolyte in Solid State Batteries.

In an all-solid-state battery, the electrical contact between its individual components is of key relevance in addition to the electrochemical stability of its interfaces. Impedance spectroscopy is particularly suited for the non-destructive investigation of interfaces and of their stability under load. Establishing a valid correlation between microscopic processes and the macroscopic impedance signal, however, is challenging and prone to errors. Here, we use a 3D electric network model to systematically investigate the effect of various electrode/sample interface morphologies on the impedance spectrum. It is demonstrated that the interface impedance generally results from a charge transfer step and a geometric constriction contribution. The weights of both signals depend strongly on the material parameters as well as on the interface morphology. Dynamic constriction results from a non-ideal local contact, e.g., from pores or voids, which reduce the electrochemical active surface area only in a certain frequency range. Constriction effects dominate the interface behavior for systems with small charge transfer resistance like garnet-type solid electrolytes in contact with a lithium metal electrode. An in-depth analysis of the origin and the characteristics of the constriction phenomenon and their dependence on the interface morphology is conducted. The discussion of the constriction effect provides further insight into the processes at the microscopic level, which are, e.g., relevant in the case of reversible metal anodes.

Ab initiodescription of disorder effects in layered cathode active materials by the coherent potential approximation.

Disorder effects in alloys are usually modeled by averaging various supercell calculations considering different positions of the alloy atoms. This approach, however, is only possible as long as the portion of the individual components of the alloy is sufficiently large. Herein, we present anab initiostudy considering the lithium insertion material Li1-x[Ni0.33Co0.33Mn0.33]O2as model system to demonstrate the power of the coherent potential approximation within the Korringa-Kohn-Rostoker Green's function method. This approach enables the description of disorder effects within alloy systems of any composition. It is applied in this study to describe the (de-)intercalation of arbitrary amounts of lithium from the cathode active material. Moreover, we highlight that using either fully optimized structures or experimental lattice parameters and atomic positions both lead to comparable results. Our findings suggest that this approach is also suitable for modeling the electronic structure of state-of-the-art materials such as high-nickel alloys.