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

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    Surfaces, Interfaces, and Applications

    3D Impedance Modeling of Metal Anodes in Solid-State Batteries–Incompatibility of Pore Formation and Constriction Effect in Physical-Based 1D Circuit Models
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    • Janis K. Eckhardt*
      Janis K. Eckhardt
      Institute for Theoretical Physics, Justus Liebig University, Heinrich-Buff-Ring 16, Giessen D-35392, Germany
      Center for Materials Research (ZfM), Justus Liebig University, Heinrich-Buff-Ring 16, Giessen D-35392, Germany
      *Email: [email protected]
      More by Janis K. Eckhardt
      Orcidhttps://orcid.org/0000-0002-2799-0599
    • Till Fuchs
      Till Fuchs
      Center for Materials Research (ZfM), Justus Liebig University, Heinrich-Buff-Ring 16, Giessen D-35392, Germany
      Institute of Physical Chemistry, Justus Liebig University, Heinrich-Buff-Ring 17, Giessen D-35392, Germany
      More by Till Fuchs
    • Simon Burkhardt
      Simon Burkhardt
      Center for Materials Research (ZfM), Justus Liebig University, Heinrich-Buff-Ring 16, Giessen D-35392, Germany
      Institute of Physical Chemistry, Justus Liebig University, Heinrich-Buff-Ring 17, Giessen D-35392, Germany
      More by Simon Burkhardt
    • Peter J. Klar
      Peter J. Klar
      Center for Materials Research (ZfM), Justus Liebig University, Heinrich-Buff-Ring 16, Giessen D-35392, Germany
      Institute of Experimental Physics I, Justus Liebig University, Heinrich-Buff-Ring 16, Giessen D-35392, Germany
      More by Peter J. Klar
      Orcidhttps://orcid.org/0000-0002-4513-0330
    • Jürgen Janek
      Jürgen Janek
      Center for Materials Research (ZfM), Justus Liebig University, Heinrich-Buff-Ring 16, Giessen D-35392, Germany
      Institute of Physical Chemistry, Justus Liebig University, Heinrich-Buff-Ring 17, Giessen D-35392, Germany
      More by Jürgen Janek
      Orcidhttps://orcid.org/0000-0002-9221-4756
    • Christian Heiliger
      Christian Heiliger
      Institute for Theoretical Physics, Justus Liebig University, Heinrich-Buff-Ring 16, Giessen D-35392, Germany
      Center for Materials Research (ZfM), Justus Liebig University, Heinrich-Buff-Ring 16, Giessen D-35392, Germany
      More by Christian Heiliger
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    ACS Applied Materials & Interfaces

    Cite this: ACS Appl. Mater. Interfaces 2022, 14, 37, 42757–42769
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    https://doi.org/10.1021/acsami.2c12991
    Published September 8, 2022
    Copyright © 2022 The Authors. Published by American Chemical Society
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    Abstract

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    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.

    Copyright © 2022 The Authors. Published by American Chemical Society

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    This article is cited by 35 publications.

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    ACS Applied Materials & Interfaces

    Cite this: ACS Appl. Mater. Interfaces 2022, 14, 37, 42757–42769
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsami.2c12991
    Published September 8, 2022
    Copyright © 2022 The Authors. Published by American Chemical Society
    Request reuse permissions

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