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Updated: Feb 13, 2026

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Published on: December 13, 2016
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Interface Instability of Fe-Stabilized Li7La3Zr2O12 versus Li Metal
Daniel Rettenwander1,2, Reinhard Wagner3, Andreas Reyer3
1Institute for Chemistry and Technology of Materials, Graz University of Technology, Graz, Austria.
Summary
Interface instability between lithium metal and cubic lithium lanthanum zirconium oxide (LLZO:Fe) ceramic electrolytes hinders all-solid-state battery development. A thick tetragonal LLZO interlayer forms, causing high impedance and limiting device performance.
Area of Science:
- Materials Science
- Electrochemistry
- Solid-State Chemistry
Background:
- All-solid-state batteries (ASSBs) offer enhanced safety using ceramic electrolytes.
- Cubic lithium lanthanum zirconium oxide (LLZO) is a promising ceramic electrolyte.
- Interfacial stability with lithium metal remains a significant challenge for ASSBs.
Purpose of the Study:
- To investigate the electrochemical performance and interfacial stability of Fe3+-stabilized LLZO (LLZO:Fe) against lithium metal.
- To understand the degradation mechanisms at the LLZO:Fe/Li metal interface.
Main Methods:
- Electrochemical testing of LLZO:Fe against Li metal.
- Post-mortem analysis of the Li metal electrode interface using Raman spectroscopy and nanosecond laser-induced breakdown spectroscopy (LIBS).
Main Results:
- LLZO:Fe exhibits high ionic conductivity (1.1 mS cm-1) but also high area specific resistance (~1 kΩ cm2) against Li metal.
- Interfacial degradation observed as black surface coloration after Li metal removal.
- Formation of a thick (130 μm) tetragonal LLZO interlayer and significant lithium deficiency (1-2 formula units) at the interface.
Conclusions:
- Cubic LLZO:Fe is unstable against Li metal, forming a detrimental tetragonal LLZO interlayer.
- The interfacial layer significantly increases resistance, hindering the performance of next-generation ASSBs.
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