Abstract
Understanding the Evolution of the Interface between Lithium and Argyrodite Solid Electrolyte Using in-Operando Raman Microscopy
Meeting abstracts (Electrochemical Society), v MA2025-02(3), 532
24 Nov 2025
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Abstract
Argyrodite solid electrolytes are attracting substantial attention for lithium-based solid-state batteries due to their good room-temperature ionic conductivities, desirable mechanical properties, and low temperature processibility. However, poor interfacial contact with electrodes driven by surface inhomogeneities and formation of adverse reaction products on the surface of lithium limit their commercial applications. Studying the nature and evolution of the solid electrolyte/Li interface is crucial as its properties can impact overall cell performance and long-term cycling stability. The thermodynamic instabilities with lithium metal cause the formation of a passivating layer which increases interfacial resistance and hinders lithium-ion transport. The investigation of this thin interface is complex due to its buried nature and requires specialized analytical techniques and cell design.Herein, we directly observe the potential dependent evolution of the interfacial chemistry of argyrodite solid electrolyte (Li6PS5Cl0.5Br0.5) in an “anode-free” cell configuration with a thin film metal electrode using in operando Raman microscopy. Operando Raman successfully showed the formation of Li2S as the major degradation product (along with some Li2Sx - lithium polysulfides) during Li plating and stripping. The degradation products formed in the first cycle remained at the interface during subsequent cycles revealing the irreversibility of the reaction. Post-mortem XPS confirmed the presence of degradation products detected by Raman and further indicated the presence of phosphorous containing species. In operando EIS measurements showed a drastic increase in cell impedance owing to the insulating nature of Li2S and other interfacial products. The spatial heterogeneity of Li6PS5Cl0.5Br0.5 decomposition was also observed using Raman mapping. The degradation products were localized and the surface inhomogeneities led to poor electrode/solid electrolyte contact. The drastic changes in morphology after cycling were further confirmed using post-mortem SEM.This study demonstrated that in operando Raman is a powerful technique to understand the dynamics of the electrode/solid electrolyte interfacial evolution and its impact on electrochemistry of the cell. A comprehensive understanding of the reaction chemistry at the interface will enable the development of new materials for solid-state batteries that have improved interfacial stability and electrochemical performance.
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Details
- Title
- Understanding the Evolution of the Interface between Lithium and Argyrodite Solid Electrolyte Using in-Operando Raman Microscopy
- Creators
- Subhadra Jamkar - Cornell UniversityRhyz Pereira - Drexel UniversityAyush Morchhale - The Ohio State UniversityZhenghuan Tang - The Ohio State UniversityJung-Hyun Kim - The Ohio State UniversityVibha Kalra - Cornell University
- Publication Details
- Meeting abstracts (Electrochemical Society), v MA2025-02(3), 532
- Publisher
- The Electrochemical Society, Inc
- Number of pages
- 1
- Resource Type
- Abstract
- Language
- English
- Academic Unit
- Chemical and Biological Engineering
- Other Identifier
- 991022135743404721