Imaging the evolution of lithium-solid electrolyte interface using operando scanning electron microscopy

Abstract The quality of Li–solid electrolyte interface is crucial for the performance of solid-state lithium metal batteries, particularly at low stack pressure, but its dynamics during cell operation remain poorly understood due to a lack of reliable operando characterization techniques. Here, we r...

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Main Authors: Lihong Zhao, Min Feng, Chaoshan Wu, Liqun Guo, Zhaoyang Chen, Samprash Risal, Qing Ai, Jun Lou, Zheng Fan, Yue Qi, Yan Yao
Format: Article
Language:English
Published: Nature Portfolio 2025-05-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-59567-8
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author Lihong Zhao
Min Feng
Chaoshan Wu
Liqun Guo
Zhaoyang Chen
Samprash Risal
Qing Ai
Jun Lou
Zheng Fan
Yue Qi
Yan Yao
author_facet Lihong Zhao
Min Feng
Chaoshan Wu
Liqun Guo
Zhaoyang Chen
Samprash Risal
Qing Ai
Jun Lou
Zheng Fan
Yue Qi
Yan Yao
author_sort Lihong Zhao
collection DOAJ
description Abstract The quality of Li–solid electrolyte interface is crucial for the performance of solid-state lithium metal batteries, particularly at low stack pressure, but its dynamics during cell operation remain poorly understood due to a lack of reliable operando characterization techniques. Here, we report the evolution of Li–electrolyte interface with high spatial resolution using operando scanning electron microscopy under realistic operating conditions. By tracking the stripping process of both Li and Li-rich Li-Mg alloy anodes, we show that multiple voids coalesce into a single gap and eventually delaminate the interface in Li, whereas the voids split and collapse to partially recover interfacial contact in Li-Mg. Density functional theory calculations show that the stronger Mg-S interaction at the metal–electrolyte interface attracts Mg toward the interface and repels Li-vacancies into the bulk, resulting in a reduced number of voids. The pressure-dependent voltage profiles of Li and Li-Mg stripping suggest that loss of contact due to void formation, rather than Mg accumulation at the interface, is the origin of high overpotential that limits the utilization of metal anodes. Improved interfacial contact enables stable cycling of all-solid-state lithium full cell at low stack pressure (1 MPa) and moderate rate (2 mA cm−2) simultaneously. The real-time visualization of Li–electrolyte interface dynamics provides critical insights into the rational design of solid-state battery interfaces.
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spelling doaj-art-ed1b965e28e24db684fb02eabec02d532025-08-20T03:09:19ZengNature PortfolioNature Communications2041-17232025-05-0116111110.1038/s41467-025-59567-8Imaging the evolution of lithium-solid electrolyte interface using operando scanning electron microscopyLihong Zhao0Min Feng1Chaoshan Wu2Liqun Guo3Zhaoyang Chen4Samprash Risal5Qing Ai6Jun Lou7Zheng Fan8Yue Qi9Yan Yao10Department of Electrical and Computer Engineering and Texas Center for Superconductivity at the University of Houston, University of HoustonSchool of Engineering, Brown UniversityDepartment of Electrical and Computer Engineering and Texas Center for Superconductivity at the University of Houston, University of HoustonDepartment of Electrical and Computer Engineering and Texas Center for Superconductivity at the University of Houston, University of HoustonDepartment of Electrical and Computer Engineering and Texas Center for Superconductivity at the University of Houston, University of HoustonMaterials Science and Engineering Program, University of HoustonDepartment of Materials Science and Nanoengineering and the Rice Advanced Materials Institute, Rice UniversityDepartment of Materials Science and Nanoengineering and the Rice Advanced Materials Institute, Rice UniversityMaterials Science and Engineering Program, University of HoustonSchool of Engineering, Brown UniversityDepartment of Electrical and Computer Engineering and Texas Center for Superconductivity at the University of Houston, University of HoustonAbstract The quality of Li–solid electrolyte interface is crucial for the performance of solid-state lithium metal batteries, particularly at low stack pressure, but its dynamics during cell operation remain poorly understood due to a lack of reliable operando characterization techniques. Here, we report the evolution of Li–electrolyte interface with high spatial resolution using operando scanning electron microscopy under realistic operating conditions. By tracking the stripping process of both Li and Li-rich Li-Mg alloy anodes, we show that multiple voids coalesce into a single gap and eventually delaminate the interface in Li, whereas the voids split and collapse to partially recover interfacial contact in Li-Mg. Density functional theory calculations show that the stronger Mg-S interaction at the metal–electrolyte interface attracts Mg toward the interface and repels Li-vacancies into the bulk, resulting in a reduced number of voids. The pressure-dependent voltage profiles of Li and Li-Mg stripping suggest that loss of contact due to void formation, rather than Mg accumulation at the interface, is the origin of high overpotential that limits the utilization of metal anodes. Improved interfacial contact enables stable cycling of all-solid-state lithium full cell at low stack pressure (1 MPa) and moderate rate (2 mA cm−2) simultaneously. The real-time visualization of Li–electrolyte interface dynamics provides critical insights into the rational design of solid-state battery interfaces.https://doi.org/10.1038/s41467-025-59567-8
spellingShingle Lihong Zhao
Min Feng
Chaoshan Wu
Liqun Guo
Zhaoyang Chen
Samprash Risal
Qing Ai
Jun Lou
Zheng Fan
Yue Qi
Yan Yao
Imaging the evolution of lithium-solid electrolyte interface using operando scanning electron microscopy
Nature Communications
title Imaging the evolution of lithium-solid electrolyte interface using operando scanning electron microscopy
title_full Imaging the evolution of lithium-solid electrolyte interface using operando scanning electron microscopy
title_fullStr Imaging the evolution of lithium-solid electrolyte interface using operando scanning electron microscopy
title_full_unstemmed Imaging the evolution of lithium-solid electrolyte interface using operando scanning electron microscopy
title_short Imaging the evolution of lithium-solid electrolyte interface using operando scanning electron microscopy
title_sort imaging the evolution of lithium solid electrolyte interface using operando scanning electron microscopy
url https://doi.org/10.1038/s41467-025-59567-8
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