Origins of lithium inventory reversibility with an alloying functional layer in anode-free lithium metal batteries

Abstract Alloying coatings are widely accepted to boost the reversibility of lithium inventory in anode-free cell configurations. While diminished capacity losses are evident from electrochemical data, their impact beyond decreasing the nucleation overpotential remains elusive. Herein, in situ 7Li N...

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Main Authors: Lennart Wichmann, Shi-Kai Jiang, Johannes Helmut Thienenkamp, Marvin Mohrhardt, Bing Joe Hwang, Martin Winter, Gunther Brunklaus
Format: Article
Language:English
Published: Nature Portfolio 2025-08-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-62289-6
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author Lennart Wichmann
Shi-Kai Jiang
Johannes Helmut Thienenkamp
Marvin Mohrhardt
Bing Joe Hwang
Martin Winter
Gunther Brunklaus
author_facet Lennart Wichmann
Shi-Kai Jiang
Johannes Helmut Thienenkamp
Marvin Mohrhardt
Bing Joe Hwang
Martin Winter
Gunther Brunklaus
author_sort Lennart Wichmann
collection DOAJ
description Abstract Alloying coatings are widely accepted to boost the reversibility of lithium inventory in anode-free cell configurations. While diminished capacity losses are evident from electrochemical data, their impact beyond decreasing the nucleation overpotential remains elusive. Herein, in situ 7Li NMR spectroscopy is applied to differentiate capacity losses in pouch cells with representative electrochemical behavior. Next to an accelerated interphase formation, the alloying layer diminishes the formation of dead lithium deposits notably. In contrast to previous reports, the capacity lost to electronically insulated lithium deposits is not related to their tortuosity and surface area. Though alloy formation reduces the nucleation overpotential with coated copper, deconvolution of 7Li NMR spectra as well as scanning electron microscopy evidence predominantly compact lithium deposits in the initial cycles and a similar increase of high-surface area morphologies with bare and coated copper negative electrodes. Instead of improved lithium deposit morphology, the enhanced reversibility with the alloying layer is bestowed by improved interfacial transport towards the end of lithium dissolution. These insights add to the mechanistic understanding of dead lithium formation, exploiting impedance spectroscopy in the discharged state as a valuable tool to assess the ability to dissolve lithium metal from a given substrate.
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issn 2041-1723
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spelling doaj-art-c019c1fc07d145c498dcc31e5e5995f52025-08-20T03:46:15ZengNature PortfolioNature Communications2041-17232025-08-0116111810.1038/s41467-025-62289-6Origins of lithium inventory reversibility with an alloying functional layer in anode-free lithium metal batteriesLennart Wichmann0Shi-Kai Jiang1Johannes Helmut Thienenkamp2Marvin Mohrhardt3Bing Joe Hwang4Martin Winter5Gunther Brunklaus6Helmholtz-Institute Münster, IMD-4, Forschungszentrum Jülich GmbHNano-electrochemistry Laboratory, Department of Chemical Engineering, National Taiwan University of Science and TechnologyHelmholtz-Institute Münster, IMD-4, Forschungszentrum Jülich GmbHHelmholtz-Institute Münster, IMD-4, Forschungszentrum Jülich GmbHNano-electrochemistry Laboratory, Department of Chemical Engineering, National Taiwan University of Science and TechnologyHelmholtz-Institute Münster, IMD-4, Forschungszentrum Jülich GmbHHelmholtz-Institute Münster, IMD-4, Forschungszentrum Jülich GmbHAbstract Alloying coatings are widely accepted to boost the reversibility of lithium inventory in anode-free cell configurations. While diminished capacity losses are evident from electrochemical data, their impact beyond decreasing the nucleation overpotential remains elusive. Herein, in situ 7Li NMR spectroscopy is applied to differentiate capacity losses in pouch cells with representative electrochemical behavior. Next to an accelerated interphase formation, the alloying layer diminishes the formation of dead lithium deposits notably. In contrast to previous reports, the capacity lost to electronically insulated lithium deposits is not related to their tortuosity and surface area. Though alloy formation reduces the nucleation overpotential with coated copper, deconvolution of 7Li NMR spectra as well as scanning electron microscopy evidence predominantly compact lithium deposits in the initial cycles and a similar increase of high-surface area morphologies with bare and coated copper negative electrodes. Instead of improved lithium deposit morphology, the enhanced reversibility with the alloying layer is bestowed by improved interfacial transport towards the end of lithium dissolution. These insights add to the mechanistic understanding of dead lithium formation, exploiting impedance spectroscopy in the discharged state as a valuable tool to assess the ability to dissolve lithium metal from a given substrate.https://doi.org/10.1038/s41467-025-62289-6
spellingShingle Lennart Wichmann
Shi-Kai Jiang
Johannes Helmut Thienenkamp
Marvin Mohrhardt
Bing Joe Hwang
Martin Winter
Gunther Brunklaus
Origins of lithium inventory reversibility with an alloying functional layer in anode-free lithium metal batteries
Nature Communications
title Origins of lithium inventory reversibility with an alloying functional layer in anode-free lithium metal batteries
title_full Origins of lithium inventory reversibility with an alloying functional layer in anode-free lithium metal batteries
title_fullStr Origins of lithium inventory reversibility with an alloying functional layer in anode-free lithium metal batteries
title_full_unstemmed Origins of lithium inventory reversibility with an alloying functional layer in anode-free lithium metal batteries
title_short Origins of lithium inventory reversibility with an alloying functional layer in anode-free lithium metal batteries
title_sort origins of lithium inventory reversibility with an alloying functional layer in anode free lithium metal batteries
url https://doi.org/10.1038/s41467-025-62289-6
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