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The influence of pressure on lithium dealloying in solid-state and liquid electrolyte batteries

Nature Materials volume 24, pages 907–916 (2025)Cite this article

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Abstract

Dealloying reactions underpin the operation of next-generation battery electrodes and are also a synthesis route for porous metals, but the influence of mechanical stress on these processes is not well understood. Here we investigate how the applied stack pressure affects structural evolution and electrochemical reversibility during the alloying/dealloying of Li alloy materials (Li–Al, Li–Sn, Li–In and Li–Si) using solid-state and liquid electrolytes. The extent of porosity formation during the dealloying of metals is found to be universally governed by stack pressure, with pressures of at least 20% of the yield strength required to achieve ~80% relative density. This concept is correlated to the cycling of alloy electrodes in solid-state batteries, with a yield-strength-dependent threshold pressure needed for reversible high Li-storage capacity due to densification. With this understanding, we design Al and Si anodes with a densified interfacial layer enabling stable cycling at low stack pressures (2 MPa), providing guidance towards practical high-energy solid-state batteries.

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Fig. 1: Pressure effects on electrochemical alloying of metals with liquid electrolyte and SSE.
Fig. 2: Pressure effects on electrochemical dealloying of metals with liquid electrolyte and SSE.
Fig. 3: Quantifying effects of stack pressure on electrochemical dealloying of metals.
Fig. 4: Pressure effects on electrochemical alloying and dealloying of Si with liquid electrolyte and SSE.
Fig. 5: Stack pressure effects on cycling performance of alloy anodes in SSBs.
Fig. 6: Engineering interfaces to reduce the stack pressure for SSBs with alloy anodes.

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The data supporting the findings of this study are available within the article and its Supplementary Information. Source data are provided with this paper.

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Acknowledgements

We acknowledge support from the National Science Foundation, award no. DMR-2209202 (M.T.M.). Partial support is acknowledged from Novelis Inc. This work was performed in part at the Georgia Tech Institute for Matter and Systems, a member of the National Nanotechnology Coordinated Infrastructure (NNCI), which is supported by the National Science Foundation (ECCS-2025462).

Author information

Authors and Affiliations

  1. George W. Woodruff School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, GA, USA

    Congcheng Wang, Timothy Chen, Mu Lu, Elif Pınar Alsaç, Sun Geun Yoon, Shuman Xia & Matthew T. McDowell

  2. School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, GA, USA

    Yuhgene Liu, Won Joon Jeong, Douglas Lars Nelson, Kelsey Anne Cavallaro & Matthew T. McDowell

  3. Novelis Inc., Kennesaw, GA, USA

    Sazol Das, Diptarka Majumdar & Rajesh Gopalaswamy

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Contributions

Conceptualization: C.W. and M.T.M. Methodology: C.W. Investigation: C.W., Y.L., W.J.J., T.C., M.L., D.L.N., E.P.A., S.G.Y. and K.A.C. Formal analysis: C.W., M.L., S.X. and M.T.M. Validation: C.W. and M.T.M. Writing—original draft: C.W. Writing—review and editing: C.W., S.D., D.M., R.G., S.X. and M.T.M. Visualization: C.W. and M.T.M. Project administration: S.D., D.M., R.G. and M.T.M. Resources: M.T.M. Supervision: M.T.M. Funding acquisition: M.T.M.

Corresponding author

Correspondence to Matthew T. McDowell.

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Competing interests

C.W., Y.L., T.C., S.D., D.M., R.G. and M.T.M. are inventors on patent applications related to alloy anode materials for Li batteries. The other authors declare no competing interests.

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Nature Materials thanks Yuki Orikasa, Haoshen Zhou and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 Pressure effects on Li trapping behaviour during electrochemical dealloying of metals with liquid and solid-state electrolytes.

Trapped Li capacity versus applied stack pressure \(\sigma\) during electrochemical dealloying of the three metals in liquid electrolyte (a) and solid-state electrolyte (b). The trapped Li capacity was measured from the Li dealloying current curves in Fig. 2a–c and normalized to the lithiation capacity measured from the Li alloying curves in Fig. 1a–c.

Extended Data Fig. 2 The influence of the dealloying rate using solid-state electrolyte on morphology evolution.

a, XRD characterization of In electrodes after galvanostatic dealloying at different current densities using the same stack pressure (1 MPa). b–d, Cross-sectional SEM images of In electrodes after galvanostatic dealloying at different current densities under 1 MPa of stack pressure. All scale bars are 1 µm.

Extended Data Fig. 3 In situ stack pressure measurement of a cell with a Si wafer electrode during alloying and dealloying using SSE at 2 MPa stack pressure.

a, Galvanostatic voltage curve from the alloying of a Si wafer working electrode along with measured stress in the cell. A current density of 0.1 mA cm−2 was used. b, Current density curve from potentiostatic dealloying (1.0 V versus Li/Li+) of a Si wafer electrode along with measured stress in the cell. A LiIn counter electrode was used in both cases.

Extended Data Fig. 4 Pressure effects on relative density and Li trapping behaviour during electrochemical dealloying of Si with liquid and solid-state electrolytes.

a, Measured relative density \(\varphi\) versus applied stack pressure \(\sigma\) during electrochemical dealloying of Si. Relative density and error bars were calculated based on measurements at 10 different positions. Data in (a) are presented as mean values ± the standard error of the mean, where the number of replicates (n) is 10. b, Trapped Li capacity versus applied stack pressure \(\sigma\) during electrochemical dealloying of Si. The trapped Li capacity was measured from the Li dealloying current curves in Fig. 4d and normalized to the lithiation capacity measured from the Li alloying curves in Fig. 4a.

Extended Data Fig. 5 EDS maps of the Al and Si anodes with In coating.

a, b, Al. c, d, Si. All scale bars are 5 µm.

Supplementary information

Supplementary Information

Supplementary Figs. 1–19, Tables 1–4, Equations (1) and (2) and References.

Source data

Source Data Fig. 1

Source data for the electrochemical tests shown in Fig. 1, including dealloying of Li from various metal electrodes in liquid electrolytes and SSEs.

Source Data Fig. 2

Source data for the electrochemical tests shown in Fig. 2, including dealloying of Li from various metal electrolytes in liquid electrolytes and SSEs.

Source Data Fig. 4

Source data for the electrochemical tests shown in Fig. 4, including the electrochemical lithiation and dealloying data for silicon electrodes.

Source Data Fig. 5

Source data for the electrochemical tests shown in Fig. 5, including the galvanostatic charge–discharge and cycling data of Al, Sn, In and Si electrodes in SSBs at different stack pressures.

Source Data Fig. 6

Source data for the electrochemical tests shown in Fig. 6, including the electrochemical cycling behaviour of Al and Si electrodes with In coatings.

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Wang, C., Liu, Y., Jeong, W.J. et al. The influence of pressure on lithium dealloying in solid-state and liquid electrolyte batteries. Nat. Mater. 24, 907–916 (2025). https://doi.org/10.1038/s41563-025-02198-7

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