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Spontaneous evolution of bicontinuous nanostructures in dealloyed Li-based systems

Nature Materials volume 12, pages 1102–1106 (2013)Cite this article

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Abstract

Dealloying, the selective dissolution of one or more of the elemental components of an alloy, is an important corrosion mechanism and a technologically relevant process used to fabricate nanoporous metals for a variety of applications including catalysis1, sensing2, actuation3, supercapacitors4 and radiation-damage-resistant materials5. In noble-metal alloy systems for which the ambient-temperature solid-state diffusivity is minuscule, dealloying occurs at a composition-dependent critical potential above which bicontinuous nanoporous structures evolve and below which a full-coverage layer of the more-noble component forms causing the alloy surface to become passive6,7. In contrast, for alloy systems exhibiting significant solid-state diffusive transport, our understanding of dealloying-induced morphologies and the electrochemical parameters controlling this are largely unexplored. Here, we examine dealloying of Li from Li–Sn alloys and show that depending on alloy composition, particle size and dealloying rate, all known dealloyed morphologies evolve including bicontinuous nanoporous structures and hollow core–shell particles. Furthermore, we elucidate the role of bulk diffusion in morphology evolution using chronopotentiometry and linear sweep voltammetry. Our results may have implications for lithium-ion battery development while significantly broadening the spectrum of strategies for obtaining new nanoporous materials through dealloying.

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Figure 1: Dealloyed structures and steady-state length scales.
Figure 2: Potentiostatic dealloying (1 V versus Li+/Li) results of Sn particle morphologies as a function of Li composition obtained by a single alloying/dealloying cycle in 1 M LiPF6 in ethylene carbonate/diethylcarbonate, 1:1 v/v at room temperature.
Figure 3: The effect of particle size on dealloyed morphologies.
Figure 4: The effect of dealloying rate on morphology evolution.

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Acknowledgements

The authors would like to thank C. K. Chan and J. Erlebacher for valuable discussions. This work was supported by the National Science Foundation under award DMR-0855969.

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Authors and Affiliations

  1. Ira A. Fulton School of Engineering, Arizona State University, Tempe, Arizona 85281, USA

    Qing Chen & Karl Sieradzki

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  1. Qing Chen
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Q.C. and K.S. designed the research and wrote the manuscript. Q.C. performed the experiments.

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Correspondence to Karl Sieradzki.

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The authors declare no competing financial interests.

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Chen, Q., Sieradzki, K. Spontaneous evolution of bicontinuous nanostructures in dealloyed Li-based systems. Nature Mater 12, 1102–1106 (2013). https://doi.org/10.1038/nmat3741

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