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Galvanic Replacement of Magnesium Nanowire Arrays to Form Templated Antimony Frameworks

  • Mechanistic Interactions in Energy Storage
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Abstract

The emerging criticality of key constituents of Li-ion batteries has focused attention on more earth-abundant battery chemistries. Realizing the promise of alternative chemistries such as multivalent batteries requires the effective utilization of metal anodes. Utilization of pure magnesium as a negative electrode has been stymied by challenges such as formation of passivation layers, proclivity to form 3D deposits, and electromechanical instabilities. As such, considerable recent attention has focused on the design of composites that blend magnesium with a less electrochemically active metal. Here, we report a facile electroless galvanic replacement reaction to prepare 3D scaffolds incorporating antimony through the reaction of antimony halides with large-area electrodeposited magnesium nanowire arrays. The kinetics of the galvanic replacement reaction and the morphology of the resulting products are modulated by varying the activity coefficient and concentration of dissolved antimony-ions, which in turn is controlled through choice of the halide precursor and its solution concentration. The obtained products range from speckled antimony particles deposited across magnesium nanowires to continuous antimony scaffolds encasing electroactive magnesium cores and core–shell structures. The design of antimony-scaffolded composite architectures that nevertheless permit electrochemical accessibility of a magnesium core represents a promising scalable approach to the design of anodic frameworks.

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Acknowledgements

The authors gratefully acknowledge partial support from the National Science Foundation under DMR 1809866. RDD acknowledges support from the Intelligence Community Postdoctoral Research Fellowship Program administered by Oak Ridge Institute for Science and Education (ORISE) through an interagency agreement between the US Department of Energy and the Office of the Director of National Intelligence (ODNI). Use of the TAMU Materials Characterization Facility is acknowledged. The authors additionally acknowledge initial help with synthesis from Joshua Diaz.

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Authors and Affiliations

  1. Department of Chemistry, Texas A&M University, College Station, TX, 77842-3012, USA

    Luis Carrillo, Parker Schofield, Seth Zercher, Jaehyen Jung, Rachel Davidson & Sarbajit Banerjee

  2. Department of Materials Science and Engineering, Texas A&M University, College Station, TX, 77843-3003, USA

    Luis Carrillo, Parker Schofield, Rachel Davidson & Sarbajit Banerjee

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  1. Luis Carrillo
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Carrillo, L., Schofield, P., Zercher, S. et al. Galvanic Replacement of Magnesium Nanowire Arrays to Form Templated Antimony Frameworks. JOM 76, 1143–1152 (2024). https://doi.org/10.1007/s11837-023-06275-7

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