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Lithium-mediated nitrogen reduction to ammonia via the catalytic solid–electrolyte interphase

Nature Catalysis volume 7, pages 231–241 (2024)Cite this article

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Abstract

The lithium-mediated nitrogen reduction reaction (LiNRR) produces ammonia in ambient conditions. This electrochemical pathway is dependent on a catalytic solid–electrolyte interphase—a nanoscale passivation layer formed from reductive electrolyte decomposition on the surface of lithium metal. The catalytic solid–electrolyte interphase is a unique nanostructured environment that exists on reactive metal surfaces and intimately influences product selectivity. Here we explore recent progress made in the field of lithium-mediated nitrogen reduction to ammonia, especially in light of growing knowledge about the nature of the catalytic solid–electrolyte interphase. We systematically analyse the observed chemical species and reactions that occur within the solid–electrolyte interphase. We also summarize key developments in kinetic and transport models, as well as highlight the cathodic and complementary anodic reactions. Trends in ammonia selectivities and rates with varying electrolyte compositions, cell designs and operating conditions are extracted and used to articulate a path forward for continued development of lithium-mediated nitrogen reduction to ammonia.

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Fig. 1: Overview and history of LiNRR.
Fig. 2: Reaction network governing LiNRR conducted in THF with LiBF4 and ethanol.
Fig. 3: Comparison of selectivity and rate across different electrolyte salts and cell form factors.

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Acknowledgements

This material is based on work supported by the National Science Foundation (grant no. 2204756). We gratefully acknowledge support from the Resnick Sustainability Institute. K.M. gratefully acknowledges support from the Sloan Foundation. W.C. acknowledges funding support from the Arnold and Mabel Beckman Foundation via a 2022 Arnold O. Beckman Postdoctoral Fellowship in Chemical Sciences. F.R. acknowledges funding support from the Independent Research Fund Denmark (DFF), case no. 0217-00234B. We also thank M. Yusov, C. Klein and G. Lee for productive and helpful feedback and discussions.

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  1. These authors contributed equally: Wesley Chang, Anukta Jain.

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  1. Division of Chemistry and Chemical Engineering, Caltech, Pasadena, CA, USA

    Wesley Chang, Anukta Jain, Fateme Rezaie & Karthish Manthiram

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W.C. conducted the initial meta-analysis from literature sources, analysed the data and generated the figures. A.J. brought the manuscript to submission-ready completion with detailed edits. W.C. and A.J. led the majority of the work, with input from the whole group. F.R. helped decide our cell-naming convention. K.M. mentored, edited and financed the work. All authors contributed to manuscript proofreading.

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Correspondence to Karthish Manthiram.

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Chang, W., Jain, A., Rezaie, F. et al. Lithium-mediated nitrogen reduction to ammonia via the catalytic solid–electrolyte interphase. Nat Catal 7, 231–241 (2024). https://doi.org/10.1038/s41929-024-01115-6

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