https://www.nature.com/articles/s41586-022-05108-y Skip to main content Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript. Advertisement Advertisement Nature * View all journals * Search * Log in * Explore content * About the journal * Publish with us * Subscribe * Sign up for alerts * RSS feed 1. nature 2. articles 3. article * Article * Published: 22 July 2022 Electroreduction of nitrogen with almost 100% current-to-ammonia efficiency * Hoang-Long Du ORCID: orcid.org/0000-0003-4729-2963^1,2, * Manjunath Chatti^1,2, * Rebecca Y. Hodgetts ORCID: orcid.org/0000-0001-9569-0873^1,2, * Pavel V. Cherepanov^2, * Cuong K. Nguyen^1,2, * Karolina Matuszek^2, * Douglas R. MacFarlane ORCID: orcid.org/0000-0001-5963-9659^1,2 & * ... * Alexandr N. Simonov ORCID: orcid.org/0000-0003-3063-6539^1,2 Show authors Nature volume 609, pages 722-727 (2022)Cite this article * 33k Accesses * 99 Citations * 106 Altmetric * Metrics details Subjects * Chemical hydrogen storage * Electrocatalysis Abstract In addition to its use in the fertilizer and chemical industries^1, ammonia is currently seen as a potential replacement for carbon-based fuels and as a carrier for worldwide transportation of renewable energy^2. Implementation of this vision requires transformation of the existing fossil-fuel-based technology for NH[3] production^3 to a simpler, scale-flexible technology, such as the electrochemical lithium-mediated nitrogen-reduction reaction^3,4. This provides a genuine pathway from N[2] to ammonia, but it is currently hampered by limited yield rates and low efficiencies^4,5,6,7,8,9,10,11,12. Here we investigate the role of the electrolyte in this reaction and present a high-efficiency, robust process that is enabled by compact ionic layering in the electrode-electrolyte interface region. The interface is generated by a high-concentration imide-based lithium-salt electrolyte, providing stabilized ammonia yield rates of 150 +- 20 nmol s^-1 cm^-2 and a current-to-ammonia efficiency that is close to 100%. The ionic assembly formed at the electrode surface suppresses the electrolyte decomposition and supports stable N[2] reduction. Our study highlights the interrelation between the performance of the lithium-mediated nitrogen-reduction reaction and the physicochemical properties of the electrode-electrolyte interface. We anticipate that these findings will guide the development of a robust, high-performance process for sustainable ammonia production. Access through your institution Buy or subscribe This is a preview of subscription content, access via your institution Relevant articles Open Access articles citing this article. * Laser-induced nitrogen fixation + Huize Wang + , Ranga Rohit Seemakurthi + ... Markus Antonietti Nature Communications Open Access 13 September 2023 Access options Access through your institution Access through your institution Change institution Buy or subscribe Access Nature and 54 other Nature Portfolio journals Get Nature+, our best-value online-access subscription $29.99 / 30 days cancel any time Learn more Subscribe to this journal Receive 51 print issues and online access $199.00 per year only $3.90 per issue Learn more Rent or buy this article Prices vary by article type from$1.95 to$39.95 Learn more Prices may be subject to local taxes which are calculated during checkout Additional access options: * Log in * Learn about institutional subscriptions * Read our FAQs * Contact customer support Fig. 1: Electrolyte effects in the Li-NRR. [41586_2022_5108_Fig1_HTML] Fig. 2: Influence of the potential on the composition of the electrode surface during N[2] electroreduction mediated by 2 M LiNTf [2]. [41586_2022_5108_Fig2_HTML] Fig. 3: Li-NRR performance with a bare Ni wire electrode (geometric surface area 0.15 cm^2) as a function of time. [41586_2022_5108_Fig3_HTML] Fig. 4: Longer-term Li-NRR performance with isolated Ni electrodes. [41586_2022_5108_Fig4_HTML] Data availability All data are available in the paper and its Supplementary Information . Source data that support the findings of this study are available from the corresponding authors upon reasonable request. References 1. Fowler, D. et al. The global nitrogen cycle in the twenty-first century. Phil. Trans. R. Soc. B 368, 20130164 (2013). Article Google Scholar 2. MacFarlane, D. R. et al. Liquefied sunshine: transforming renewables into fertilizers and energy carriers with electromaterials. Adv. Mater. 32, 1904804 (2020). Article CAS Google Scholar 3. MacFarlane, D. R. et al. A roadmap to the ammonia economy. Joule 4, 1186-1205 (2020). Article CAS Google Scholar 4. Tsuneto, A., Kudo, A. & Sakata, T. 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Insight into cathode microstructure effect on the performance of molten carbonate fuel cell. J. Power Sources 491, 229562 (2021). Article CAS Google Scholar 35. Hodgetts, R. Y., Du, H.-L., Nguyen, T. D., MacFarlane, D. & Simonov, A. N. Electrocatalytic oxidation of hydrogen as an anode reaction for the Li-mediated N[2] reduction to ammonia. ACS Catal. 12, 5231-5246 (2022). Article CAS Google Scholar Download references Acknowledgements We acknowledge funding of this work by the Australian Research Council (Discovery Project DP200101878, Centre of Excellence for Electromaterials Science CE140100012, Future Fellowship to A.N.S. (FT200100317)) and the Australian Renewable Energy Agency ('Renewable Hydrogen for Export' project 2018RND/009 DM015); and the Monash Centre for Electron Microscopy, Monash X-ray platform and Monash Analytical platform for providing access to the physical characterization and spectroscopic facilities. We thank Nippon Shokubai for a gift of LiFSI and F. Shanks for his assistance with the Fourier-transform infrared attenuated total reflectance spectroscopic measurements. Author information Authors and Affiliations 1. The ARC Centre of Excellence for Electromaterials Science, Monash University, Clayton, Victoria, Australia Hoang-Long Du, Manjunath Chatti, Rebecca Y. Hodgetts, Cuong K. Nguyen, Douglas R. MacFarlane & Alexandr N. Simonov 2. School of Chemistry, Monash University, Clayton, Victoria, Australia Hoang-Long Du, Manjunath Chatti, Rebecca Y. Hodgetts, Pavel V. Cherepanov, Cuong K. Nguyen, Karolina Matuszek, Douglas R. MacFarlane & Alexandr N. Simonov Authors 1. Hoang-Long Du View author publications You can also search for this author in PubMed Google Scholar 2. Manjunath Chatti View author publications You can also search for this author in PubMed Google Scholar 3. Rebecca Y. Hodgetts View author publications You can also search for this author in PubMed Google Scholar 4. Pavel V. Cherepanov View author publications You can also search for this author in PubMed Google Scholar 5. Cuong K. Nguyen View author publications You can also search for this author in PubMed Google Scholar 6. Karolina Matuszek View author publications You can also search for this author in PubMed Google Scholar 7. Douglas R. MacFarlane View author publications You can also search for this author in PubMed Google Scholar 8. Alexandr N. Simonov View author publications You can also search for this author in PubMed Google Scholar Contributions H.-L.D. conceived and did the electrochemical experiments, viscosity and conductivity measurements and co-wrote the manuscript. M.C. did the XRD and Fourier-transform infrared attenuated total reflectance spectroscopic analyses, and assisted with monitoring long-term experiments. R.Y.H. contributed to the reproducibility studies and performed the ^1H NMR analysis of ammonia. P.V.C. collected and analysed XPS data. C.K.N. did nitrite/nitrate measurements, and the SEM and EDS analyses. K.M. contributed to conductivity measurements and collected the NMR data for the electrolyte stability. D.R.M. and A.N.S. conceived the experiments, directed the project and co-wrote the manuscript. Corresponding authors Correspondence to Douglas R. MacFarlane or Alexandr N. Simonov. Ethics declarations Competing interests H.-L.D., D.R.M. and A.N.S. are inventors on an Australian provisional patent application that covers aspects of the work reported here, and which has been licensed to Jupiter Ionics. D.R.M. and A.N.S. have minority equity ownership, as well as management and consulting roles, in Jupiter Ionics. Peer review Peer review information Nature thanks anonymous reviewers for their contribution to the peer review of this work. Peer reviewer reports are available. Additional information Publisher's note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. Supplementary information Supplementary Information This file contains Supplementary Figs. 1-40, Supplementary Tables 1-18 and references. Peer Review File Rights and permissions Springer Nature or its licensor holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law. Reprints and Permissions About this article Check for updates. Verify currency and authenticity via CrossMark Cite this article Du, HL., Chatti, M., Hodgetts, R.Y. et al. Electroreduction of nitrogen with almost 100% current-to-ammonia efficiency. Nature 609, 722-727 (2022). https://doi.org/10.1038/s41586-022-05108-y Download citation * Received: 21 November 2021 * Accepted: 13 July 2022 * Published: 22 July 2022 * Issue Date: 22 September 2022 * DOI: https://doi.org/10.1038/s41586-022-05108-y Share this article Anyone you share the following link with will be able to read this content: Get shareable link Sorry, a shareable link is not currently available for this article. Copy to clipboard Provided by the Springer Nature SharedIt content-sharing initiative This article is cited by * A cleaner route to ammonia + James Mitchell Crow Nature (2023) * The mosaic art of interphases + Eric J. McShane + Matteo Cargnello Nature Energy (2023) * Laser-induced nitrogen fixation + Huize Wang + Ranga Rohit Seemakurthi + Markus Antonietti Nature Communications (2023) * Prospects and challenges of green ammonia synthesis + Dongpei Ye + Shik Chi Edman Tsang Nature Synthesis (2023) * Calcium-mediated nitrogen reduction for electrochemical ammonia synthesis + Xianbiao Fu + Valerie A. Niemann + Ib Chorkendorff Nature Materials (2023) Comments By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate. 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