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Imaging nitrogen fixation at lithium solid electrolyte interphases via cryo-electron microscopy

Steinberg, Katherine and Yuan, Xintong and Lazouski, Nikifar and Klein, Channing K. and Manthiram, Karthish and Li, Yuzhang (2022) Imaging nitrogen fixation at lithium solid electrolyte interphases via cryo-electron microscopy. . (Unpublished) https://resolver.caltech.edu/CaltechAUTHORS:20220414-26022000

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Abstract

Electrifying ammonia synthesis will be vital to the decarbonization of the chemical industry, as the Haber-Bosch process contributes significantly to global carbon emissions. A lithium-mediated pathway is among the most promising ambient-condition electrochemical ammonia synthesis methods. However, the role of metallic lithium and its passivation layer, the solid electrolyte interphase (SEI), remains unresolved. Here, we apply a multiscale approach that leverages the powerful cryogenic transmission electron microscopy (cryo-TEM) technique to reveal new insights that were previously inaccessible with conventional methods. We discover that the proton donor (e.g. ethanol) governs lithium reactivity toward nitrogen fixation. Without ethanol, the SEI passivates lithium metal, rendering it inactive for ammonia production. Ethanol disrupts this passivation layer, enabling continuous reactivity at the lithium surface. As a result, metallic lithium is consumed via reactions with nitrogen, proton donor, and other electrolyte components. This reactivity across the SEI is vital to device-level performance of lithium-mediated ammonia synthesis.


Item Type:Report or Paper (Discussion Paper)
Related URLs:
URLURL TypeDescription
https://doi.org/10.26434/chemrxiv-2022-9v3nwDOIDiscussion Paper
ORCID:
AuthorORCID
Steinberg, Katherine0000-0002-8232-7714
Lazouski, Nikifar0000-0002-4655-2041
Manthiram, Karthish0000-0001-9260-3391
Additional Information:The content is available under CC BY NC ND 4.0 License. This material is based upon work supported by the National Science Foundation under Grant No. 2204756. K.S. and N.L. acknowledge support from the National Science Foundation Graduate Research Fellowship under Grant No. 1745302. Data was acquired at the Electron Imaging Center for Nanomachines (EICN) at the University of California, Los Angeles’s California for NanoSystems Institute (CNSI). This work also made use of the MRSEC Shared Experimental Facilities at MIT, supported by the National Science Foundation under award number DMR-1419807. We thank the staff scientists at both UCLA EICN and MIT MRSEC for their training and expertise. We also thank Matt Wolski of Daramic for providing us with polyporous separator samples, Felice Frankel for feedback on figure design, and Kindle Williams, Nathan Corbin, and all the members of the Li and Manthiram research groups for productive and helpful discussions. Author contributions: K.S., K.M, and Y.L. conceptualized the paper. K.S. developed the experimental methodology for product quantification, sample preparation for imaging and characterization, and collection of XPS spectra. X.Y. and Y.L. developed the experimental methodology for SEM and cryo-TEM. K.S. performed product quantification, SEM, and XPS experiments, and prepared samples for cryo-EM. X.Y. carried out cryo-TEM and SEM imaging. C.K. and K.S. performed the validation. K.S. wrote the original draft of the manuscript and N.L, Y.L., K.M., C.K., X.Y., and K.S. reviewed and edited its contents. K.M. and Y.L. supervised the work. The authors declare no competing interests. The author(s) have declared ethics committee/IRB approval is not relevant to this content.
Funders:
Funding AgencyGrant Number
NSFCBET-2204756
NSF Graduate Research FellowshipDGE-1745302
NSFDMR-1419807
Subject Keywords:electrochemistry; ammonia synthesis; lithium-mediated; solid electrolyte interphase; cryo-electron microscopy; chemical corrosion; nitrogen fixation
DOI:10.26434/chemrxiv-2022-9v3nw
Record Number:CaltechAUTHORS:20220414-26022000
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20220414-26022000
Official Citation:Steinberg K, Yuan X, Lazouski N, Klein CK, Manthiram K, Li Y. Imaging nitrogen fixation at lithium solid electrolyte interphases via cryo-electron microscopy. ChemRxiv. 2022. doi:10.26434/chemrxiv-2022-9v3nw
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:114294
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:19 Apr 2022 20:43
Last Modified:19 Apr 2022 23:34

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