Operando investigations of the solid electrolyte interphase in the lithium mediated nitrogen reduction reaction

Deissler, Niklas H.; Mygind, J. Bjarke V.; Li, Katja; Niemann, Valerie A.; Benedek, Peter; Vinci, Valentin; Li, Shaofeng; Fu, Xianbiao; Vesborg, Peter K.; Jaramillo, Thomas F.; Kibsgaard, Jakob; Drnec, Jakub; Chorkendorff, Ib

doi:10.1039/d3ee04235a

Title: Operando investigations of the solid electrolyte interphase in the lithium mediated nitrogen reduction reaction

Journal Article · 19 April 2024 · Energy & Environmental Science

DOI: https://doi.org/10.1039/d3ee04235a · OSTI ID:2446553

^[1];

^[2];

^[3];

^[3]; Vinci, Valentin ^[4]; Li, Shaofeng ^[2]; Fu, Xianbiao ^[2];

^[2];

^[3];

^[2]; Drnec, Jakub ^[4];

^[2]

Technical Univ. of Denmark, Lyngby (Denmark); SLAC
Technical Univ. of Denmark, Lyngby (Denmark)
Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis
European Synchrotron Radiation Facility (ESRF), Grenoble (France)

The lithium-mediated nitrogen reduction reaction (Li-NRR) represents a promising approach for electrochemical nitrogen activation, in which the solid electrolyte interphase (SEI) layer formed on the electrochemically plated lithium plays a key role. Herein, we used time-resolved, operando, grazing incidence wide-angle X-ray scattering (GI WAXS) to identify SEI species and reaction intermediates in the Li-NRR, comparing LiBF₄ and LiClO₄ as electrolyte salts. In this study, we demonstrated how the SEI composition influences the Li-NRR performance by regulating proton transport to the plated Li. When LiBF₄ is used as the electrolyte salt, the formation of LiF and lithium ethoxide (LiEtO) is observed. Reaction intermediates such as LiH and LiN_xH_y species were found and provide insight into reaction pathways towards undesired and desired products, respectively. Observed restructuring of the Cu (111) single crystal substrate also indicates interaction with plated Li that could possibly influence the Li-NRR performance. Together, these experiments give molecular insight into how to design Li-NRR systems and their SEI layers for optimal performance.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); Villum Foundation

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 2446553

Journal Information:: Energy & Environmental Science, Journal Name: Energy & Environmental Science Journal Issue: 10 Vol. 17; ISSN 1754-5692

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (41)

Poor Stability of Li ₂ CO ₃ in the Solid Electrolyte Interphase of a Lithium‐Metal Anode Revealed by Cryo‐Electron Microscopy Han, Bing; Zhang, Zhen; Zou, Yucheng Advanced Materials, Vol. 33, Issue 22 https://doi.org/10.1002/adma.202100404	journal	April 2021
Interfacial Speciation Determines Interfacial Chemistry: X‐ray‐Induced Lithium Fluoride Formation from Water‐in‐salt Electrolytes on Solid Surfaces Steinrück, Hans‐Georg; Cao, Chuntian; Lukatskaya, Maria R. Angewandte Chemie International Edition, Vol. 59, Issue 51 https://doi.org/10.1002/anie.202007745	journal	October 2020
A Combined Theory‐Experiment Analysis of the Surface Species in Lithium‐Mediated NH ₃ Electrosynthesis Schwalbe, Jay A.; Statt, Michael J.; Chosy, Cullen ChemElectroChem, Vol. 7, Issue 7 https://doi.org/10.1002/celc.201902124	journal	January 2020
Is Ethanol Essential for the Lithium‐Mediated Nitrogen Reduction Reaction? Bjarke Valbæk Mygind, Jon; Pedersen, Jakob B.; Li, Katja ChemSusChem, Vol. 16, Issue 22 https://doi.org/10.1002/cssc.202301011	journal	September 2023
Elektrolytische Bindung von komprimiertem Stickstoff bei gewöhnlicher Temperatur Fichter, Fr.; Girard, Pierre; Erlenmeyer, Hans Helvetica Chimica Acta, Vol. 13, Issue 6 https://doi.org/10.1002/hlca.19300130604	journal	December 1930
On the possibility of LiH formation on Li surfaces in wet electrolyte solutions Aurbach, Doron; Weissman, Idit Electrochemistry Communications, Vol. 1, Issue 8 https://doi.org/10.1016/S1388-2481(99)00064-8	journal	August 1999
Thermodynamic evaluation of Cu–Li phase diagram from EMF measurements and DTA study Gąsior, W.; Onderka, B.; Moser, Z. Calphad, Vol. 33, Issue 1 https://doi.org/10.1016/j.calphad.2008.10.006	journal	March 2009
Electrolyte acidification from anode reactions during lithium mediated ammonia synthesis Krempl, Kevin; Pedersen, Jakob B.; Kibsgaard, Jakob Electrochemistry Communications, Vol. 134 https://doi.org/10.1016/j.elecom.2021.107186	journal	January 2022
Elongating the cycle life of lithium metal batteries in carbonate electrolyte with gradient solid electrolyte interphase layer Lu, Wei; Sun, Liqun; Zhao, Yang Energy Storage Materials, Vol. 34 https://doi.org/10.1016/j.ensm.2020.09.017	journal	January 2021
Thermodynamic of LiF dissolution in alkylcarbonates and some of their mixtures with water Jones, Jennifer; Anouti, Mérièm; Caillon-Caravanier, Magaly Fluid Phase Equilibria, Vol. 285, Issue 1-2 https://doi.org/10.1016/j.fluid.2009.07.020	journal	November 2009
Lithium-mediated electrochemical nitrogen reduction: Mechanistic insights to enhance performance Cai, Xiyang; Fu, Cehuang; Iriawan, Haldrian iScience, Vol. 24, Issue 10 https://doi.org/10.1016/j.isci.2021.103105	journal	October 2021
Understanding Continuous Lithium-Mediated Electrochemical Nitrogen Reduction Lazouski, Nikifar; Schiffer, Zachary J.; Williams, Kindle Joule, Vol. 3, Issue 4 https://doi.org/10.1016/j.joule.2019.02.003	journal	April 2019
A Roadmap to the Ammonia Economy MacFarlane, Douglas R.; Cherepanov, Pavel V.; Choi, Jaecheol Joule, Vol. 4, Issue 6 https://doi.org/10.1016/j.joule.2020.04.004	journal	June 2020
Electrosynthesis of ammonia with high selectivity and high rates via engineering of the solid-electrolyte interphase Li, Shaofeng; Zhou, Yuanyuan; Li, Katja Joule, Vol. 6, Issue 9 https://doi.org/10.1016/j.joule.2022.07.009	journal	September 2022
Synthesis and electrochemical properties of self-doped solid polymer electrolyte based on lithium 4-styrene sulfonate with BF3-THF Kwon, Nam-Sook; Ryu, Sang-Woog Solid State Ionics, Vol. 361 https://doi.org/10.1016/j.ssi.2021.115563	journal	March 2021
Interface Stability in Solid-State Batteries Richards, William D.; Miara, Lincoln J.; Wang, Yan Chemistry of Materials, Vol. 28, Issue 1 https://doi.org/10.1021/acs.chemmater.5b04082	journal	December 2015
Stability of Solid-Electrolyte Interphase (SEI) on the Lithium Metal Surface in Lithium Metal Batteries (LMBs) Ramasubramanian, Ajaykrishna; Yurkiv, Vitaliy; Foroozan, Tara ACS Applied Energy Materials, Vol. 3, Issue 11 https://doi.org/10.1021/acsaem.0c01605	journal	November 2020
Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations Zhu, Yizhou; He, Xingfeng; Mo, Yifei ACS Applied Materials & Interfaces, Vol. 7, Issue 42 https://doi.org/10.1021/acsami.5b07517	journal	October 2015
Proton Donors Induce a Differential Transport Effect for Selectivity toward Ammonia in Lithium-Mediated Nitrogen Reduction Lazouski, Nikifar; Steinberg, Katherine J.; Gala, Michal L. ACS Catalysis, Vol. 12, Issue 9 https://doi.org/10.1021/acscatal.2c00389	journal	April 2022
Increasing Current Density of Li-Mediated Ammonia Synthesis with High Surface Area Copper Electrodes Li, Katja; Shapel, Sarah G.; Hochfilzer, Degenhart ACS Energy Letters, Vol. 7, Issue 1 https://doi.org/10.1021/acsenergylett.1c02104	journal	November 2021
Lithium-Mediated Electrochemical Nitrogen Reduction: Tracking Electrode–Electrolyte Interfaces via Time-Resolved Neutron Reflectometry Blair, Sarah J.; Doucet, Mathieu; Browning, James F. ACS Energy Letters, Vol. 7, Issue 6 https://doi.org/10.1021/acsenergylett.1c02833	journal	May 2022
A Versatile Li_0.5FePO₄ Reference Electrode for Nonaqueous Electrochemical Conversion Technologies McShane, Eric J.; Benedek, Peter; Niemann, Valerie A. ACS Energy Letters, Vol. 8, Issue 1 https://doi.org/10.1021/acsenergylett.2c02190	journal	November 2022
Water Increases the Faradaic Selectivity of Li-Mediated Nitrogen Reduction Spry, Matthew; Westhead, Olivia; Tort, Romain ACS Energy Letters, Vol. 8, Issue 2 https://doi.org/10.1021/acsenergylett.2c02792	journal	January 2023
Quantifying Influence of the Solid-Electrolyte Interphase in Ammonia Electrosynthesis McShane, Eric J.; Niemann, Valerie A.; Benedek, Peter ACS Energy Letters, Vol. 8, Issue 10, p. 4024-4032 https://doi.org/10.1021/acsenergylett.3c01534	journal	September 2023
NMR Chemical Shifts of Trace Impurities: Common Laboratory Solvents, Organics, and Gases in Deuterated Solvents Relevant to the Organometallic Chemist Fulmer, Gregory R.; Miller, Alexander J. M.; Sherden, Nathaniel H. Organometallics, Vol. 29, Issue 9 https://doi.org/10.1021/om100106e	journal	May 2010
Identification and elimination of false positives in electrochemical nitrogen reduction studies Choi, Jaecheol; Suryanto, Bryan H. R.; Wang, Dabin Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-19130-z	journal	November 2020
Imaging of nitrogen fixation at lithium solid electrolyte interphases via cryo-electron microscopy Steinberg, Katherine; Yuan, Xintong; Klein, Channing K. Nature Energy, Vol. 8, Issue 2, p. 138-148 https://doi.org/10.1038/s41560-022-01177-5	journal	December 2022
A rigorous electrochemical ammonia synthesis protocol with quantitative isotope measurements Andersen, Suzanne Z.; Čolić, Viktor; Yang, Sungeun Nature, Vol. 570, Issue 7762 https://doi.org/10.1038/s41586-019-1260-x	journal	May 2019
Electroreduction of nitrogen with almost 100% current-to-ammonia efficiency Du, Hoang-Long; Chatti, Manjunath; Hodgetts, Rebecca Y. Nature, Vol. 609, Issue 7928 https://doi.org/10.1038/s41586-022-05108-y	journal	July 2022
Long-term continuous ammonia electrosynthesis Li, Shaofeng; Zhou, Yuanyuan; Fu, Xianbiao Nature, Vol. 629, Issue 8010 https://doi.org/10.1038/s41586-024-07276-5	journal	March 2024
Non-aqueous gas diffusion electrodes for rapid ammonia synthesis from nitrogen and water-splitting-derived hydrogen Lazouski, Nikifar; Chung, Minju; Williams, Kindle Nature Catalysis, Vol. 3, Issue 5 https://doi.org/10.1038/s41929-020-0455-8	journal	May 2020
Lithium trapping in alloy forming electrodes and current collectors for lithium based batteries Rehnlund, David; Lindgren, Fredrik; Böhme, Solveig Energy & Environmental Science, Vol. 10, Issue 6 https://doi.org/10.1039/C7EE00244K	journal	January 2017
Increasing stability, efficiency, and fundamental understanding of lithium-mediated electrochemical nitrogen reduction Andersen, Suzanne Z.; Statt, Michael J.; Bukas, Vanessa J. Energy & Environmental Science, Vol. 13, Issue 11 https://doi.org/10.1039/D0EE02246B	journal	January 2020
Towards understanding of electrolyte degradation in lithium-mediated non-aqueous electrochemical ammonia synthesis with gas chromatography-mass spectrometry Sažinas, Rokas; Andersen, Suzanne Zamany; Li, Katja RSC Advances, Vol. 11, Issue 50 https://doi.org/10.1039/D1RA05963G	journal	January 2021
Combined, time-resolved, in situ neutron reflectometry and X-ray diffraction analysis of dynamic SEI formation during electrochemical N₂ reduction Blair, Sarah J.; Doucet, Mathieu; Niemann, Valerie A. Energy & Environmental Science, Vol. 16, Issue 8 https://doi.org/10.1039/D2EE03694K	journal	January 2023
The intrinsic behavior of lithium fluoride in solid electrolyte interphases on lithium He, Mingfu; Guo, Rui; Hobold, Gustavo M. Proceedings of the National Academy of Sciences, Vol. 117, Issue 1 https://doi.org/10.1073/pnas.1911017116	journal	December 2019
Enhancement of lithium-mediated ammonia synthesis by addition of oxygen Li, Katja; Andersen, Suzanne Z.; Statt, Michael J. Science, Vol. 374, Issue 6575 https://doi.org/10.1126/science.abl4300	journal	December 2021
Continuous-flow electrosynthesis of ammonia by nitrogen reduction and hydrogen oxidation Fu, Xianbiao; Pedersen, Jakob B.; Zhou, Yuanyuan Science, Vol. 379, Issue 6633 https://doi.org/10.1126/science.adf4403	journal	February 2023
Modeling Solid-Electrolyte Interphase (SEI) Fracture: Coupled Mechanical/Chemical Degradation of the Lithium Ion Battery Deshpande, Rutooj D.; Bernardi, Dawn M. Journal of The Electrochemical Society, Vol. 164, Issue 2 https://doi.org/10.1149/2.0841702jes	journal	December 2016
Simulations of a LiF Solid Electrolyte Interphase Cracking on Silicon Anodes Using Molecular Dynamics Galvez-Aranda, Diego E.; Seminario, Jorge M. Journal of The Electrochemical Society, Vol. 165, Issue 3 https://doi.org/10.1149/2.0991803jes	journal	January 2018
Efficient Electrochemical Reduction of N ₂ to NH ₃ Catalyzed by Lithium Tsuneto, Akira; Kudo, Akihiko; Sakata, Tadayoshi Chemistry Letters, Vol. 22, Issue 5 https://doi.org/10.1246/cl.1993.851	journal	May 1993

Similar Records

Performance Improvement of Lithium Metal Batteries Enabled By LiBF ₃ CN as a New Electrolyte Additive

Journal Article · 2022 · Journal of the Electrochemical Society · OSTI ID:1896935

Chae, Oh B.; Adiraju, Venkata A. K.; Lucht, Brett L.

Cathodic discharge of lithium borofluoride promoted by quinoline as a primary lithium cell

Journal Article · 1990 · Journal of the Electrochemical Society; (USA) · OSTI ID:6731166

Dohzono, M; Yamada, T; Aikawa, Y; +2 more

Trace LiBF₄ Enabling Robust LiF-Rich Interphase for Durable Low-Temperature Lithium-Ion Pouch Cells

Journal Article · 2024 · ACS Energy Letters · OSTI ID:2571558

Qin, Nan; Chen, Jing; Lu, Yanyan; +7 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Operando investigations of the solid electrolyte interphase in the lithium mediated nitrogen reduction reaction

Citation Formats

References (41)

Similar Records

Related Subjects