<i>Operando</i> 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 C. K.; Jaramillo, Thomas F.; Kibsgaard, Jakob; Drnec, Jakub; Chorkendorff, Ib

doi:10.1039/d3ee04235a

Cited by 6 publications

(8 citation statements)

References 51 publications

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“…The Li and H-containing species would then react to form LiH, indicative of the side reaction pathway towards H2, which has previously been theoretically predicted to form but difficult to observe ex situ. 26,51 Recently, it has been detected in operando, 14 and our results show the conditions that favor its formation and growth into the outer SEI.…”

Section: Sustained Current Leads To the Accumulation Of Lihsupporting

confidence: 60%

“…License: CC BY-NC-ND 4.0 decomposition species. 14,49,50 Cracking could explain the transition from a lithiated inner layer to an inner layer comprised of electrolyte decomposition as current density increases.…”

Section: Libf4 Forms Well-defined Interfaces At Higher Current and Mo...mentioning

confidence: 99%

“…52,53 BF4may also decompose into LiF and BF3, and that the BF3 reacts with organics to form part of the porous, outer layer, which has been hypothesized. 14,52,54 The presence of boron in the SEI could confer beneficial structural and compositional properties for Li-N2R, which will be the focus of future work. 9,35,53,54 https://doi.org/10.26434/chemrxiv-2024-8g61h ORCID: https://orcid.org/0000-0002-9565-022X Content not peer-reviewed by ChemRxiv.…”

Section: In Situ Detection Of Boron-containing Species In the Seimentioning

confidence: 99%

“…The proton donor can be incorporated into the SEI and can also form LiH, indicative of H2 formation. 14,26,27 Based on previous work, we infer three pathways for proton-containing species: forming the SEI, producing the undesired species (e.g., H2), and producing the desired species, NH3. 28 The Li-N2R SEI is both a passivating layer for reactive Li and also serves to define the reaction microenvironment.…”

Section: Introductionmentioning

confidence: 99%

“…A recent operando study used grazing-incidence wide-angle X-ray scattering (GIWAXS) to detect the presence of SEI species, including intermediates and LiH, and concluded that the enhanced performance of the LiBF4 SEI was likely due to its ability to limit proton transport. 14 Key insights could be obtained using a technique that can track the location and longer-range structure of the SEI containing these species, with sensitivity to LiH to understand the conditions under which it forms. Open questions remain as to how the structure and composition of the SEI change with current density and time; how the SEI forms; what the relative proton contributions of the proton-donor and solvent are; why LiBF4 might perform better than other fluorinated salts; and how LiH, an indicator of major side product, H2, forms.…”

Section: Introductionmentioning

confidence: 99%

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In situ neutron reflectometry reveals the interfacial microenvironment driving electrochemical ammonia synthesis

Niemann,

Doucet,

Benedek

et al. 2024

Preprint

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Electrified interfaces are critical to the performance of energy systems and often demonstrate substantial complexity under operating conditions. Nanoscale understanding of the interfacial microenvironment, i.e., the solid electrolyte interphase (SEI), in lithium-mediated nitrogen reduction (Li-N2R) is key for realizing efficient ammonia production. Using in situ neutron reflectometry, we found the Li-N2R SEI comprises a thick, diffuse outer layer and a thin, compact inner layer at low current cycling. Increasing current density resulted in a thinner outer layer with a thicker inner layer; sustained current led to LiH formation. Neutron absorption indicated boron uptake in the SEI. Time-resolved tracking of SEI growth with isotope contrasting revealed the proton donor modifies the inner layer, and the solvent modifies the outer layer. Li dendritic growth was observed in the absence of a proton donor. Our results inform Li-based systems and reaction microenvironments, and these methods can be applied broadly to interfacial energy technologies.

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Section: Sustained Current Leads To the Accumulation Of Lihsupporting

confidence: 60%

Section: Libf4 Forms Well-defined Interfaces At Higher Current and Mo...mentioning

confidence: 99%

Section: In Situ Detection Of Boron-containing Species In the Seimentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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In situ neutron reflectometry reveals the interfacial microenvironment driving electrochemical ammonia synthesis

Niemann,

Doucet,

Benedek

et al. 2024

Preprint

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Localized High‐Concentration Electrolyte in Li‐Mediated Nitrogen Reduction for Ammonia Synthesis

Yun,

Lim,

Kwon

et al. 2024

Advanced Materials

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The lithium‐mediated nitrogen reduction reaction (Li‐NRR) is a promising green alternative to the Haber–Bosch process for ammonia synthesis. The solid electrolyte interphase (SEI) is crucial for high efficiency and stability, as it regulates reactant diffusion and suppresses side reactions. The SEI properties are greatly influenced by the Li+ ion solvation structure, which is controllable through electrolyte engineering. Although anion‐derived SEI enhances selectivity and stability, it has typically been engineered using high‐concentration electrolytes (HCEs), which face mass transfer, viscosity, and cost issues. In this study, a localized high‐concentration electrolyte (LHCE) in the Li‐NRR is first introduced, enabling the formation of anion‐derived SEI in a low‐concentration electrolyte (LCE) by enhancing the Li–anion coordination using an antisolvent. Among various antisolvents, 1,1,2,2‐tetrafluoroethyl‐2,2,3,3‐tetrafluoropropyl ether (TTE) achieves the highest ammonia Faradaic efficiency (73.6 ± 2.5%), more than double that of the LCE (34.3 ± 2.8%) and exceeding the HCE (56.0 ± 2.8%). Systematic calculations and experimental analyses show that the LHCE exhibits anion‐rich solvation structures and forms thin, inorganic SEI. Moreover, the LHCE has advantages of low viscosity and high N2 solubility, which facilitate mass transport. This study suggests the application of LHCE as an effective electrolyte engineering strategy to enhance the Li‐NRR efficiency.

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Structural regulation strategies of nitrogen reduction electrocatalysts

Chen,

Guan

2024

Chinese Journal of Catalysis

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

Abstract: 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...

Cited by 6 publications

References 51 publications

In situ neutron reflectometry reveals the interfacial microenvironment driving electrochemical ammonia synthesis

In situ neutron reflectometry reveals the interfacial microenvironment driving electrochemical ammonia synthesis

Localized High‐Concentration Electrolyte in Li‐Mediated Nitrogen Reduction for Ammonia Synthesis

Structural regulation strategies of nitrogen reduction electrocatalysts

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