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; Saccoccio, Mattia; Krempl, Kevin; Pedersen, Jakob B.; Kibsgaard, Jakob; Vesborg, Peter Christian Kjærgaard; Chakraborty, Debashis; Chorkendorff, Ib

doi:10.1039/d1ra05963g

Cited by 43 publications

(71 citation statements)

References 26 publications

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“…In conventional electrochemical cells used for nitrogen reduction experiments, the counter and working electrode are usually immersed in the same electrolyte compartment or just separated by a thin porous membrane. This makes it easy for anodic decomposition products to diffuse to the working electrode, potentially affecting the overall net nitrogen reduction rate negatively [12] . The electrochemical cell used in this study, however, strictly separates the working electrode compartment from the counter electrode with a long capillary and a microporous frit.…”

Section: Resultsmentioning

confidence: 99%

“…This makes it easy for anodic decomposition products to diffuse to the working electrode, potentially affecting the overall net nitrogen reduction rate negatively. [12] The electrochemical cell used in this study, however, strictly separates the working electrode compartment from the counter electrode with a long capillary and a microporous frit. This increases the diffusion timescale of anodic decomposition products to reach the working electrode significantly compared to the timescale at which nitrogen reduction experiments are carried out.…”

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confidence: 99%

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Quantitative Operando Detection of Electro Synthesized Ammonia Using Mass Spectrometry

Krempl

Hochfilzer

Cavalca³

et al. 2022

ChemElectroChem

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In this work the successful operando detection of synthesized ammonia from nitrogen reduction in non‐aqueous electrolytes with an electron‐ionization mass spectrometer was reported. Using selective ionization at 22 eV together with a highly sensitive micro‐chip‐based electrochemistry mass spectrometry set‐up, quantitative detection of produced ammonia down to few pmol s−1 in non‐aqueous as well as aqueous electrolytes was demonstrated. The well‐defined electrochemical and mass transport environment of the thin‐layer electrochemical cell allowed for fundamental studies of the nitrogen reduction process, which was shown to produce ammonia at faradaic efficiencies of 49±3 % at ambient pressure. Moreover, through the operando capabilities of the developed method, it was shown that ammonia production proceeded even after lithium electroplating had been terminated This potentially explained why higher faradaic efficiencies of lithium mediated ammonia synthesis were observed under dynamic cycling conditions. Two possible mechanisms for this behavior were proposed and an outlook towards future research in operando studies of lithium mediated ammonia synthesis was given.

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Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

Quantitative Operando Detection of Electro Synthesized Ammonia Using Mass Spectrometry

Krempl

Hochfilzer

Cavalca³

et al. 2022

ChemElectroChem

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“… 12 − 14 Our recent work on stability of LiMEAS monitored using GC with high-resolution MS for chemical and structural elucidation is a pioneering approach toward stability of LiMEAS in different organic electrolytes. 11 , 14 …”

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confidence: 99%

“…We assume that the main reason for such a high CE potential is electrolyte (THF and EtOH) oxidation and formation of the products reported elsewhere. 11 …”

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confidence: 99%

“…The freshly obtained electrolytes were transferred to the GCMS after LiMEAS followed by immediate analysis of the electrolytes to limit reaction of the electrolyte with air and moisture. The experimental details regarding the GCMS experiments and analysis of the samples are described in brief in the Supporting Information and were reported by us in detail in ref ( 11 ). Longer GCMS recording time did not reveal any eluents from the samples, and all the byproducts of LiMEAS eluted in less than 15 min.…”

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Oxygen-Enhanced Chemical Stability of Lithium-Mediated Electrochemical Ammonia Synthesis

Sažinas

Andersen

et al. 2022

J. Phys. Chem. Lett.

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Although oxygen added to nonaqueous lithium-mediated electrochemical ammonia synthesis (LiMEAS) enhances Faradaic efficiency, its effect on chemical stability and byproducts requires understanding. Therefore, standardized high-resolution gas chromatography–mass spectrometry and nuclear magnetic resonance were employed. Different volatile degradation products have been qualitatively analyzed and quantified in tetrahydrofuran electrolyte by adding some oxygen to LiMEAS. Electrodeposited lithium and reduction/oxidation of the solvent on the electrodes produced organic byproducts to different extents, depending on the oxygen concentration, and resulted in less decomposition products after LiMEAS with oxygen. The main organic component in solid-electrolyte interphase was polytetrahydrofuran, which disappeared by adding an excess of oxygen (3 mol %) to LiMEAS. The total number of byproducts detected was 14, 9, and 8 with oxygen concentrations of 0, 0.8, and 3 mol %, respectively. The Faradaic efficiency and chemical stability of the LiMEAS have been greatly improved with addition of optimal 0.8 mol % oxygen at 20 bar total pressure.

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Electrochemical Nitrogen Fixation for Green Ammonia: Recent Progress and Challenges

et al. 2023

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Ammonia, a key feedstock used in various industries, has been considered a sustainable fuel and energy storage option. However, NH3 production via the conventional Haber–Bosch process is costly, energy‐intensive, and significantly contributing to a massive carbon footprint. An electrochemical synthetic pathway for nitrogen fixation has recently gained considerable attention as NH3 can be produced through a green process without generating harmful pollutants. This review discusses the recent progress and challenges associated with the two relevant electrochemical pathways: direct and indirect nitrogen reduction reactions. The detailed mechanisms of these reactions and highlight the recent efforts to improve the catalytic performances are discussed. Finally, various promising research strategies and remaining tasks are presented to highlight future opportunities in the electrochemical nitrogen reduction reaction.

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Towards understanding of electrolyte degradation in lithium-mediated non-aqueous electrochemical ammonia synthesis with gas chromatography-mass spectrometry

Abstract: Lithium-mediated non-aqueous electrochemical ammonia synthesis (LiMEAS) as an efficient and green ammonia production way was studied by GCMS in different organic electrolytes to evaluate the stability of electrochemical systems.

Cited by 43 publications

References 26 publications

Quantitative Operando Detection of Electro Synthesized Ammonia Using Mass Spectrometry

Quantitative Operando Detection of Electro Synthesized Ammonia Using Mass Spectrometry

Oxygen-Enhanced Chemical Stability of Lithium-Mediated Electrochemical Ammonia Synthesis

Electrochemical Nitrogen Fixation for Green Ammonia: Recent Progress and Challenges

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