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Notable Reactivity of Acetonitrile Towards Li2O2/LiO2 Probed by NAP XPS During Li–O2 Battery Discharge

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Abstract

One of the key factors responsible for the poor cycleability of Li–O2 batteries is a formation of byproducts from irreversible reactions between electrolyte and discharge product Li2O2 and/or intermediate LiO2. Among many solvents that are used as electrolyte component for Li–O2 batteries, acetonitrile (MeCN) is believed to be relatively stable towards oxidation. Using near ambient pressure X-ray photoemission spectroscopy (NAP XPS), we characterized the reactivity of MeCN in the Li–O2 battery. For this purpose, we designed the model electrochemical cell assembled with solid electrolyte. We discharged it first in O2 and then exposed to MeCN vapor. Further, the discharge was carried out in O2 + MeCN mixture. We have demonstrated that being in contact with Li–O2 discharge products, MeCN oxidizes. This yields species that are weakly bonded to the surface and can be easily desorbed. That’s why they cannot be detected by the conventional XPS. Our results suggest that the respective chemical process most probably does not give rise to electrode passivation but can decrease considerably the Coulombic efficiency of the battery.

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Acknowledgements

This work of A.K-G., J.J.V-V. and D.M.I. was supported by the Russian Ministry of Science and Education (RFMEFI61614×0007) and Bundesministerium für Bildung and Forschung (Project No. 05K2014) in the framework of the joint Russian-German research project “SYnchrotron and NEutron STudies for Energy Storage (SYNESTESia)”. T.K.Z acknowledges Center for Electrochemical Energy of Skolkovo Institute of Science and Technology for financial support. The work of O.O.K., A.I.B and L.V.Y. is performed within the joint project of the Russian Science Foundation (16-42-01093) and DFG (LA655-17/1). We are grateful to HZB for beamtime granted at ISISS and RGBL beamlines. T.K.Z. and A.S.F. thank to the Russian German laboratory at HZB for support provided. Authors are appreciated to Victor Vizgalov for solid electrolyte membrane preparation. Travelling of T.K.Z. was supported by German-Russian Interdisciplinary Science Center (G-RISC).

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Authors and Affiliations

  1. Lomonosov Moscow State University, Leninskie gory, Moscow, Russia, 119991

    Tatiana K. Zakharchenko, Alina I. Belova, Alexander S. Frolov, Olesya O. Kapitanova, Daniil M. Itkis & Lada V. Yashina

  2. Depatment of Inorganic Chemistry, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 1495, Berlin, Germany

    Juan-Jesus Velasco-Velez & Axel Knop-Gericke

  3. IKERBASQUE, Basque Foundation for Science, 48011, Bilbao, Spain

    Denis Vyalikh

  4. Departamento de Fisica de Materiales and CFM-MPC UPV/EHU, Donostia International Physics Center (DIPC), 20080, San Sebastian, Spain

    Denis Vyalikh

  5. Department of Heterogeneous Reactions, Max-Planck-Institute for Chemical Energy Conversion, Stiftstraße 34,36, 45413, Mülheim, Germany

    Axel Knop-Gericke

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  1. Tatiana K. Zakharchenko
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Correspondence to Lada V. Yashina.

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Zakharchenko, T.K., Belova, A.I., Frolov, A.S. et al. Notable Reactivity of Acetonitrile Towards Li2O2/LiO2 Probed by NAP XPS During Li–O2 Battery Discharge. Top Catal 61, 2114–2122 (2018). https://doi.org/10.1007/s11244-018-1072-5

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