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Translational Mobility in Ternary Systems “Lithium Acetate–Cesium Acetate–Water” According to PFG NMR Data

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Abstract

The development of ecofriendly electrolytes for lithium-ion batteries is one of the actual tasks of modern electrochemistry. In particular, to this purpose, the highly concentrated ternary aqueous systems based on lithium acetate (LiOAc) have been actively investigated. Here, the diffusion coefficients of 7Li+ and 133Cs+ cations, OAc– anion, as well as water (1H), in ternary aqueous solutions of cesium and lithium acetates in a range of temperature (– 15 ÷ 35 °C) have been measured using the PFG NMR method. A direct attempt to interpret the obtained dependences within the framework of the Stokes–Einstein model led to the fact that the calculated hydrodynamic radius of the Cs+ cation turned out to be noticeably smaller than its crystallographic one. An approach to describing the high rate of diffusion of cesium cations is proposed, based on taking into account the local viscosity near cations of both types. The use of the approach allowed us to calculate more correctly the hydrodynamic radii of cations, while remaining within the framework of the Stokes–Einstein model. As a result, it has been possible to describe the features of translational motion of components in a complex system that is interesting for electrochemical applications.

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References

  1. S. Chen, M. Zhang, P. Zou, B. Sun, S. Tao, Historical development and novel concepts on electrolytes for aqueous rechargeable batteries. Energy Environ. Sci. 15(5), 1805–1839 (2022). https://doi.org/10.1039/D2EE00004K

    Article  Google Scholar 

  2. S.K. Sharma et al., Progress in electrode and electrolyte materials: path to all-solid-state Li-ion batteries. Energy Adv. 8(1), 457–510 (2022). https://doi.org/10.1039/D2YA00043A

    Article  ADS  Google Scholar 

  3. M.R. Lukatskaya et al., Concentrated mixed cation acetate “water-in-salt” solutions as green and low-cost high voltage electrolytes for aqueous batteries. Energy Environ. Sci. 11(10), 2876–2883 (2018). https://doi.org/10.1039/C8EE00833G

    Article  Google Scholar 

  4. V.V. Matveev, O.N. Pestova, K.V. Tyutyukin, V.I. Chizhik, Molecular mobility in mixed “water-in-salt” solutions of LiOAc and KOAc according to NMR data. Appl. Magn. Reson. 54(10), 971–978 (2023). https://doi.org/10.1007/s00723-023-01558-3

    Article  Google Scholar 

  5. S. Chen, R. Lan, J. Humphreys, S. Tao, Effect of cation size on alkali acetate-based ‘water-in-bisalt’ electrolyte and its application in aqueous rechargeable lithium battery. Appl. Mater. Today 20, 100728 (2020). https://doi.org/10.1016/j.apmt.2020.100728

    Article  Google Scholar 

  6. S. Liu et al., Caesium acetate-based electrolytes for aqueous electrical double layer capacitors. ChemElectroChem 9(22), e20220071 (2022). https://doi.org/10.1002/celc.202200711

    Article  MathSciNet  Google Scholar 

  7. L. Liangbin et al., Patent CN, no. CN116283548A, 2023.

  8. V.I. Chizhik, Magnetic Resonance and Its Applications (Springer, Cham, 2014)

    Book  Google Scholar 

  9. M.H. Levitt, Spin Dynamics: Basics of Nuclear Magnetic Resonance, 2nd edn. (Wiley, Chichester, 2008)

    Google Scholar 

  10. D. Burstein, Stimulated echoes: description, applications, practical hints. Concepts Magn. Reson.Magn. Reson. 8(4), 269–278 (1996). https://doi.org/10.1002/(SICI)1099-0534(1996)8:4%3c269::AID-CMR3%3e3.0.CO;2-X

    Article  Google Scholar 

  11. E.O. Stejskal, J.E. Tanner, Spin diffusion measurements: spin echoes in the presence of a time-dependent field gradient. J. Chem. Phys. 42(1), 288–292 (1965). https://doi.org/10.1063/1.1695690

    Article  ADS  Google Scholar 

  12. G.H. Sorland, Dynamic Pulsed-Field-Gradient. NMR Springer Series in Chemical Physics (Springer, Berlin, 2014), p.110

    Book  Google Scholar 

  13. K. Hayamizu, Yu. Chiba, T. Haishi, Dynamic ionic radius of alkali metal ions in aqueous solution: a pulsed-field gradient NMR study. RSC Adv. 11, 20252 (2021). https://doi.org/10.1039/D1RA02301B

    Article  ADS  Google Scholar 

  14. K. Hayamizu, S. Tsuzuki, S. Seki, Y. Umebayashi, Nuclear magnetic resonance studies on the rotational and translational motions of ionic liquids composed of 1-ethyl-3-methylimidazolium cation and bis(trifluoromethanesulfonyl)amide and bis(fluorosulfonyl)amide anions and their binary systems including lithium salts. J. Chem. Phys. 135, 084505 (2011). https://doi.org/10.1063/1.3625923

    Article  ADS  Google Scholar 

  15. V.I. Chizhik, NMR relaxation and microstructure of aqueous electrolyte solutions. Mol. Phys. 90, 653–659 (1997). https://doi.org/10.1080/00268979709482647

    Article  ADS  Google Scholar 

  16. J.D. Bernal, R.H. Fowler, A theory of water and ionic solution, with particular reference to hydrogen and hydroxyl ions. J. Chem. Phys. 1(8), 515–548 (1933). https://doi.org/10.1063/1.1749327

    Article  ADS  Google Scholar 

  17. R.D. Shannon, Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr. Sect. A Found. Crystallogr. 32, 751–767 (1976). https://doi.org/10.1107/S0567739476001551

    Article  ADS  Google Scholar 

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Acknowledgements

NMR measurements were carrying out in the Center for Magnetic Resonance of Research Park of St. Petersburg State University.

Funding

This work was supported by the Russian Science Foundation (Project no. 23-23-00049).

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Authors and Affiliations

  1. Department of General and Inorganic Chemistry, Chemistry Institute, Saint Petersburg State University, St. Petersburg, Russia

    Kirill A. Mukhin & Olga N. Pestova

  2. Department of Nuclear Physics Research Methods, Saint Petersburg State University, St. Petersburg, Russia

    Kirill A. Mukhin, Vladimir V. Matveev & Vladimir I. Chizhik

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  1. Kirill A. Mukhin
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  2. Olga N. Pestova
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  3. Vladimir V. Matveev
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  4. Vladimir I. Chizhik
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Contributions

K.A.M. prepared samples, conducted experimental measurements and processing results, prepared all figures; O.N.P. synthesized anhydrous cesium acetate, participated in the explanation of the results; V.V.M. analyzed the literature data, interpreted the results and participated in preparing the article text; V.I.C. analyzed the experimental results obtained, developed an approach for interpreting the results and participated in preparing the article text.

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Correspondence to Vladimir V. Matveev.

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Mukhin, K.A., Pestova, O.N., Matveev, V.V. et al. Translational Mobility in Ternary Systems “Lithium Acetate–Cesium Acetate–Water” According to PFG NMR Data. Appl Magn Reson (2024). https://doi.org/10.1007/s00723-024-01670-y

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  • DOI: https://doi.org/10.1007/s00723-024-01670-y

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