Abstract
The results of the study of electrolytes based on gel solutions of DMSO-PVDF-lithium salt with concentrations up to 0.05 m.f. and above 0.1 m.f. are presented. It is shown that the conductivity of electrolytes is close to the conductivity of lithium salt solutions in pure DMSO and obeys the Arrhenius equation in the studied range of temperatures and concentrations. The calculated activation energies for electrolytes with a salt concentration of up to 0.05 m.f. are 14–15.4 KJ/Mol, and for electrolytes with a salt concentration above 0.1 m.f. - 16.9–20.6 KJ/Mol indicate a fast ion transfer, which in more concentrated solutions is inhibited by an increase in their crystallinity. The analysis of the equivalent circuit models of the Li-Li systems electrochemical impedance spectra showed the tendency of electrolytes to form capacitive elements at the lithium electrode-electrolyte interface. It was recognized the presence of semi-infinite diffusion in LiClO4 and LiIm with salt concentration of 0.05 m.f., due to the imperfection of the film formed on the electrode surface. The efficiency of using DMSO-PVDF-lithium gel electrolytes on steel and platinum electrodes was analyzed by voltammograms.
References
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3. Abraham K.M., Jiang Z. A polymer electrolyte‐based rechargeable lithium/oxygen battery. J. Electrochem. Soc. 1996. 143 (1): 1.
4. Ogasawara T., Débart A., Holzapfel M., Novák P., Bruce P.G. Rechargeable Li2O2 Electrode for Lithium Batteries. J. Am. Chem. Soc. 2006. 128 (4) 1390.
5. Li F., Zhang T., Zhou H. Challenges of non-aqueous Li–O2 batteries: electrolytes,
catalysts, and anodes. Energy Environ. Sci. 2013. 6 (4): 1125.
6. Zhang D., Li R., Huang T., Yu A. Novel composite polymer electrolyte for lithium air batteries. J. Power Sources. 2010. 195 (4): 1202.
7. Abraham K.M., Jiang Z., Carroll B. Highly conductive PEO-like polymer electrolytes. Chem. Mater. 1997. 9 (9): 1978.
8. Mohamed S.N., Johari N.A., Ali A.M.M., Harun M.K., Yahya M.Z.A. Electrochemical studies on epoxidised natural rubber-based gel polymer electrolytes for lithium–air cells. J. Power Sources. 2008. 183 (1): 351.
9. Richardson P.M., Voice A.M., Ward I.M. Two distinct lithium diffusive species for polymer gel electrolytes containing LiBF4, propylene carbonate (PC) and PVDF. Int. J. Hydrog. Energy. 2014. 39 (6): 2904.
10. Li G., Li Z., Zhang P., Zhang H., Wu Y. Research on a gel polymer electrolyte for Li-ion batteries. Pure Appl. Chem. 2008. 80 (11): 2553.
11. Pang C., Ding F., Sun W., Liu J., Hao M., Wang Y., Liu X., Xu Q. A novel dimethyl sulfoxide/1,3-dioxolane based electrolyte for lithium/carbon fluorides batteries with a high discharge voltage plateau. Electrochim. Acta. 2015. 174: 230.
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13. Mozhzhukhina N., Méndez De Leo L.P., Calvo E.J. Infrared spectroscopy studies on stability of dimethyl sulfoxide for application in a Li–air battery. J. Phys. Chem. C. 2013. 117 (36): 18375.
14. Morita M., Tachihar F., Matsuda Y. Dime-thyl sulfoxide-based electrolytes for rechargeable lithium batteries. Electrochim. Acta. 1987. 32 (2): 299.
15. Patent UA Diamant V.A., Globa. N.I., Potapenko A.V., Prisyazhnyi V.D. Synthesis of lithium bis(oxalato)borate. 2010.
16. Kirillov S.A., Gorobets M.I., Tretyakov D.O., Ataev M.B., Gafurov M.M. Phase diagrams and conductivity of lithium salt systems in dimethyl sulfoxide, propylene car-bonate and dimethyl carbonate. J. Mol. Liq. 2015. 205: 78.
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19. Henderson W.A. Glyme−lithium salt phase behavior. J. Phys. Chem. B. 2006. 110 (26): 13177.
20. Abe T., Fukuda H., Iriyama Y., Ogumi Z. Solvated Li-Ion Transfer at Interface Be-tween Graphite and Electrolyte. J. Electrochem. Soc. 2004. 151 (8): A1120.
21. Abouzari M.S., Berkemeier F., Schmitz G., Wilmer D. On the physical interpretation of constant phase elements. Solid State Ion. 2009. 180 (14–16): 922.
22. Song J., Bazant M.Z. Effects of Nanoparticle Geometry and Size Distribution on Diffusion Impedance of Battery Electrodes. J. Electrochem. Soc. 2013. 160 (1): A15.
23. Hirschorn B., Orazem M.E., Tribollet B., Vivier V., Frateur I., Musiani M. Determi-nation of effective capacitance and film thickness from constant-phase-element parameters. Electrochim. Acta. 2010. 55 (21): 6218.
24. Churikov A.V. Ion transport mechanism in solid electrolyte films on lithium. Tech. Phys. 2005 50 (11): 1490.
25. Kerner Z., Pajkossy T. On the origin of capacitance dispersion of rough electrodes. Electrochim. Acta. 2000. 46 (2–3): 207.
26. Ushakov P.A., Sorokin A.P. Analysis of the application of the generalized Duhamel integral for calculating the temperature field of reactor fuel elements. High Temp. 1978. 16 (4): 672. [in Russian].
27. Ulyanov S.A. Electromagnetic transition processes in electrical systems. (Moscow: Energiya, 1970). [in Russian].
28. Riabokin, O., Boichuk, O., Pershina, K. Assessment of mechanical damages in the primary Zn-MnO2 batteries by electrochemical impedance spectroscopy.Ukrainian Chemistry Journal. 2019. 85(8): 59.
29. Riabokin O.L., Boichuk A.V., Pershina K.D. Control of the State of Primary Alkaline Zn–MnO2 Cells Using the Electro-chemical Impedance Spectroscopy Method. Surface Engineering and Applied Electrochemistry. 2018. 54(6): 614.
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