Specialties of the structure and conductivity of the non-aqueous electrolytes based on alkali metal bis (salicyl) borates and bis (oxalate) borates
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Keywords

non-aqueous electrolyte, alkali metal bis (salicyl) borates, conductivity, structure, labile complex, ion transport.

How to Cite

Diamant, V., Trachevskii, V., Pershina, K., Ogenko, V., Donchu, C., Huawen, H., Min, C., Xiaowen, W., & Menglei, C. (2019). Specialties of the structure and conductivity of the non-aqueous electrolytes based on alkali metal bis (salicyl) borates and bis (oxalate) borates. Ukrainian Chemistry Journal, 85(3), 49-55. https://doi.org/10.33609/0041-6045.85.3.2019.49-55

Abstract

The structure and coordination environment of non-aqueous electrolytes based on bis(salicyl)borates of lithium, sodium, potassium, tetramethylammonium (MeBSB) and bis(oxalato)borates from lithium to cesium (MeBOB) using NMR spectroscopy have been investigated. Bis(salicyl)borates (BSB) and bis(oxalate)borates (BOB) of alkali metals and organic cations are considered as promising electroconductive components of electrolytes of modern chemical sources of current (lithium, sodium ion batteries and super-capacitors). The salts were synthesized by the microwave radiation method. The 13C and 11B NMR spectra analysis determined the presence of symmetric structure in BOB anion and the presence of two optical conformations of the BSB anion with labile coordination environment of boron. The conformations of the BSB are the result of the ion contact pairs formation. In the case of tetramethylammonium cation the presence of conformations are depended on the reactive medium.

The conformational lability of the coordination sphere of NaBSB dissolved in DMAA is connected with increasing of the integral intensity of carboxyl group singles relatively signals of carbon atoms in fragments of another functional affiliation when the time delay between radio frequencies varies within 2-15 seconds. The difference in the structure of these anions leads to a change in the thermal dependence of the electrical conductivity of BSB and the transport of ions in non-aqueous solvents. Maximum electrical conductivity of salt solutions in DMFA is achieved at close concentrations of 0.75 m for KBSB and 0.77-1 m for NaBSB. The solubility of BSB is better than the BOB. Based on the measurements of the conductivity and the data of electrochemical impedance spectroscopy (the angle of inclination of spectra in the Nyquist coordinates in the low frequency range, the phase angle shift at a frequency) it was proposed the existence of two ways of ions and charge transfer in the electrolytes: diffusion and relay transport. The possibility of formation of a labile salt complex with a solvent due to hydrogen bonds is established.

 

https://doi.org/10.33609/0041-6045.85.3.2019.49-55
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References

Zhao-Ming X., et al. New lithium salts with croconato-complexes of boron for lithium battery electrolytes. Journal of Power Sources. 2007. 171 (2): 944-947.

Zhao-Ming X., et al. A new lithium salt with 3-fluoro-1, 2-benzenediolato and oxalato complexes of boron for lithium battery electrolytes. Journal of Power Sources. 2010. 195 (11): 3689-3692.

Chunhua G., et al. Synthesis of novel organic-ligand-doped sodium bis (oxalate)-borate complexes with tailored thermal stability and enhanced ion conductivity for sodium ion batteries J. Power Sources. 2014. 248: 77-82.

Nanbu N., Ebina T., Uno H., Ishizawa S. Physical and electrochemical properties of quaternary ammonium bis(oxalato)borates and their application to electric double-layer capacitors. Electrochimica Acta. 2006. 52 (4): 1763–1770.

Shiyou L., et al. Electrochemical performances of two kinds of electrolytes based on lithium bis (oxalate) borate and sulfolane for advanced lithium ion batteries. Journal of Power Sources. 2012. 209: 295-300.

Gorobets M. I., Kirillov S. A., Gafurov M. M., Ataev M. B., Tret'yakov, D. O. Solvation and Association of ions in the LiClO4—dimethyl sulfoxide system // Reports of NAS of Ukraine – 2014. – № 1. – p. 125-129.

Kirillov S. A., Gorobets M. I., Gafurov M M. Rabadanov K. S., Ataev M. B. Temperature dependence of DMSO associative equilibria in the Raman spectra. Journal of physical chemistry. 2014. 88 (1): 140-140.

Gafurov M. M., Kirillov S. A., Rabadanov K. S., Ataev M. B., Tret'yakov, D. O. Spectroscopic study of solvation processes and ionic association in lithium salt solutions with ionic and aprotic solvents. Journal of Structural Chemistry. 2014. 55, (1): 67-71.

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 carbonate and dimethyl carbonate. Journal of Molecular Liquids. 2015. 205: 78-84.

Gafurov M. M., Kirillov S. A., Gorobets M. A., Rabadanov K. S., Ataev M. I., Tretyakov D. O., Aydemirov K. M. Phase equilibria and ionic solvation in the lithium tetrafluoroborate–dimethylsulfoxide system. Journal of Applied Spectroscopy. 2015. 81 (6): 912-918.

Patent of Ukraine for invention № 90234, Synthesis of bis(oxalato)lithium borate / Globa N.I., Prysyazhnyi B. D., Diamant V. A., Potapenko O. V. - published 12.04.2010

Chunhua G., et al. Synthesis of novel organic-ligand-doped sodium bis (oxalate)-borate complexes with tailored thermal stability and enhanced ion conductivity for sodium ion batteries J. Power Sources. 2014. 248: 77-82.

Zavalij P. Y., Shoufeng Y., Whittingham S. M. Structures of potassium, sodium and lithium bis (oxalato) borate salts from powder diffraction data. Acta Crystallographica Section B: Structural Science. 2003. 59 (6): 753-759.

Garcia-Belmonte, A. Munar, E. Barea M., J. Bisquert, I. Ugarte, R. Pacios Charge carrier mobility and lifetime of organic bulk heterojunctions analyzed by impedance spectroscopy. Organic Electronics. 2008. 9: 847–851

Riabokin O. L., Boichuk A. V., Pershina K. D. Control of the State of Primary Alkaline Zn–MnO2 Cells Using the Electrochemical Impedance Spectroscopy Method. Surface Engineering and Applied Electrochemistry. 2018. 54 (6): 614-622

G. Vlaikov G., Trachevsky V. V. Transport phenomena and local fields in condensed media. - Kyiv: Technical center. - 2013. - 338 p.

Pershina E. D., Kokhanenko V. V., Maslyuk L. N., Kazdobin K. A. Conductivity of aqueous suspensions of alumosilicates. Surface Engineering and Applied Electrochemistry. 2011. 47 (5): 441-445

Pershina E. D., Kazdobin K. A. The conductivity of aqueous media as an alternative to electronic and ion transport. Chemistry and technology of water. 2008. 30 (6): 627-642

Diamant, A. V., Malovanyy M. S., Pershina K. D., Kazdobin K. A. Electrochemical properties of Sodium bis [salicylato (2-)]-borate-γ-butyrolactone Electrolytes in Sodium Battery. Materials Today: Proceedings. 2019. 6: 86-94

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