Chemical Current Source Express Diagnostics Using Noise Spectroscopy on the Example of Lithium-Thionyl Chloride Battery

Lithium-thionyl chloride battery voltage is practically not changing during the discharge process and drops sharply being completely discharged. In this regard, the problem of non-destructive quality control of the chemical current sources (first of all, the discharge degree) before installation thereof in the equipment becomes of particular importance. Microcalorimetric studies make it possible to rather correctly determine the current source internal self-discharge rate, predict the LCCS shelf life and its performance term. However, the heat release absolute value in current sources with sufficient storability, i.e., with low self-discharge, is very small; therefore, it is necessary to use sensitive, stationary and large-sized equipment. This makes such diagnostics impossible when operating in the stand-alone conditions. The impedance spectroscopy method could be proposed to solve this problem. However, satisfactory results are only obtained in the 0--70 % residual capacitance range. Determination of residual capacitance in the 70--100 % range appears to be rather difficult due to the absence of noticeable alteration in the informative parameter within the limits of its absolute deviation from the mean value. In this regard, it looks advisable to use noise spectroscopy as a physically independent method in diagnosing the state of chemical current sources to expand the residual capacitance diagnostics range to the 70--100 % domain, as well as to increase reliability of the chemical current source diagnostic estimate in the range of 50--70 %. Results of the electrochemical noise measurement analysis confirm promising application of the noise spectroscopy method in estimating current state of the primary chemical current sources in their low discharge domains

References

[1] Li N., Hu R.-Z. Determination of thermal conductivities of solids by microcalorimetry. Thermochim. Acta, 1994, vol. 231, pp. 317--331. DOI: https://doi.org/10.1016/0040-6031(94)80034-0

[2] Nizhnikovskiy E.A. Microcalorimetry for diagnostics of lithium chemical current sources. Avtonomnaya energetika: technicheskiy progress i ekonomika, 2006, vol. 22, pp. 3--12 (in Russ.).

[3] Nizhnikovskiy E.A. Microcalorimetry as non-destructive test for batteries. Elektrokhimicheskaya energetika [Electrochemical Energetics], 2003, vol. 3, no. 2, pp. 80--85 (in Russ.).

[4] Korobov V.A., Yakusheva A.G. Superposition method for calculation of non-stationary temperature fields. Avtonomnaya energetika, 1996, no. 7, pp. 24--27 (in Russ.).

[5] Skundin A.M., Efimov O.N., Yarmolenko O.V. The state-of-the-art and prospects for the development of rechargeable lithium batteries. Russ. Chem. Rev., 2002, vol. 71, no. 4, pp. 329--346. DOI: https://doi.org/10.1070/RC2002v071n04ABEH000706

[6] Petrenko E.M., Dribinskiy A.V., Lukovtsev V.P., et al. Methodical maintenance impedance spectroscopy for lithium chemical power sources. Elektrokhimicheskaya energetika [Electrochemical Energetics], 2010, vol. 10, no. 3, pp. 128--132 (in Russ.).

[7] Dribinskiy A.V., Lukovtsev V.P., Maksimov E.M., et al. Sposob opredeleniya ostatochnoy emkosti pervichnogo istochnika toka [Method for determining remaining capacity of primary current source]. Patent RU 2295139. Appl. 21.04.2005, publ. 10.03.2007 (in Russ.).

[8] Lukovtsev V.P., Rotenberg Z.A., Dribinskii A.V., et al. Estimating depth of discharge of lithium-thionyl chloride batteries from their impedance characteristics. Russ. J. Electrochem., 2005, vol. 41, no. 10, pp. 1097--1100. DOI: https://doi.org/10.1007/s11175-005-0187-8

[9] Kanevskiy L.S., Bagotskiy V.S., Nizhnikovskiy E.A. The possibility of using impedance meter to diagnose elements state of lithium-thionyl chloride system. Elektrokhimiya, 1995, vol. 31, no. 4, pp. 376--382 (in Russ.).

[10] Rahmoun A., Loske M., Rosin A. Determination of the impedance of lithium-ion batteries using methods of digital signal processing. Energy Procedia, 2014, vol. 46, pp. 204--213. DOI: https://doi.org/10.1016/j.egypro.2014.01.174

[11] Tyagay V.A. Noise of electrochemical systems. Elektrokhimiya, 1974, vol. 10, no. 1, pp. 3--24 (in Russ.).

[12] Boinet M., Marlot D., Lenain J.C., et al. First results from coupled acousto-ultrasonics and electrochemical noise techniques applied to gas evolving electrodes. Electrochem. Commun., 2007, vol. 9, iss. 9, pp. 2174--2178. DOI: https://doi.org/10.1016/j.elecom.2007.05.026

[13] Gabrielli C., Huet F., Nogueira R.P. Fluctuations of concentration overpotential generated at gas-evolving electrodes. Electrochimica Acta, 2005, vol. 50, iss. 18, pp. 3726--3736. DOI: https://doi.org/10.1016/j.electacta.2005.01.019

[14] Meszaros G., Szenes I., Lengyel B., Measurement of charge transfer noise. Electrochem. Commun., 2004, vol. 6, iss. 11, pp. 1185--1191. DOI: https://doi.org/10.1016/j.elecom.2004.09.017

[15] Tan Y., Xie Q., Huang J., et al. Study on glucose biofuel cells using an electrochemical noise device. Electroanalysis, 2008, vol. 20, iss. 14, pp. 1599--1606. DOI: https://doi.org/10.1002/elan.200804220

[16] Astafev E.A. Electrochemical noise measurement of a Li/SOCl₂ primary battery. J. Solid State Electrochem., 2018, vol. 22, pp. 3569--3577. DOI: https://doi.org/10.1007/s10008-018-4067-z

[17] Astafev E.A. Wide frequency band electrochemical noise measurement and analysis of a Li/SOCl₂ primary battery. J. Solid State Electrochem., 2019, vol. 2, pp. 389--396. DOI: https://doi.org/10.1007/s10008-018-4151-4

[18] Astafev E.A. State-of-charge determination of Li/SOCl₂ primary battery by means of electrochemical noise measurement. J. Solid State Electrochem., 2019, vol. 23, pp. 1493--1504. DOI: https://doi.org/10.1007/s10008-019-04251-3

[19] Bobov K.N., Kubantsev I.S., Lukovtsev V.P., et al. Diagnostics chemical current sources state using noise spectroscopy. Aktual’nye problemy gumanitarnykh i estestvennykh nauk, 2016, no. 12-1, pp. 16--19 (in Russ.).

[20] Klyuev A.L., Grafov B.M., Davydov A.D., et al. Analysis of discrete spectra of electrochemical noise of lithium power sources. J. Solid State Electrochem., 2019, vol. 23, no. 2, pp. 497--502. DOI: https://doi.org/10.1007/s10008-018-4156-z