Model describing of the process of electrodeposition of loose zinc deposits in pulsed potential modes

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Abstract

The structural characteristics of loose zinc deposits obtained in pulsed potential modes were calculated using a phenomenological model. Increasing the duty cycle leads to increased anodic dissolution during pauses and obtaining denser deposits, due to the formation of dendrites with fewer vertices, but with a larger diameter compared to deposits obtained in the potentiostatic mode. The linear dependence of the diameter of the tips of dendrites forming a loose zinc deposit on the duty cycle was found. It is shown that there is a critical time corresponding to the achievement of zero deposit growth rate when the metal deposited during the pulse will completely dissolve during the pause.

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About the authors

V. S. Nikitin

Ural Federal University named after the first President of Russia B.N. Yeltsin

Author for correspondence.
Email: nikitin-viachieslav@mail.ru

Institute of Chemical Engineering

Russian Federation, Yekaterinburg

T. N. Ostanina

Ural Federal University named after the first President of Russia B.N. Yeltsin

Email: ostni@mail.ru

Institute of Chemical Engineering

Russian Federation, Yekaterinburg

V. M. Rudoy

Ural Federal University named after the first President of Russia B.N. Yeltsin

Email: nikitin-viachieslav@mail.ru

Institute of Chemical Engineering

Russian Federation, Yekaterinburg

References

  1. Sharifi, B., Mojtahedi, M., Goodarzi, М., and Vahdati, K.J., Effect of alkaline electrolysis conditions on current efficiency and morphology of zinc powder, Hydrometallurgy, 2009, vol. 99, p. 72.
  2. Коровин, Н.В., Скундин, А.М. Химические источники тока: Справочник, М.: Изд-во МЭИ, 2003. 740 с. [Korovin, N.V. and Skundin, A.M., Chemical sources of current: Handbook (in Russian), Moscow: Publ. House of MEI, 2003. 740 p.]
  3. Кромптон, Т.Р. Первичные источники тока (пер. с англ.), М.: Мир, 1986. 328 с. [Crompton, T.R., Small Batteries: Primary Cells, London, Basingstoke: The Macmillan Press Ltd., 1982. 241 p.]
  4. Толстошеева, С.И., Степин, С.Н., Давыдова, М.С., Вахин, А.В. Влияние наноразмерного цинкового порошка на защитные свойства протекторных покрытий. Вестник КТУ. 2012. Т. 15. С. 98. [Tolstosheeva, S.I., Stepin, S.N., Davydova, M.S., and Vakhin, A.V., The effect of nanoscale zinc powder on the protective properties of tread coatings, Vestnik Kazanskovo Tekhnologicheskovo Universiteta (in Russian), 2012, vol. 15, p. 98.]
  5. Таныгина, Е.Д., Пономарева, М.В., Прусаков, А.В., Урядников, А.А. Модифицированные порошком цинка и графита антикоррозионные составы на основе продуктов рафинирования низкоэрукового рапсового масла. Вестник ТГУ. 2009. Т. 14. С. 100. [Tanygina, E.D., Ponomareva, M.V., Prusakov, A.V., and Uryadnikov, A.A., Anticorrosive compositions modified with zinc and graphite powder based on refining products of low-grade rapeseed oil, Vestnik Tomskovo Gosudarstvennovo Universiteta (in Russian), 2009, vol. 14, p. 100.]
  6. Алкацев, М.И. Процессы цементации в цветной металлургии. М.: Металлургия, 1981. 116 с. [Alkatsev, M.I., Cementation processes in non-ferrous metallurgy (in Russian), Moscow: Metallurgy, 1981. 116 p.]
  7. Steinfeld, A., Solar thermochemical production of hydrogen – a review, Sol. Energy, 2005, vol. 78, p. 603.
  8. Villasmil, W., Meier, A., and Steinfeld, A., Dynamic modeling of a solar reactor for zinc oxide thermal dissociation and experimental validation using IR thermography, J. Sol. Energy Eng., 2014, vol. 6, p. 010901.
  9. Weidenkaff, A., Steinfeld, A., Wokaun, A., Auer, P., Eichler, B., and Reller, A., Direct solar thermal dissociation of zinc oxide: condensation and crystallisation of zinc in the presence of oxygen, Sol. Energy, 1999, vol. 65, p. 59.
  10. Vishnevetsky, I. and Epstein, M., Production of hydrogen from solar zinc in steam atmosphere, Intern. J. Hydrogen Energy, 2007, vol. 32, p. 2791.
  11. Bhosale, R.R., Solar hydrogen production via ZnO/Zn based thermochemical water splitting cycle: Effect of partial reduction of ZnO, Intern. J. Hydrogen Energy, 2020, vol. 46, p. 4739.
  12. Tamaura, Y., Kojima, M., Sano, T., Ueda, Y., Hasegawa, N., and Tsuji, M., Thermodynamic evaluation of water splitting by a cation-excessive (Ni, Mn) ferrite, Intern. J. Hydrogen Energy, 1998, vol. 23, p. 1185.
  13. Ullah, S., Badshah, A., Ahmed, F., Raza, R., Altaf, A.A., and Hussain, R., Electrodeposited zinc electrodes for high current Zn/AgO Bipolar Batteries, Intern. J. Electrochem. Sci., 11, p. 3801.
  14. Neikov, O.D., Nabojchenko, S.S., Murashova, I.B., Gopienko, V.G., Frishberg, I.V., and Lotsko D.V., Handbook of Non-ferrous Metal Powders: Technologies and applications, London, N-Y, Amsterdam: Elsevier, 2009. 634 p.
  15. Помосов, А.В., Мурашова, И.Б. Исследование влияния режимов электролиза на дисперсность и насыпной вес никелевого порошка. Порошковая металлургия. 1966. № 6. С. 1. [Pomosov, A.V. and Murashova, I.B., Investigation of the effect of electrolysis modes on the dispersion and bulk weight of nickel powder, Poroshkovaya Metallurgiya (in Russian), 1966, no. 6, p. 1.]
  16. Diggle, J.W., Despić, A.R., and Bockris, J.O’M., The mechanism of the dendritic electrocrystallization of zinc, J. Electrochem. Soc., 1969, vol. 116, p. 1503.
  17. Popov, K.I., Djikić, L.М., Pavlović, M.J., and Maksimović, M.D., The critical overpotential for copper dendrite formation, J. Appl. Electrochem., 1979, vol. 9, p. 527.
  18. Nikolić, N.D., Branković, G., Maksimović, V.M., Pavlović, M.G., and Popov, K.I., Influence of potential pulse conditions on the formation of honeycomb-like copper electrodes, J. Electroanal. Chem., 2009, vol. 635, p. 111.
  19. Popov, K.I., Nikolić, N.D., Živković, P.M., Branković, G., and Popov, K.I., The effect of the electrode surface roughness at low level of coarseness on the polarization characteristics of electrochemical processes, Electrochim. Acta, 2010, vol. 55, p. 1919.
  20. Nikolić, N.D., Branković, G., and Popov, K.I., Optimization of electrolytic process of formation of open and porous copper electrodes by the pulsating current (PC) regime, Mater. Chem. and Phys., 11, vol. 5, p. 587.
  21. Nikolić, N.D., Branković, G., and Pavlović, M.G., Correlate between morphology of powder particles obtained by the different regimes of electrolysis and the quantity of evolved hydrogen, Powder Technol., 2012, vol. 221, p. 271.
  22. Nikolić, N.D. and Branković, G., Effect of parameters of square-wave pulsating current on copper electrodeposition in the hydrogen co-deposition range, Electrochem. Commun., 2010, vol. 12, p. 740.
  23. Nikolić, N.D., Branković, G., Maksimović, V.M., Pavlović, M.G., and Popov, K.I., Influence of potential pulse conditions on the formation of honeycomb-like copper electrodes, J. Electroanal. Chem., 2009, vol. 635, p. 111.
  24. Karimi Tabar Shafiei, F., Jafarzadeh, K., Madram, A.R., and Nikolić, N.D., A novel route for electrolytic production of very branchy copper dendrites under extreme conditions, J. Electrochem. Soc., 2021, vol. 8, p. 043502.
  25. Ostanina, T.N., Rudoy, V.M., Nikitin, V.S., Darintseva, A.B., and Demakov S.L., Change in the physical characteristics of the dendritic zinc deposits in the stationary and pulsating electrolysis, J. Electroanal. Chem., 2017, vol. 784, p. 13.
  26. Никитин, В.С., Останина, Т.Н., Рудой, В.М. Влияние параметров режима импульсного потенциала на концентрационные изменения в объеме рыхлого осадка цинка и его свойства. Электрохимия. 2018. Т. 54. С. 767. [Nikitin, V.S., Ostanina, T.N., and Rudoi, V.M., Effect of parameters of pulsed potential mode on concentration changes in the bulk loose zinc deposit and its properties, Russ. J. Electrochem., 2018, vol. 54, p. 665.]
  27. Despić, A.R., Diggle, J., and Bockris, J.O., Mechanism of formation of zinc dendrites, J. Electrochem. Soc., 1968, vol. 115, p. 507.
  28. Popov, K.J., Pavlović, M.G., Spasogević, M.D., and Nakić, V.M., The critical overpotential for zinc dendrite formation, J. Appl. Electrochem., 1979, vol. 9, p. 533.
  29. Мурашова, И.Б., Помосов, А.В., Эделева, Н.А. Динамическая модель развития дисперсного осадка в гальваностатических условиях: влияние кислотности электролита на кинетику роста дендритов. Электрохимия. 1979. Т. 15. С. 182. [Murashova, I.B., Pomosov, A.V., and Edeleva, N.A., Dynamic model of dispersed deposit development under galvanostatic conditions: The effect of electrolyte acidity on the kinetics of dendrite growth, Russ. J. Electrochem., 1979, vol. 15, p. 182.]
  30. Мурашова, И.Б., Помосов, А.В., Воробьев, В.И., Музгина, Е.В. Динамическая модель роста дендритного осадка в гальваностатических условиях: влияние материала катода на скорость роста дендритов. Электрохимия. 1981. Т. 27. С. 548. [Murashova, I.B., Pomosov, A.V., Vorobyov, V.I., and Muzgina, E.V., Dynamic model of dendritic deposit growth under galvanostatic conditions: Influence of cathode material on dendrite growth rate, Russ. J. Electrochem., 1981, vol. 27, p. 548.]
  31. Мурашова, И.Б., Помосов, А.В., Тишкина, Т.Н. Динамическая модель развития дисперсного осадка в гальваностатических условиях: влияние природы разряжающегося металла на динамику роста дендритов. Электрохимия. 1982. Т. 18. С. 449. [Murashova, I.B., Pomosov, A.V., and Tishkina, T.N., Dynamic model of dispersed deposit development under galvanostatic conditions: Influence of the nature of the discharged metal on the dynamics of dendrite growth, Russ. J. Electrochem., 1982, vol. 18, p. 449.]
  32. Мурашова, И.Б., Бурханова, Н.Г. Расчет структурных изменений дендритного осадка в процессе гальваностатического электролиза. Электрохимия. 2001. Т. 37. С. 871. [Murashova, I.B. and Burhanova, N.G., Calculation of structural changes of dendritic deposit during galvanostatic electrolysis, Russ. J. Electrochem., 2001, vol. 37, p. 871.]
  33. Ostanina, T.N., Rudoi, V.M., Patrushev, A.V., Darintseva, A.B., and Farlenkov, A.S., Modelling the dynamic growth of copper and zinc dendritic deposits under the galvanostatic electrolysis conditions, J. Electroanal. Chem., 2015, vol. 750, p. 9.
  34. Никитин, В.С., Останина, Т.Н., Рудой, В.М., Останин, Н.И. Модельное описание процесса электроосаждения рыхлых осадков цинка в импульсных режимах задания тока. Электрохимия. 2023. Т. 59. С. 391.
  35. Гамбург, Ю.Д., Зангари, Дж. Теория и практика электроосаждения металлов (пер. с англ.), М.: Бином. Лаборатория знаний, 2015. 439 с. [Gamburg, Y.D. and Zangari, G., Theory and practice of metal electrodeposition, N.Y.: Springer Science & Business Media, 2011. 378 p.]
  36. Плит, В. Электрохимия в материаловедении (пер. с англ.), М.: Бином. Лаборатория знаний, 2015. 446 с. [Plieth, W., Electrochemistry for Materials Science, Amsterdam, Netherlands: Elsevier Science, 2008. 432 p.]
  37. де Векки, Д.А., Москвин, А.В., Петров, М.Л., Резников, А.Н., Скворцов, Н.К., Тришин, Ю.Г. Новый справочник химика и технолога. Основные свойства неорганических, органических и элементоорганических соединений, С.-Пб.: Мир и Семья, 2002. С. 348. [de Vecchi, D.A., Moskvin, A.V., Petrov, M.L., Reznikov, A.N., Skvortsov, N.K., and Trishin, Yu.G., New handbook of chemist and technologist. Basic properties of inorganic, organic and elementoorganic compounds (in Russian), Saint-Petersburg: “Mir i Sem’ya”, 2002. p. 348.]
  38. Никитин, В.С., Останина, Т.Н., Кумков, С.И., Рудой, В.М., Останин, Н.И. Определение периода наращивания рыхлого осадка цинка с использованием методов интервального анализа. Известия вузов. Порошковая металлургия и функциональные покрытия. 2020. № 1. С. 11. [Nikitin, V.S., Ostanina, T.N., Kumkov, S.I., Rudoy, V.M., and Ostanin, N.I., Determination of the growth time period of loose zinc deposit using interval analysis methods, Russ. J. Non-Ferrous Met., 2020, vol. 61, p. 540.]

Supplementary files

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2. Fig. 1. Diagram (a) and photo (b) of a cylindrical electrode of height H with a layer of loose sediment of thickness y(t); d0 is the initial diameter of the electrode; D(t) is the diameter of the electrode with sediment at time t.

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3. Fig. 2. Change in current strength over time during zinc deposition in potentiostatic mode (E = –0.38 V).

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4. Fig. 3. Current change during zinc deposition in the pulsed potential setting mode (C = 2.5, τimp/τp = 20 s / 30 s). The inset shows an enlarged image of the 47th and 48th electrolysis cycles.

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5. Fig. 4. Change in the thickness of loose zinc deposits during electrolysis. The numbers on the graphs indicate the duty cycle values. Markers are experimental data; line is approximation according to equation (12).

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6. Fig. 5. Change in the differential yield of zinc by current during electrolysis. The numbers on the graph indicate the duty cycle values. Markers are experimental data; line is approximation according to equation (13).

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7. Fig. 6. Total amount of electricity in potentiostatic mode (C = 1). The inset shows an enlarged image of the first minutes of electrolysis. The dotted line is the curve obtained by numerical integration of the I(t) dependence (equation (16)); the solid line is the approximation using polynomial (20).

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8. Fig. 7. Effective amount of electricity in pulsed modes of potential setting. The numbers on the graph indicate the duty cycle values. The dotted line is the curve obtained by numerical integration of the I(t) dependence (equation (17)); the solid line is the approximation using the polynomial (20).

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9. Fig. 8. Change in the number and density of the dendritic vertices at the sediment growth front in the stationary (a) and pulsed modes of setting the potential (b). The numbers on the graphs indicate the duty cycle values. Solid lines are Nsp curves; dotted lines are N curves.

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10. Fig. 9. Change in the average distance between the vertices of zinc dendrites over time in different potential setting modes. The numbers on the graph indicate the duty cycle values.

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11. Fig. 10. Dependence of the diameter of the dendritic tips on the duty cycle.

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12. Fig. 11. Change in density of loose zinc sediment by its thickness. The numbers on the graph indicate the porosity values. Markers are experimental values ​​obtained according to equation (26) using the experimental values ​​of y, CedZn and QZn; lines are approximations according to equation (30).

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13. Fig. 12. Change in the ratio between the cathode and anode amounts of electricity during electrolysis. The numbers on the graphs indicate the duty cycle values.

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14. Fig. 13. Micrographs of loose zinc deposits obtained in potentiostatic (a) and pulsed mode (30 s/30 s, C = 2) (b). Deposition time 10 min.

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