Effect of oxygen on the morphology of silicon deposits

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In this work, a series of experiments were performed to study the effect of oxygen on the morphology of silicon obtained by electrodeposition from KCl‒K2SiF6 melt. SiO2 was chosen as the oxygen carrier. The concentration of the additive was determined from the results of the study of the effect of SiO2 additive on the concentration of free F‒ ions. According to the obtained dependence, assumptions about the nature of interaction between the components of the melt were made. The inflection points registered on the dependence ω(KF)‒ω(SiO2) indicate a change in the character of interaction of SiO2 with the investigated melt. Based on the results of the study of the kinetics of the cathodic process on glassy carbon, taking into account the theory of autocomplex structure, an assumption was made about the structure of discharging complex ions in KCl‒K2SiF6 and KCl‒K2SiF6‒SiO2 melts. The kinetics was investigated by cyclic voltammetry. When SiO2 was added, a broadening of the silicon discharge potential region was observed, as well as a disproportionate increase in the cathodic current with increasing SiO2 concentration in the melt. One of the possible explanations for the obtained results is the change in the structure of the discharging complex ions. The obtained data on the kinetics of the cathodic process, as well as assumptions about the structure of the discharging complex, became the basis for the choice of parameters of potentiostatic electrolysis. A series of experiments on electrodeposition of silicon from the studied melts at varying the value of cathodic overvoltage from 0.10 to 0.25 V were carried out during the research. The morphology of cathodic precipitates was investigated by electron‒scanning microscopy. It is assumed that changes in the morphology of the obtained cathodic precipitates are associated with changes in the structure of the discharging complexes.

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作者简介

T. Gevel

Ural Federal University

编辑信件的主要联系方式.
Email: Timofey.gevel@urfu.ru
ORCID iD: 0000-0001-9719-6596
俄罗斯联邦, Ekaterinburg

А. Suzdaltsev

Ural Federal University

Email: Timofey.gevel@urfu.ru
ORCID iD: 0000-0003-3004-7611
俄罗斯联邦, Ekaterinburg

参考

  1. Feng K., Li M., Liu W., Kashkooli A.G., Xiao X., Cai M., Chen Z. Silicon‒based anodes for lithium‒ion batteries: From fundamentals to practical applications // Small. 2018. 14. 1702737.
  2. Hasan A., Sarwar J., Shan A.H. Concentrated photovoltaic: A review of thermal aspects, challenges and opportunities // Renewable and Sustainable Energy Reviews. 2018. 94. 835‒852.
  3. Xiao W., Jin X., Deng Y., Wang D., Chen G.Z., Rationalisation and optimisation of solid‒state electro‒reduction of SiO₂ to Si in molten CaCl₂ in accordance with dynamic three‒phase interlines based voltammetry // J. Electroanal. Chem. 2010. 639, 130‒140.
  4. Nohira T, Yasuda K, Ito Y. Pinpoint and bulk electrochemical reduction of insulating silicon dioxide to silicon // Nature Mater. 2003. 2(6). 397‒401.
  5. Yasuda K., Nohira T., Amezawa K., Ogata Y., Ito Y. Mechanism of direct electrolytic reduction of solid SiO₂ to Si in molten CaCl₂ // J. Electrochem. Soc. 2005. 152. 69‒71.
  6. Yasuda K., Nohira T., Ogata Y., Ito Y. Direct electrolytic reduction of solid silicon Dioxide in molten LiCl‒KCl‒CaCl₂ at 773 K // J. Electrochem. Soc. 2005. 152. 208‒212.
  7. Padamata S.K., Haarberg G.M., Saevarsdottir G. Electrochemical behaviour of silicon ions in NaCl‒KCl mixture with low KF concentration // Silicon. 2025. 17. 111‒120.
  8. Zhuk S., Isakov A., Apisarov A., Grishenkova O., Isaev V., Vovkotrub E., Zaykov Yu. Electrodeposition of continuous silicon coatings from the KF‒KCl‒K₂SiF₆ melts // J. Electrochem. Soc. 2017. 164. H5135‒H5138.
  9. Zaikov Yu., Redkin A., Apisarov A., Korzun I., Kulik N., Isakov A., Kataev A., Chemezov O. Silica solubility in molten fluoride–chloride electrolytes and density of KF‒KCl‒K₂SiF₆‒SiO₂ melts // J. Chem. Eng. Data. 2013. 58. 932‒937.
  10. Trofimov A.A., Leonova A.M., Leonova N.M., Gevel T.A. Electrodeposition of silicon from molten KCl‒K₂SiF₆ for lithium‒ion batteries / J. Electrochem. Soc. 2022. 169. 020537.
  11. Suzuki Yu., Inoue Y., Yokota M., Goto T. Effects of Oxide Ions on the Electrodeposition Process of Silicon in Molten Fluorides // J. Electrochem. Soc. 2019. 166. D564‒D568.
  12. Norikawa Yu., Kondo A., Yasuda K., Nohira T. Electrodeposition of crystalline Si in molten alkali metal fluoride–chloride mixtures: Comparative study of Li, Na, K, and Cs systems // Electrochimica Acta. 2022. 434. 141255.
  13. Nikolaev A.Yu., Mullabaev A.R., Suzdaltsev A.V., Kovrov V.A., Kholkina A.S., Shishkin V.Yu., Zaikov Yu.P. Purification of alkali‒metal chlorides by zone recrystallization for the use in pyrochemical processing of spent nuclear fuel // Atomic Energy. 2022. 131. 195‒201.
  14. Ustinova Yu., Pavlenko О., Gevel T., Zhuk S., Suzdaltsev A., Zaikov Yu. Electrodeposition of silicon from the low‒melting LiCl‒KCl‒CsCl‒K₂SiF₆ electrolytes // J. Electrochem. Soc. 2022. 169. 032506.
  15. Parasotchenko Yu., Gevel T.A., Suzdaltsev A.V., Zaikov Yu.P. On the stability of the concentration of silicon ions in LiCl‒KCl‒CsCl‒K₂SiF₆ melts during electrolysis // Silicon, 2024. 16. 5625‒5636.
  16. Rajkovic M., Novakovic I. Determination of fluoride content in drinking water and tea infusions using fluoride ion selective electrode // J. Agricultural Sciences. 2007. 52. 155‒168.
  17. Gevel T.A., Zhuk S.I., Ustinova Yu.A., Suzdaltsev A.V., Zaikov Yu.P. //Elektrovydeleniye kremniya iz rasplava KCl–K₂SiF₆ [Silicon electroreduction from the KCl‒K₂SiF₆ melt] // Rasplavy (Melts). 2021. №2. 187‒198. [In Russian].
  18. Minchenko V.I. Stepanov V.P. Ionnyye rasplavy: uprugiye i kalorimetricheskiye svoystva. [Ionic melts: elastic and calorimetric properties]. Ekaterinburg: Ural Branch of the Russian Academy of Sciences. 2008. [In Russian].

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2. Fig. 1. Schematic diagram of the experimental setup: 1 – working electrode, 2 – gas inlet fitting, 3 – quartz retort, 4, 5 – counter electrode and quasi-reference electrode, 6 – glassy carbon beaker.

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3. Fig. 2. Photographs of the cathode deposit obtained during the electrolysis of the KCl‒K₂SiF₆ melt at a temperature of 790 ℃ and a cathode overvoltage of 0.25, 0.15 and 0.10 V.

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4. Fig. 3. Dependence of the content of free ion F– on the amount of SiO₂ additive.

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5. Fig. 4. Photographs of the cathode deposit obtained during the electrolysis of the KCl‒K₂SiF₆ melt with the addition of 0.34 wt.% SiO₂ at a temperature of 790℃ and a cathode overvoltage of 0.25, 0.15 and 0.10 V.

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6. Fig. 5. Micrograph of the cathode deposit obtained during electrolysis of the melt (wt.%) 95KCl–5K₂SiF₆ at a temperature of 790℃ and a cathode overvoltage of 0.25, 0.15 and 0.10 V.

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7. Fig. 6. Micrograph of the cathode deposit obtained during the electrolysis of the KCl‒K₂SiF₆ melt with the addition of 0.34 wt.% SiO₂ at a temperature of 790℃ and a cathode overvoltage of 0.25, 0.15 and 0.10 V.

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8. Fig. 7. Cyclic voltammograms for the KCl‒K₂SiF₆ system with and without SiO₂ additive, at a scan rate of 0.4 V/s.

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