Abstract
The development of methods for producing silicon and materials based on it with controllable morphology and composition of microimpurities is a challenging problem, since such materials are widely used in modern microelectronics and power engineering. In this work, the influence of the substrate material and the parameters of silicon electrodeposition from a low-melting low-fluoride LiCl–KCl–CsCl melt with a K2SiF6 addition at a temperature of 545°C on the morphology of the deposit is studied. To determine the range of electrodeposition parameters, the regularities in the cathodic process in this melt are studied on glassy carbon, molybdenum, and nickel using cyclic voltammetry and square-wave voltammetry. This process is shown not to be electrochemically reversible on all the substrates and to proceed in two stages. Varying the electrodeposition parameters, three silicon deposits are formed for each of the substrates. On glassy carbon, a silicon film in the form of spherical dendrites uniformly distributed over the electrode surface and silicon fibers are deposited depending on the electrodeposition conditions. On molybdenum, silicon is deposited in the form of ordered dendrites, fibers, and a continuous coating consisting of spherical particles, as in the case of glassy carbon, depending on the electrolysis conditions. On nickel electrodes, nickel silicides and also silicon dendrites and fibers are deposited.
REFERENCES
J. Roger, L. Schorn, M. Heydarian, A. Farag, T. Feeney, D. Baumann, H. Hu, F. Laufer, W. Duan, K. Ding, A. Lambertz, P. Fassi, and M. Worgull, “Laminated monolithic perovskite/silicon tandem photovoltaics,” Adv. Energy Mater. 12, 2200961 (2022).
A. Kuchmizhak, V. Il’yaschenko, A. Sergeev, A. Gerasimenko, A. Gutakovskii, E. Mitsai, A. Amosov, and A. Shevlyagin, “Mg2Si is the new black: Introducing a black silicide with >95% average absorption at 200–1800 nm wavelengths,” Appl. Surf. Sci. 602, 154321(2022).
I. M. Anfimov, S. P. Kobeleva, M. D. Malinkovich, I. V. Shchemerov, O. V. Toporova, and Yu. N. Parkhomenko, “Mechanisms of electroconductivity in silicon–carbon nanocomposites with nanosized tungsten inclusions within a temperature range of 20–200°C,” Russ. Microelectronics 42, 488–491 (2013).
A. M. Leonova, O. A. Bashirov, N. M. Leonova, A. S. Lebedev, A. A. Trofimov, and A. V. Suzdaltsev, “Synthesis of C/SiC mixtures for composite anodes for lithium-ion power sources,” Appl. Sci. 13, 901 (2023).
A. Y. Galashev, “Computer development of silicone anodes for lithium-ion batteries: a review,” Electrochem. Mater. Technol. 1 (1), 20221005 (2022).
F. Wang, P. Li, W. Li, and D. Wang, “Electrochemical synthesis of multidimensional nanostructured silicon as a negative electrode material for lithium-ion battery,” ACS Nano 16, 7689–7700 (2022).
A. A. Trofimov, A. M. Leonova, N. M. Leonova, and T. A. Gevel, “Electroposition of silicon from molten KCl–K2SiF6 for lithium-ion batteries,” J. Electrochem. Soc. 169, 020537 (2022).
T. L. Kulova, “New electrode materials for lithium-ion batteries (review),” Russ. J. Electrochem. 49, 1–25 (2013).
T. Gevel, S. Zhuk, N. Leonova, A. Leonova, A. Trofimov, A. Suzdaltsev, and Yu. Zaikov, “Electrochemical synthesis of nano-sized silicon from KCl–K2SiF6 melts for powerful lithium-ion batteries,” Appl. Sci. 11, 10927 (2021).
A. V. Kosov, O. L. Semerikova, S. V. Vakarin, O. V. Drishenkova, A. A. Trofimov, A. M. Leonova, N. M. Leonova, and Yu. P. Zaikov, “Effect of electrochemical treatment of silicon surface in K2WO4–Na2WO4–WO3 melt on its photovoltaic response,” J. Electrochem. Soc. 168 (12), 126503 (2021).
X. Zou, L. Ji, J. Ge, D. R. Sadoway, E. T. Yu, and A. J. Bard, “Electrodeposition of crystalline silicon films from silicon dioxide for low-cost photovoltaic applications,” Nature Comm. 10, 5772 (2019).
A. V. Kaibichev and I. A. Kaibichev, “Features of technical silicon cleaning in melting in helium with impact on electric field melt on molybdenum and graphite electrode,” Rasplavy, No. 3, 258–264 (2019).
S. Medjahed, A. Kheloufi, E. Bobocioiu, A. Kefaifi, F. Kerkar, and Kh. Lebbou, “Quartz ore beneficiation by reverse flotation for silicon production,” Silicon 14, 87–97 (2022).
A. V. Suzdaltsev, “Silicon electrodeposition for microelectronics and distributed energy: a mini-review,” Electrochem. 3 (4), 760–768 (2022).
M. V. Laptev, A. V. Isakov, O. V. Grishenkova, A. S. Vorob’ev, A. O. Khudorozhkova, L. A. Akashev, and Y. P. Zaikov, “Electrodeposition of thin silicon films from the KF–KCl–KI–K2SiF6 melt,” J. Electrochem. Soc. 167, 042506 (2020).
H. **e, H. Zhao, J. Liao, and H. Yin, “Electrochemically controllable coating of a functional silicon film on carbon materials,” Electrochim. Acta 269, 610–616 (2018).
T. A. Gevel, S. I. Zhuk, N. M. Leonova, A. M. Leonova, A. V. Suzdaltsev, and Yu. P. Zaikov, “Electroposition of silicon from the KCl–CsCl–K2SiF6 melt,” Russ. Met. (Metally), No. 8, 958–964 (2022).
R. K. Abdurakhimova, M. V. Laptev, N. M. Leonova, A. M. Leonova, A. S. Shmygalev, and A. V. Suzdaltsev, “Electroreduction of silicon from the NaI–KI–K2SiF6 melt for lithium-ion power sources,” Chimica Techno Acta 9 (4), 20229424 (2022).
K. Yasida and T. Nohira, “Electrochemical production of silicon,” High Temp. Mater. & Proc. 41, 247–278 (2022).
S. I. Zhuk, A. V. Isakov, A. P. Apisarov, O. V. Grishenkova, V. A. Isaev, E. G. Vovkotrub, and Yu. P. Zaikov, “Electrodeposition of continuous silicon coatings from the KF–KCl–K2SiF6 melts,” J. Electrochem. Soc. 164, H5135–H5138 (2017).
T. Gevel, S. Zhuk, A. V. Suzdaltsev, and Yu. P. Zaikov, “Study into the possibility of silicon electrodeposition from a low-fluoride KCl–K2SiF6 melt,” Ionics 28, 3537–3545 (2022).
S. K. Padamata and G. Saevarsdottir, “Silicon electrowinning by molten salts electrolysis,” Frontiers in Chemistry 11, 1133990 (2023).
M. Cai, Zh. Zhao, X. Qu, J. Qu, Z. Hu, H. Shi, Sh. Gao, D. Wang, and H. Yin, “Refreshing the liquid–gas reaction interface to provoke the zincothermic reduction of SiCl4 to prepare lithium-storage nano silicon,” Energy Stor. Mater. 57, 568–576 (2023).
Zh. Zhao, M. Cai, H. Zhao, Q. Ma, H. **e, P. **ng, Y. X. Zhuang, and H. Yin, “Zincothermic-reduction-enabled harvesting of an Si/C composite from rice husks for a Li-ion battery anode,” ACS Sustainable Chem. Eng. 10 (15), 5035–5042 (2022).
Yu. Zaikov, V. Batukhtin, N. Shurov, and A. Suzdaltsev, “High-temperature electrochemistry of calcium,” Electrochem. Mater. Technol. 1 (1), 20221007 (2022).
Y. Ustinova, O. Pavlenko, T. Gevel, S. Zhuk, A. Suzdal’tsev, and Y. Zaikov, “Electrodeposition of silicon from the low-melting LiCl–KCl–CsCl–K2SiF6 electrolytes,” J. Electrochem. Soc. 169, 032506 (2022).
O. B. Pavlenko, Yu. A. Ustinova, S. I. Zhuk, A. V. Suzdaltsev, and Yu. P. Zaikov, “Silicon electrodeposition from the low-melting LiCl–KCl–CsCl melts,” Russ. Met. (Metally), No. 8, 818–824 (2022).
Yu. Parasotchenko, A. Suzdaltsev, O. Pavlenko and Yu. Zaikov, “Study of the silicon electrochemical nucleation in LiCl–KCl–SCsCl–K2SiF6 melt,” J. Electrochem. Soc. 170 (2), 022505 (2023).
A. Yu. Mikolaev, A. R. Mullabaev, A. V. Suzdaltsev, V. A. Kovrov, A. S. Kholkina, V. Yu. Shishkin, and Yu. P. Zaikov, “Purification of alkali-metal chlorides by zone recrystallization for the use in pyrochemical processing of spent nuclear fuel,” Atom. Energy 131 (4), 195–201 (2022).
ACKNOWLEDGMENTS
Scanning electron microscopy was carried out in the Shared Access Center Composition of Compounds, Institute of High-Temperature Electrochemistry, Ural Branch, Russian Academy of Sciences.
Funding
This work was performed in the framework of agreement no. 075-03-2022-011 of January 14, 2022 (project no. FEUZ-2020-0037 in EGISU NIOKTR).
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Translated by Yu. Ryzhkov
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Pavlenko, O.B., Parasotchenko, Y.A., Suzdal’tsev, A.V. et al. Effect of the Substrate Material and the Parameters of Silicon Electrodeposition from the LiCl–KCl–CsCl–K2SiF6 Melt on the Morphology of the Deposit. Russ. Metall. 2023, 235–243 (2023). https://doi.org/10.1134/S0036029523020155
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DOI: https://doi.org/10.1134/S0036029523020155