For citation:
Goffman V. G., Saratseva A. R., Bainyashev A. M., Maksimova L. A., Gorokhovskii A. V. Electrode materials with electrochemically active titanate coatings grown on the surface of titanium foil. Electrochemical Energetics, 2026, vol. 26, iss. 1, pp. 29-38. DOI: 10.18500/1608-4039-2026-26-1-29-38, EDN: OJMUCM
Electrode materials with electrochemically active titanate coatings grown on the surface of titanium foil
A method for forming electrode structured microsystems based on titanium foil was developed. These microsystems can be used in electrochemical energy storage devices. The method includes a three-stage chemical treatment of the titanium foil surface: etching in concentrated HCl to create a microrelief, processing in the aqueous solution of KOH to form a layer of potassium polytitanate and the subsequent modification in the solution of manganese sulfate with the following heat treatment at 750°C. Using the SEM and XRD methods, it was shown that the coating, obtained by the chemical and heat treatment, consists of submicron particles of hollandite-like solid solution of KxMnyTi8−yO16 that filled the pits on the surface of titanium which were formed by acid etching. Electrochemical studies (cyclic voltammetry) in a three-electrode cell (electrolyte – 5% aqueous KCl solution) showed that the synthesized hybrid electrode materials have a significantly higher specific capacity (up to 3.2 F/cm2 ) compared with the electrodes treated only with acid and alkali (0.22 F/cm2 ) and raw titanium (∼1 F/cm2 ). The high cyclic stability of the obtained electrodes was demonstrated.
- Cai K., Lai M., Yang W., Hu R., Xin R., Liu Q., Sung K. Surface engineering of titanium with potassium hydroxide and its effects on the growth behavior of mesenchymal stem cells. Acta Biomaterialia, 2010, vol. 6, no. 6, pp. 2314–2321. https://doi.org/10.1016/j.actbio.2009.11.034
- Tanaka S. I., Tobimatsu H., Maruyama Y., Tanaki T., Jerkiewicz G. Preparation and characterization of microporous layers on titanium. ACS Applied Materials & Interfaces, 2009, vol. 1, no. 10, pp. 2312– 2319. https://doi.org/10.1021/am900474h
- Wen H. B., Liu Q., De Wijn J. R., De Groot K., Cui F. Z. Preparation of bioactive microporous titanium surface by a new two-step chemical treatment. Journal of Materials Science: Materials in Medicine, 1998, vol. 9, no. 3, pp. 121–128. https://doi.org/10.1023/A:1008859417664
- Jonášová L., Müller F. A., Helebrant A., Strnad J., Greil P. Biomimetic apatite formation on chemically treated titanium. Biomaterials, 2004, vol. 25, no. 7–8, pp. 1187–1194. https://doi.org/10.1016/j.biomaterials.2003.08.009
- Li F., Feng Q. L., Cui F. Z., Li H. D., Schubert H. A simple biomimetic method for calcium phosphate coating. Surface and Coatings Technology, 2002, vol. 154, no. 1, pp. 88–93. https://doi.org/10.1016/S0257-8972(01)01710-8
- Mantsurov A. A., Gorokhovskii A. V., Burmistrov I. N., Tret’yachenko E. V. Structure and properties of biocompatible surface layers obtained by chemical treatment of titanium implants. Fundamental’nye issledovaniya [Fundamental Research], 2014, no. 11, pp. 311–315 (in Russian).
- Noami K., Muraoka Y., Wakita T., Hirai M., Kato Y., Muro T., Tamenori Y., Yokoya T. Room temperature ferromagnetic behavior in the hollanditetype titanium oxide. Journal of Applied Physics, 2010, vol. 107, no. 7, art. 073910. https://doi.org/10.1063/1.3369500
- Besprozvannykh N. V., Sinel’shchikova O. Y., Morozov N. A., Kuchaeva S. K., Galankina O. L. Combustion synthesis and electrophysical properties of hollandites of the system K2O–MeO–TiO2 (Me = Mg, Ni, Cu). Ceramics International, 2022, vol. 48, no. 17, pp. 24283–24289. https://doi.org/10.1016/j.ceramint. 2022.04.048
- Tsyganov A., Artyukhov D., Vikulova M., Morozova N., Zotov I., Brudnik S., Asmolova A., Zheleznov D., Gorokhovsky A., Gorshkov N. Synthesis and Dielectric Relaxation Studies of KxFeyTi8−yO16 (x = 1.4–1.8 and y = 1.4–1.6) Ceramics with Hollandite Structure. Ceramics, 2023, vol. 6, no. 1, pp. 619–629. https://doi.org/10.3390/ceramics6010037
- Pearsall F., Farahmand N., Lombardi J., Dehipawala S., Gai Z., O’Brien S. Structure–property trends in a hollandite multiferroic by Fe doping: Structural, magnetic and dielectric characterization of nanocrystalline BaMn3−xFexTi4O14+δ. Journal of Materials Chemistry C, 2020, vol. 8, no. 23, pp. 7916–7927. https://doi.org/10.1039/D0TC00703J
- Jiang J., Li J., Long X., Zhao D., Su K., Xu D., Yang C., Qian D. Sol–gel synthesis of K1.33Mn8O16 nanorods and their applications for aqueous K-ion hybrid supercapacitors. Materials Research Bulletin, 2019, vol. 109, pp. 29–33. https://doi.org/10.1016/j.materresbull.2018.09.024
- Goffman V. G., Gorokhovskii A. V., Burte E. P., Sleptsov V. V., Gorshkov N. V., Kovyneva N. N., Vikulova M. A., Nikitina N. V. Modified titanium electrodes for energy storage devices. Electrochemical Energetics, 2017, vol. 17, no. 4, pp. 225–234 (in Russian). https://doi.org/10.18500/1608-4039-2017-17-4-225-234
- Tumurugoti P., Betal S., Sundaram S. K. Hollandites’ crystal chemistry, properties, and processing: A review. International Materials Reviews, 2021, vol. 66, no. 3, pp. 141–159. https://doi.org/10.1080/09506608.2020.1743592
- Tie D., Huang S., Wang J., Ma J., Zhang J., Zhao Y. Hybrid energy storage devices: Advanced electrode materials and matching principles. Energy Storage Materials, 2019, vol. 21, pp. 22–40. https://doi.org/10.1016/j.ensm.2018.12.018
- Dubal D. P., Ayyad O., Ruiz V., GomezRomero P. Hybrid energy storage: The merging of battery and supercapacitor chemistries. Chemical Society Reviews, 2015, vol. 44, no. 7, pp. 1777–1790. https://doi.org/10.1039/c4cs00266k