Anionic carbonate activation of layered (α+β) nickel hydroxide

Authors

  • Vadym Kovalenko Ukrainian State University of Chemical Technology Gagarina ave., 8, Dnipro, Ukraine, 49005 Vyatka State University Moskovskaya str., 36, Kirov, Russian Federation, 610000, Ukraine https://orcid.org/0000-0002-8012-6732
  • Valerii Kotok Ukrainian State University of Chemical Technology Gagarina ave., 8, Dnipro, Ukraine, 49005 Vyatka State University Moskovskaya str., 36, Kirov, Russian Federation, 610000, Ukraine https://orcid.org/0000-0001-8879-7189

DOI:

https://doi.org/10.15587/1729-4061.2019.169461

Keywords:

carbonate, activation, nickel hydroxide, layered (α β) structure, alkaline accumulator, slit-diaphragm electrolyzer.

Abstract

Nickel hydroxide is widely used as the active material in supercapacitors. Samples of Ni(OH)2 with the (α+β) layered structure, synthesized in the slit-diaphragm electrolyzer, are the most active. The possibility of carbonate activation of layered (α+β) Ni(OH)2 was studied by the synthesis of samples in the slit-diaphragm electrolyzer using a mixture of sodium hydroxide and sodium carbonate as the electrolyte. The molar part of sodium carbonate in the NaOH+Na2CO3 mixture was controlled by acid titration in the presence of two indicators. The synthesis of nickel hydroxide samples was conducted at the molar part of carbonate from 0.16 (NaOH without the additional introduction of carbonate) to 0.83. The crystal structure of the samples was studied by means of X-ray diffraction analysis, electrochemical characteristic – by means of cyclic voltammetry and galvanostatic charge-discharge cycling in the accumulator regime. By means of XRD analysis, it was found that upon increasing the molar part of carbonate in the anolyte to 0.49, the crystallinity of the monophase layered (α+β) structure increases. It was found that a further increase of the carbonate part results in a more amorphous structure due to a partial breakdown of the hydroxide lattice with the formation of basic salts and formation of the bi-phase system. This conclusion is supported by cyclic voltammetry and discharge curves. The study of the electrochemical characteristics revealed, that for the molar part of carbonate below 0.39, carbonate activation of hydroxide occurs resulting in an improved specific capacity. Increasing the carbonate part to 0.49 results in a lower specific capacity, and even further increase results in the breakdown of hydroxide into basic salts and a significant drop in electrochemical activity. Thus, it was found, that to achieve the maximum activating effect, the optimal molar part of sodium carbonate (in a mixture with sodium hydroxide) should be about 40 %. The specific capacity of nickel hydroxide under this optimal condition is 234 mA·h/g, and this sample is found to be susceptible to activation with cobalt compounds, which further improved capacity to 254 mA·h/g.

Author Biographies

Vadym Kovalenko, Ukrainian State University of Chemical Technology Gagarina ave., 8, Dnipro, Ukraine, 49005 Vyatka State University Moskovskaya str., 36, Kirov, Russian Federation, 610000

PhD, Associate Professor

Department of Analytical Chemistry and Food Additives and Cosmetics

Senior Researcher

Competence center "Ecological technologies and systems"

Valerii Kotok, Ukrainian State University of Chemical Technology Gagarina ave., 8, Dnipro, Ukraine, 49005 Vyatka State University Moskovskaya str., 36, Kirov, Russian Federation, 610000

PhD, Associate Professor

Department of Processes, Apparatus and General Chemical Technology

Senior Researcher

Competence center "Ecological technologies and systems"

References

  1. Hall, D. S., Lockwood, D. J., Bock, C., MacDougall, B. R. (2014). Nickel hydroxides and related materials: a review of their structures, synthesis and properties. Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences, 471 (2174), 20140792–20140792. doi: https://doi.org/10.1098/rspa.2014.0792
  2. Vidotti, M., Torresi, R., Torresi, S. I. C. de. (2010). Nickel hydroxide modified electrodes: a review study concerning its structural and electrochemical properties aiming the application in electrocatalysis, electrochromism and secondary batteries. Química Nova, 33 (10), 2176–2186. doi: https://doi.org/10.1590/s0100-40422010001000030
  3. Chen, J. (1999). Nickel Hydroxide as an Active Material for the Positive Electrode in Rechargeable Alkaline Batteries. Journal of The Electrochemical Society, 146 (10), 3606. doi: https://doi.org/10.1149/1.1392522
  4. Sun, Y.-K., Lee, D.-J., Lee, Y. J., Chen, Z., Myung, S.-T. (2013). Cobalt-Free Nickel Rich Layered Oxide Cathodes for Lithium-Ion Batteries. ACS Applied Materials & Interfaces, 5 (21), 11434–11440. doi: https://doi.org/10.1021/am403684z
  5. Lang, J.-W., Kong, L.-B., Liu, M., Luo, Y.-C., Kang, L. (2010). Asymmetric supercapacitors based on stabilized α-Ni(OH)2 and activated carbon. Journal of Solid State Electrochemistry, 14 (8), 1533–1539. doi: https://doi.org/10.1007/s10008-009-0984-1
  6. Lang, J.-W., Kong, L.-B., Wu, W.-J., Liu, M., Luo, Y.-C., Kang, L. (2009). A facile approach to the preparation of loose-packed Ni(OH)2 nanoflake materials for electrochemical capacitors. Journal of Solid State Electrochemistry, 13 (2), 333–340. doi: https://doi.org/10.1007/s10008-008-0560-0
  7. Aghazadeh, M., Ghaemi, M., Sabour, B., Dalvand, S. (2014). Electrochemical preparation of α-Ni(OH)2 ultrafine nanoparticles for high-performance supercapacitors. Journal of Solid State Electrochemistry, 18 (6), 1569–1584. doi: https://doi.org/10.1007/s10008-014-2381-7
  8. Zheng, C., Liu, X., Chen, Z., Wu, Z., Fang, D. (2014). Excellent supercapacitive performance of a reduced graphene oxide/Ni(OH)2 composite synthesized by a facile hydrothermal route. Journal of Central South University, 21 (7), 2569–2603. doi: https://doi.org/10.1007/s11771-014-2218-7
  9. Wang, B., Williams, G. R., Chang, Z., Jiang, M., Liu, J., Lei, X., Sun, X. (2014). Hierarchical NiAl Layered Double Hydroxide/Multiwalled Carbon Nanotube/Nickel Foam Electrodes with Excellent Pseudocapacitive Properties. ACS Applied Materials & Interfaces, 6 (18), 16304–16311. doi: https://doi.org/10.1021/am504530e
  10. Kotok, V., Kovalenko, V. (2017). The properties investigation of the faradaic supercapacitor electrode formed on foamed nickel substrate with polyvinyl alcohol using. Eastern-European Journal of Enterprise Technologies, 4 (12 (88)), 31–37. doi: https://doi.org/10.15587/1729-4061.2017.108839
  11. Kotok, V. A., Kovalenko, V. L., Solovov, V. A., Kovalenko, P. V., Ananchenko, B. A. (2018). Effect of deposition time on properties of electrochromic nickel hydroxide films prepared by cathodic template synthesis. ARPN Journal of Engineering and Applied Sciences, 13 (9), 3076–3086.
  12. Kotok, V., Kovalenko, V. (2018). A study of the effect of tungstate ions on the electrochromic properties of Ni(OH)2 films. Eastern-European Journal of Enterprise Technologies, 5 (12 (95)), 18–24. doi: https://doi.org/10.15587/1729-4061.2018.145223
  13. Wang, Y., Zhang, D., Peng, W., Liu, L., Li, M. (2011). Electrocatalytic oxidation of methanol at Ni–Al layered double hydroxide film modified electrode in alkaline medium. Electrochimica Acta, 56 (16), 5754–5758. doi: https://doi.org/10.1016/j.electacta.2011.04.049
  14. Huang, W., Li, Z. L., Peng, Y. D., Chen, S., Zheng, J. F., Niu, Z. J. (2005). Oscillatory electrocatalytic oxidation of methanol on an Ni(OH)2 film electrode. Journal of Solid State Electrochemistry, 9 (5), 284–289. doi: https://doi.org/10.1007/s10008-004-0599-5
  15. Fan, Y., Yang, Z., Cao, X., Liu, P., Chen, S., Cao, Z. (2014). Hierarchical Macro-Mesoporous Ni(OH)2 for Nonenzymatic Electrochemical Sensing of Glucose. Journal of the Electrochemical Society, 161 (10), B201–B206. doi: https://doi.org/10.1149/2.0251410jes
  16. Miao, Y., Ouyang, L., Zhou, S., Xu, L., Yang, Z., Xiao, M., Ouyang, R. (2014). Electrocatalysis and electroanalysis of nickel, its oxides, hydroxides and oxyhydroxides toward small molecules. Biosensors and Bioelectronics, 53, 428–439. doi: https://doi.org/10.1016/j.bios.2013.10.008
  17. Ramesh, T. N., Kamath, P. V., Shivakumara, C. (2005). Correlation of Structural Disorder with the Reversible Discharge Capacity of Nickel Hydroxide Electrode. Journal of The Electrochemical Society, 152 (4), A806. doi: https://doi.org/10.1149/1.1865852
  18. Zhao, Y., Zhu, Z., Zhuang, Q.-K. (2006). The relationship of spherical nano-Ni(OH)2 microstructure with its voltammetric behavior. Journal of Solid State Electrochemistry, 10 (11), 914–919. doi: https://doi.org/10.1007/s10008-005-0035-5
  19. Jayashree, R. S., Kamath, P. V., Subbanna, G. N. (2000). The Effect of Crystallinity on the Reversible Discharge Capacity of Nickel Hydroxide. Journal of The Electrochemical Society, 147 (6), 2029. doi: https://doi.org/10.1149/1.1393480
  20. Jayashree, R. S., Kamath, P. V. (1999). Factors governing the electrochemical synthesis of α-nickel (II) hydroxide. Journal of Applied Electrochemistry, 29 (4), 449–454. doi: https://doi.org/10.1023/a:1003493711239
  21. Ramesh, T. N., Kamath, P. V. (2006). Synthesis of nickel hydroxide: Effect of precipitation conditions on phase selectivity and structural disorder. Journal of Power Sources, 156 (2), 655–661. doi: https://doi.org/10.1016/j.jpowsour.2005.05.050
  22. Rajamathi, M., Vishnu Kamath, P., Seshadri, R. (2000). Polymorphism in nickel hydroxide: role of interstratification. Journal of Materials Chemistry, 10 (2), 503–506. doi: https://doi.org/10.1039/a905651c
  23. Hu, M., Yang, Z., Lei, L., Sun, Y. (2011). Structural transformation and its effects on the electrochemical performances of a layered double hydroxide. Journal of Power Sources, 196 (3), 1569–1577. doi: https://doi.org/10.1016/j.jpowsour.2010.08.041
  24. Córdoba de Torresi, S. I., Provazi, K., Malta, M., Torresi, R. M. (2001). Effect of Additives in the Stabilization of the α Phase of Ni(OH)2 Electrodes. Journal of The Electrochemical Society, 148 (10), A1179–A1184. doi: https://doi.org/10.1149/1.1403731
  25. Zhang, Z., Zhu, Y., Bao, J., Zhou, Z., Lin, X., Zheng, H. (2012). Structural and Electrochemical Performance of Additives-doped α-Ni(OH)2. Journal of Wuhan University of Technology-Mater. Sci. Ed., 27 (3), 538–541. doi: https://doi.org/10.1007/s11595-012-0500-9
  26. Sugimoto, A., Ishida, S., Kenzo, H. (1999). Preparation and Characterization of Ni/Al-Layered Double Hydroxide. Journal of The Electrochemical Society, 146 (4), 1251–1255. doi: https://doi.org/10.1149/1.1391754
  27. Zhen, F. Z., Quan, J. W., Min, Y. L., Peng, Z., Jun, J. L. (2004). A study on the structure and electrochemical characteristics of a Ni/Al double hydroxide. Metals and Materials International, 10 (5), 485–488. doi: https://doi.org/10.1007/bf03027353
  28. Liu, B., Wang, X. Y., Yuan, H. T., Zhang, Y. S., Song, D. Y., Zhou, Z. X. (1999). Physical and electrochemical characteristics of aluminium-substituted nickel hydroxide. Journal of Applied Electrochemistry, 29 (7), 853–858. doi: https://doi.org/10.1023/a:1003537900947
  29. Caravaggio, G. A., Detellier, C., Wronski, Z. (2001). Synthesis, stability and electrochemical properties of NiAl and NiV layered double hydroxides. Journal of Materials Chemistry, 11 (3), 912–921. doi: https://doi.org/10.1039/b004542j
  30. Li, Y. W., Yao, J. H., Liu, C. J., Zhao, W. M., Deng, W. X., Zhong, S. K. (2010). Effect of interlayer anions on the electrochemical performance of Al-substituted α-type nickel hydroxide electrodes. International Journal of Hydrogen Energy, 35 (6), 2539–2545. doi: https://doi.org/10.1016/j.ijhydene.2010.01.015
  31. Zhao, Y. L., Wang, J. M., Chen, H., Pan, T., Zhang, J. Q., Cao, C. N. (2004). Al-substituted α-nickel hydroxide prepared by homogeneous precipitation method with urea. International Journal of Hydrogen Energy, 29 (8), 889–896. doi: https://doi.org/10.1016/j.ijhydene.2003.10.006
  32. Lei, L., Hu, M., Gao, X., Sun, Y. (2008). The effect of the interlayer anions on the electrochemical performance of layered double hydroxide electrode materials. Electrochimica Acta, 54 (2), 671–676. doi: https://doi.org/10.1016/j.electacta.2008.07.004
  33. Faour, A., Mousty, C., Prevot, V., Devouard, B., De Roy, A., Bordet, P. et. al. (2012). Correlation among Structure, Microstructure, and Electrochemical Properties of NiAl–CO3 Layered Double Hydroxide Thin Films. The Journal of Physical Chemistry C, 116 (29), 15646–15659. doi: https://doi.org/10.1021/jp300780w
  34. Kotok, V., Kovalenko, V., Vlasov, S. (2018). Investigation of Ni–Al hydroxide with silver addition as an active substance of alkaline batteries. Eastern-European Journal of Enterprise Technologies, 3 (6 (93)), 6–11. doi: https://doi.org/10.15587/1729-4061.2018.133465
  35. Kovalenko, V., Kotok, V. (2017). Study of the influence of the template concentration under homogeneous precepitation on the properties of Ni(OH)2 for supercapacitors. Eastern-European Journal of Enterprise Technologies, 4 (6 (88)), 17–22. doi: https://doi.org/10.15587/1729-4061.2017.106813
  36. Kovalenko, V., Kotok, V. (2017). Obtaining of Ni–Al layered double hydroxide by slit diaphragm electrolyzer. Eastern-European Journal of Enterprise Technologies, 2 (6 (86)), 11–17. doi: https://doi.org/10.15587/1729-4061.2017.95699
  37. Kovalenko, V., Kotok, V. (2017). Definition of effectiveness of β-Ni(OH)2 application in the alkaline secondary cells and hybrid supercapacitors. Eastern-European Journal of Enterprise Technologies, 5 (6 (89)), 17–22. doi: https://doi.org/10.15587/1729-4061.2017.110390
  38. Li, J., Luo, F., Tian, X., Lei, Y., Yuan, H., Xiao, D. (2013). A facile approach to synthesis coral-like nanoporous β-Ni(OH) 2 and its supercapacitor application. Journal of Power Sources, 243, 721–727. doi: https://doi.org/10.1016/j.jpowsour.2013.05.172
  39. Kovalenko, V., Kotok, V. (2018). Influence of ultrasound and template on the properties of nickel hydroxide as an active substance of supercapacitors. Eastern-European Journal of Enterprise Technologies, 3 (12 (93)), 32–39. doi: https://doi.org/10.15587/1729-4061.2018.133548
  40. Kovalenko, V. L., Kotok, V. A., Sykchin, A. A., Mudryi, I. A., Ananchenko, B. A., Burkov, A. A. et. al. (2016). Nickel hydroxide obtained by high-temperature two-step synthesis as an effective material for supercapacitor applications. Journal of Solid State Electrochemistry, 21 (3), 683–691. doi: https://doi.org/10.1007/s10008-016-3405-2
  41. Miao, C., Zhu, Y., Zhao, T., Jian, X., Li, W. (2015). Synthesis and electrochemical performance of mixed phase α/β nickel hydroxide by codoping with Ca2+ and PO4 3−. Ionics, 21 (12), 3201–3208. doi: https://doi.org/10.1007/s11581-015-1507-y
  42. Li, Y., Yao, J., Zhu, Y., Zou, Z., Wang, H. (2012). Synthesis and electrochemical performance of mixed phase α/β nickel hydroxide. Journal of Power Sources, 203, 177–183. doi: https://doi.org/10.1016/j.jpowsour.2011.11.081
  43. Kovalenko, V., Kotok, V. (2018). Comparative investigation of electrochemically synthesized (α+β) layered nickel hydroxide with mixture of α-Ni(OH)2 and β-Ni(OH)2. Eastern-European Journal of Enterprise Technologies, 2 (6 (92)), 16–22. doi: https://doi.org/10.15587/1729-4061.2018.125886
  44. Kotok, V., Kovalenko, V., Malyshev, V. (2017). Comparison of oxygen evolution parameters on different types of nickel hydroxide. Eastern-European Journal of Enterprise Technologies, 5 (12 (89)), 12–19. doi: https://doi.org/10.15587/1729-4061.2017.109770
  45. Kotok, V., Kovalenko, V. (2018). Definition of the aging process parameters for nickel hydroxide in the alkaline medium. Eastern-European Journal of Enterprise Technologies, 2 (12 (92)), 54–60. doi: https://doi.org/10.15587/1729-4061.2018.127764
  46. Burmistr, M. V., Boiko, V. S., Lipko, E. O., Gerasimenko, K. O., Gomza, Y. P., Vesnin, R. L. et. al. (2014). Antifriction and Construction Materials Based on Modified Phenol-Formaldehyde Resins Reinforced with Mineral and Synthetic Fibrous Fillers. Mechanics of Composite Materials, 50 (2), 213–222. doi: https://doi.org/10.1007/s11029-014-9408-0
  47. Vlasova, E., Kovalenko, V., Kotok, V., Vlasov, S. (2016). Research of the mechanism of formation and properties of tripolyphosphate coating on the steel basis. Eastern-European Journal of Enterprise Technologies, 5 (5 (83)), 33–39. doi: https://doi.org/10.15587/1729-4061.2016.79559
  48. Kovalenko, V., Kotok, V. (2019). Influence of the carbonate ion on characteristics of electrochemically synthesized layered (α+β) nickel hydroxide. Eastern-European Journal of Enterprise Technologies, 1 (6 (97)), 40–46. doi: https://doi.org/10.15587/1729-4061.2019.155738
  49. Volynskii, V. V., Volynskii, V. A., Merzlova, E. V., Popova, S. S. (1999). On the mechanism of joint effect of zinc and cobalt compounds on parameters of nickel-cadmium batteries. Russian Journal of Applied Chemistry, 72 (6), 1008–1011.
  50. Ezhov, B. B., Malandin, O. G. (1991). Structure modification and change of electrochemical activity of nickel hydroxides. Journal of The Electrochemical Society, 138 (4), 885–889. doi: https://doi.org/10.1149/1.2085741
  51. Ezhov, B. B., Rozovskiy, V. M. (1991). Anions as activatore for nickel hydroxides electrode. 42th Meet. of the Int. Soc. Electrochem. Montreux, Abstract No. 7-026.
  52. Ezhov, B. B., Rozovskiy, V. M. (1991). Anionic activation of the nickel hydroxide electrode used in alkaline storage batteries. 33rd IUPAC Congress. Budapest, Abstract No. 3030.
  53. Kovalenko, V., Kotok, V., Kovalenko, I. (2018). Activation of the nickel foam as a current collector for application in supercapacitors. Eastern-European Journal of Enterprise Technologies, 3 (12 (93)), 56–62. doi: https://doi.org/10.15587/1729-4061.2018.133472
  54. Kotok, V., Kovalenko, V. (2017). Optimization of nickel hydroxide electrode of the hybrid supercapacitor. Eastern-European Journal of Enterprise Technologies, 1 (6 (85)), 4–9. doi: https://doi.org/10.15587/1729-4061.2017.90810

Downloads

Published

2019-06-04

How to Cite

Kovalenko, V., & Kotok, V. (2019). Anionic carbonate activation of layered (α+β) nickel hydroxide. Eastern-European Journal of Enterprise Technologies, 3(6 (99), 44–52. https://doi.org/10.15587/1729-4061.2019.169461

Issue

Section

Technology organic and inorganic substances