Activation of the Process of Cathode Synthesis of Calcium Anodes in Aproton Solutions of Calcium Salts of Various Anion Composition

This is an open access article distributed under the terms of Creative Commons Attribution 4.0 International License (CC-BY 4.0).


Matrix electrodes based on copper and lead, CuCa, PbCa, CuBiCa, PbBiCa, CuPbBiCa, were obtained by cathode intercalation, their composition was identified in aprotic organic solutions of calcium salts of various anionic composition by means of X-ray phase analysis and open-circuit potential measurement. The effect of the component (transition metal) in the structure of the copper and lead matrix on the efficiency of cycling of CuCa, PbCa, CuBiCa, PbBiCa, CuPbBiCa-electrodes in chloride, acetate and nitrate aprotic calcium salt solutions was studied.

It has been found that the diffusion-kinetic characteristics of the process of calcium intercalation into copper and lead electrodes modified with bismuth and lead increase in the series of anions: CH3COO << NO3<Cl, which is due to the peculiarities of their structure and physicochemical properties, and as a result, the importance of the role of the processes of association and solvation in this series.

It has been established that the calcium content in the surface layer of all the electrodes under investigation is the highest, if it is intercalated from a solution of calcium chloride CaCl2. The presence of oxygen-containing phases in the electrode matrix, which differ in the value of the oxidation-reduction potential, contributes to the accumulation of calcium in the electrode. When bismuth and lead are intercalated into the composition of copper and lead electrodes, which are easily integrated into the structure due to the possibility of electronic transitions of Cu(I) ↔ Cu(II), Bi(II) ↔ Bi(III), Pb(II) ↔ Pb(IV) their cycling efficiency and the capacitance of the electrodes increase.


1. Shcherbinina O. N., Popova S. S., Medvedeva N. G. Protsess vnedreniya kal’tsiya v medno-vismutovyy tonkoplenochnnyy elektrod [The process of intercalation of calcium into a copper-bismuth thin-film electrode]. Izvestiya vuzov. Khimiya i khimicheskaya tekhnologiya [News of Higher Schools. Chemistry and Chemical Technology], 2009, vol. 52, no. 7, pp. 69–72 (in Russian).

2. Shcherbinina O. N., Popova S. S., Medvedeva N. G. Elektrokhimicheskoye modifitsirovaniye matrichnykh struktur na osnove svintsa kal’tsiyem [Electrochemical modification of matrix structures based on lead by calcium]. Zhurnal prikladnoy khimii [Journal of Applied Chemistry], 2009, vol. 182, no. 4, pp. 19–21 (in Russian).

3. Olshanskaya L. N., Popova S. S., Zakirova S. M. Vliyaniye prirody tret’yego komponeta na kineticheskiye zakonomernosti elektrokhimicheskogo formirovaniya splava Li-Al na alyuminiii [Influence of the nature of the third component on the kinetic regularities of the electrochemical formation of Li-Al alloy on aluminum]. Elektrokhimiya [Electrochemistry], 2000, vol. 36, no. 8, pp. 951–958 (in Russian).

4. Guterman V. E., Grigoriev V. P., Saenko O. E. Zaryadno-razryadnyye kharakteristiki litiy soderzhashchikh alyuminiyevykh splavov v nevodnykh rastvorakh. Vliyaniye legiruyushchikh komponentov na effektivnost’ tsiklirovaniya litiya [Charging-discharging characteristics of lithium-containing aluminum alloys in non-aqueous solutions. Effect of alloying components on the efficiency of lithium cycling]. Elektrokhimiya [Electrochemistry], 1994, vol. 30, no. 7, pp. 852–858 (in Russian).

5. Popova S. S., Olshanskaya L. N., Pominova Т. V. Vliyaniye prirody aniona na elektrokhimicheskuyu litizatsiyu grafita v atsetonitril’nykh rastvorakh [Influence of the anion nature on the electrochemical lithiation of graphite in acetonitrile solutions]. Elektrokhimiya [Electrochemistry], 2002, vol. 38, no. 4, pp. 412–417 (in Russian).

6. Shluger M. A., Tok L. D. Gal’vanicheskiye pokrytiya v mashinostroyenii. Spravochnik: v 2 t. Pod red. M. A. Shlugera, L. D. Toka [Galvanic coatings in mechanical engineering: in 2 vols. Ed. by M. A. Shluger, L. D. Tok]. Moscow, Mashinostroyeniye, 1985, vol. 2, 248 p.

7. Fetter K. Elektrokhimicheskaya kinetika [Electrochemical kinetics]. Moscow, Khimiya, 1967. 856 p. (in Russian).

8. Lyakisheva N. P. Diagrammy sostoyaniya metallicheskikh sistem: v 2 t. [Diagrams of the state of metallic systems: in 2 vol.] Moskow, Mashinostroyeniye, 1996, vol. 1, 992 p.

9. Kabanov B. N., Astakhov I. I., Kiseleva I. G. Vnedreniye – novoye napravleniye v izuchenii kinetiki elektrokhimicheskogo vydeleniya i rastvoreniya metallov [Introduction – a new direction in the study of kinetics of electrochemical separation and dissolution of metals]. Kinetika slozhnykh elektrokhimicheskikh reaktsiy [Kinetics of complex electrochemical reactions]. Moscow, Nauka, 1981, pp. 200–239 (in Russian).

Full Text (PDF):
(downloads: 522)