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

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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.


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