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Vol 60, No 2 (2024)

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Articles

Supercapacitors for extreme temperatures. Review

Volfkovich Y.M.

Abstract

This review considers the literature on electrochemical supercapacitors (ECSC) operating at extreme temperatures from –80°C to +220°C, which is very important for practice. The influence of the following methods and factors on the efficiency of the ECSC at extreme temperatures is considered: the use of ionic liquids as an electrolyte: the use of a modified gel electrolyte, a combined electrolyte, aqueous electrolytes with a low freezing point; the use of acetonitrile as an electrolyte solvent; the use of clay as a solid electrolyte; application of solid-state EСSC; application of electrodes with an optimized porous structure; the use of graphene and pseudocapacitive electrodes; the use of solar cells; use of combined techniques to create supercapacitors for extreme temperatures. Undoubtedly. This review will be of great interest both for fundamental electrochemistry and for practice.

Èlektrohimiâ. 2024;60(2):95–123
pages 95–123 views

Model describing of the process of electrodeposition of loose zinc deposits in pulsed potential modes

Nikitin V.S., Ostanina T.N., Rudoy V.M.

Abstract

The structural characteristics of loose zinc deposits obtained in pulsed potential modes were calculated using a phenomenological model. Increasing the duty cycle leads to increased anodic dissolution during pauses and obtaining denser deposits, due to the formation of dendrites with fewer vertices, but with a larger diameter compared to deposits obtained in the potentiostatic mode. The linear dependence of the diameter of the tips of dendrites forming a loose zinc deposit on the duty cycle was found. It is shown that there is a critical time corresponding to the achievement of zero deposit growth rate when the metal deposited during the pulse will completely dissolve during the pause.

Èlektrohimiâ. 2024;60(2):124–138
pages 124–138 views

Electrochemically induced phosphorus-methyl bond formation involving the complex [Co(Ph2PCH2P(Ph) 2PPPPP(Ph) 2CH2PPh2)]BF4

Kuchkaev A.M., Kuchkaev A.M., Sukhov A.V., Ivanov A.S., Khayarov K.R., Dobrynin A.B., Sinyashin O.G., Yakhvarov D.G.

Abstract

The electrochemical properties of [Co(Ph2PCH2P(Ph)2PPPPP(Ph)2CH2PPh2)]BF4 complex have been studied by the method of cyclic voltammetry. The electrochemical methylation of this complex have been cunducted in the presence of iodomethane which has led to the formation of phosphonium salt—ethylene bis(methyldiphenylphosphonium) diiodide as final product. It was found, that this reaction proceeds with the breakage of the P–P bonds in polyphosphorus ligand and with the formation of new P–C bonds.

Èlektrohimiâ. 2024;60(2):139–145
pages 139–145 views

Electrochemical properties of superionic conductors CsAg4Br3-хI2+х

Glukhov A.A., Reznitskikh O.G., Yaroslavtseva T.V., Urusova N.V., Ukshe A.E., Dobrovolsky Y.A., Bushkova O.V.

Abstract

CsAg4Br3–хI2+х solid solutions with x=0.38; 0.50; 0.63 were prepared by solid-phase synthesis; the single-phase of the products was confirmed by X-ray diffraction and differential scanning calorimetry. Studies of the electrical transport characteristics of CsAg4Br3–хI2+х included measurements of the ionic conductivity by the four-probe method in the range of –50…+120°C and an evaluation of the electronic component of the conductivity by the Hebb-Wagner method. It was shown that the ionic conductivity of CsAg4Br3–хI2+х solid solutions in the studied range of compositions is practically independent of x and is very close to that of the well-known superionic conductor RbAg4I5. The activation energy of conduction for all studied compounds is about 10 kJ mol–1. The oxidation potential determined by the stepwise polarization technique for CsAg4Br3–хI2+х solid solutions is noticeably higher than that of RbAg4I5, and is in the range of 0.75–0.78 V (vs. Ag0/Ag+). The high electrochemical characteristics of CsAg4Br3–хI2+х (0.38≤x≤0.63) and the absence of polymorphic transitions in the studied range from –160°C to the melting point (175 – 178°С) make these materials promising for use in electrochemical devices based on solid electrolytes, especially for low temperature applications.

Èlektrohimiâ. 2024;60(2):146–153
pages 146–153 views

Depolarization at electrodeposition of the negative component of the eutectic alloy

Gamburg Y.D.

Abstract

At electrochemical deposition of alloys various phenomena are observed that lead to changes in the kinetics and thermodynamics of these processes. So, as a result of changing the nature of the electrode surface, the exchange current densities of each of the components and the transfer coefficients change. Further, during the formation of solid solutions, the equilibrium potentials of the components change due to the non-zero enthalpy of mixing and entropy of mixing. At deposition of eutectic-type alloys (that is, a mixture of grains of individual components), each of the metals is not deposited on the entire surface of the electrode, but only on its own surface. In the latter case, there is a change in the diffusion pattern of the components compared to the deposition of individual metals: it remains unchanged in the outer part of the diffusion layer but near the surface there is a condensation of the diffusion fields of the components, similar to how it is observed during diffusion to the matrix of microelectrodes or to individual nuclei of a new phase. This also leads to a change in the diffusion part of the overpotential at deposition of components. The diffusion of ions of a discharging negative component of an alloy representing a mechanical mixture of metal grains A and B to the grain surface of this component in the model of a partially blocked electrode is considered. It is shown that at a constant potential, the local current density of the component is increased as a result of diffusion acceleration. The magnitude of the relative increase in current and the corresponding magnitude of apparent depolarization is found as compared between the deposition of an individual metal and the codeposition of the same component into an alloy.

Èlektrohimiâ. 2024;60(2):154–158
pages 154–158 views

Production and electrocatalytic activity of graphene-phosphorene structures decorated with cobalt atoms

Manzhos R.A., Komarova N.S., Kotkin A.S., Kochergin V.K., Prikhodchenko T.R., Krivenko A.G.

Abstract

Nitrogen-doped few-layer graphene structures were synthesized by the plasma-assisted electrochemical exfoliation of graphite and were used to prepare composites with phosphorene structures obtained as a result of ultrasonic exfoliation of a black phosphorus porous electrode with cobalt preliminarily deposited on it. The catalytic activity towards hydrogen evolution reaction of few-layer graphene and phosphorene structures, as well as their mixtures was studied, and mixed electrocatalysts was shown to demonstrate the highest activity towards hydrogen evolution reaction.

Èlektrohimiâ. 2024;60(2):159–164
pages 159–164 views

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