Mechanism of capacitive charge of electrodes on the basis of activated carbon materials in ZnI2 solution
DOI:
https://doi.org/10.15587/1729-4061.2016.65444Keywords:
Frumkin adsorption, activated carbon materials, specific pseudocapacity, molecular energy storageAbstract
The electrochemical and thermodynamic features of the iodine electrosorption process on the surface of microporous activated carbon materials (ACM) (ST BET=1600–1900m2×g-1) in 25 % ZnI2 aqueous solution are investigated. The kinetic reversibility of the process, electrode polarization, fractional surface coverage by iodine atoms (θІ) are found. The thermodynamic analysis of the surface adsorption compound of ACM with iodine allows using the known Frumkin adsorption ratios to describe the iodine adsorption process. Comparison of theoretical adsorption isotherms (TAI) and the relationship between the specific pseudocapacity (Cp) and θІ (Сp–θІ) with practical galvanostatic discharge curves built from experimental data is made, and the parameter of the interatomic interaction (g) in the adsorption monolayer is determined. Correlation of the data of electrochemical impedance spectroscopy (EIS) with the data of galvanostatic cycles (GC) is found. Good agreement of the EIS experimental data with transmission electrical equivalent circuit for the porous electrode is obtained. The study provides insights into the process mechanism, the EEC of the interface between electrode and electrolyte, and efficiency of the material as a positive electrode in molecular energy storage (MES) systems. Sufficiently high efficiency of GC of electrodes based on ACM1 (ST BET=1600 m2×g-1), and ACM2 (ST BET=1900 m2×g-1) in the MES system is obtained. The specific discharge of ACM1 Cd=1200 C×g-1 (θІ=0.99) with the Coulomb efficiency η=95 % almost reaches its maximum theoretical value 1,216 C×g-1 (θІ=1). The similarity of the experimental desorption isotherm and Сp-θІ- relationship of ACM1 gives an indication of the process mechanism by the Frumkin model with g=–0,88. The maximum value of ACM1 Cp=F×8.8 m2 obtained according to the EIS is close to 9.4 F×m-2 obtained according to the GC. At the same time, 70 % of the total pseudocapacity of ACM1 has a low time constant τ=RC=82 c.
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