Immobilization of Polyiodide Redox Species in Porous Carbon for Battery-Like Electrodes in Eco-Friendly Hybrid Electrochemical Capacitors

Abstract

Hybrid electrochemical capacitors have emerged as attractive energy storage option, which perfectly fill the gap between electric double-layer capacitors (EDLCs) and batteries, combining in one device the high power of the former and the high energy of the latter. We show that the charging characteristics of the positive carbon electrode are transformed to behave like a battery operating at nearly constant potential after it is polarized in aqueous iodide electrolyte (1 mol L−1 NaI). Thermogravimetric analysis of the positive carbon electrode confirms the decomposition of iodides trapped inside the carbon pores in a wide temperature range from 190 C to 425 C, while Raman spectra of the positive electrode show characteristic peaks of I3− and I5− at 110 and 160 cm−1, respectively. After entrapment of polyiodides in the carbon pores by polarization in 1 mol L−1 NaI, the positive electrode retains the battery-like behavior in another cell, where it is coupled with a carbon-based negative electrode in aqueous NaNO3 electrolyte without any redox species. This new cell (the iodide-ion capacitor) demonstrates the charging characteristics of a hybrid capacitor with capacitance values comparable to the one using 1 mol L−1 NaI. The constant capacitance profile of the new hybrid cell in aqueous NaNO3 for 5000 galvanostatic charge/discharge cycles at 0.5 A g−1 shows that iodide species are confined to the positive battery-like electrode exhibiting negligible potential decay during self-discharge tests, and their shuttling to the negative electrode is prevented in this system.

Persistent and Reversible Solid Iodine Electrodeposition in Nanoporous Carbons

“…With increasing cell voltage, the widths of the G-and D-modes increase, while they are slightly redand blue-shifted, respectively and the ID-to-IG ratio is lowered. This can be explained by a superposition of charge transfer and an increase of defects [33][34][35][36] , which is qualitatively consistent with ex situ results reported earlier 18,37 .…”

“…Confinement in such electrodes may change rates of individual reaction steps and hence the stability of I2 and I3 -. While the polyiodides I3and I5are generally accepted to form during Ioxidation, described mechanisms are ambiguous 2, 3,7,8,[18][19][20] . The rather slow self-discharge of iodine-based electrochemical energy storage devices is currently attributed to immobile I3and I5confined in the narrow carbon pores of below 1 nm diameter 7,8,18 .…”

“…While the polyiodides I3and I5are generally accepted to form during Ioxidation, described mechanisms are ambiguous 2, 3,7,8,[18][19][20] . The rather slow self-discharge of iodine-based electrochemical energy storage devices is currently attributed to immobile I3and I5confined in the narrow carbon pores of below 1 nm diameter 7,8,18 . However, based on the known reaction mechanism on planar platinum electrodes 16,17 and the use of battery electrodes with physically impregnated I2 6,7 , alternative electrodeposition of solid I2 in carbon nanopores ought to be considered.…”

Persistent and reversible solid iodine electrodeposition in nanoporous carbons

“…Works on carbon-iodine battery cathodes 15,21 suggest that the physico-chemical mechanism during iodide/ iodine oxidation/reduction is similar in both organic and aqueous electrolytes. The rather slow self-discharge of iodine-based electrochemical energy storage devices is currently attributed to immobile I 3 − and I 5 − confined in the narrow carbon pores of below 1 nm diameter 7,8,18 . However, given the known reaction mechanism on planar platinum electrodes 16,17 and the use of battery electrodes with physically impregnated I 2 6,7 , alternative electrodeposition of solid I 2 in carbon nanopores ought to be considered.…”

Persistent and Reversible Solid Iodine Electrodeposition in Nanoporous Carbons

“…Confinement in such electrodes may change rates of individual reaction steps and hence the stability of I2 and I3 -. While the polyiodides I3and I5are generally accepted to form during Ioxidation, described mechanisms are ambiguous 2,3,7,8,[18][19][20] . The rather slow self-discharge of iodine-based electrochemical energy storage devices is currently attributed to immobile I3and I5confined in the narrow carbon pores of below 1 nm diameter 7,8,18 .…”