| Summary: | 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<sup>−1</sup> 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 I<sub>3</sub><sup>−</sup> and I<sub>5</sub><sup>−</sup> at 110 and 160 cm<sup>−1</sup>, respectively. After entrapment of polyiodides in the carbon pores by polarization in 1 mol L<sup>−1</sup> NaI, the positive electrode retains the battery-like behavior in another cell, where it is coupled with a carbon-based negative electrode in aqueous NaNO<sub>3</sub> electrolyte without any redox species. This new cell (<i>the</i> <i>iodide-ion capacitor</i>) demonstrates the charging characteristics of a hybrid capacitor with capacitance values comparable to the one using 1 mol L<sup>−1</sup> NaI. The constant capacitance profile of the new hybrid cell in aqueous NaNO<sub>3</sub> for 5000 galvanostatic charge/discharge cycles at 0.5 A g<sup>−1</sup> 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.
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