A universal equivalent circuit is proposed for carbon-based supercapacitors. The circuit, which actually applies to all porous electrodes having non-branching pores, consists of a single vertical ladder network in series with an RC parallel network. This elegant arrangement explains the three most important shortcomings of present-day supercapacitors, namely open circuit voltage decay, capacitance loss at high frequency, and voltammetric distortion at high scan rate. It also explains the shape of the complex plane impedance plots of commercial devices and reveals why the equivalent series capacitance increases with temperature. Finally, the construction of a solid-state supercapacitor simulator is described. This device is based on a truncated version of the universal equivalent circuit, and it allows experimenters to explore the responses of different supercapacitor designs without having to modify real supercapacitors.
Ionic liquids are a natural choice for supercapacitor electrolytes. However, their cost is currently high. In the present work, we report the use of ternary mixtures of sulfolane, 3-methyl sulfolane, and quaternary ammonium salts (quats) as low-cost alternatives. Sulfolane was chosen because it has a high Hildebrand solubility parameter (δ H = 27.2 MPa 1/2 ) and an exceptionally high dipole moment (μ = 4.7 D), which means that it mixes readily with ionic liquids. It also has a high flash point (165 °C), a high boiling point (285 °C), and a wide two-electrode (full-cell) voltage stability window (>7 V). The only problem is its high freezing point (27 °C). However, by using a eutectic mixture of sulfolane with 3-methyl sulfolane, we could depress the freezing point to −17 °C. A second goal of the present work was to increase the electrical conductivity of the electrolyte beyond its present-day value of 2.1 mS cm −1 at 25 °C, currently provided by butyltrimethylammonium bis(trifluoromethylsulfonyl)imide (BTM-TFSI). We explored two methods of doing this: (1) mixing the ionic liquid with the sulfolane eutectic and (2) replacing the low-mobility TFSI anion with the high-mobility MTC anion (methanetricarbonitrile). At the optimum composition, the conductivity reached 12.2 mS cm −1 at 25 °C.
Poly(bisphenol) polymers are identified as a new class of passivating agents for carbon electrodes in ionic liquids. They are inert and can readily be deposited as thin, conformal films by electropolymerization. Unlike conventional poly(monophenol) polymers, a single voltammetric scan is sufficient to accomplish their deposition. This is seen, for example, in the cases of poly(bisphenol A) and poly(bisphenol P). In each case, the thickness of the electropolymerized films is determined by the quantum tunneling distance of the faradaic electrons. Thus, film growth terminates when the faradaic electrons can no longer transit the film at a measurable rate. At that point, all the faradaic reactions cease, while the capacitive charging processes continue unabated. Experimentally, film thicknesses are observed in the range 4−30 nm. A challenging test for the poly(bisphenol) polymers is to coat them onto arrays of microelectrodes (RAM electrodes). Normally, microelectrodes are difficult to coat by electropolymerization due to the intense flux of soluble intermediates away from their surfaces. In the present work, however, coating is facile due to the extreme insolubility of the intermediates. This same property makes the films strongly adherent. Such remarkable behavior suggest that poly(bisphenol) films may have an important role to play as passivating agents in supercapacitors. They may also find application in other areas of technology that require thin-film passivity, such as nanostructural engineering and device physics.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.