Optical and thermal effects in asymmetric supercapacitors, whose active-carbon (AC) electrodes were embedded with nano-Si (n-Si) quantum dots (QD), are reported. We describe two structures: (1) p-n like, obtained by using a polyethylimine (PEI) binder for the n-like electrode and a polyvinylpyrrolidone (PVP) binder for the p-like electrode; (2) a single component binder, poly(methyl methacrylate) (PMMA). In general, AC appears black to the naked eye and one may assume that it acts as a black body absorber, namely, indiscriminately absorbing all light spectra. Yet, on top of a flat lossy spectra, AC (from two manufacturers) exhibited two distinct absorption bands: one in the blue (~ 400 nm) and the other one in the near IR (~ 840 nm). The n-Si material accentuated the absorption in the blue and bleached the IR absorption. Both bands contributed to capacitance increase: (a) when using aqueous solution and a PMMA binder, the optical related increased capacitance was 20% at low n-Si concentration and more than 100% for a high concentration dose; (b) when using IL electrolyte, the large, thermal capacitance increase (of ca 40%) was comparable to the optical effect (of ca 42%) and hence was assigned as an optically-induced thermal effect. The experimental data point to an optically induced capacitance increase even in the absence of the n-Si dots; this could be attributed to the absorption of AC in the blue.
Supercapacitors (aka electrostatic double-layer capacitors -- EDLCs) offer excellent power storage capacity and kinetics, but suffer under rapid self-discharge. We introduced a zeolite framework into the active capacitor electrode, with the goal to tailor the free desorption energy and thus the self-discharge rate of supercapacitors. Low-cost carbonaceous materials and benchtop production methods were used to create supercapacitor electrodes with a measured specific capacitance of 17.25 F g$^{-1}$, a coulombic efficiency of 100%, and charge retention of over 25% over 24 hours determined by gal…
The development of novel electrolytes and electrodes for supercapacitors is hindered by a gap of several orders of magnitude between experimentally measured and theoretically predicted charging timescales. Here, we propose an electrode model, containing many parallel stacked electrodes, that explains the slow charging dynamics of supercapacitors. At low applied potentials, the charging behavior of this model is described well by an equivalent circuit model. Conversely, at high potentials, charging dynamics slow down and evolve on two relaxation time scales: a generalized $RC$ time and a diffus…
Supercapacitors are energy storage devices able to deliver electricity with a high power. They consist of porous carbon electrodes in a concentrated electrolyte. Charged is stored by the adsorption of ions at the electrode surface. Nanoporous carbons allow to store more electricity thanks to a charging mechanism that differs from carbons with larger pores. This mechanism has recently been uncovered by combining in situ experiments (nuclear magnetic resonance, electrochemical quartz microbalance) and molecular simulations.
Asymmetric behaviors of capacitance and charging dynamics in the cathode and anode are general for nanoporous supercapacitors. Understanding this behavior is essential for the optimal design of supercapacitors. Herein, we perform constant-potential molecular dynamics simulations to reveal asymmetric features of porous supercapacitors and their effects on capacitance and charging dynamics. Our simulations show that, counterintuitively, charging dynamics can be fast in pores providing slow ion diffusion and vice versa. Unlike electrodes with single-size pores, multi-pore electrodes show overchar…
This study aims at demonstrating that wastes from anaerobic biodigester plants can be effectively valorized as functional materials to be implemented in technologies that enable efficient energy management and water treatment, therefore simultaneously addressing the Water-Energy-Waste Nexus challenges. Lignin, the main solid residue of the biodigester plant, has been valorized into activated biochar with a mild activation agent, like KHCO3, to produce electrode of supercapacitors and microbial fuel cells. In addition, the same sludge that is the liquid effluent of the biodigester plant has bee…
This review paper highlights the recent developments in supercapacitors by pointing out the significance of appropriate electrode and device designs. We reported ten extremely high-performance supercapacitors with specific capacitance values among the highest available until now to the best of our knowledge. These state-of-the-art designs employing innovative electrode materials have been discussed along with their short descriptions. The supercapacitors collected here possess the most promising potential for facilitating next-generation systems in energy harvesting and storage. This review is…
Supercapacitors (S-C) are short-term energy storage elements that find many applications, e.g., electronic charging devices and suppressors of power fluctuations in grids that are interfaced with sustainable sources. The capacitance of an ordinary capacitor increases when dispersing metallic colloids in its dielectric. A similar strategy for S-C means a deployment of nano-scale metal colloids (in our case, Au nano particles, or AuNPs) at the very narrow interface between an electrolyte and the porous electrode (here, active-carbon film on a grafoil current collector). This is achieved by makin…
Electric double layer supercapacitors are a fast-rising class of high-power energy storage devices based on porous electrodes immersed in a concentrated electrolyte or ionic liquid. As of yet there is no microscopic theory to describe their surprisingly large capacitance per unit volume (volumetric capacitance) of ~ 100 F/cm^3, nor is there a good understanding of the fundamental limits on volumetric capacitance. In this paper we present a non-mean-field theory of the volumetric capacitance of a supercapacitor that captures the discrete nature of the ions and the exponential screening of their…
Supercapacitors, S-C - capacitors that take advantage of the large capacitance at the interface between an electrode and an electrolyte - have found many short-term energy applications. We concentrate here on optically induced, electrical and thermal effects. The parallel plate cells were made of two transparent electrodes (ITO), each covered with semiconductor-embedded, active carbon (A-C) layer. While A-C appears black, it is not an ideal blackbody absorber that absorbs all spectral light indiscriminately. In addition to relatively flat optical absorption background, A-C exhibits two distinc…
As renewable energy is becoming a critical energy source to meet the global demand, electrochemical energy storage devices become indispensable for the efficient energy storage and reliable supply. The electrode material is the key factor determining the energy storage capacity and the power delivery of the devices. Carbon-based materials are emerging as a viable candidate for electrodes, yet their low energy densities impede the development of advanced energy storage materials. Nanoparticle decoration of the carbon structures is one of the most promising and easy-to-implement a strategy to en…
Current supercapacitors present several distinct limitations that severely inhibit the efficiency, power, and electrical capacitance of energy storage devices. Supercapacitors present an exciting prospect that has countless applications in renewable energy storage and modern day electronic devices. In recent years the exciting development of carbon nanotubes (CNTs) has presented an advantage in electrode development. CNTs, however beneficial for their increased electrode surface area, have severe limitations regarding conductivity and electrode density. Creating a nanocomposite hybrid out of a…
In this work we describe the synthesis and electrochemical properties of nitridated hierarchical TiO$_2$ nanotubes as an electrode for supercapacitors. The hierarchical TiO$_2$ nanostructures are formed by a controlled layer-by-layer TiO2 nanoparticle decoration on self-organized spaced TiO$_2$ nanotubes. These structures are then annealed in NH$_3$ atmosphere at elevated temperature to convert the material to a nitride structure -- this drastically enhances their electron-transport properties. The areal capacitance of hierarchical structures can be tuned by changing the number of decorated Ti…
Oxygen functional groups are one of the most important subjects in the study of electrochemical properties of carbon materials which can change the wettability, conductivity and pore size distributions of carbon materials, and can occur redox reactions. In the electrode materials of carbon-based supercapacitors, the oxygen functional groups have widely been used to improve the capacitive performance. In this paper, we not only analyzed the reasons for the increase of the capacity that promoted by oxygen functional groups in the charge-discharge cycling tests, but also analyzed the mechanism ho…
Nanoporous supercapacitors are an important player in the field of energy storage that fill the gap between dielectric capacitors and batteries. The key challenge in the development of supercapacitors is the perceived trade-off between capacitance and power delivery. Current efforts to boost the capacitance of nanoporous supercapacitors focus on reducing the pore size so that they can only accommodate a single layer of ions. However, this tight packing compromises the charging dynamics and hence power density. We show via an analytical theory and Monte Carlo simulations that charging is sensit…
The influence of spatial confinement on the thermally excited stochastic cation dynamics of the room-temperature ionic liquid 1-N-butylpyridinium bis-((trifluoromethyl)sulfonyl)imide ([BuPy][Tf_2N]) inside porous carbide-derived carbons with various pore sizes in the sub- to a few nanometer range are investigated by quasi-elastic neutron spectroscopy. Using the potential of fixed window scans, i.e. scanning a sample parameter, while observing solely one specific energy transfer value, an overview of the dynamic landscape within a wide temperature range is obtained. It is shown that already the…
Heterostructures constructed from two-dimensional building blocks have shown promise for field-effect transistors, memory devices, photosensors and other electronic applications1,2. 2D nanosheet crystals can be constructed into multilayer heterostructures using layer-by-layer methods3, but that method cannot be used to fabricate large-scale and thick heterostructures, due to the time-consuming nature and low efficiency of the process. An alternative approach to deposit different two-dimensional materials is by inkjet printing4-7. Here we show the fabrication of a nanosheet supercapacitor by in…
An application of quantum size carbon structures--graphenes as electrodes of supercapacitors is studied. A fundamental limit of energy and power density arising from quantum nature of objects due to singularity in graphene density of states near Dirac point is determined and technical solutions to partially offset the negative factors are considered. The maximum possible specific capacitance of nanostructured electrode materials is determined.
We demonstrate that the capacitance of ionic-liquid filled supercapacitors is substantially increased by placing a diode-like structure on the separator membrane. We call the structured separator: gate, and demonstrate that the order of a p-n layout with respect to the auxiliary electrode affects the overall cell's capacitance. The smallest ESR and the largest capacitance values are noted when the p-side is facing the auxiliary electrode.
Supercapacitors are electric devices able to deliver a large power, enabling their use e.g. for the recovery of breaking energy in cars. This is achieved by using two carbon electrodes and an electrolyte solution or a pure ionic liquid (Room Temperature Ionic Liquid, RTIL). Energy is stored by the adsorption of ions at the surface of the electrodes, but the microscopic mechanism underlying the exceptional performance of Carbide Derived Carbon (CDC) electrodes remained unknown. Using molecular simulation with realistic electrode structures and under constant voltage conditions, we investigate t…
We study the influence of a scanning nano-electrode on fluorescence excitation spectra of single terrylene molecules embedded in thin p-terphenyl films at cryogenic temperatures. We show that applied voltages less than 10 V can result in reversible Stark shifts of up to 100 times and linewidth increase greater than 10 times the natural linewidth. We discuss the potential of our experimental scheme for direct imaging of individual two-level systems (TLS) in the nanometer vicinity of single molecules.
Nanoconfinement generally leads to drastic effect on the physical and chemical properties of ionic liquids. Here we investigate how the electrochemical reactivity in such media may be impacted inside nanoporous carbon electrodes. To this end, we study a simple electron transfer reaction using molecular dynamics simulations. The electrodes are held at constant electric potential by allowing the atomic charges on the carbon atoms to fluctuate. We show that the $\mathrm{Fe^{3+}}/\mathrm{Fe^{2+}}$ couple dissolved in an ionic liquid exhibits a deviation with respect to Marcus theory. This behavior…
While it is well-known that electrode conductivity has a critical impact on rate-performance in battery electrodes, this relationship has been quantified only by computer simulations. Here we investigate the relationship between electrode conductivity and rate-performance in Lithium-Nickel-Manganese-Cobalt-Oxide (NMC) cathodes filled with various quantities of carbon black, single-walled carbon nanotubes and graphene. The electrode conductivity is always extremely anisotropic with the out-of-plane conductivity, which is most relevant to rate-performance, roughly 1000 smaller than the in-plane …
