Thermal Oxidation of Carbonaceous Nanomaterials Revisited: Evidence of Mechanism Changes.

Kinetic data, for example, activation energy and reaction order, are crucial for the understanding of chemical reactions and processes. Here, we describe a novel method for obtaining kinetic data based on thermogravimetric measurements (TGA) that exploits in each measurement multiple successive isothermal steps (SIS). We applied this method to the notoriously challenging carbon combustion process for vastly different carbons for oxygen molar fractions between 1.4 % and 90 %. Our obtained apparent EA values are within the wide range of results in the literature and vary in a systematic way with the oxygen partial pressure. The improved accuracy and large amount of obtainable data allowed us to show that the majority of experimentally obtained apparent data for apparent EA are neither in a kinetic regime nor in a diffusion-controlled one but rather in a transition regime.

Sparsely Pillared Graphene Materials for High-Performance Supercapacitors: Improving Ion Transport and Storage Capacity.

Graphene-based materials are extensively studied as promising candidates for supercapacitors (SCs) owing to the high surface area, electrical conductivity, and mechanical flexibility of graphene. Reduced graphene oxide (RGO), a close graphene-like material studied for SCs, offers limited specific capacitances (100 F·g-1) as the reduced graphene sheets partially restack through π-π interactions. This paper presents pillared graphene materials designed to minimize such graphitic restacking by cross-linking the graphene sheets with a bifunctional pillar molecule. Solid-state NMR, X-ray diffraction, and electrochemical analyses reveal that the synthesized materials possess covalently cross-linked graphene galleries that offer additional sites for ion sorption in SCs. Indeed, high specific capacitances in SCs are observed for the graphene materials synthesized with an optimized number of pillars. Specifically, the straightforward synthesis of a graphene hydrogel containing pillared structures and an interconnected porous network delivered a material with gravimetric capacitances two times greater than that of RGO (200 F·g-1 vs 107 F·g-1) and volumetric capacitances that are nearly four times larger (210 F·cm-3 vs 54 F·cm-3). Additionally, despite the presence of pillars inside the graphene galleries, the optimized materials show efficient ion transport characteristics. This work therefore brings perspectives for the next generation of high-performance SCs.

Capacitance of Nanoporous Carbon-Based Supercapacitors Is a Trade-Off between the Concentration and the Separability of the Ions.

Nanoporous carbon-based supercapacitors store electricity through adsorption of ions from the electrolyte at the surface of the electrodes. Room temperature ionic liquids, which show the largest ion concentrations among organic liquid electrolytes, should in principle yield larger capacitances. Here, we show by using electrochemical measurements that the capacitance is not significantly affected when switching from a pure ionic liquid to a conventional organic electrolyte using the same ionic species. By performing additional molecular dynamics simulations, we interpret this result as an increasing difficulty of separating ions of opposite charges when they are more concentrated, that is, in the absence of a solvent that screens the Coulombic interactions. The charging mechanism consistently changes with ion concentration, switching from counterion adsorption in the diluted organic electrolyte to ion exchange in the pure ionic liquid. Contrarily to the capacitance, in-pore diffusion coefficients largely depend on the composition, with a noticeable slowing of the dynamics in the pure ionic liquid.

Confinement, Desolvation, And Electrosorption Effects on the Diffusion of Ions in Nanoporous Carbon Electrodes.

Supercapacitors are electrochemical devices which store energy by ion adsorption on the surface of a porous carbon. They are characterized by high power delivery. The use of nanoporous carbon to increase their energy density should not hinder their fast charging. However, the mechanisms for ion transport inside electrified nanopores remain largely unknown. Here we show that the diffusion is characterized by a hierarchy of time scales arising from ion confinement, solvation, and electrosorption effects. By combining electrochemistry experiments with molecular dynamics simulations, we determine the in-pore conductivities and diffusion coefficients and their variations with the applied potential. We show that the diffusion of the ions is slower by 1 order of magnitude compared to the bulk electrolyte. The desolvation of the ions occurs on much faster time scales than electrosorption.

TiC-carbide derived carbon electrolyte adsorption study by ways of X-ray scattering analysis.

Understanding ion adsorption in nanoporous carbon electrodes is of great importance for designing the next-generation of high energy density electrical double-layer capacitors. In this work, X-ray scattering is used for investigating the impregnation of nanoporous carbons with electrolytes in the absence of applied potential. We are able to show that interactions between the carbon surface and electrolytes allow adsorption to take place in sub-nanopores, thus confirming experimentally for the first time the results predicted by molecular dynamic simulations.

On the dynamics of charging in nanoporous carbon-based supercapacitors.

Supercapacitors are electricity storage systems with high power performances. Their short charge/discharge times are due to fast adsorption/desorption rates for the ions of the electrolyte on the electrode surface. Nanoporous carbon electrodes, which give larger capacitances than simpler geometries, might be expected to show poorer power performances because of the longer times taken by the ions to access the electrode interior. Experiments do not show such trends, however, and this remains to be explained at the molecular scale. Here we show that carbide-derived carbons exhibit heterogeneous and fast charging dynamics. We perform molecular dynamics simulations, with realistically modeled nanoporous electrodes and an ionic liquid electrolyte, in which the system, originally at equilibrium in the uncharged state, is suddenly perturbed by the application of an electric potential difference between the electrodes. The electrodes respond by charging progressively from the interface to the bulk as ions are exchanged between the nanopores and the electrolyte region. The simulation results are then injected into an equivalent circuit model, which allows us to calculate charging times for macroscopic-scale devices.