Energy Materials

Nuclear magnetic resonance (NMR) spectroscopy is increasingly being used to study the adsorption of molecules in porous carbons, a process which underpins applications ranging from electrochemical energy storage to water purification. Here we present density functional theory (DFT) calculations of the nucleus-independent chemical shift (NICS) near various sp2-hybridized carbon fragments to explore the structural factors that may affect the resonance frequencies observed for adsorbed species. The domain size of the delocalized electron system affects the calculated NICSs, with larger domains giving rise to larger chemical shieldings. In slit-pores, overlap of the ring current effects from the pore walls is shown to increase the chemical shielding. Finally, curvature in the carbon sheets is shown to have a significant effect on the NICS. The trends observed are consistent with existing NMR results as well as new spectra presented for an electrolyte adsorbed on carbide-derived carbons prepared at different temperatures.

Template-based chemical vapor deposition is an efficient one step process to synthesize carbon nanotubes (CNTs) for a wide range of applications. In this process, the choice of template dictates certain physical features of the CNT, such as length and outer diameter, while the process itself affects other features, such as tube wall thickness, carbon deposition rate and carbon morphology. Although it is generally understood that the process affects important CNT properties, little is known about how parameters affect synthesized CNTs. In this report, a systematic parametric study was conducted to determine how three key process parameters (deposition time, temperature, and gas flow rate) affect overall carbon mass deposition rate and CNT wall thickness and morphology. The findings show that process parameters can be independently utilized to produce CNTs with similar or differing cross-sectional dimensions and other useful features, each with distinct advantages.

The expansion of porous carbons used in electrochemical double layer capacitors during positive or negative charging has been investigated in several studies, however, the underlying mechanisms are not well understood yet. We therefore investigated dimensional changes of three different carbons in various electrolytes including ionic liquids e.g. [EMIM][BF4] with and without solvent and [EMIM][TFSI]. For all carbon/electrolyte combinations the expansion during positive charging was smaller than for negative charging. The expansion increased with decreasing average pore size of the carbon. Addition of solvents, such as acetonitrile or propylene carbonate, significantly increased the expansion for negative charging. These observations are discussed in the view of various existing models for charge induced strain of carbons.

This study investigates carbons onions (∼400 m2g-1)as a conductive additive for supercapacitor electrodes of activated carbon and compares their performance with carbon black with high or low internal surface area. We provide a study of the electrical conductivity and electrochemical behavior between 2.5 and 20 mass% addition of each of these three additives to activated carbon. Structural characterization shows that the density of the resulting film electrodes depends on the degree of agglomeration and the amount of additive. Additions of low surface area carbon black (∼80 m2g-1) enhances the power handling of carbon electrodes but significantly lowers the specific capacitance even when adding small amounts of carbon black. A much lower decrease in specific capacitance is observed for carbon onions and the best values are seen for carbon black with a high surface area (∼1390 m2·g-1). The overall performance benefits from the addition of any of the studied additives only at either high scan rates and/or electrolytes with high ion mobility. Normalization to the volume shows a severe decrease in volumetric capacitance and only at high current densities nearing 10 A g-1 we can see an improvement of the electrode capacitance.

Herein we show that heating 2D Ti3C2 in air resulted in TiO2 nanocrystals on thin sheets of disordered graphitic carbon structure that can handle extremely high cycling rates when tested as anodes in lithium ion batteries. Oxidation of 2D Ti3C2 in either CO2 or pressurized water also resulted in TiO2/C hybrid structure. Similarly, other hybrids can be produced, as we show here for Nb2O5/C from 2D Nb2C.

The electrochemical flow capacitor (EFC) has been recently introduced as a new concept for rapid and capacitive energy storage using flowable carbon-electrolyte suspensions. In our study, we investigate the EFC under static and constant flow condition. Unlike static carbon suspensions where poor particle-particle-contact and particle settling yield a highly resistive and time-dependent behavior, we show that flow operation of carbon suspensions reach high Coulombic efficiency and stable energy density performance. Our results also indicate that the specific capacitance per total mass of carbon electrodes in flow operation is comparable to conventional binder-bound carbon film electrodes.

Capacitive technologies, such as capacitive deionization and energy harvesting based on mixing energy ("capmix" and "CO2 energy"), are characterized by intermittent operation: phases of ion electrosorption from the water are followed by system regeneration. From a system application point of view, continuous operation has many advantages, to optimize performance, to simplify system operation, and ultimately to lower costs. In our study, we investigate as a step towards second generation capacitive technologies the potential of continuous operation of capacitive deionization and energy harvesting devices, enabled by carbon flow electrodes using a suspension based on conventional activated carbon powders. We show how the water residence time and mass loading of carbon in the suspension influence system performance. The efficiency and kinetics of the continuous salt removal process can be improved by optimizing device operation, without using less common or highly elaborate novel materials. We demonstrate, for the first time, continuous energy generation via capacitive mixing technology using differences in water salinity, and differences in gas phase CO2 concentration. Using a novel design of cylindrical ion exchange membranes serving as flow channels, we continuously extract energy from available concentration differences that otherwise would remain unused. These results may contribute to establishing a sustainable energy strategy when implementing energy extraction for sources such as CO2-emissions from power plants based on fossil fuels.

Extracting electric energy from small temperature differences is an emerging field in response to the transition toward sustainable energy generation. We introduce a novel concept for producing electricity from small temperature differences by the use of an assembly combining ion exchange membranes and porous carbon electrodes immersed in aqueous electrolytes. Via the temperature differences, we generate a thermal membrane potential that acts as a driving force for ion adsorption/desorption cycles within an electrostatic double layer, thus converting heat into electric work. We report for a temperature difference of 30 °C a maximal energy harvest of ~2 mJ/m2, normalized to the surface area of all the membranes.

Electrochemical double layer capacitors (EDLCs) are inherently high power devices when compared to rechargeable batteries. While capacitance and energy storage ability are mainly increased by optimizing the electrode active material or the electrolyte, the power capability could be improved by including conductive additives in the electrode formulations. This publication deals with the use of four different carbon additives – two carbon blacks and two graphites – in standard activated carbon based EDLC electrodes. The investigations include: (i) physical characterization of carbon powder mixtures such as surface area, press density, and electrical resistivity measurements, and (ii), electrochemical characterization via impedance spectroscopy and cyclic voltammetry of full cells made with electrodes containing 5 wt.% of carbon additive and compared to cells made with pure activated carbon electrodes in organic electrolyte. Improved cell performance was observed in both impedance and cyclic voltammetry responses. The results are discussed considering the main characteristics of the different carbon additives, and important considerations about electrode structure and processability are drawn.

Most efforts to improve the energy density of supercapacitors are currently dedicated to optimized porosity or hybrid devices employing pseudocapacitive elements. Little attention has been given to the effects of the low charge carrier density of carbon on the total material capacitance. To study the effect of graphitization on the differential capacitance, carbon onion (also known as onion-like carbon) supercapacitors are chosen. The increase in density of states (DOS) related to the low density of charge carriers in carbon materials is an important effect that leads to a substantial increase in capacitance as the electrode potential is increased. Using carbon onions as a model, it is shown that this phenomenon cannot be related only to geometric aspects but must be the result of varying graphitization. This provides a new tool to significantly improve carbon supercapacitor performance, in addition to having significant consequences for the modeling community where carbons usually are approximated to be ideal metallic conductors. Data on the structure, composition, and phase content of carbon onions are presented and the correlation between electrochemical performance and electrical resistance and graphitization is shown. Highly graphitic carbons show a stronger degree of electrochemical doping, making them very attractive for enhancing the capacitance.