Prof. Dr. Volker Presser

Polyvinylpyrrolidone (PVP) is presented as a "greener" alternative to commonly used supercapacitor binders, namely polyvinylidenedifluoride (PVDF) or polytetrafluoroethylene (PTFE). The key advantages of using PVP are that it is non-toxic and soluble in ethanol and it can be used to spray coat or drain cast activated carbon (AC) electrodes directly on a current collector such as aluminum foil – in contrast to PTFE that requires rolling or PVDF that requires toxic N-methylpyrrolidone (NMP). The electrodes with the best mechanical stability incorporated 3.5 mass% of 1.300.000 g mol−1 PVP. Compared to PTFE or PVDF, the resulting pore volume was significantly higher and the specific surface area significantly larger when using PVP (normalized to the amount of AC). A good electrochemical performance was observed in organic electrolytes for AC–PVP electrodes: 112 or 97 F g−1 at 0.1 A g−1 in 1 M TEA–BF4 in propylene carbonate or acetonitrile, respectively. The performance stability was comparable to PTFE-bound electrodes when adjusting the maximum cell voltage to 2.5 V while preserving the manufacturing features of PVDF–AC films. (Electro)chemical stability is shown by electrochemical testing and infrared vibrational spectroscopy for propylene carbonate and acetonitrile.

The thermal conductivity of supercapacitor film electrodes composed of activated carbon (AC), AC with 15 mass% multi-walled carbon nanotubes (MWCNTs), AC with 15 mass% onion-like carbon (OLC), and only OLC, all mixed with polymer binder (polytetrafluoroethylene), has been measured. This was done for dry electrodes and after the electrodes have been saturated with an organic electrolyte (1 M tetraethylammonium-tetrafluoroborate in acetonitrile, TEA-BF4). The thermal conductivity data was implemented in a simple model of generation and transport of heat in a cylindrical cell supercapacitor systems. Dry electrodes showed a thermal conductivity in the range of 0.09-0.19 W K-1 m-1 and the electrodes soaked with an organic electrolyte yielded values for the thermal conductivity between 0.42 and 0.47 W K-1 m-1. It was seen that the values related strongly to the porosity of the carbon electrode materials. Modeling of the internal temperature profiles of a supercapacitor under conditions corresponding to extreme cycling demonstrated that only a moderate temperature gradient of several degrees Celsius can be expected and which depends on the ohmic resistance of the cell as well as the wetting of the electrode materials.

Room temperature ionic liquids (RTIL) are an emerging class of electrolytes enabling high cell voltages and, in return, high energy density of advanced supercapacitors. Yet, the low temperature behavior, including freezing and thawing, is little understood when confined in the narrow space of nanopores. This study shows that RTILs may show a tremendously different thermal behavior when comparing bulk with nanoconfined properties as a result of the increased surface energy of carbon pore walls. In particular, continuous increase in viscosity is accompanied with slowed-down charge/discharge kinetics during in-situ electrochemical characterization. Freezing reversibly collapses the energy storage ability – while thawing fully restores the initial energy density of the material. For the first time, a different thermal behavior in positively and negatively polarized electrodes is demonstrated. This leads to different freezing and melting points in the two electrodes. Compared to bulk, RTIL in the confinement of electrically charged nanopores, shows the unique behavior of being highly affine for supercooling; that is, the electrode freezing during heating.

Electrical energy storage (EES) is one of the most critical areas of technological research around the world. Storing and efficiently using electricity generated by intermittent sources and the transition of our transportation fleet to electric drive depend fundamentally on the development of EES systems with high energy and power densities. Supercapacitors are promising devices for highly efficient energy storage and power management, yet they still suffer from moderate energy densities compared to batteries. To establish a detailed understanding of the science and technology of carbon/carbon supercapacitors, this review discusses the basic principles of the electrical double-layer (EDL), especially regarding the correlation between ion size/ion solvation and the pore size of porous carbon electrodes. We summarize the key aspects of various carbon materials synthesized for use in supercapacitors. With the objective of improving the energy density, the last two sections are dedicated to strategies to increase the capacitance by either introducing pseudocapacitive materials or by using novel electrolytes that allow to increasing the cell voltage. In particular, advances in ionic liquids, but also in the field of organic electrolytes, are discussed and electrode mass balancing is expanded because of its importance to create higher performance asymmetric electrochemical capacitors.

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.

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.