Prof. Dr. Volker Presser

Capacitive deionization (CDI) is an emerging technology for the facile removal of charged ionic species from aqueous solutions, and is currently being widely explored for water desalination applications. The technology is based on ion electrosorption at the surface of a pair of electrically charged electrodes, commonly composed of highly porous carbon materials. The CDI community has grown exponentially over the past decade, driving tremendous advances via new cell architectures and system designs, the implementation of ion exchange membranes, and alternative concepts such as flowable carbon electrodes and hybrid systems employing a Faradaic (battery) electrode. Also, vast improvements have been made towards unraveling the complex processes inherent to interfacial electrochemistry, including the modelling of kinetic and equilibrium aspects of the desalination process. In our perspective, we critically review and evaluate the current state-of-the-art of CDI technology and provide definitions and performance metric nomenclature in an effort to unify the fast-growing CDI community. We also provide an outlook on the emerging trends in CDI and propose future research and development directions.

Here we report direct physical evidence that confinement of molecular hydrogen (H2) in an optimized nanoporous carbon results in accumulation of hydrogen with characteristics commensurate with solid H2 at temperatures up to 67 K above the liquid-vapor critical temperature of bulk H2. This extreme densification is attributed to confinement of H2 molecules in the optimally sized micropores, and occurs at pressures as low as 0.02 MPa. The quantities of contained, solid-like H2 increased with pressure and were directly evaluated using in situ inelastic neutron scattering and confirmed by analysis of gas sorption isotherms. The demonstration of the existence of solid-like H2 challenges the existing assumption that supercritical hydrogen confined in nanopores has an upper limit of liquid H2 density. Thus, this insight offers opportunities for the development of more accurate models for the evaluation and design of nanoporous materials for high capacity adsorptive hydrogen storage.

Carbon onions derived by thermal annealing of nanodiamonds are an intriguing material for various applications that capitalize the nanoscopic size, high electrical conductivity, or moderately high external surface area. Yet, the impact on synthesis conditions and possible post-synthesis treatment on the pore characteristics lacks a detailed parametric understanding. We present a comprehensive model describing the change of structure, morphology, specific surface area (SSA), and pore size distribution (PSD) of carbon onions derived via thermal annealing of nanodiamonds as a function of synthesis parameters and the effect of physical activation in air. Different heating rates, temperatures, holding times, as well as two different nanodiamond precursors were used. During thermal annealing the increase in SSA occurs along with a loss of surface functional groups and volatile impurities. The sp3-to-sp2 conversion results in a much lower density and an increase in SSA of up to ∼160%. At high temperatures, a sintering and carbon redistribution process limits the increase in SSA and leading to the formation of micrometer-sized graphitic particles with a very low SSA. Oxidation in air is a facile way for the effective removal of predominately amorphous carbon between carbon onion particles and the removal of outer shells.

We present a comprehensive study on the influence of the synthesis atmosphere on the structure and properties of nanodiamond-derived carbon onions. Carbon onions were synthesized at 1300 and 1700 °C in high vacuum or argon flow, using rapid dynamic heating and cooling. High vacuum annealing yielded carbon onions with nearly perfect spherical shape. An increase in surface area was caused by a decrease in particle density when transitioning from sp3 to sp2 hybridization and negligible amounts of disordered carbon were produced. In contrast, carbon onions from annealing nanodiamonds in flowing argon are highly interconnected by few-layer graphene nanoribbons. The presence of the latter improves the electrical conductivity, which is reflected by an enhanced power handling ability of supercapacitor electrodes operated in an organic electrolyte (1 M tetraethylammonium tetrafluoroborate in acetonitrile). Carbon onions synthesized in argon flow at 1700 °C show a specific capacitance of 20 F/g at 20 A/g current density and 2.7 V cell voltage which is an improvement of more than 40% compared to vacuum annealing. The same effect was measured for a synthesis temperature of 1300 °C, with a 140% higher capacitance at 20 A/g for argon flow compared to vacuum annealing.

The energy performance of carbon onions can be significantly enhanced by introducing pseudocapacitive materials, but this is commonly at the cost of power handling. In this study, a novel synergistic electrode preparation method was developed by using carbon-fiber substrates loaded with quinone-decorated carbon onions. The electrodes are free standing, binder free, extremely conductive, and the interfiber space filling overcomes the severely low apparent density commonly found for electrospun fibers. Electrochemical measurements were performed in organic and aqueous electrolytes. For both systems, a high electrochemical stability after 10 000 cycles was measured, as well as a long-term voltage floating test for the organic electrolyte. The capacitance in 1 M H2SO4 was 288 F g−1 for the highest loading of quinones, which is similar to literature values, but with a very high power handling, showing more than 100 F g−1 at a scan rate of 2 Vs−1.

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.