Energie-Materialien

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.

Aluminum coatings were deposited on glass substrates by chemical vapor deposition using N-methylpiperidine (nmp) stabilized dichloroalane [Cl2AlH•2nmp] as aluminum precursor. With regard to temperature, the experimental conditions were varied between 75 °C and 125 °C for the precursor and between 250 °C and 450 °C for the substrate. Depending on these parameters, highly textured layers could be deposited. The substrates have been consistently covered by a layer of idiomorphic, mostly distorted octahedra of aluminum single crystals. The morphologies of the structures and the degree of orientation of the crystals were investigated by scanning electron microscopy and X-ray diffraction measurements. The high order of [111] orientation was found to decrease with increasing precursor and substrate temperature. We propose a mechanism for the generation of the octahedral structures based on the formation of mesocrystals. On heating, the dichloroalane (stabilized with nmp) loses the nmp ligands together with hydrogen and chlorine. The amine (nmp) seems to trigger the formation of aluminum crystals depending on the temperature and thus influences the texture of the Al-layer and the formation of well-formed octahedron-like structures.

Thermal signature of supercapacitors are investigated in-situ and ex-situ using commercial supercapacitors. Regarding the in-situ method, four supercapacitors were connected in series, with thermocouples embedded between the supercapacitors. As the applied current was increased, the temperature measured at the intrinsic positions also increased. When cycling at a current density of 0.11 A cm−2 the centre temperature increased by 14 K compared to the stack surface temperature. This is an important figure as literature states that an increase of 10 K leads to a corresponding decrease in the lifetime by a factor of 2. Using the obtained temperature profiles, the effective thermal conductivity of the stack was found to vary between 0.5 W K−1 m−1 and 1.0 W K−1 m−1, depending on the compaction of the stack. For the ex-situ measurements, the thermal conductivity and the thicknesses of the supercapacitor material layers were measured individually in order to determine the corresponding thermal conductivity of the stack. When using this method an effective thermal conductivity of the stack of 0.53 ± 0.06 W K−1 m−1 was obtained. The analysis also demonstrated that the main contributor to the thermal resistivity and conductivity of the supercapacitor construction is the electrodes. This demonstrates that when managing heat from supercapacitors it is important to focus on the thermal conductivity of the components materials.

Onion-like carbon, also known as carbon onions, is a highly conductive material enabling supercapacitor electrodes with a very high power density. However, the moderate specific capacitance (circa 30 F/g) is insufficient for many energy storage applications. In our study, we show how decoration of carbon onions with quinones provides a facile method to increase the energy density up to one order of magnitude, namely, from 0.5 Wh/kg to 4.5 Wh/kg, while retaining a high power density and long lifetime. We present data for carbon onions modified with three different kinds of quinones: 1,4-naphthoquinone, 9,10-phenanthrenequinone, and 4,5-pyrenedione. Quinone-decorated carbon onion electrodes are investigated considering the actual quinone loading and the resulting electrochemical performance is probed in 1 M H2SO4 as the electrolyte using cyclic voltammetry and galvanostatic charge/discharge. The maximum capacitance, 264 F/g, is found for carbon onions modified with 4,5-pyrenedione, which also shows the smallest fade in specific capacitance, namely 3%, over 10,000 charge and discharge cycles at a high current density of 1.3 A/g.

Electrochemical double layer capacitors (EDLC) are rapidly emerging as a promising energy storage technology offering extremely large power densities. Despite significant experimental progress, nanoscale operation mechanisms of the EDLCs remain poorly understood and it is difficult to separate processes at multiple time and length scales involved in operation including that of double layer charging and ionic mass transport. Here we explore the functionality of EDLC microporous carbon electrodes using a combination of classical electrochemical measurements and scanning probe microscopy based dilatometry, thus separating individual stages in charge/discharge processes based on strain generation. These methods allowed us to observe two distinct modes of EDLC charging, one fast charging of the double layer unassociated with strain, and another much slower mass transport related charging exhibiting significant sample volume changes. These studies open the pathway for the exploration of electrochemical systems with multiple processes involved in the charge and discharge, and investigation of the kinetics of those processes.