Energie-Materialien

A new carbon model derived from in situ small-angle X-ray scattering (SAXS) enables a quantitative description of the voltage-dependent arrangement and transport of ions within the nanopores of carbon-based electric double-layer capacitors. In the first step, ex situ SAXS data for nanoporous carbon-based electrodes are used to generate a three-dimensional real-space model of the nanopore structure using the concept of Gaussian random fields. This pore model is used to derive important pore size characteristics, which are cross-validated against the corresponding values from gas sorption analysis. In the second step, simulated in situ SAXS patterns are generated after filling the model pore structure with an aqueous electrolyte and rearranging the ions via a Monte Carlo simulation for different applied electrical potentials. These simulated SAXS patterns are compared with in situ SAXS patterns recorded during voltage cycling. Experiments with different cyclic voltammetry scan rates revealed a systematic time lag between ion transport processes and the applied voltage signal. Global transport into and out of nanopores was found to be faster than the accommodation of the local equilibrium arrangement in favor of sites with a high degree of confinement.

A detailed understanding of confinement and desolvation of ions in electrically charged carbon nanopores is the key to enable advanced electrochemical energy storage and water treatment technologies. Here, we present the synergistic combination of experimental data from in situ small-angle X-ray scattering with Monte Carlo simulations of length-scale-dependent ion arrangement. In our approach, the simulations are based on the actual carbon nanopore structure and the global ion concentrations in the electrodes, both obtained from experiments. A combination of measured and simulated scattering data provides compelling evidence of partial desolvation of Cs+ and Cl− ions in water even in mixed micro–mesoporous carbons with average pore size well above 1 nm. A tight attachment of the aqueous solvation shell effectively prevents complete desolvation in carbons with subnanometre average pore size. The tendency of counter-ions to change their local environment towards high confinement with increasing voltage determines conclusively the performance of supercapacitor electrodes.

This work establishes molybdenum disulfide/carbon nanotube electrodes for the desalination of high molar saline water. Capitalizing on the two-dimensional layered structure of MoS2, both cations and anions can be effectively removed from a feed water stream by faradaic ion intercalation. The approach is based on the setup of capacitive deionization (CDI), where an effluent water stream is desalinated via the formation of an electrical double-layer at two oppositely polarized carbon electrodes. Yet, CDI can only be effectively applied to low concentrated solutions due to the intrinsic limitation of the electrosorption mechanism. By replacing the conventional porous carbon with MoS2/CNT binder-free electrodes, deionization of sodium and chloride ions was achieved by ion intercalation instead of ion electrosorption. This enabled stable desalination performance over 25 cycles in various molar concentrations, with salt adsorption capacities of 10, 13, 18, and 25 mg g-1 in 5, 25, 100, and 500 mM NaCl aqueous solutions, respectively. This novel approach of faradaic deionization (FDI) paves the way towards a more energy-efficient desalination of brackish water and even sea water.

Capacitive deionization (CDI) is a promising technology for the desalination of brackish water due to its potentially high energy efficiency and its relatively low costs. One of the most challenging issues limiting current CDI cell performance is poor cycling stability. CDI can show highly reproducible salt adsorption capacities (SACs) for hundreds of cycles in oxygen-free electrolyte, but by contrast poor stability when oxygen is present due to a gradual oxidation of the carbon anode. This oxidation leads to increased concentration of oxygen-containing surface functional groups within the micropores of the carbon anode, increasing parasitic co-ion current and decreasing SAC. In this work, activated carbon (AC) was chemically modified with titania to achieve additional catalytic activity for oxygen-reduction reactions on the electrodes, preventing oxygen from participating in carbon oxidation. Using this approach, we show that the SAC can be increased and the cycling stability prolonged in electrochemically highly demanding oxygen-saturated saline media (5 mM NaCl). The electrochemical oxygen reduction reaction (ORR) occurring in our CDI cell was evaluated by the number of electron transfers during charging and discharging. It was found that, depending on the amount of titania, different ORR pathways take place. A loading of 15 mass% titania presents the best CDI performance and also demonstrates a favorable three-electron transfer ORR.

We explore different electrode microstructures and the associated implications on the electrochemical stability of activated carbon/lithium titanate (Li4Ti5O12, LTO) composite electrodes by incrementally increasing the LTO content. At low LTO concentrations, the electrochemical stability is progressively improved with respect to neat activated carbon based electrodes. This trend is abruptly changed for high LTO concentrations (72 mass%) as the electrolyte starts to decompose unexpectedly far below the electrochemical stability boundaries of the single materials. We attribute this to a loss of electrical percolation and local degradation spots caused by peculiarities of the carbon distribution: Initially the sub-micrometer-sized LTO solely occupies spaces between the large, micrometer-sized activated carbon. With increasing LTO content the activated carbon particles get separated in an insulating LTO matrix. Electrochemical stability can be reestablished with electronic conduction paths of well distributed sub-micrometer-sized carbon black particles. By this way, cell degradation can be reduced and the cycle life of cells with high LTO concentration is prolonged from 10 to >36,000 cycles. Finally, we propose a simple method to distinguish cell fading caused by electrolyte decomposition from cell fading caused by poor electrical percolation.

Nitrogen-doped nanoporous carbons were synthesized by a solvent-free mechanochemically induced one-pot synthesis. This facile approach involves the mechanochemical treatment and carbonization of three solid materials: potassium carbonate, urea, and lignin, which is a waste product from pulp industry. The resulting nitrogen-doped porous carbons offer a very high specific surface area up to 3000 m2 g−1 and large pore volume up to 2 cm3 g−1. The mechanochemical reaction and the impact of activation and functionalization are investigated by nitrogen and water physisorption and high-resolution X-ray photoelectron spectroscopy (XPS). Our N-doped carbons are highly suitable for electrochemical energy storage as supercapacitor electrodes, showing high specific capacitances in aqueous 1 m Li2SO4 electrolyte (177 F g−1), organic 1 m tetraethylammonium tetrafluoroborate in acetonitrile (147 F g−1), and an ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate; 192 F g−1). This new mechanochemical pathway synergistically combines attractive energy-storage ratings with a scalable, time-efficient, cost-effective, and environmentally favorable synthesis.

This work introduces for the first time titanium disulfide (TiS2)/carbon nanotube (CNT) electrodes for desalination of high molarity saline water. Capitalizing on the two-dimensional layered structure of TiS2, cations can be effectively removed from a feedwater stream by intercalation. The TiS2–CNT hybrid electrode is paired in an asymmetric cell with microporous activated carbon cloth without an ion exchange membrane. By electrochemical analysis, the correlation between the state of charge and the stability of TiS2 was investigated. By using post-mortem X-ray diffraction, the sodium-ion intercalation mechanism gives an insight into how the state of charge affects the structure and cyclic stability. Our system showed stable desalination performance over 70 cycles at high molar concentration (600 mM), with a cell salt removal capacity of 14 mg/g (equivalent to a sodium removal capacity of 35.8 mg/g normalized to the mass of TiS2–CNT). This novel approach of membrane-free hybrid Faradaic capacitive deionization paves the way toward energy-efficient desalination of seawater.

Capacitive deionization (CDI) is a promising salt removal technology with high energy efficiency when applied to low molar concentration aqueous electrolytes. As an interfacial process, ion electrosorption during CDI operation is sensitive to the pore structure and the total pore volume of carbon electrodes limits the maximum salt adsorption capacity (SAC). Thus, activation of carbons as a widely used method to enhance the porosity of a material should also be highly attractive for improving SAC values. In our study, we use easy-to-scale and facile-to-apply CO2-activation at temperatures between 950 °C and 1020 °C to increase the porosity of commercially available activated carbon. While the pore volume and surface area can be significantly increased up to 1.51 cm3 g−1 and 2113 m2 g−1, this comes at the expense of making the carbon more hydrophobic. We present a novel strategy to capitalize on the improved pore structure by admixing as received (more hydrophilic) carbon with CO2-treated (more hydrophobic) carbon for CDI electrodes without using membranes. This translates into an enhanced charge storage ability in high and low molar concentrations (1 M and 5 mM NaCl) and significantly improved CDI performance (at 5 mM NaCl). In particular, we obtain stable CDI performance at 0.86 charge efficiency with 13.1 mg g−1 SAC for an optimized 2:1 mixture (by mass).

Supercapacitors are devices for rapid and efficient electrochemical energy storage and commonly employ carbon coated aluminum foil as the current collector. However, the thickness of the metallic foil and the corresponding added mass lower the specific and volumetric performance on a device level. A promising approach to drastically reduce the mass and volume of the current collector is to directly sputter aluminum on the freestanding electrode instead of adding a metal foil. Our work explores the limitations and performance perspectives of direct sputter coating of aluminum onto carbon film electrodes. The tight and interdigitated interface between the metallic film and the carbon electrode enables high power handling, exceeding the performance and stability of a state-of-the-art carbon coated aluminum foil current collector. In particular, we find an enhancement of 300% in specific power and 186% in specific energy when comparing aluminum sputter coated electrodes with conventional electrodes with Al current collectors.

Atomic layer deposition (ALD) is a facile process to decorate carbon surfaces with redox-active nanolayers. This is a particularly attractive route to obtain hybrid electrode materials for high performance electrochemical energy storage applications. Using activated carbon and carbon onions as representatives of substrate materials with large internal or external surface area, we have studied the enhanced energy storage capacity of vanadium oxide coatings. While the internal porosity of activated carbon readily becomes blocked by obstructing nanopores, carbon onions enable the continued deposition of vanadia within their large interparticle voids. Electrochemical benchmarking in lithium perchlorate in acetonitrile (1 M LiClO4) showed a maximum capacity of 122 mAh/g when using vanadia coated activated carbon and 129 mAh/g for vanadia coated carbon onions. There is an optimum amount of vanadia between 50-65 wt.% for both substrates that results in an ideal balance between redox-activity and electrical conductivity of the hybrid electrode. The stability of both systems is promising, with a capacity retention of ~95 % after 3,000 cycles. Assembling asymmetric (charge balanced) full cells, a maximum specific energy of 38 Wh/kg and 29 Wh/kg was found for the system employing carbon onions or activated carbon, respectively.