Energie-Materialien

A hybrid membrane pseudocapacitive deionization (MPDI) system consisting of a hydrated vanadium pentoxide (hV2O5)-decorated multi-walled carbon nanotube (MWCNT) electrode and one activated carbon electrode enables sodium ions to be removed by pseudocapacitive intercalation with the MWCNT–hV2O5 electrode and chloride ion to be removed by non-faradaic electrosorption of the porous carbon electrode. The MWCNT–hV2O5 electrode was synthesized by electrochemical deposition of hydrated vanadium pentoxide on the MWCNT paper. The stable electrochemical operating window for the MWCNT–hV2O5 electrode was between −0.5 V and +0.4 V versus Ag/AgCl, which provided a specific capacity of 44 mAh g−1 (corresponding with 244 F g−1) in aqueous 1 m NaCl. The desalination performance of the MPDI system was investigated in aqueous 200 mm NaCl (brackish water) and 600 mm NaCl (seawater) solutions. With the aid of an anion and a cation exchange membrane, the MPDI hybrid cell was operated from −0.4 to +0.8 V cell voltage without crossing the reduction and oxidation potential limit of both electrodes. For the 600 mm NaCl solution, the NaCl salt adsorption capacity of the cell was 23.6±2.2 mg g−1, which is equivalent to 35.7±3.3 mg g−1 normalized to the mass of the MWCNT–hV2O5 electrode. Additionally, we propose a normalization method for the electrode material with faradaic reactions based on sodium uptake capacities.

A key challenge for present-day electric energy storage systems, such as supercapacitors and batteries, is to meet the world's growing demand for high performances, low cost, and environmental-friendliness. Here, we introduce a hybrid energy storage system combining zinc iodide (ZnI2) as redox electrolyte with a nanoporous activated carbon fiber (ACF) cathode and a zinc disk anode. We found that the nanopores (<1 nm) of ACF lead to a strong adsorption behavior of iodide and triiodide. Hence, this system exhibits low self-discharge rates without applying an ion exchange membrane. The high power performance (20.0 kW kg-1) originates from the enhanced redox kinetics of the iodide system as evidenced by electrochemical analysis. Considering the high specific energy (226 W h kg-1), the ACF/Zn ZnI2 battery represents an alternative for lead acid, Ni-Zn, and Ni-Cd batteries, while providing a supercapacitor-like power performance in the range of seconds to minutes charging times.

In recent decades, redox-active electrolytes have been applied in stationary energy storage systems, benefitting from Faradaic reactions of the electrolyte instead of the electrode material. One of the challenging tasks is to balance the redox activities between the negative and positive electrode. As a possible solution, a mixed electrolyte with vanadyl and tin sulfate was previously suggested; however, a low power performance is a great challenge to be overcome. Here, we found that the origin of the poor power performance in the mixture electrolyte system (vanadium complex and tin solution) is the reduction of the pore volume at the positive electrode via irreversible tin dioxide formation. To prevent the latter, we introduce a hybrid energy storage system exhibiting both battery-like and supercapacitor-like features via asymmetric redox electrolytes at the microporous activated carbon electrodes; SnF2 solution as anolyte and VOSO4 as catholyte. By employing an anion exchange membrane, the irreversible SnO2 formation at the positive electrode is effectively suppressed; thus, an asymmetric 1 M SnF2|3 M VOSO4 system provides a high maximum specific power (3.8 kW kg-1 or 1.5 kW L-1), while still exhibiting a high maximum specific energy up to 58.4 W h kg-1 (23.4 W h L-1) and a high cycling stability over 6500 cycles.

A solvent-free synthesis of hierarchical porous carbons is conducted by a facile and fast mechanochemical reaction in a ball mill. By means of a mechanochemical ball-milling approach, we obtained titanium(IV) citrate-based polymers, which have been processed via high temperature chlorine treatment to hierarchical porous carbons with a high specific surface area of up to 1814 m2 g−1 and well-defined pore structures. The carbons are applied as electrode materials in electric double-layer capacitors showing high specific capacitances with 98 F g−1 in organic and 138 F g−1 in an ionic liquid electrolyte as well as good rate capabilities, maintaining 87% of the initial capacitance with 1 M TEA-BF4 in acetonitrile (ACN) and 81% at 10 A g−1 in EMIM-BF4.

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.