Prof. Dr. Volker Presser

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.

In this proof-of-concept study, we introduce and demonstrate MXene as a novel type of intercalation electrode for desalination via capacitive deionization (CDI). Traditional CDI cells employ nanoporous carbon electrodes with significant pore volume to achieve a large desalination capacity via ion electrosorption. By contrast, MXene stores charge by ion intercalation between the sheets of its two-dimensional nanolamellar structure. By this virtue, it behaves as an ideal pseudocapacitor, that is, showing capacitive electric response while intercalating both anions and cations. We synthesized Ti3C2-MXene by the conventional process of etching ternary titanium aluminum carbide i.e., the MAX phase (Ti3AlC2) with hydrofluoric acid. The MXene material was cast directly onto the porous separator of the CDI cell without added binder, and exhibited very stable performance over 30 CDI cycles with an average salt adsorption capacity of 13 ± 2 mg g−1.

The energy storage mechanism of electric double-layer capacitors is governed by ion electrosorption at the electrode surface. This process requires high surface area electrodes, typically highly porous carbons. In common organic electrolytes, bare ion sizes are below one nanometer but they are larger when we consider their solvation shell. In contrast, ionic liquid electrolytes are free of solvent molecules, but cation-anion coordination requires special consideration. By matching pore size and ion size, two seemingly conflicting views have emerged: either an increase in specific capacitance with smaller pore size or a constant capacitance contribution of all micro- and mesopores. In our work, we revisit this issue by using a comprehensive set of electrochemical data and a pore size incremental analysis to identify the influence of certain ranges in the pore size distribution to the ion electrosorption capacity. We see a difference in solvation of ions in organic electrolytes depending on the applied voltage and a cation-anion interaction of ionic liquids in nanometer sized pores.

In this study, we investigate two different activated carbons and four conductive additive materials, all produced in industrial scale from commercial suppliers. The two activated carbons differed in porosity: one with a narrow microporous pore size distribution, the other showed a broader micro-mesoporous pore structure. Electrochemical benchmarking was carried out in one molar tetraethylammonium tetrafluoroborate in acetonitrile. Comprehensive structural, chemical, and electrical characterization was carried out by varied techniques. This way, we correlate the electrochemical performance with composite electrode properties, such as surface area, pore volume, electrical conductivity, and mass loading for different admixtures of conductive additives to activated carbon. The electrochemical rate handling (from 0.1 A g−1 to 10 A g−1) and long-time stability testing via voltage floating (100 h at 2.7 V cell voltage) show the influence of functional surface groups on carbon materials and the role of percolation of additive particles.

Carbon beads with sub-micrometer diameter were produced with a self-emulsifying novolac-ethanol-water system. A physical activation with CO2 was carried out to create a high microporosity with a specific surface area varying from 771 (DFT) to 2237 m2/g (DFT) and a total pore volume from 0.28 to 1.71 cm3/g. The carbon particles conserve their spherical shape after the thermal treatments. The controllable porosity of the carbon spheres is attractive for the application in electrochemical double layer capacitors. The electrochemical characterization was carried out in aqueous 1 M Na2SO4 (127 F/g) and organic 1 M tetraethylammonium tetrafluoroborate in propylene carbonate (123 F/g). Furthermore, an aqueous redox electrolyte (6 M KI) was tested with the highly porous carbon and a specific energy of 33 W·h/kg (equivalent to 493 F/g) was obtained. In addition to a high specific capacitance, the carbon beads also provide an excellent rate performance at high current and potential in all tested electrolytes, which leads to a high specific power (>11 kW/kg) with an electrode thickness of ca. 200 ?m.

We demonstrate stable hybrid electrochemical energy storage performance of a redox-active electrolyte, namely potassium ferricyanide in aqueous media in a supercapacitor-like setup. Challenging issues associated with such a system are a large leakage current and high self-discharge, both stemming from ion redox shuttling through the separator. The latter is effectively eliminated when using an ion exchange membrane instead of a porous separator. Other critical factors toward the optimization of a redox-active electrolyte system, especially electrolyte concentration and volume of electrolyte, have been studied by electrochemical methods. Finally, excellent long-term stability is demonstrated up to 10 000 charge/discharge cycles at 1.2 and 1.8 V, with a broad maximum stability window of up to 1.8 V cell voltage as determined via cyclic voltammetry. An energy capacity of 28.3 Wh/kg or 11.4 Wh/L has been obtained from such cells, taking the nonlinearity of the charge–discharge profile into account. The power performance of our cell has been determined to be 7.1 kW/kg (ca. 2.9 kW/L or 1.2 kW/m2). These ratings are higher compared to the same cell operated in aqueous sodium sulfate. This hybrid electrochemical energy storage system is believed to find a strong foothold in future advanced energy storage applications.