Publikationen

MXene-transition metal dichalcogenide (TMD) heterostructures are synthesized through a one-step heat treatment of Nb2C and Nb4C3. These MXenes are used without delamination or any pre-treatment. Heat treatments accomplish the sacrificial transformation of these MXenes into TMD (NbS2) at 700 and 900 °C under H2S. This work investigates, for the first time, the role of starting MXene phase in the derivative morphology. It is shown that while treatment of Nb2C at 700 °C leads to the formation of pillar-like structures on the parent MXene, Nb4C3 produces nano-mosaic layered NbS2. At 900 °C, both MXene phases, of the same transition metal, fully convert into nano-mosaic layered NbS2 preserving the parent MXene's layered morphology. When tested as electrodes for hydrogen evolution reaction, Nb4C3-derived hybrids show better performance than Nb2C derivatives. The Nb4C3-derived heterostructure exhibits a low overpotential of 198 mV at 10 mA cm−2 and a Tafel slope of 122 mV dec−1, with good cycling stability in an acidic electrolyte.

The capacitance of the electrochemical interface has traditionally been separated into two distinct types: non-Faradaic electric double-layer capacitance, which involves charge induction, and Faradaic pseudocapacitance, which involves charge transfer. However, the electrochemical interface in most energy technologies is not planar but involves porous and layered materials that offer varying degrees of electrolyte confinement. We suggest that understanding electrosorption under confinement in porous and layered materials requires a more nuanced view of the capacitive mechanism than that at a planar interface. In particular, we consider the crucial role of the electrolyte confinement in these systems to reconcile different viewpoints on electrochemical capacitance. We propose that there is a continuum between double-layer capacitance and Faradaic intercalation that is dependent on the specific confinement microenvironment. We also discuss open questions regarding electrochemical capacitance in porous and layered materials and how these lead to opportunities for future energy technologies.

Abstract High-entropy sulfides (HESs) containing 5 equiatomic transition metals (M), with different M:S ratios, are prepared by a facile one-step mechanochemical approach. Two new types of single-phase HESs with pyrite (Pa-3) and orthorhombic (Pnma) structures are obtained and demonstrate a homogeneously mixed solid solution. The straightforward synthesis method can easily tune the desired metal to sulfur ratio for HESs with different stoichiometries, by utilizing the respective metal sulfides, even pure metals, and sulfur as precursor chemicals. The structural details and solid solution nature of HESs are studied by X-ray diffraction, transmission electron microscopy, energy-dispersive X-ray spectroscopy, electron energy loss spectroscopy, X-ray photoelectron spectroscopy, inductively coupled plasma optical emission spectroscopy, and Mössbauer spectroscopy. Since transition metal sulfides are a very versatile material class, here the application of HESs is presented as electrode materials for reversible electrochemical energy storage, in which the HESs show high specific capacities and excellent rate capabilities in secondary Li-ion batteries.

Abstract Environmentally sustainable, low-cost, flexible, and lightweight energy storage technologies require advancement in materials design in order to obtain more efficient organic metal-ion batteries. Synthetically tailored organic molecules, which react reversibly with lithium, may address the need for cost-effective and eco-friendly anodes used for organic/lithium battery technologies. Among them, carboxylic group-bearing molecules act as high-energy content anodes. Although organic molecules offer rich chemistry, allowing a high content of carboxyl groups to be installed on aromatic rings, they suffer from low conductivity and leakage to the electrolytes, which restricts their actual capacity, the charging/discharging rate, and eventually their application potential. Here, a densely carboxylated but conducting graphene derivative (graphene acid (GA)) is designed to circumvent these critical limitations, enabling effective operation without compromising the mechanical or chemical stability of the electrode. Experiments including operando Raman measurements and theoretical calculations reveal the excellent charge transport, redox activity, and lithium intercalation properties of the GA anode at the single-layer level, outperforming all reported organic anodes, including commercial monolayer graphene and graphene nanoplatelets. The practical capacity and rate capability of 800 mAh g−1 at 0.05 A g−1 and 174 mAh g−1 at 2.0 A g−1 demonstrate the true potential of GA anodes in advanced lithium-ion batteries.

Energy-efficient technologies for the remediation of water and generation of drinking water is a key towards sustainable technologies. Electrochemical desalination technologies are promising alternatives towards established methods, such as reverse osmosis or nanofiltration. In the last few years, hydrogen-driven electrochemical water purification has emerged. This review article explores the concept of desalination fuel cells and capacitive-Faradaic fuel cells for ion separation.

P2-type layered oxides with the general Na-deficient composition Na x TMO2 (x < 1, TM: transition metal) are a promising class of cathode materials for sodium-ion batteries. The open Na+ transport pathways present in the structure lead to low diffusion barriers and enable high charge/discharge rates. However, a phase transition from P2 to O2 structure occurring above 4.2 V and metal dissolution at low potentials upon discharge results in rapid capacity degradation. In this work, we demonstrate the positive effect of configurational entropy on the stability of the crystal structure during battery operation. Three different compositions of layered P2-type oxides were synthesized by solid-state chemistry, Na0.67(Mn0.55Ni0.21Co0.24)O2, Na0.67(Mn0.45Ni0.18Co0.24Ti0.1Mg0.03)O2 and Na0.67(Mn0.45Ni0.18Co0.18Ti0.1Mg0.03Al0.04Fe0.02)O2 with low, medium and high configurational entropy, respectively. The high-entropy cathode material shows lower structural transformation and Mn dissolution upon cycling in a wide voltage range from 1.5 to 4.6 V. Advanced operando techniques and post-mortem analysis were used to probe the underlying reaction mechanism thoroughly. Overall, the high-entropy strategy is a promising route for improving the electrochemical performance of P2 layered oxide cathodes for advanced sodium-ion battery applications.

Lithium-ion batteries are the primary power source for electric vehicles and portable electronic devices, creating a massive demand to mine and extract lithium. So far, lithium extraction has focused on brine and geological deposits. Yet, access to the enormous amount of lithium (at low concentration) in the earth’s oceans and other aqueous media remains challenging. Electrodialysis with Li-selective ceramic membranes could effectively separate lithium from seawater but at a high energy cost. Reversible electrochemical processes, like redox flow batteries, can overcome the limitation of electrodialysis-based systems. Herein we propose a system combining Li-selective ceramic membranes and a simple redox flow electrolyte to accomplish continuous lithium recovery from seawater. The lithium-extraction redox flow battery (LE-RFB) extracts dissolved lithium with a purity of 93.5% from simulated seawater, corresponding to a high Li/Mg selectivity factor of about 500.000:1. Benefiting from a low operating voltage, 1 g of lithium is extracted with only 2.5 Wh of energy consumption.

Summary Electrochemical seawater desalination has drawn significant attention as an energy-efficient technique to address the global issue of water remediation. Microporous carbons, that is, carbons with pore sizes smaller than 2 nm, are commonly used for capacitive deionization. However, micropores are ineffective for capacitive deionization at high molar strength because of their inability to permselectively uptake ions. In our work, we combine experimental work with molecular dynamics simulation and reveal the ability of sub-nanometer pores (ultramicropores) to effectively desalinate aqueous media at seawater-like molar strength. This is done without any ion-exchange membrane. The desalination capacity in 600 mM reaches 12 mg/g, with a charge efficiency of 94% and high cycling stability over 200 cycles (97% of charge efficiency retention). Using molecular dynamic simulations and providing experimental data, our work makes it possible both to understand and to calculate desalination capacity and charge efficiency at high molar strength as a function of pore size.

As freshwater shortage has become a global issue, water desalination technique is of great importance to meet the increasing demand for freshwater resources of human beings. Capacitive deionization (CDI) has attracted significant attention in the current desalination technology portfolio. This is because of the use of low-cost electrode materials and the promise of high energy efficiency when including the energy recovery process. CDI, which has its advantage for applying low ionic strength by using various materials, has been explored to improve the system's performance. However, very few have addressed the importance of proper parameter designs, especially the electrodes. In our work, the same activated carbon of different average particle sizes has been studied by applying different desalination parameters (flow rate, holding time, salt concentrations). Our data show that larger particles limit intraparticle ion transportation because of the increased diffusion path length. We also see that a higher packing density, often favored by smaller particles or distribution of particle sizes, is detrimental to interparticle ion transportation. Our work addressed the importance of proper electrode and desalination parameter design for higher desalination performances.

Electrolyte confinement inside carbon nanopores strongly affects ion electrosorption in capacitive deionization. A thorough understanding of the intricate pore size influence enables enhanced charge storage performance and desalination in addition to ion separation. In subnanometer pores, where the pore size is smaller than hydrated ion size, a dehydration energy barrier must be overcome before the ions can be electrosorbed into the pores. Ion sieving is observed when the dehydration energy is larger than the applied energy. However, when a high electrochemical potential is used, the ions can desolvate and enter the pores. Capitalizing on the difference in size and dehydration energy barriers, this work applies the subnanometer porous carbon material, and a high electrochemical ion selectivity for Cs+ and K+ over Na+, Li+, Mg2+, and Ca2+ is observed. This establishes a possible way for selective heavy metal removal by varying pore and solvated ion sizes. Our work also shows the transition from double-layer capacitance to diffusion-limited electrochemical features in narrow ultramicropores.