Scientific publications

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.

A nanocomposite of graphene, cobalt hydroxide and nickel can conveniently be synthesized on gold-silver alloy lines. Using a two-step electrodeposition method, the scaly morphology is pre-deposited on a Ni film, followed by the interconnecting corrugated graphene/cobalt hydroxide composite nanomaterial. Due to the pre-deposited Ni film, the area capacity of the graphene/cobalt hydroxide/Ni electrode is 1.6-times of the graphene/cobalt hydroxide electrode. The kinetic analysis of the graphene/cobalt hydroxide/Ni electrode displays diffusion and non-diffusion contributions of 38% and 62% at 10 mV s−1, respectively. X-ray photoelectron spectroscopy exhibits the oxidation of Co2+ to Co3+ dedicated to the OH- ion insertion. Furthermore, graphene/cobalt hydroxide/Ni//activated carbon flexible micro-supercapacitor (MSC) was assembled by gel KOH-PVA electrolyte, graphene/cobalt hydroxide/Ni (positive electrode), and activated carbon (negative electrode), which manifests maximum volumetric energy of 18.6 mWh cm−3. Moreover, MSC retains over 94% capacitance after 10,000 cycles. After 1,000 continuous bending/unbending cycles at a 180° bending angle with the frequency of 100 mHz, the capacitance retention of MSC is still maintained at 97% of the initial value. The results show outstanding flexibility and mechanical stability of MSC based on graphene/cobalt hydroxide/Ni electrode and confirm that further chemical and physical optimization may lead to the development of quasi-solid-state hybrid MSCs.

Highly water-soluble, persistent, and mobile organic compounds (PMOCs) are more and more often detected in surface and groundwater, evoking potential threats to the environment and human health. Traditional water treatment strategies, including adsorption by activated carbon materials, fail to efficiently remove PMOCs due to their hydrophilic nature. Electro-assisted sorption processes offer a clean, facile, and promising solution to remove PMOCs on activated carbon-based electrodes and potentially allow an easy on-site sorbent regeneration (trap&release). In this work, the electrosorption of five selected PMOCs, that is, tetrapropylammonium (TPA+), benzyltrimethylammonium (BTMA+), p-tosylate (p-TsO-), p-toluenesulfonamide (p-TSA), and methyl-tert-butyl ether (MTBE), were investigated on two comprehensively characterized activated carbon felt (ACF) types carrying different surface functionalities. Significant enrichment factors in ranges of 102 to 103 for charged PMOCs were expected by our first estimation for electro-assisted trap&release on ACFs in flow systems applying potentials in the range of −0.1 V/+0.6 V vs. SHE for ad-/desorption, respectively. Defunctionalized ACF carrying larger density in surface π-systems and lower O-content promises a higher capability in electrosorption processes than the pristine material in terms of better material stability (tested for 5 cycles over 500 h) and better removal efficiency of ionic PMOCs. To improve ACFs adsorption performance for cationic and anionic PMOCs, permanent chemical surface modification and reversible electric polarization as alternative strategies are compared. Our findings explore future electrode and process design of electrosorption for applications to treat water contaminated by emerging PMOCs.

We consider the off-lattice two-dimensional q-state active clock model (ACM) as a natural discretization of the Vicsek model (VM) describing flocking. The ACM consists of particles able to move in the plane in a discrete set of q equidistant angular directions, as in the active Potts model (APM), with an alignment interaction inspired by the ferromagnetic equilibrium clock model. We find that for a small number of directions, the flocking transition of the ACM has the same phenomenology as the APM, including macrophase separation and reorientation transition. For a larger number of directions, the flocking transition in the ACM becomes equivalent to the one of the VM and displays microphase separation and only transverse bands, i.e., no re-orientation transition. Concomitantly also the transition of the q → ∞ limit of the ACM, the active XY model (AXYM), is in the same universality class as the VM. We also construct a coarse-grained hydrodynamic description for the ACM and AXYM akin to the VM.

CD4+ T cells are essential players in orchestrating the specific immune response against intracellular pathogens, and in inhibiting tumor development in an early stage. The activation of T cells is triggered by engagement of T cell receptors (TCRs). Here, CD3 and CD28 molecules are key factors, (co)stimulating signaling pathways essential for activation and proliferation of CD4+ T cells. T cell activation induces the formation of a tight mechanical bond between T cell and target cell, the so-called immunological synapse (IS). Due to this, mechanical cell properties, including stiffness, play a significant role in modulating cell functions. In the past, many approaches were made to investigate mechanical properties of immune cells, including micropipette aspiration, microplate-based rheometry, techniques based on deformation during cytometry, or the use of optical tweezers. However, the stiffness of T lymphocytes at a subcellular level at the IS still remains largely elusive.With this protocol, we introduce a method based on atomic force microscopy (AFM), to investigate the local cellular stiffness of T cells on functionalized glass/Polydimethylsiloxan (PDMS) surfaces, which mimicks focal stimulation of target cells inducing IS formation by T cells. By applying the peak force nanomechanical mapping (QNM) technique, cellular surface structures and the local stiffness are determined simultaneously, with a resolution of approximately 60 nm. This protocol can be easily adapted to investigate the mechanical impact of numerous factors influencing IS formation and T cell activation.Graphical abstract: Overview of the experimental workflow.Individual experimental steps are shown on the left, hands on and incubation times for each step are shown right.

Triple-negative breast cancer (TNBC) is an aggressive subtype of breast cancer (BC), which is characterized by the total absence of human epidermal growth factor receptor 2 (HER2), progesterone receptor (PR), and estrogen receptor (ER) expression. Cinobufacini injection (CI) is the aqueous extract from the dry skin of Bufo gargarizans, which is broadly used for the treatment of malignant tumors. However, the potential mechanism of CI against TNBC has not been fully revealed. In this study, we found that CI inhibited the proliferation of MDA-MB-231 and 4T1 cells in a time- and dose-dependent manner. RNA-seq data showed that downregulated and upregulated genes were mainly enriched in biological processes related to tumor cell proliferation, including cell cycle arrest and regulation of apoptosis signaling pathways. Indeed, after CI treatment, the protein level of CDK1 and Bcl-2/Bax decreased, indicating that CI induced the cell cycle of MDA-MB-231 arrest in the G2/M phase and increased the rate of apoptosis. Meanwhile, CI significantly inhibited the growth of tumor in vivo, and RNA-seq data showed that the TAZ signaling pathway played a vital role after CI treatment. Both immunohistochemistry and Western blot analysis confirmed the downregulation of Pin1 and TAZ, caused by CI treatment. Furthermore, the bioinformatics analysis indicated that Pin1 and TAZ were indeed elevated in TNBC patients, with poor staging, classification, and patient survival rate. In conclusion, CI effectively inhibited the proliferation of TNBC in vitro and in vivo and induced their apoptosis and cycle arrest through the Pin1–TAZ pathway.