Chemische Charakterisierung und Spurenanalytik
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This contribution provides an overview of the BAMline synchrotron radiation beamline, which specializes in hard X-ray spectroscopy techniques for materials research. The BAMline offers X-ray absorption spectroscopy (XAS), x-ray fluorescence spectroscopy (XRF), and tomography to study materials' electronic structure, chemical composition, and structure. Key capabilities include standard and dispersive XAS for electronic structure, micro-XRF for elemental mapping, coded aperture imaging, and depth-resolved grazing exit XAS. The BAMline enables in situ characterization during materials synthesis and functions for energy, catalysis, corrosion, biology, and cultural heritage applications.
Ongoing developments like the implementation of machine learning techniques for experiment optimization and data analysis will be discussed. For instance, Bayesian optimization is being used to improve beamline alignment and scanning. An outlook to the future, where the BAMline will continue pioneering dynamic and multi-scale characterization, aided by advanced data science methods, to provide unique insights into materials research, will be given.
The vanadium redox flow battery (VRFB) is currently a potential candidate for stationary energy storage. A major challenge is the unintended vanadium transport through the separator, which results in a fade of capacity. To overcome this issue, it is necessary to understand the transport processes in the membrane on a more fundamental level. In this work, the vanadium species distribution in Nafion™ 117 after cyclization was investigated. Two membranes, one from a charged VRFB and another from a discharged VRFB, were analyzed using ultraviolet–visible spectroscopy (UV/VIS) and X-ray absorption near edge structure spectroscopy (XANES). Little difference between the two membranes was recognizable according to the UV/VIS results. In comparison, the XANES results showed that the membrane from the charged VRFB contains more V3+ than VO2+, whereas for the discharged case, more VO2+ is present in the membrane.
Polymer electrolyte membranes (PEM) are polymers which act as separator in an electrochemical cell and allow ionic charge flow to close the circuit. Widely used membranes are perfluorinated sulfonic-acid (PFSA) ionomers (e.g. Nafion™), a class of ion-conducting polymers with remarkable ion conductivity and chemical-mechanical stability. A nanoscopic water system around the sulfonic acid capped side-chains of the otherwise hydrophobic polymer allows the ion transport. Only approx. 14 molecules of water per sulfonic group are present in the fully hydrated state. In vanadium redox flow batteries (VRFB) ideally only protons are transported. The weak ion selectivity of Nafion™ is the main cause for the transportation of vanadium, briefly vanadium crossover, in VRFBs a system we have investigated more closely, lately. The consequences of crossover are a concentration imbalance and a self-discharge of the battery, which leads to a decrease of the capacity. The development of efficient energy storage systems is crucial for the transformation towards a renewable energy based economy. The VRFB has a great potential as a commercial electrochemical energy storage system due to properties including, but not limited to, no cross-contamination, a long cycle-life and a theoretically unlimited capacity. VRFB consists of two half-cells, which are linked to electrolyte tanks and separated by a membrane. The membrane plays a major role in overall cell performance. So far, vanadium transportation models, which include diffusion, migration, electroosmotic convection and pressure gradients, are inconsistent. There is no agreement in the literature on the diffusion coefficients of vanadium species (e.g. published diffusion coefficients of V2+ are located between 3.13·10-12 m²s-1 and 9.44·10-12 m²s-1) indicate that thevanadium crossover is not well understood and there is a lack on a more fundamental level. Since the membrane transport is the rate-determining step of the crossover as well as of the proton exchange it is extremely important to understand these phenomena on a fundamental level. This will eventually allow us to design better membranes. Alternative materials need to show equivalent performance compared with Nafion™ and ideally be more selective regarding ion cross-membrane transport.There are several options to approach the chemistry i.e. the interaction of dissolved and bound ions inside the confined water body of ionomeric membranes. Vanadium ions are a versatile model as UV/VIS data can be used to distinguish between the 5 species V2+, V3+, VO2+, VO2+ and V2O33+ of the electrolyte. Infrared spectroscopy has been applied to study the interaction of sulfonic groups and the ions. Molecular dynamic modeling is another approach to study the distribution and distances of ions. We now introduce X-ray absorption near edge structure spectroscopy (XANES) to study species and species changes inside Nafion™ and a novel membrane based on poly(1,1-difluoroethylene) (PVDF). We evaluated the methods and investigated the influence of irradiation, temperature and hydration on the measurements.
Vanadium redoxflow batteries (VRFB)are currently one of the most promising candidates for stationary energys torage.For large scale applications the ion conducting membranes currently in use need to be improved. Ideally,they need to become more cost efficient and selective regarding the vanadium crossover.For a better understanding of the vanadium crossover, the development of reliable analytical methods and procedures, that elucidate uptake and transport of vanadium ions in the membrane, is necessary. First, we present the uptake of V2+,V3+,VO2+, VO2+ and V2O33+ in Nafion™ and in a novel membrane based onpoly(1,1-difluoroethylene)(PVDF). In preliminary discharge/charge experiments the ETFE-based membrane, the precursor of PVDF-based membrane, performed comparable to Nafion™. The methods of choice for speciation are UV/Vis and X-ray absorption near edge structure spectroscopy (XANES). According to the results, V2O33+, formed from VO2+ and VO2+, diffuses also into the membrane. In present models, the diffusion of V2O33+ is neglected. In addition,we study whether reactions could take place inside the membranes’ nanoscopic water body using XANES. Exposing Nafion™ from one site with V3+a nd from the other site with VO2+ realized the experiment. The results verified that VO2+ was formed inside the membrane. However,in present models reactions inside the membrane are neglected, too.
Bundling analytical capacities to understand phase formation in recycling of functional materials
(2019)
Transitioning from combustion engine-driven transportation to e-mobility demands a paradigm shift – from a system geared to maximize energy efficiency (i.e. fuel consumption) to a system that may be constrained by the availability of high technology (critical) metals required for electrical energy storage systems and drives. In the wake of these developments efforts in securing new resources of these metals from recycling of end-of-life products are increasing steadily.
Recycling of Li-Ion batteries has recently been evaluated. The results pinpoint to a critical need for understanding slag Formation and its dependence on metal components like Mn under extreme conditions. This will allow researchers to predict optimal Operation setting and to react quickly to changing market demands (which may be Li or Co at one point but may also shift to Ni or rare earth elements (REE)). The long-term goal is to control the formation of specific phases in slags allowing for a Maximum yield of elements of interest and optimal recovery in the separation processes that follows. The combination of data on the physical micro structure and local chemistry of the multi-Phase products during and after processing will help to understand and derive thermodynamic and kinetic data on its formation.
In this paper we are giving an overview on the analytical challenges and approaches to provide robust data on local element concentration and species (especially Mn which is a common component of next generation Li-ion batteries cathodes), spanning the dimensions from the nanometer scale to the bulk material. The complementary interactions of X-rays and electrons make them ideal probes to collect Interface and “in-depth” information. Before- and -after studies as well as in situ structural changes and Phase (trans)formation, changes in elemental and elemental species (e.g. oxidation state) distribution may be tracked by X-ray diffraction (XRD), X-ray fluorescence microscopy and X-ray Absorption spectroscopy. The application of such advanced analytical tools will not only provide essential clues during early lab-based experiments towards the development of new recycling technologies, but may also be deployed for on-line and in-line monitoring of industrial processes.
Synchrotron radiation sources with their unique properties in terms of intensity, polarization and adjustability offer a wide range of possibilities in materials research. A basic introduction about the creation and special properties of synchrotron radiation will be given. Examples of current work at BAMline, the high-energy measuring facility of the Federal Institute for Materials Research and Testing at the synchrotron BESSY, are used to illustrate the possibilities and limitations of existing measuring methods. It will be shown how the formation of corrosion layers can be tracked, how the abrasion of implants leads to the introduction of heavy metals into the surrounding bone matrix and how the detection of smallest impurities in gold is possible by optimizing the measuring conditions. Finally, an outlook at the hardware and software developments to be expected in the coming years is given.
X-ray absorption fine structure spectroscopy (XAFS) is a frequently employed technique in order to investigate structural composition and change of chemical compounds such as catalytic species. These structural properties are essential (i) to understand underlying reaction mechanism and (ii) to further improve the design of efficient catalysts.
This investigation is based on a newly developed XAFS setup comprising both time- and lateral-resolved XAFS information simultaneously in a single-shot (S2XAFS). The primary broadband beam is generated by a filter/X-ray-mirror combination (bandpass). The transmitted beam through the sample is diffracted by a convexly bent Si (111) crystal, producing a divergent beam. This, in turn, is collected by an area sensitive detector with a theta to 2 theta geometry. This facile, stable and scanningless setup was tested at the BAMline @ BESSY-II (Berlin, Germany).
This contribution focuses on further experimental optimizations allowing the characterization of supported vanadium oxide (VOx) based catalysts at the lower hard X-ray regime (5 to 6 keV). First S2XAFS measurements of these catalysts are presented herein. Supported VOx catalysts show promising results in the oxidation of methane to formaldehyde.
S2XAFS allows determining the structural composition of the metal (i.e. vanadium) based on a fast and smart setup. It is therefore an ideal tool to identify crucial roles of chemical compounds in catalytic reactions.
XAFS@BAMline
(2018)
X-ray Absorption fine structure spectroscopy (XAFS) is a frequently employed technique in order to investigate structural composition and Change of chemical compounds such as catalytic species or corrosion processes. These structural properties are essential (i) to understand underlying reaction mechanism and (ii) to further improve the design of materials.
While XAFS measurements are usually performed with ionization Chambers or simple fluorescence detectors, we at BAMline specialize in measurements with innovative set-ups that meet Specialrequirements such as time resolution, (3D-) spatial Resolution or demanding sample environments.
This contribution presents various available XAFS configurations with their corresponding applications. In particular, these comprise single -shot XAFS for time- resolved measurements, grazing-exit XAFS with energy and a spatially resolved detector for the characterization of thin films and an in situ grazing incidence Setup for the characterization of corrosion layers.
Additionally,the possibility of analyzing Minute samples in total-reflection geometry is demonstrated.