04 Fakultät Energie-, Verfahrens- und Biotechnik

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    Application of ion chromatography for the reliable quantification of ammonium in electrochemical ammonia synthesis experiments : a practical guide
    (2023) Bragulla, Sebastian C. H.; Lorenz, Julian; Harms, Corinna; Wark, Michael; Friedrich, K. Andreas
    Assessing novel electrocatalysts for the electrochemical ammonia synthesis (EAS) requires reliable quantitative trace analysis of electrochemically produced ammonia to infer activity and selectivity. This study concerns the development of an ion chromatography (IC) method for quantitative trace analysis of ammonium in 0.1 M sulfuric acid electrolyte, which is applied to EAS gas-diffusion electrode (GDE) experiments with commercial chromium nitride as electrocatalyst. The developed IC method is highly sensitive, versatile, and reliable, achieving a limit of quantification (LOQ) of 6 μg l-1 (6 ppbmol) ammonium. The impacts of the sample matrix, dilution, and neutralization, as well as contamination, on the quantitative analysis by IC are analyzed. Experimental constraints result in an effective LOQ including dilution of 60 μg l-1 for the determination of ammonium in 0.1 M sulfuric acid electrolyte, owing to necessary sample dilution. The practical guide presented herein is intended to be very relevant for the field of EAS as a guideline and applicable to a broad range of catalyst systems and ion chromatography devices.
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    Temperature reduction as operando performance recovery procedure for polymer electrolyte membrane fuel cells
    (2024) Zhang, Qian; Schulze, Mathias; Gazdzicki, Pawel; Friedrich, Kaspar Andreas
    To efficiently mitigate the reversible performance degradation of polymer electrolyte membrane fuel cells, it is crucial to thoroughly understand recovery effects. In this work, the effect of operando performance recovery by temperature reduction is evaluated. The results reveal that operando reduction in cell temperature from 80 °C to 45 °C yields a performance recovery of 60-70% in the current density range below 1 A cm-2 in a shorter time (1.5 h versus 10.5 h), as opposed to a known and more complex non-operando recovery procedure. Notably, the absolute recovered voltage is directly proportional to the total amount of liquid water produced during the temperature reduction. Thus, the recovery effect is likely attributed to a reorganization/rearrangement of the ionomer due to water condensation. Reduction in the charge transfer and mass transfer resistance is observed after the temperature reduction by electrochemical impedance spectroscopy (EIS) measurement. During non-operando temperature reduction (i.e., open circuit voltage (OCV) hold during recovery instead of load cycling) an even higher recovery efficiency of >80% was achieved.
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    Effect of polytetrafluorethylene content in Fe‐N‐C‐based catalyst layers of gas diffusion electrodes for HT‐PEM fuel cell applications
    (2024) Zierdt, Tanja; Müller‐Hülstede, Julia; Schmies, Henrike; Schonvogel, Dana; Wagner, Peter; Friedrich, K. Andreas
    Fe-N-C catalysts are a promising alternative to replace cost-intensive Pt-based catalysts in high temperature polymer electrolyte membrane fuel cell (HT-PEMFC) electrodes. However, the electrode fabrication needs to be adapted for this new class of catalysts. In this study, gas diffusion electrodes (GDEs) are fabricated using a commercial Fe-N-C catalyst and different polytetrafluorethylene (PTFE) binder ratios, varying from 10 to 50 wt % in the catalyst layer (CL). The oxygen reduction reaction performance is investigated under HT-PEMFC conditions (160 °C, conc. H3PO4 electrolyte) in a half-cell setup. The acidophilic character of the Fe-N-C catalyst leads to intrusion of phosphoric acid electrolyte into the CL. The strength of the acid penetration depends on the PTFE content, which is visible via the contact angles. The 10 wt % PTFE GDE is less capable to withdraw product water and electrolyte and results into the lowest half-cell performance. Higher PTFE contents counterbalance the acid drag into the CL and impede flooding. The power density at around 130 mA mgCatalyst−2 increases by 34 % from 10 to 50 wt % PTFE.
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    PEM single cells under differential conditions : full factorial parameterization of the ORR and HOR kinetics and loss analysis
    (2022) Gerling, Christophe; Hanauer, Matthias; Berner, Ulrich; Friedrich, K. Andreas
    The anode and cathode kinetics are parameterized based on differential cell measurements. Systematic parameter variations are evaluated to disentangle the dependencies of the electrochemical impedance spectroscopy (EIS) signatures in H2/H2 mode. We introduce a new CO recovery protocol for both electrodes that enables to accurately characterize the hydrogen oxidation reaction (HOR) kinetics. Then, we demonstrate that a compact Tafel kinetics law captures the oxygen reduction reaction (ORR) kinetics for a full factorial grid of conditions, covering a wide range of relative humidities (rH), temperatures, oxygen partial pressures and current densities. This yields the characteristic activation energy and effective reaction order, and we reconcile models that make different assumptions regarding the rH dependency. Moreover, we analyze O2 transport contributions by steady-state and transient limiting current techniques and heliox measurements. Although the rising uncertainty of loss corrections at high current densities makes it impossible to unambiguously identify an intrinsic potential-dependent change of the Tafel slope, our data support that such effect needs not be considered for steady-state cathodic half-cell potentials above 0.8 V.
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    Wetting behavior of aprotic Li-air battery electrolytes
    (2021) Kube, Alexander; Bienen, Fabian; Wagner, Norbert; Friedrich, Kaspar Andreas
    The open architecture of cathodes in Li–air batteries implies the need for open porosity with adequate pore size distribution and surface energy optimization with regard to the electrolyte. The interaction of liquid and cathode material, especially the wetting properties, which depend on cathode material, roughness and porosity, and electrolyte properties, needs to be understood properly to avoid flooding and assure high active areas. In this work, contact angle goniometry, capillary rise method, and pressure saturation curves are used to investigate the wetting properties of dimethyl sulfoxide (DMSO), tetraethylene glycol dimethyl ether (Tetraglyme), a 1:1 mixture of ethylene carbonate and dimethyl carbonate (EC:DMC) and water on a gas diffusion layer (GDL) Sigracet 39BC, and a pure flat polytetrafluorethylene (PTFE) foil. Contact angle measurement shows that all three organic solvents wet the GDL hydrophobic agent PTFE. Capillary rise measurements show that all sample liquids slowly imbibe into the porous network. While for Tetraglyme an efficient penetration is limited by the high viscosity, water flow rate is slowed down by the hydrophobic pore network of the GDL. Pressure saturation curves for DMSO, Tetraglyme, and EC:DMC can be obtained for the first time and are compared with the water pressure saturation curve.
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    Meteorological and air quality measurements in a city region with complex terrain : influence of meteorological phenomena on urban climate
    (2023) Samad, Abdul; Kiseleva, Olga; Holst, Christopher Claus; Wegener, Robert; Kossmann, Meinolf; Meusel, Gregor; Fiehn, Alina; Erbertseder, Thilo; Becker, Ralf; Roiger, Anke; Stanislawsky, Peter; Klemp, Dieter; Emeis, Stefan; Kalthoff, Norbert; Vogt, Ulrich
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    High-resolution analysis of ionomer loss in catalytic layers after operation
    (2018) Morawietz, T.; Handl, M.; Oldani, C.; Gazdzicki, P.; Hunger, Jürgen; Wilhelm, Florian; Blake, John; Friedrich, K. Andreas; Hiesgen, R.
    The function of catalytic layers in fuel cells and electrolyzers depends on the properties of the ionically conductive phase, which are most commonly perfluorinated ionomers based on Nafion and Aquivion. An analysis by atomic force microscopy reveals that the ultrathin ionomer films around Pt/C agglomerates have a thickness distribution ranging from 3.5 nm to 20 nm. Their conductivity and gas permeation properties determine the fuel cell performance to a large extend. For electrodes in Aquivion-based membrane-electrode-assemblies operation-induced structure changes were investigated by means of material- and conductivity-sensitive atomic force microscopy, infrared spectroscopy and electron-dispersive X-ray analysis. The observed thinning of the ultrathin ionomer films was mainly caused by polymer degradation deduced from reduced swelling after long-time operation and a significant loss of ionomer with operation time detected by infrared spectroscopy. From the linear thickness increase of the ultrathin films with rising humidity, a mainly layered structure of the ionomer was deduced. An influence of thickness of such ultrathin ionomer films on fuel cell lifetime was found by analysis of differently prepared membrane-electrode-assemblies, where a linear increase of irreversible degradation rate with ionomer film thickness in the electrodes of unused membrane-electrode-assemblies was found.
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    To prevent or promote grid expansion? : analyzing the future role of power transmission in the European energy system
    (2021) Cao, Karl-Kiên; Pregger, Thomas; Haas, Jannik; Lens, Hendrik
    Future energy supply systems must become more flexible than they are today to accommodate the significant contributions expected from intermittent renewable power sources. Although numerous studies on planning flexibility options have emerged over the last few years, the uncertainties related to model-based studies have left the literature lacking a proper understanding of the investment strategy needed to ensure robust power grid expansion. To address this issue, we focus herein on two important aspects of these uncertainties: the first is the relevance of various social preferences for the use of certain technologies, and the second is how the available approaches affect the flexibility options for power transmission in energy system models. To address these uncertainties, we analyze a host of scenarios. We use an energy system optimization model to plan the transition of Europe’s energy system. In addition to interacting with the heating and transport sectors, the model integrates power flows in three different ways: as a transport model, as a direct current power flow model, and as a linearized alternating current power flow model based on profiles of power transfer distribution factors. The results show that deploying transmission systems contribute significantly to system adequacy. If investments in new power transmission infrastructure are restricted - for example, because of social opposition - additional power generation and storage technologies are an alternative option to reach the necessary level of adequacy at 2% greater system costs. The share of power transmission in total system costs remains widely stable around 1.5%, even if cost assumptions or the approaches for modeling power flows are varied. Thus, the results indicate the importance of promoting investments in infrastructure projects that support pan-European power transmission. However, a wide range of possibilities exists to put this strategy into practice.
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    Influence of cycling profile, depth of discharge and temperature on commercial LFP/C cell ageing : post-mortem material analysis of structure, morphology and chemical composition
    (2020) Simolka, Matthias; Heger, Jan-Frederik; Kaess, Hanno; Biswas, Indro; Friedrich, K. Andreas
    The paper presents post-mortem analysis of commercial LiFePO4 battery cells, which are aged at 55 °C and - 20 °C using dynamic current profiles and different depth of discharges (DOD). Post-mortem analysis focuses on the structure of the electrodes using atomic force microscopy (AFM) and scanning electron microscopy (SEM) and the chemical composition changes using energy dispersive X-ray spectroscopy (SEM-EDX) and X-ray photoelectron spectroscopy (XPS). The results show that ageing at lower DOD results in higher capacity fading compared to higher DOD cycling. The anode surface aged at 55 °C forms a dense cover on the graphite flakes, while at the anode surface aged at - 20 °C lithium plating and LiF crystals are observed. As expected, Fe dissolution from the cathode and deposition on the anode are observed for the ageing performed at 55 °C, while Fe dissolution and deposition are not observed at - 20 °C. Using atomic force microscopy (AFM), the surface conductivity is examined, which shows only minor degradation for the cathodes aged at - 20 °C. The cathodes aged at 55 °C exhibit micrometer size agglomerates of nanometer particles on the cathode surface. The results indicate that cycling at higher SOC ranges is more detrimental and low temperature cycling mainly affects the anode by the formation of plated Li.
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    Bridging granularity gaps to decarbonize large‐scale energy systems : the case of power system planning
    (2021) Cao, Karl‐Kiên; Haas, Jannik; Sperber, Evelyn; Sasanpour, Shima; Sarfarazi, Seyedfarzad; Pregger, Thomas; Alaya, Oussama; Lens, Hendrik; Drauz, Simon R.; Kneiske, Tanja M.
    The comprehensive evaluation of strategies for decarbonizing large‐scale energy systems requires insights from many different perspectives. In energy systems analysis, optimization models are widely used for this purpose. However, they are limited in incorporating all crucial aspects of such a complex system to be sustainably transformed. Hence, they differ in terms of their spatial, temporal, technological, and economic perspective and either have a narrow focus with high resolution or a broad scope with little detail. Against this background, we introduce the so‐called granularity gaps and discuss two possibilities to address them: increasing the resolutions of the established optimization models, and the different kinds of model coupling. After laying out open challenges, we propose a novel framework to design power systems in particular. Our exemplary concept exploits the capabilities of power system optimization, transmission network simulation, distribution grid planning, and agent‐based simulation. This integrated framework can serve to study the energy transition with greater comprehensibility and may be a blueprint for similar multimodel analyses.