04 Fakultät Energie-, Verfahrens- und Biotechnik
Permanent URI for this collectionhttps://elib.uni-stuttgart.de/handle/11682/5
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Item Open Access 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. AndreasAssessing 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.Item Open Access 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. AndreasFe-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.Item Open Access 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. AndreasThe 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.Item Open Access 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.Item Open Access Advancement of segmented cell technology in low temperature hydrogen technologies(2020) Biswas, Indro; Sánchez, Daniel G.; Schulze, Mathias; Mitzel, Jens; Kimmel, Benjamin; Gago, Aldo Saul; Gazdzicki, Pawel; Friedrich, K. AndreasThe durability and performance of electrochemical energy converters, such as fuel cells and electrolysers, are not only dependent on the properties and the quality of the used materials. They strongly depend on the operational conditions. Variations in external parameters, such as flow, pressure, temperature and, obviously, load, can lead to significant local changes in current density, even local transients. Segmented cell technology was developed with the purpose to gain insight into the local operational conditions in electrochemical cells during operation. The operando measurement of the local current density and temperature distribution allows effective improvement of operation conditions, mitigation of potentially critical events and assessment of the performance of new materials. The segmented cell, which can replace a regular bipolar plate in the current state of the technology, can be used as a monitoring tool and for targeted developments. This article gives an overview of the development and applications of this technology, such as for water management or fault recognition. Recent advancements towards locally resolved monitoring of humidity and to current distributions in electrolysers are outlined.Item Open Access 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. AndreasThe 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.Item Open Access A new approach to modeling solid oxide cell reactors with multiple stacks for process system simulation(2022) Tomberg, M.; Heddrich, M. P.; Sedeqi, F.; Ullmer, D.; Ansar, S. A.; Friedrich, K. AndreasReactors with solid oxide cells (SOC) are highly efficient electrochemical energy converters, which can be used for electricity generation and production of chemical feedstocks. The technology is in an upscaling phase. Thereby demanding development of strategies for robust and efficient operation or large SOC reactors and plants. The present state of technology requires reactors with multiple stacks to achieve the appropriate power. This study aims to establish and apply a simulation framework to investigate process systems containing SOC reactors with multiple stacks. Focusing especially on the operating behavior of SOC reactors under transient conditions, by observing the performance of all cells in the reactor. For this purpose, a simulation model of the entire SOC reactor consisting of multiple stacks, pipes, manifolds, and thermal insulation was developed. After validation on stack and reactor level, the model was used to investigate the fundamental behavior of the SOC reactors and the individual stacks in various operation modes. Additionally, the influences of local degradation and reactor scaling on the performance were examined. The results show that detailed investigation of the reactors is necessary to ensure operability and to increase efficiency and robustness. Furthermore, the computing performance is sufficient to develop and validate system controls.Item Open Access Experimental analysis of the co-electrolysis operation under pressurized conditions with a 10 layer SOC stack(2020) Riedel, Marc; Heddrich, Marc P.; Friedrich, K. AndreasThis study examines the performance of a solid oxide cell (SOC) stack during co-electrolysis of CO2 and H2O at elevated pressures up to 8 bar. Steady-state and dynamically recorded U(i)-curves were performed in order to evaluate the performance over a wide temperature range and to quantify the area specific resistance (ASR) at different pressure levels. Furthermore, the outlet gas composition at various current densities was analyzed and compared with the thermodynamic equilibrium. The open circuit voltage (OCV) was found to increase with higher pressure due to well known thermodynamic relations. An increase of the limiting current density at elevated pressure was not observed for the investigated stack with electrolyte supported cells. The ASR of the stack was found to decrease slightly with higher pressure. It revealed an increase of the cell resistance with lower H/C ratios in the feed at lower temperatures, whereas the performance of the co-electrolysis was very similar to steam electrolysis for temperatures above 820 °C. Within an impedance study for steam, co- and CO2 electrolysis operation it was shown that pure CO2 electrolysis exhibits a higher pressure sensitivity compared to pure steam or co-electrolysis due to significantly increased activation and diffusion resistances.Item Open Access Racing for green hydrogen economics with polymer electrolyte water electrolysis : how to be achieved(2024) Stiber, Svenja; Gago, Aldo; Friedrich, K. AndreasFor renewable hydrogen production, polymer electrolyte membrane water electrolysis is the most promising technology. However, the technology is not yet competitive with conventional hydrogen production in terms of cost. The impact of cost reduction options on CAPEX and OPEX is investigated. Depending on the hours of operation, the main cost factor is the production and manufacturing of components or the price of electricity. Clearly a tremendous need to implement low‐cost electrolysis cells on a large scale to bring green hydrogen production costs to a level 1-3 € kg-1 hydrogen.Item Open Access Tolerance of silicon oxide‐coated Pt/C catalyst toward CO and H2S contamination in hydrogen for proton exchange membrane fuel cells(2023) Prass, Sebastian; Nerlich, Leon; Singh, Rajveer; Godoy, Andres O.; Jankovic, Jasna; Friedrich, K. Andreas; Zamel, NadaPlatinum on graphitized low surface area carbon (Pt/C) is coated with a silicon oxide thin film and is employed as anode catalyst to manipulate the tolerance of proton exchange membrane fuel cells toward carbon monoxide and hydrogen sulfide contamination. The SiO2 coating, prepared by successive hydrolysis of 3-aminopropyl-triethoxisilane and tetraethoxysilane, forms clusters in proximity to Pt in sizes comparable to the catalyst particles, leaving most of the carbon surfaces free. The performance with and without CO is investigated in situ at relative humidities (RH) of 100%, 70%, and 40%. When operated with neat hydrogen, SiO2-Pt/C shows marginally better performance owing to an improved protonic conduction due to the water retaining hydrophilic SiO2. Upon operation with CO-contaminated fuel, the SiO2-Pt/C performs worse than that of Pt/C particularly at high RH. CO stripping measurements reveal an increase in CO oxidation potential for the SiO2-Pt/C, suggesting an increased CO coverage and consequently higher anode overpotentials during operation with CO-contaminated fuel. Upon operation with H2S in the fuel, the SiO2 coating extends the lifetime until the cell voltage broke down, which is attributed to the enhanced water retention due to SiO2 and the solubility of sulfuric species.