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The principle of the electrochemical decomposition of water in an electrolysis cell has already been known for more than 230 years. The first generation of hydrogen by electricity was done as early as 1789 by van Troostwijk and Deiman using an electrostatic generator as the direct current source. Shortly after Volta invented the voltaic pile in 1800, Carlisle and Nicholson used such a device to decompose water into hydrogen and oxygen. In the same year, Ritter performed comparable experiments in Jena, Germany. Moreover, Cruickshank used a voltaic pile for the electrochemical decomposition of NaCl to hydrogen and chlorine at the beginning of the 19th century. Nevertheless, it took decades before the processes were used in the first technical applications. Around 1890 Charles Renard constructed a water electrolysis unit to generate hydrogen for French military airships. It is estimated that around 1900 more than 400 industrial alkaline water electrolyzers were in operation worldwide and large-scale deployment of the chlor-alkali process started. Later, different types of commercial alkaline water electrolyzers were developed in the 20th century to generate hydrogen needed to produce ammonia fertilizers based on low-cost hydroelectricity. As the 20th century progressed, the more cost-effective production of hydrogen by steam reforming of methane increasingly replaced water electrolysis, and by the end of the 20th century, the process was only used in niche applications. In the late 1960s the development of proton exchange membrane electrolysis began at General Electric using an acidic fluorinated ionomer as a solid electrolyte. But the technology became established in the following decades only in laboratory, military, and space applications due to the high material costs. At about the same time, General Electric, and the Brookhaven National Laboratory also started to develop high-temperature electrolysis with solid oxide cells. In Germany, Dornier followed in the HOT ELLY project this technology until the mid-1980s. But despite of all technical progress made commercialization of the membrane and solid oxide electrolysis could not be launched in that time. But new interest in water electrolysis was stimulated already in the 1990s as hydrogen was regarded as a green energy carrier for renewable energy sources like wind and solar power and to power fuel cells, e.g., in automotive applications. However, it is only in the last 10 years that we have seen a significant increase in global interest for water electrolysis, with the adoption of ambitious national climate protection programs. Water electrolysis is regarded as the central element for sector coupling and is expected to make an important contribution to reducing greenhouse gas (GHG) emissions close to net-zero by 2050.

In order to be a real competitor to other industrial-scale hydrogen production technologies, solid oxide electrolysis cells (SOEC) must present essential features such as high hydrogen production rates, load flexibility and high system efficiency. However, operating conditions necessary to achieve these objectives can induce undesired performance deterioration and microstructural degradation negatively influencing the long-term stability of SOECs. This work provides the results of experimental investigations on the performance of SOECs operated under different operating conditions. In order to induce and accelerate specific degradation phenomena high steam partial pressures, fast load changes, high voltages, high steam conversion rates and alternating mode were applied. Different kinds and degrees of impact on performance and microstructure were observed and analyzed in detail. Correlations between performance changes and their underlying processes were investigated and useful connections between them were discovered. The major findings are summarized in the form of a suggestion for accelerated stress test (AST) protocols for SOECs. The developed ASTs enable deeper understanding of several degradation phenomena induced by different operating conditions and present methods for identification thereof. Further, the ASTs were estimated to have potential to predict performance changes over long-term operating periods.

The combination of aerosol-jet printing and laser micromilling technology makes it possible to fabricate the ceramics MEMS platforms and SMD packages by using their digital models. It is shown that combination of platinum metallization for the heater and ceramic materials is the best choice for the microelectronic MEMS actuator and sensor package which should be installed in devices aimed for work under harsh environmental conditions. The developed metal-oxide semiconductor gas sensors in miniaturized package with low power consumption can be extremely useful in modern agriculture facilities. The idea of their integration into livestock facilities, food-storage, forestry, fish farming and horticulture seems quite promising for developing smart agriculture, where devices must work under harsh environmental conditions such as high humidity level and temperature. To fulfill the demand of these types of sensors their mass production should be cheap and not require a clean room. In this work we present a way of fabrication of all parts of gas sensor including a package using only one setup, which allows us to reduce the cost of the final product and simplify the whole production process in order to make the technology available for many different agricultural applications.

The efficient high temperature electrolysis is of high interest for potential application in a renewable energy system. The possibility to use high temperature heat for the electrolysis reaction makes the SOEC technology an attractive option for the integration in process concepts for the production of valuable chemicals from renewable energies. Moreover, the SOEC allows the electrolysis of water and carbon dioxide in a so-called Co-electrolysis. The produced syngas can be used in a subsequent synthesis step, e.g. a Fischer-Tropsch synthesis. The development of these power-to-product processes as well as of necessary components are in focus of current research activities at IKTS. The main component is the high temperature electrolyzer (SOEC). In collaboration with Plansee SE, the CFY stack technology has been developed. This stack technology can be applied for SOFC, SOEC and reversible operation (rSOC) and establishes an universal platform for different applications. Performance maps of a MK352 CFY stack in steam- (H2O) and Co- (H2O/CO2) electrolysis operation show a difference in electric power demand of less than 5 %. This low additional power demand of Co-electrolysis together with the advantages of direct syngas production makes it promising for highly efficient integration within a process concept for the production of valuable hydrocarbons. The output syngas can be directly adjusted by choosing appropriate operating conditions for the SOEC to typical compositions used for reactions like Fischer-Tropsch synthesis. Based on this approach the operating conditions were set and durability tests with stacks (>1500 h) were conducted. The results raised several scientific questions which were answered by splitting the “black box” of the stack in separate parallel investigated experiments in the fields of cell tests, tests of interconnect materials, contact resistances, protective layer and glasses. The surprising behavior of reversible degradation of the stacks was analyzed by single cell experiments and could be reduced by adjusting of operating conditions and resulted in a fine tuning of the electrode design. Nevertheless still an irreversible degradation of about 1%/1000 h was detected. Several material tests consolidated the common understanding of degradation phenomena and will be shown with comparison to the real stack tests. The results show the excellent suitability of the CFY stack for electrolysis applications and give an outlook on further improvements. Figure: 30-cell MK352 stack for SOFC/SOEC and rSOC operation Figure 1

The progress of the Internet of Things stimulates the development of sensors of small size and low power consumption. Miniaturized metal-oxide semiconductor (MOX) gas sensors (e.g. methane, hydrogen or carbon monoxide detection) can be integrated into agro-industrial facilities such as livestock facilities, fish farming, forestry, food-storage and horticulture, where they support future-oriented plant production (smart agriculture). The central part of a MOX gas sensor is a micro-hotplate, which is mainly responsible for the sensor power consumption at operating temperatures from 450 °C to 600 °C. Under harsh environmental conductions, ceramic materials are the best choice for the micro-hotplate substrate and sensor housing (ceramic MEMS) in combination with platinum metallization for the heater. To realize such gas sensors with low power consumption (

Despite long and successful development history of Solid Oxide Cells (SOC) continuous improvement in performance, longevity, manufacturing and system integration is necessary to bring this highly efficient technology to the market. The activities on material development and optimization at IKTS are focused mainly on enhancement of durability in SOFC, SOEC and rSOC operation and on boosting the power density for electrolysis operation. The recent results show considerable enhancement in cell longevity and power density. The SOC priorities in applied research are moving from materials to industrialization and Fraunhofer as applied R&D service provider is following this trend. During recent years considerable efforts on simplification and automation of cell and stack manufacturing processes has been addressed at IKTS. The manufacturing processes for electrode manufacturing have been adjusted for high yield automated printing on thin electrolytes with integrated quality control measures. The efficient ways for reduction of time and energy consumption for sealing process of SOC stacks have been found and shown in pilot production as well as automated assembling of components to stacks demonstrated. Furthermore the stack integration into modules utilizing stacks of different providers has been addressed during last years and reliable solutions for building of compact stack modules of higher power (2 to 10 kW) has been developed and tested with industrial partners. The increasing interest in “green hydrogen” generated multiple opportunities for SOEC technology to be considered as inherent part of industrial and chemical processes. IKTS pioneering work on coupled operation of SOEC module with Fischer-Tropsch reactor provided first demonstration of feasibility of this approach for waxes production. The process design and analysis of steel, using SOEC technology, has been performed and resulted in multiple demonstration activities in last four years. Recently novel approaches for ammonia production are addressed at IKTS showing opportunity for transportable chemicals/fuel production without need of CO2 source. High power electrolysis applications (>10 MW) will need new approaches for stack design and put higher requirements on durability. High power electrolysis applications will also open a new window of opportunities for industrial SOFC power plants. This vision is considered as outline for our future research.

A stationary SOFC system utilizing gas from a biomass updraft gasifier is under development within the project “HiEffBioPower” by MAWERA, BIOS, Bosal, AVL, Calida Cleantech, Fraunhofer IKTS, Wuppertal Institute and University Utrecht (European Union Horizon2020 No. 727330). The system is based on Mk352-CFY-stack with Chromium based (CFY) interconnects and electrolyte supported cells. These stacks are robust, redox stable and demonstrated low degradation rates. The stacks are arranged to modules of eight 30-cell stacks and are electrically connected in series. The stack module was pre-tested at the test rig at IKTS and showed performance in accordance with system requirements. Stationary power points were measured to compare the behaviour of the stack module with the system tests at MAWERA. AVL designed and installed the overall SOFC system (heat exchangers, stack, catalytic afterburner, process control and visualisation) with a nominal capacity of 6 kWel. After shipping all parts of the SOFC system to MAWERA in Hard (AT), the coupling of the biomass gasifier, the gas cleaning unit and the SOFC system was conducted. The system is operated by an automated process control. The highest efforts needed the novel gas cleaning unit, consisting of a high temperature filter, a desulphurisation unit as well as a novel catalytic gas reforming stage developed by BIOS. The biomass gasifier has been operated with wood chips of different quality. The high tar contents of the product gas make a tar cracking essential to reach a high calorific value of the gas for the SOFC system. The novel gas cleaning system shows good performance and reaches the defined SOFC requirements. The SOFC system developed and operated by AVL reached stable conditions for several days. The operating results of the stack module at lab conditions and at the real system are in a good agreement. The SOFC stack module performance in terms of cell voltages, stack temperature distribution and fuel utilization under biomass reformate fuel will be shown and supported by several simulation to get an overall energy balance. Examples of optimization for several components by CFD simulation and component tests will be given.

Membrane-electrode-assembly (MEA) is a heart component of SOFC and defines the limits for power density, efficiency and durability available for exploitation in stacks and systems. MEA performance is often given as measure for possibilities of fuel cell technology. Most widespread way to communicate the MEA performance is to present the I-U-characteristic at a constant temperature and to estimate the area specific resistance from the slope of this curve. Other methods for characterization of performance like current density, impedance and local resistance measurement under defined operating conditions also have been used for this purpose. The fuel composition worldwide used for MEA tests (from dry hydrogen to H2:H2O=50:50) is connected with open circuit voltage which has great impact on measured performance. Moreover the realized fuel utilization strongly depends on operating conditions and varies in broad range. For these reasons it is difficult to compare results achieved by different researchers. It is beneficial to define unified value which would characterise electrochemical MEA performance. To resolve this challenge the voltage drop during the cell performance have been mathematically separated in two parts: (i) voltage drop due to change of Nernst voltage as a result of fuel utilization (and humidification) by current flow and (ii) voltage drop due to ohmic and polarization losses in the cell. This approach allows to separate the influence of non-linearity of Nernst voltage dependence from current on estimated cell resistance. It was found that at temperatures above 750°C the area specific resistance of the cell corrected to the Nernst voltage drop (fuel utilization) is a constant value, which only weakly depend on fuel composition. Favourable operating conditions as well as influence of operating conditions for estimation of cell resistance will be presented.

The stack concept of electrolyte supported cells (ESC) is applicable for both, solid oxide fuel cells as well as solid oxide electrolysis cells. High power densities and efficiencies comparable to anode supported cells (ASC) can be achieved, however, for the stack design presented in this paper, in unison with high robustness. Incorporating an electrolyte made of fully scandia stabilized zirconia paired with chromium-based CFY (Cr5FeY) interconnects of matched CTE (coefficient of thermal expansion), a feasible stack concept was created with the focus on long-term stability in regard to high temperature corrosion and thermal cycling. Stack data of more than 20.000 hours of a single stack is presented in addition to industrial onward development of the stack design. Using the same material combinations and the same footprint as for the MK351-design, the newly developed MK352-design was simulated, drafted and produced and allows for easier stack setup and system integration. Minor changes in interconnect (IC) design enable lower pressure drops over the stack, which, paired with enhanced tolerance chains lead to enhanced stack performance, especially in regard to thermal cycling. Cross-checked, test results for the MK352-stack are in good agreement with the simulation.

Iron or chromium based alloys are currently the most preferred materials for SOFC interconnects. The poisoning of the cathode of the membrane electrode assembly (MEA) due to evaporation of chromium species from the metallic interconnect (MIC) and the oxidation of the interconnect surface during stack operation at elevated (800-900 °C) temperatures are regarded to be the major mechanisms affecting the degradation behaviour of the SOFC stack. The oxidation at the cathode side of the interconnect can cause up to one third of the total stack degradation. Despite intensive investigations on corrosion stability of MIC for SOFC application over the past decades, the main attention was focused mainly on the material properties in the cathode side gas conditions (ambient air). The growth behavior and the composition of oxides grown in the SOFC anode gas environment as well as the influence of the oxides on the contact resistance between MIC and anode contacting are still not investigated comprehensively. The MIC materials have to be stable over more than 40,000 hours to satisfy a demand for a continuous increase of operation times of the SOFC stacks. Real time tests over such long time scales are cost intensive. A modification of standard material test procedures, with the aim to accelerate material degradation, is therefore necessary. In order to realize this, three ferritic steels (Crofer 22 APU, Crofer 22 H, AISI 441) and a chromium-based alloy were tested in SOFC anode gas environment in a temperature range between 725 – 875°C. The experiments were carried out under variation of the water vapor content in the gas mixture for different exposure times in order to create the accelerated degradation testing conditions for MIC and to investigate the behavior of these materials caused by the formation of growing chromium oxide based scales. Both gravimetric measurements and FESEM/EDX data, as well as polished microimage sections were analyzed to characterize the oxidation kinetics and the microstructure of the oxide scales and interconnect materials. A clear correlation between increasing temperatures and increasing oxide growth rate constants kp,w can be demonstrated in all materials. This interrelation results in thicker surface oxide scales. A comparison of surface oxide thicknesses after 1000 h oxidation in reducing atmosphere show an increase between 725°C and 875°C with a maximum factor of about 3.8 in ferritic steels and 2.4 for CFY. The comparison of kp,w values at temperatures between 725 and 875°C show acceleration factors of 8,2-11.9 in ferritic steels and 2.3 for CFY. No significant dependence of the oxide growth rate in ferritic steels and CFY by variation of the water content in fuel gas for concentrations within H2/H2O=87/13 vol.% and H2/H2O= 50/50 vol.% was found. The structures of the oxide layers are specific for each material and consist mainly of Cr2O3 (CFY) and Cr2O3/(Cr,Mn)3O4 in ferritic steels with different element distributions and thickness ratios. Beside this, the zone of an inner oxidation of MICs with the Al-, Si- and Ti- rich oxide inclusions can be seen in ferritic samples, whose microstructures differ depending on analyzed materials and temperatures. In Nb containing materials (Crofer H, AISI 441), Silicon precipitations as Laves phases as well as continuous SiO2 scales were observed beneath the formed Cr2O3 top layer. Furthermore, an increase of the internal oxidation zone was identified with increasing temperatures in ferritic steels. In CFY, the internal oxidation zone with Cr2O3 inclusions in the material bulk remains almost constant over 1000 h oxidation in the tested temperature range. Electrical measurements in the dual gas atmosphere reveal also an increase of resistance within 1000 h material exposure under anode gas conditions. Comparison of these results suggests that materials, forming such isolating SiO2 layers, show a higher resistance increase. The results of the oxide scale formation under the anode gas conditions in tested Crofer 22 APU and CFY samples are compared with data derived from the real SOFC stacks. Only minor differences in the oxide thicknesses were observed between the gas inlet and gas outlet (region with higher water content) at the anode side of the stacks. This behavior is similar to the results of our artificially oxidized MIC samples in which we also have not found a clear evidence for an increase in oxide scale growth rate with higher water content in the humidification range tested. Such effects can indicate, that the reactions at phase boundary are dominated by solid-state diffusion and the rate supply of adsorbed oxygen species (from H2O) is not the limiting factor (in the tested H2O concentrations range).