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In this work, the influence of increased potentials during the start-up/shut-down process on metallic bipolar plates (316L) with the coating system Cr/a-C based on graphite-like carbon is investigated. In comparison to commonly applied post-coated bipolar plates, a new low-cost manufacturing process based on pre-coated metal sheets for bipolar plates was evaluated. By developing a vehicle near start-up/shut-down cycle, a relative humidity of 140% and anode residence time of 0.94 s show the greatest damage potential of the cycle variations. After 2000 start-up/shut-down cycles, pre-coated metallic bipolar plates show no increased voltage loss compared to conventional coatings. Nevertheless, the resistances increase for Cr/a-C post- and pre-coating at the H2 outlet. This correlates with an increased surface roughness of the bipolar plate but otherwise only minor surface changes can be observed. The coating variation has no effect on the extent of catalyst coated membrane thinning or increased content of metal ions.

The mechanical recharge of zinc-air batteries is described in this chapter. These systems can be divided into mechanically rechargeable systems with cassettes and hydraulically rechargeable systems with either pumped electrolyte or pumped zinc slurry. A zinc slurry usually consists of zinc particles in a binder-stabilized alkaline electrolyte. A special feature of the hydraulic systems is that the power (size of the active electrode area) and the capacity of the battery (size of the electrolyte tank) can be scaled independently of each other. Hydraulically rechargeable zinc-air technologies can either be operated below or above the zincate solubility limit. These two operation modes show significant differences with respect to the maximum achievable specific capacity and specific energy of the battery system. Further characteristics of zinc slurry electrodes are described with focus on the energy density and the electrolyte conductivity. The chapter also contains a description of discharge characteristics which includes power densities and depth-of-discharge with passivation effects, as well as methods to determine the state of charge. In addition, an overview on the development history of mechanically rechargeable zinc-air batteries is given. This includes among others the work at Compagnie Generale d'Electricite (CGE) and Pinnacle Research Institute with slurry-based systems. The work with pumped electrolyte systems with a static bed of zinc articles at Lawrence Livermore National Laboratory and Metallic Power/Zincnyx/MGX Renewables are also described. Additionally the work with mechanically rechargeable cassettes at Electric Fuel Limited is reported. The chapter concludes with an assessment of the operational capability of mechanically and hydraulically rechargeable zinc-air batteries and a comparison with other metal-air batteries.

Polymer electrolyte membrane fuel cells (PEMFCs) operating at low temperature (60–80 °C, up to 110 °C) are mostly limited in their performance by the kinetics of the oxygen reduction reaction (ORR), leading to high loadings of platinum (Pt) in the cathode. Pt catalysts are without alternative in numerous industrial applications, and since Pt resources are limited, the associated high costs for low temperature fuel cells are hindering among other factors their commercialization. In order to increase the fraction of electrocatalytically available Pt towards ORR, this work is devoted to the factors responsible for the microstructure of the PEMFC cathodes. Typically, the active layers are coated by processes like spraying, doctor blading, printing etc. Therefore, the final structure actually is strongly dependent on the coating process and the physicochemical properties of the catalyst dispersions used. Selecting commercially available electrocatalysts from Johnson-Matthey and Tanaka as active material and ultrasonically assisted spraying as the coating method, systematic variations of the surface chemistry of the catalyst particles and their influence on catalyst layer morphology and therefore electrical and electrochemical properties of resulting membrane electrode assemblies (MEA) have been investigated. It could be shown, that the colloid–chemical properties of the catalyst dispersions have a profound influence not only on the microstructure of the MEAs but also on the performance under operating conditions.

Traffic related air pollutants cause power losses and decrease the lifetime of proton exchange membrane fuel cell (PEMFC). The relevance of this influence for vehicles is not exactly known due to a lack of studies under realistic conditions. Therefore, the present study aims at a better understanding. For the first time ever the influence of selected air pollutants on automobile fuel cell short stacks with different platinum loadings and a realistic driving cycle is examined. The driving cycle used, is an existing course near the city of Stuttgart, Germany. The experiments were accompanied with online measurements of relevant contaminant concentrations on the course. Furthermore, tests with a semi-dynamic profile have been executed for more than 1500 h and show an irreversible damage of the PEMFC by nitrogen oxides. With respect to the present results, spontaneous power losses of about 5% and over 10% in special situations by the nitrogen oxides can be expected for fuel cell vehicles in urban areas. NH3 will lead to a spontaneous power loss of less than 3%, but causes a progressive irreversible damage. Together the tests reveal that air pollutants have a significant negative influence on fuel cell vehicles in urban areas.

Centrifugal fans are suitable for the air supply of fuel cells because of their relatively high efficiency and low power consumption. Fuel cells are operated over a broad range of current densities, which is proportional to the air mass flow rate, i.e., the air supply system needs to provide high efficiencies over a wide range of mass flow. To achieve this target, a centrifugal fan equipped with a diffuser and volute with variable cross-sectional area is developed based on numerical simulations (CFD), laser-optical flow measurements (PIV) and performance measurements of the centrifugal fan. The geometrical variability is achieved by a movable backplate of the diffuser and the volute. The variable cross-sectional area of the diffuser and volute allows maintaining high efficiencies and pressure ratios for operating points at off-design. A small diffuser width is suitable for low mass flow rates, and a large diffuser width for high mass flow rates. Thus, efficiency of the centrifugal fan can be increased at part-load operation by up to 7.1% points by appropriately adjusting the diffuser width. As a result the parasitic power consumption of the air supply system is reduced and hence the overall efficiency of the fuel cell system increases.

The integration of cross-sectoral energy hubs into large-scale wind farms opens up existing structures to new applications and contributes to achieving renewable energy systems and climate protection targets. The offshore energy hub concept consists in establishing an artificially constructed energy conversion and distribution hub that addresses two energy-related markets by power supply to public grids and by potentially enabling the conversion of renewable electricity into hydrogen or ammonia and supplying it ashore. Hence, the energy hub concept enables smart integration of offshore wind power into gas grids. Power generation on demand from stored green gas is able to cover residual power loads at low carbon intensity. Electrofuel production provides also the opportunity to export renewable fuels for sectors with traditionally high greenhouse gas emissions, e.g., agriculture or transportation. In this contribution an energy hub system in the North Sea is modeled and simulated to determine production quantities and efficiencies of electricity, hydrogen and ammonia. When comparing the efficiencies of production, storage, and transport values of 45.1–65% for hydrogen and values of 52–52.3% for ammonia were determined. Re-conversion to electricity with fuel cells of both hydrogen and ammonia is less efficient and cost worthly than their use in electrofuel applications. Because of emerging and potential cost reductions a sensitivity analysis is performed where lower capital costs (50%) lead to cost reductions in hydrogen (42–45%) and ammonia production (40–42%). Results show that energy hubs can become sustainable pillars in future energy systems through improving cost-competitiveness of wind power.

Porous media like concrete or layers of membrane electrode assemblies (MEA) within fuel cells are affected by a cyclic frost exposure due to different damage mechanisms which could lead to essential degradation of the material. In general, frost damages can only occur in case of a specific material moisture content. In fuel cells, residual water is generally available after shut down inside the membrane i.e. the gas diffusion layer (GDL). During subsequent freezing, this could cause various damage phenomena such as frost heaves and delamination effects of the membrane electrode assembly, which depends on the location of pore water and on the pore structure itself. Porous materials possess a pore structure that could range over several orders of magnitudes with different properties and freezing behaviour of the pore water. Latter can be divided into macroscopic, structured and pre-structured water, influenced by surface interactions. Therefore below 0 °C different water modifications can coexist in a wide temperature range, so that during frost exposure a high amount of unfrozen and moveable water inside the pore system is still available. This induces transport mechanisms and shrinkage effects. The physical basics are similar for porous media. While the freezing behaviour of concrete has been studied over decades of years, in order to enhance the durability, the know-how about the influence of a frost attack on fuel cell systems is not fully understood to date. On the basis of frost damage models for concrete structures, an approach to describe the impact of cyclic freezing and thawing on membrane electrode assemblies has been developed within this research work. Major aim is beyond a better understanding of the frost induced mechanisms, the standardization of a suitable test procedure for the assessment of different MEA materials under such kind of attack. Within this contribution first results will be introduced.

A novel reactor of a natural gas (NG) fueled, 1 kW net power solid oxide fuel cell (SOFC) system with anode off-gas recirculation (AOGR) is experimentally investigated. The reactor operates as pre-reformer, is of the type radial reactor with centrifugal z-flow, has the shape of a hollow cylinder with a volume of approximately 1 L and is equipped with two different precious metal wire-mesh catalyst packages as well as with an internal electric heater. Reforming investigations of the reactor are done stand-alone but as if the reactor would operate within the total SOFC system with AOGR. For the tests presented here it is assumed that the SOFC system runs on pure CH 4 instead of NG. The manuscript focuses on the various phases of reactor operation during the startup process of the SOFC system. Startup process reforming experiments cover reactor operation points at which it runs on an oxygen to carbon ratio at the reactor inlet ( ϕ RI ) of 1.2 with air supplied, up to a ϕ RI of 2.4 without air supplied. As confirmed by a Monte Carlo simulation, most of the measured outlet gas concentrations are in or close to equilibrium.

The processing towards Si/C composites, components and synthesis parameters were selected based on the concept of Hansen solubility parameters (HSP). Si/polymer composites were generated through modified bulk polymerization and subsequent pyrolysis transformed the polymer into the desired porous carbon matrix. Coulombic efficiencies (CE) in excess of 76% after the first cycle and 99.95% after solid electrolyte interphase (SEI) formation have been achieved. A notably high specific delithiation capacity of around 1600 mAh/g with an extremely stable cycling performance even after 400 cycles is obtained. This scalable and economical synthesis approach is readily applicable to the commercial production of anode materials.

Functionalized polymers in general are claiming more and more novel applications; for example they can function as a metal replacement. Especially the E&E-market or the so-called “green technologies” require highly engineered polymers for many new needs such as a high level of thermal or electrical conductivity in polymers. To functionalize an intrinsic isolating polymer high loadings of conductive fillers, like graphite, carbon blacks, CNTs, metals and/or others, are necessary. For fuel cell application filler contents of more than 80 wt% in a thermoplastic polymer are needed. The mixtures, so-called compounds, exhibit a significantly different behavior in processing and in their properties compared to neat polymer. Especially viscosity sensitive processing techniques such as injection molding are often limiting the amount of filler that is applicable and therefore also limiting achievable conductivity. A low resistivity is critical for the use in fuel cells. At ZBT a new thermal post treatment technique was developed that can decrease resistivity of injection molded bipolar plates significantly. Reduction of resistivity ranged up to 76%. The influence of filler content, particle size, morphology, time and temperature of treatment were investigated extensively and the mechanism behind the temperature treatment was studied in detail. Using DSC and XRD method the change in crystallinity was found to be the driving factor suggesting that percolation in filled compounds is not only based upon degree of filling but also crystallinity of polymer. Furthermore temperature treatment showed great promise for implementation in future injection molding process of highly conductive compounds as even short times of thermal post treatment lead to a significant effect.

In this study, the behaviour of Polymer-Electrolyte Membrane (PEM) single cells with different types of MEA systems have been studied under thermal cycling with respect to structural and electrochemical changes. The cells have been insulated and exposed to repeated freeze-thaw cycles with a minimum temperature of −40°C inside an environmental chamber. To some extent, great differences between the degrees of damage could be found for the various types of MEA systems (e.g. catalyst coated membrane (CCM), catalyst coated substrate (CCS)).

The continuous expansion of renewable energy sources leads to changes in supply systems. More flexibility is necessary since the degree of dependency on volatile renewables increases. This new paradigm affects the runtime of conventional plants and a characteristic change of the residual load, which must be covered by controllable systems. State-of-the-art studies resolve the future flexibility challenge non-congruent because of their given viewing point. The contribution of this paper is an analysis on the sense of cogeneration plants as flexible supply option in Germany's urban energy systems. Results show that cogeneration operation is eligible to cover major fluctuations of the residual load and to avoid many issues, which arise from increasing decentral renewable power generation and relate to all sectors electricity, heat, gas, and mobility.

A novel nanocomposite consisting of gas-phased produced Si nanoparticles, carbon nanotubes (CNTs), and polyaniline (PANi) is developed as an anode material (Si-CNT/PANi) for lithium-ion batteries. This nanocomposite integrates the merits from its three components, where Si nanoparticles provide high capacity, CNTs act as an electrically conductive and mechanically flexible network, and PANi coating further enhances the electrical conductivity and protects the silicon structure. An anode made of this nanocomposite shows a high reversible capacity of 2430 mAh/g with good capacity retention over 500 cycles compared to pristine Si. The Si-CNT/PANi nanocomposite also demonstrated a high Coulombic efficiency and improved rate-capabilities.

It is known that traffic related air contaminants cause power loss, decreasing lifetime or a complete failure of proton exchange membrane fuel cell (PEMFC). Therefore, the present study aims for a better understanding and the development of a data basis for further decisions in dealing with air contaminants for automobile applications. The first section provides an overview of scientific literature about the influence of important air contaminants on proton exchange membrane fuel cells (PEMFC). The second section describes an extensive study of air contaminants at possible automotive operating conditions using a full factorial matrix test. The specific variation of temperature, cell potential and harmful gas concentration resulted in 27 operating points for each used air contaminant. The gases NO, NO2, SO2, NH3, toluene and ethane were used. The results indicate significant degradation but as well the possibility of regeneration. The degradation caused by different harmful gases is both, dependent on temperature and potential. Furthermore, a clear difference of the influence of NO and NO2 at low concentrations could be shown. The experiments give an overview of the cathode harming potential of relevant air contaminants. Hence, the work provides a basis for the development of cathode air filter and regeneration techniques for automotive applications.

In this paper, the optimization of a power management strategy of a fuel cell/battery/supercapacitor hybrid vehicular system is investigated, both offline and in real time. Two offline optimization algorithms, namely, dynamic programming and Pontryagin's minimum principle, are first compared. The offline optimum is used as a benchmark when designing a real-time strategy, which is an inevitable step since the offline optimum is not real-time capable and is oriented only toward minimizing hydrogen consumption, which may result in the unnecessary overloading of the battery. The design and optimization of the real-time strategy makes use of a multiobjective genetic algorithm while taking into account, apart from hydrogen consumption, other important factors, such as the slow dynamics of the fuel cell system and minimizing the battery power burden. As a result, the real-time strategy is found to consume slightly more hydrogen than the offline optimum; however, it dramatically improves system durability.

PEM fuel cells can be operated within a wide range of different operating conditions. In this paper, the special case of operating a PEM fuel cell with a dry cathode supply and without external humidification of the cathode, is considered. A deeper understanding of the water management in the cells is essential for choosing the optimal operation strategy for a specific system. In this study a theoretical model is presented which aims to predict the location in the flow field at which liquid water forms at the cathode. It is validated with neutron images of a PEM fuel cell visualizing the locations at which liquid water forms in the fuel cell flow field channels. It is shown that the inclusion of the GDL diffusion resistance in the model is essential to describe the liquid water formation process inside the fuel cell. Good agreement of model predictions and measurement results has been achieved. While the model has been developed and validated especially for the operation with a dry cathode supply, the model is also applicable to fuel cells with a humidified cathode stream.

The versatility of fuel cells enables a wide range of applications. Usually fuel cells are combined to stacks such that the reactant supply of the single cells is achieved via a pipe branching system, the manifold. The overall performance significantly depends on cell flow rates which are related to the fluidic interaction of the manifold and the cells. Computational Fluid Dynamics (CFD) simulations, which are often used to find a suitable design, lack experimental flow data for validation of the numerical results. To enable flow measurements within the small geometries of the manifold and to provide reliable velocity information inside a real fuel cell stack, a low-coherence Laser Doppler Anemometer (LDA) is applied, which uses multi-mode laser light to achieve a spatial resolution of

Silicon is a potential anode material for lithium-sulfur batteries. This future energy storage system has an essential higher energy density and significantly lower costs compared to lithium-ion batteries. However, a big problem by using silicon is the high volume expansion of 280 %. The volume expansion and contraction results in a break-up of the solid electrolyte interface (SEI). The SEI has to be reformed continuously during cycling, which leads to a continuous loss of lithium. One approach to compensate the lithium loss during cycling is the prelithiation of silicon anode with a stabilized lithium metal powder (SLMP ® ). SLMP can serve as an additional lithium source to mitigate the capacity loss during the first and the following cycles and improve the energy density significantly. Adding SLMP directly into the slurry during electrode production is problematic because it is incompatible with many conventional electrode components. Therefore the application of SLMP on the finished electrode as an additional layer is advantageous. For this purpose, the SLMP can be mixed in a solvent and applied to the electrode. After drying, the SLMP must still be activated by a pressing process, since the protective carbonate shell must be broken open. One problem here is the rapid separation of SLMP and solvent. A possible solution is the addition of a binder, like styrene-butadiene rubber (SBR). Here we present a silicon/graphene-based anode prelithiated with SLMP in the electrolyte systems 1 M LiTFSI, 0.2 M LiNO3 in dimethoxy ethane (DME) and 1,3-dioxolane (DOL). For this work, we used a commercially available Si/C composite material with a PAA binder. The silicon content of the electrode is 25 %. SLMP is loaded on the top of the electrode and activated by a pressing process. The advantage of a binder in the SLMP - solvent mixture will be shown, and also that the binder has no negative effect on the electrochemical properties. The electrodes are examined by galvanostatic cycling and show high coulomb efficiency of over 85 % in the first cycle. Also, the SLMP of the anode compensates the lithium loss over at least 300 cycles. We will show the improvements of the anode prelithiated with SLMP compared to pure Si/C anodes.

As one of the proposed post lithium-ion technologies, zinc-air batteries have received revived interest in the recent years, which is driven by the increased demand of high-performance, efficient, safe and environment-friendly energy storage solutions. These energy storage systems need to address variable power, capacity and profitability requests. Zinc-air flow batteries with higher specific energy density than lithium-ion and low-cost, highly available, eco-friendly active materials are suitable to fulfill these requirements. The energy density of most zinc-air flow batteries is limited by the low solubility of ZnO in the electrolyte. The use of a flow battery type with zinc-particles suspended in alkaline solution (zinc-slurry) in addition with high performance oxygen-reduction electrodes enables the development of high-power zinc-air batteries. This setup also enables the independent scaling of capacity and power. The cooperative project, ZnMobil, funded by the Federal Ministry of Economic Affairs and Energy in Germany, combines the experience of industrial and academic partners (Covestro Deutschland AG; Grillo-Werke AG; VARTA Microbattery GmbH; Accurec Recycling GmbH; Technical University Freiberg, Gottfried Wilhelm Leibniz University Hannover; University of Duisburg-Essen; the fuel cell research center ZBT GmbH) to develop a high-performance and low-cost zinc-air flow battery. The battery system consists of a 100 cm² copper plate as current collector for the zinc-suspension electrode and an oxygen reduction electrode with gas-diffusion layer (supplied by Covestro Deutschland AG). The zinc-slurry contains zinc particles (supplied by Grillo-Werke AG) suspended in alkaline solution (30 wt-% KOH) and stabilized with polyacrylic acid. Here we present a systematic study regarding the effects of the discharge products on the cell performance. Depending on the state of discharge and operation parameters the discharge product ZnO causes several important effects. The solid ZnO limits the discharge capacity in several ways. At high current densities, passivation is the main topic. If passivation is avoided, e.g. with the help of additives, the solid ZnO causes a viscosity increase until the cell is blocked. For this study we evaluated parameters like cell voltage, cell resistance, slurry viscosity, ZnO concentration in the electrolyte and other parameters in correspondence to the state of discharge. The understanding of these effects is essential to build a hydraulically rechargeable battery with high zinc usage and therefore high energy densities. Depending on parameters like current density and additive selection, it is possible to reach more than 70 % DOD, which corresponds to 287 mAh/gslurry or 574 mAh/gzinc. A demonstrator-cell was operated for more than 140 h. During this time it was successfully hydraulically recharged several times.

The possibility to use fuel cells as an electrical power source makes them interesting for a wide range of applications. In this work, computational fluid dynamics (CFD) simulations and optical measurements are performed to predict the flow distribution in a flow setup resembling the parallel flow circuits in fuel cell stacks. For the first time it is shown that by an adaptation of the port sizes in the inlet manifold to the individual fuel cells, the average global deviation between the flow rates can be reduced from 10.1% to 4.0% by means of a model experiment. The measurements are performed with a high resolution laser Doppler velocity profile sensor (LD-PS) specifically developed for measurements in small-scale channels, in this work 4 × 1 mm 2 , allowing for a spatial resolution below 2 μ m and relative velocity uncertainties below 0.1%, helping to resolve installation effects possibly occurring in fuel cells to improve their efficiency. The presented results can be used by manufacturers to increase the efficiency of their fuel cell stacks.

In this study, we present a novel anode architecture for high-performance lithium-ion batteries based on a Silicon/3-aminosilane-functionalized CNT/Carbon (Si/A-CNT/C) composite. A high-yield, low-cost approach has been developed to stabilize and support silicon as an active anode material. Silicon (Si) nanoparticles synthesized in a hot-wall reactor and aminosilane-functionalized carbon nanotubes (A-CNT) were dispersed in styrene and divinylbenzene (DVB) and subsequently polymerized forming a porous Si/A-CNT/C composite. Transmission electron microscopy showed that this method enables the interconnection and a uniform encapsulation of Si nanoparticles within a porous carbon matrix especially using aminosilane-functionalized CNT (A-CNT). Electrochemical characterization shows that this material can deliver a delithiation capacity of 2293 mAh g−1 with a capacity retention of more than 90 % after 200 cycles at lithiation and delithiation rate of 0.5 C. We conclude that the porous Si/A-CNT/C composite material can accommodate sufficient space for Si volume expansion and extraction and improve the electronic and ionic conduction. Excellent electrochemical performance during repeated cycling can thus be achieved.

One of the biggest challenges in the field of polymer electrolyte membrane fuel cells (PEMFC) is to enhance the lifetime and the long-term stability of PEMFC electrodes, especially of cathodes, furthermore, to reduce their platinum loading, which could lead to a cost reduction for efficient PEMFCs. These demands could be achieved with a new catalyst support architecture consisting of a composite of carbon structures with significant different morphologies. A highly porous cathode catalyst support layer is prepared by addition of various carbon types (carbon black particles, multi-walled carbon nanotubes (MWCNT)) to multilayer graphene (MLG). The reported optimized cathodes shows extremely high durability and similar performance to commercial standard cathodes but with 89% lower Pt loading. The accelerated aging protocol (AAP) on the membrane electrode assemblies (MEA) shows that the presence of MLG increases drastically the durability and the Pt-extended electrochemical surface area (ECSA). In fact, after the AAP slightly enhanced performance can be observed for the MLG-containing cathodes instead of a performance loss, which is typical for the commercial carbon-based cathodes. Furthermore, the presence of MLG drastically decreases the ECSA loss rate. The MLG-containing cathodes show up to 6.8 times higher mass-normalized Pt-extended ECSA compared to the commercial standard systems.

A simulation and control model for a two-step thermo-chemical water splitting cycle using metal oxids for the generation of hydrogen with a solar tower system as heat source has been developed. The simulation and control model consists of three main parts, the simulation of the solar flux distribution on the receiver, of the temperatures in the driven reactor modules and the produced hydrogen in the metal oxide. The results of the three parts of the simulation model have been evaluated by comparing and validating them with experimental data from the Hydrosol 100 kW th pilot plant at the Plataforma Solar de Almeria (PSA) in Spain. With the overall model of the hydrogen production plant that was created, an evaluation of the two-step thermochemical cycle process in combination with a solar tower system was performed. The model was used to perform parametric studies for the development of the plant and the operation strategies. For this purpose, a provision in the overall model was integrated. The simulation helps to reduce the frequency of using the flux measurement system and can be used for the heliostat field control, in particular for the temperature control in the solar chemical reactor modules. Because of these promising results the overall system model is being extended to enable a use as a control model with controller for the temperature control of the two core reactions in the process. The central control variable of the process control was the operating temperatures for the hydrogen production and the regeneration of the two modules. The process control with its PI controller turned out suitable to compensate diurnal changes of solar input power as well as certain statistical fluctuation due to cloud passage. At the same time the limits of the operability and controllability of the process became clear in terms of the minimum of solar power needed and maximum acceptable gradients. With this experience an operating strategy, the basic parameters of the system in operation, especially the starting up and shutdown procedures, regular operation and the response to disturbances were selected and optimized. With this operation/control strategy such a complex system can be operated in the future on a commercial scale automatically. The obtained results can also be adapted for other solar chemical processes.

LiFePO4/C and LiFexMn1-xPO4/C (x = 0.7) nanocomposites were successfully synthesized via scalable spray-flame synthesis followed by solid-state reaction. A solution of iron (III) acetylacetonate and tributyl phosphate in toluene was used to produce amorphous, nanosized FePO4⋅H2O in a spray-flame reactor which was then milled with Li2CO3 and glucose to produce a LiFePO4/C composite material in a solid-state reaction. The influence of calcination temperature and carbon content on the properties of the resulting material was investigated using specific surface area measurements (BET), X-ray diffraction (XRD), electron microscopy, and electrochemical characterization. The impact of manganese addition on the electrochemical behavior was analyzed using cyclic voltammetry (CV) and constant-current (CC) measurements. XRD shows that the combination of gas-phase synthesis and subsequent solid-state reaction yields highly pure LiFePO4/C. BET measurement revealed that the particle size of LiFePO4 in the composite depends on the amount of glucose. A discharge capacity of more than 140 mAh/g at C/20 is achieved for LiFePO4/C with a carbon content of 6 wt%. This material supports high charge as well as discharge rates delivering more than 60 mAh/g at 16 C and sustains good cycle stability providing 115 mAh/g at 1 C. The energy density of the olivine increases about 10 % by substituting 30 mol% of iron by manganese while preserving the electrochemical performance of pure LiFePO4/C.

In theory, district heating systems (DHS) offer an opportunity to increase the flexibility of combined heat-and-power (CHP) plants by working as short- and medium-term thermal storage. Using this capacity, it is possible to dispatch CHP units more flexibly and thus offer, e.g., operating reserve for the electric grid without any additional investments in thermal storages. State-of-the-art optimization studies use this flexibility, but do not show the lever for further tweaks. This work's contribution is to analyze the actual extent of flexibility and the reasons for current limitations in detail. To this end, a model of the propagation of temperature fronts is suggested and applied, and the general applicability of pre-charging a DHS is proved by simulation. A thorough study of design and operation parameter changes is then conducted. Results show that some system variables (e.g., the thermal demand) must be forecast precisely to determine the absorbable thermal power, and that a smart design of system parameters (e.g., supply temperatures) can increase the flexibility.

The aim of this work is to fabricate patterned nitride membranes with Si-MEMS-technology as a platform to build up new membrane-electrode-assemblies (MEA) for alkaline fuel cell applications. Two 6-inch wafer processes based on chemical vapor deposition (CVD) were developed for the fabrication of separated nitride membranes with a nitride thickness up to 1 μm. The mechanical stability of the perforated nitride membrane has been adjusted in both processes either by embedding of subsequent ion implantation step or by optimizing the deposition process parameters. A nearly 100% yield of separated membranes of each deposition process was achieved with layer thickness from 150 nm to 1 μm and micro-channel pattern width of 1μm at a pitch of 3 μm. The process for membrane coating with electrolyte materials could be verified to build up MEA. Uniform membrane coating with channel filling was achieved after the optimization of speed controlled dip-coating method and the selection of dimethylsulfoxide (DMSO) as electrolyte solvent. Finally, silver as conductive material was defined for printing a conductive layer onto the MEA by Ink-Technology. With the established IR-thermography setup, characterizations of MEAs in terms of catalytic conversion were performed successfully. The results of this work show promise for build up a platform on wafer-level for high throughput experiments.

This work describes the development of a compact ethanol fuel processor for small scale high temperature polymer electrolyte membrane fuel cell (HT-PEMFC) systems with 200–500 W electrical power output. Promising markets for reformer fuel cell systems based on ethanol are mobile or portable leisure and security power supply applications as well as small scale stationary off grid power supply and backup power. Main components of the fuel processor to be developed were the reformer reactor, the shift converter, a catalytic burner and heat exchangers. Development focused in particular on the homogeneous evaporation of the liquid reactants ethanol and water for the reformer and burner and on the development of an efficient and autarkic start-up method, respectively. Theoretical as well as experimental work has been carried out for all main components separately including for example catalyst screening and evaporator performance tests in a first project period. Afterwards all components have been assembled to a complete fuel processor which has been qualified with various operation parameter set-ups. A theoretically defined basic operation point could practically be confirmed. The overall start-up time to receive reformate gas with appropriate quality to feed an HT-PEMFC (xCO

Palladium membranes were prepared on large tubes (80 mm diameter and 150 mm length) of porous stainless steel supports (PSS) using a modified electroless plating technique. The morphology of the palladium layer was found to be depending on the container material of the coating apparatus. The use of PMMA resulted in compact palladium layers with smooth surfaces whereas PTFE led to inhomogeneous palladium coating with rough surface. Two different ceramic materials and coating methods were used to prepare an intermediate layer needed to prevent intermetallic diffusion between the palladium and the support at elevated temperatures. Wet powder spraying of TiO2 followed by sintering resulted in a smoother surface than atmospheric plasma spraying of YSZ, thus allowing for a thinner palladium coating. Pd/TiO2/PSS membranes showed about 4 times higher hydrogen permeances than Pd/YSZ/PSS membranes as a consequence of higher palladium thickness and lower porosity of the ceramic intermediate layer. The selectivity against nitrogen was comparable for both membranes. However, the YSZ intermediate layer showed better stability at elevated temperatures. Two membrane tubes were applied in the membrane reformer, which produced hydrogen successfully from a gas-to-liquid (GtL) fuel.

Gas crossover is an unavoidable phenomenon in proton exchange fuel cell membranes. Nitrogen and oxygen from the cathode pass through the membrane to the anode, while hydrogen crosses from the anode to the cathode. The hydrogen crossover leads to a reduction in efficiency due to parasitic hydrogen consumption and mixed potentials on the cathode electrode. Furthermore it causes degradation effects and pinhole formation. Hence the hydrogen crossover represents a fundamental factor for the lifetime of a fuel cell and quantification of the crossover is a key factor for membrane qualification. In this article two in situ electrochemical techniques to evaluate the hydrogen crossover are described, cyclic voltammetry and potential step method. Both methods and the achieved results are compared to each other. Finally the potential step method is applied to evaluate the hydrogen crossover as a function of the anode pressure and the hydrogen permeability coefficients are determined.

This work presents the application of nitride membranes produced with Si-MEMS-technology as a platform to build up new membrane-electrode assemblies (MEA) for alkaline fuel cells. Active alkaline fuel cell MEAs were combined by integrating hydroxide permeable electrolyte into micro-channels of 1 μm diameter in 5 to 10 μm thick MEMS-based membranes. A platinum catalyst was sprayed onto the surface and an electric conductive layer was applied on top. Taking advance of the small form factor these fuel cells can be applied in small devices with low energy demand.