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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.

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.

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.

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.

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.

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.

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.

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.

The reduction of the platinum amount for efficient PEM (polymer electrolyte membrane) fuel cells was achieved by the use of graphene/carbon composites as catalyst support. The influences of the carbon support type and also of the catalyst preparation method on the fuel cell performance were investigated with electrochemical, spectroscopic and microscopic techniques. Using pure graphene supports the final catalyst layer consists of a dense and well orientated roof tile structure which causes strong mass transport limitations for fuels and products. Thus the catalysts efficiency and finally the fuel cell performance were reduced. The addition of different carbon additives like carbon black particles or multi-walled carbon nanotubes (MWCNT) destroys this structure and forms a porous layer which is very efficient for the mass transport. The network structure of the catalyst layer and therefore the performance depends on the amount and on the morphology of the carbon additives. Due to optimizing these parameters the platinum amount could be reduced by 37% compared to a commercial standard system.

An attractive path to the production of hydrogen from water is a two-step thermo chemical cycle powered by concentrated sunlight from a solar tower system. In the first process step the redox system, a ferrite coated on a monolithic honeycomb absorber, is present in its reduced form while the concentrated solar energy hits the ceramic absorber. When water vapour is fed to the honeycomb at 800 °C, oxygen is abstracted from the water molecules, bond in the redox system and hydrogen is produced. When the metal oxide system is completely oxidised it is heated up for regeneration at 1100–1200 °C in an oxygen-lean atmosphere. Under those conditions and in the second process step, oxygen is set free from the redox system, so the metal oxide is being reduced and after completion of the reaction again capable for water splitting. Since the overall process consists of two core reaction steps, which need to be carried out sequentially in a reactor unit at two different temperature steps, a special process and plant concept had to be developed enabling the continuous supply of product regardless of the alternating nature of the solar reactor operation. The challenge of the process control is to keep the two core reaction temperatures constant and to ensure regular temperature switches after completion of the individual process steps, independent of the weather conditions, like DNI fluctuation, clouds and wind speed. Also start-up, the fast switching after completion of half-cycles and the shutdown must be controlled. State of the art is the manual switching of heliostats to fulfil those control tasks. This paper describes the development and use of a system model of this process. The model consists of three main parts: the simulation of the solar flux distribution at the receiver aperture, the simulation of the temperatures in the reactor modules and the simulation of the hydrogen generation. It can be used for the analysis of the operational behaviour. The model is intended to be used in the future for the control of the whole process.

Brennstoffzellen als elektrochemische Energiewandler haben durch gezielte Materialentwicklung Anwendungsreife erlangt. Fur die Membranbrennstoffzelle sind das insbesondere der ionenleitende, polymere Festelektrolyt, Edelmetall-Nanokatalysatoren auf korrosionsstabilen Kohlenstofftragermaterialien, Gasdiffusionsschichten mit ausgeklugeltem Porensystem sowie Werkstoffe fur die Bipolarplatte, die fur die Serienfertigung geeignet sind. Die Fortschritte der letzten Jahre auf dem Gebiet der Materialentwicklung sind beeindruckend und haben zu Brennstoffzellen mit hoher Leistungsdichte, einer guten Lebensdauer und mit robustem Betriebsverhalten gefuhrt. Fuel cells as electrochemical conversion devices are nowadays ready for use thanks to targeted material development. For membrane fuel cells, the most important materials are the ionic conducting polymer electrolyte, the noble metal nanostructured electrocatalyst and its corrosion resistant carbon carrier material, the gas diffusion layer with its highly sophisticated pore system, as well as suitable construction materials for bipolar plates, which make a mass production possible. The progress of the past years has led to fuel cells with high specific power density, good durability and also with robust operational behavior.

This work presents a three-dimensional, steady-state, non-isothermal model of a high-temperature polymer-electrolyte-membrane fuel cell (HTPEMFC) using a phosphoric acid-doped polybenzimidazole (PBI/H3PO4) sol–gel membrane. The model accounts for the gold-plated copper current collector plates, the bipolar plates, all gas flow channels (flow-field), the gas diffusion layers, the reaction layers, and the membrane. Electrochemical reactions are modeled using an agglomerate approach and include the gas diffusivity and the gas solubility. The conductivity of the membrane is modeled using the Arrhenius equation to describe the temperature dependence. Finite elements are used to discretize all computational subdomains, and a commercially available code is used to solve the problem. The predicted values are compared to typical operating conditions, and a good agreement is found. The current density, the solid- and fluid-(gas)-phase temperatures and other quantities are analyzed throughout the computational subdomains. It was observed that the Arrhenius approach is valid in a certain temperature range and may overpredict the PBI/H3PO4 sol–gel membrane conductivity at higher solid-phase temperatures. Moreover, it is shown how the fluid-(gas)-phase temperature influences the solid-phase temperature and the current density distribution. Concrete values are deduced from the simulations and discussed according to experimental test.

The thermal conductivity of commercially available thermally conductive polymer-compounds is usually between 1 W/mK and 20 W/mK what means that they are already 10 to 100 times higher than the conventional unfilled polymer. During the development at ZBT the values for thermal conductivity of polymer-compounds could be increased to more than 30 W/mK. In order to achieve such conductivities, the compound materials generally consist of a polymer, which functions as a binding matrix, and a high content (up to 80 wt.%) of conductive filler material. In various series of investigations the thermal conductivity but also the mechanical properties and the processing by extrusion and injection molding of the highly filled materials were evaluated. An orientation of filler particles by injection molding could be observed. Images by scanning-electron-microscopy of injection molded samples showed a structure of anisotropic layers which has a significant influence on the values of thermal conductivity. That’s why a dif...

An LPG-based auxiliary power unit (APU) is currently being developed at the Centre for Fuel Cell Technology (ZBT). Due to the modular design of the APU, the reformer/burner module and the CO purification module, combined in the mobile gas processor (MGP), and the low temperature PEM fuel cell (PEM FC) can be developed and characterized simultaneously. While the separate characterizations of the MGP and the PEM FC are satisfactory during the initial coupling tests, a condensation problem occurs in the PEM FC, because of the high water content in the reformate gas. This paper presents two possible solutions for the prevention of condensation inside the PEM FC, when coupled with a gas processor. Analogous testing is carried out by supplying synthesized reformate gas to the PEM FC, resulting in a 360 W maximum electrical power output at 85 °C. New membrane electrode assemblies (MEAs), which are suitable for reformate gas operation at temperatures up to 90 °C, are integrated in this PEM FC. Furthermore, the impact of CO on PEM FC performance can be minimized by adding an airbleed of 1.0 mol-% of the complete anode gas. Thus, stable operation is achieved with the separate PEM FC, by supplying a synthesized anode gas, which includes a CO concentration constantly between 30 and 50 ppm. The coupling of the MGP with the PEM FC, under the improved operating conditions, leads to an electrical power output of 351 W. The overall APU efficiency is 28.5%.

ZBT can look back on 10 years of history in successful development of hydrogen generators for residential power supply using PEM fuel cells. ZBT has always focused on efficient steam reforming and heat integration. All hydrogen generators contain a steam reformer, a shift unit, a CO-purification unit, evaporator, heat exchanger and burner. The core technology is protected by international patents (1). Especially the requirements obtained from industrial partners were used to optimise the hydrogen generator to meet the demands of residential applications. Sometimes not all of these demands can be fulfilled and compromises are necessary. For example high efficiency requires heat integration which leads to high complexity of the system, higher volume/weight and finally elevated production costs or short start-up time requires a radical temperature gradient which has a negative impact on life time (2). All these correlations have to be discussed between product management and development to identify reasonable compromises.

The University of Duisburg-Essen and the Center for Fuel Cell Technology (ZBT Duisburg GmbH) have developed a compact multi-fuel steam reformer suitable for natural gas, propane and butane. Fuel processor prototypes based on this concept were built up in the power range from 2.5 to 12.5 kW thermal hydrogen power for different applications and different industrial partners. The fuel processor concept contains all the necessary elements, a prereformer step, a primary reformer, water gas shift reactors, a steam generator, internal heat exchangers, in order to achieve an optimised heat integration and an external burner for heat supply as well as a preferential oxidation step (PrOx) as CO purification. One of the built fuel processors is designed to deliver a thermal hydrogen power output of 2.5 kW according to a PEM fuel cell stack providing about 1 kW electrical power and achieves a thermal efficiency of about 75% (LHV basis after PrOx), while the CO content of the product gas is below 20 ppm. This steam reformer has been combined with a 1 kW PEM fuel cell. Recirculating the anodic offgas results in a significant efficiency increase for the fuel processor. The gross efficiency of the combined system was already clearly above 30% during the first tests. Further improvements are currently investigated and developed at the ZBT.

The development of bipolar plates that can be produced by standard mass production techniques is a main issue for the commercialization of PEM fuel cells, as bipolar plates contribute significantly to the cost structure of PEM stacks. In recent years, the University of Duisburg-Essen together with the Zentrum fur BrennstoffzellenTechnik GmbH (ZBT) has identified a number of carbon–polymer composites with densities of 1.6 g/cm3, specific bulk conductivities between 5 and 150 S/cm and material prices between 2 and 10 €/kg. Standard composite mixtures consist of a thermoplast and a carbon compound mixture with additional additives to increase the conductivity of the compound material. The composites generally show high corrosion resistance in the PEM fuel cell environment. Composite material samples proved to be absolutely stable in immersion tests in sulphuric acid and deionized water under pure oxygen atmosphere for several thousand hours. ZBT has successfully demonstrated the production of bipolar plates by injection moulding with cycle times of 30–60 s. With the help of tailored moulds injection moulding of bipolar plates becomes price competitive even for comparatively small series in the range of several thousand plates. PEM stacks with injection moulded bipolar plates of 2.5–4 mm thickness and an electrical power of up to 200 W have been constructed and successfully operated.

The University of Duisburg–Essen has developed a compact multi-fuel steam reformer suitable for natural gas, propane and butane. This steam reformer was combined with a polymer electrolyte membrane fuel cell (PEM FC) and a system test of the process chain was performed. The fuel processor comprises a prereformer step, a primary reformer, water gas shift reactors, a steam generator, internal heat exchangers in order to achieve an optimised heat integration and an external burner for heat supply as well as a preferential oxidation step (PROX) as CO purification. The fuel processor is designed to deliver a thermal hydrogen power output from 500 W to 2.5 kW. The PEM fuel cell stack provides about 1 kW electrical power. In the following paper experimental results of measurements of the single components PEM fuel cell and fuel processor as well as results of the coupling of both to form a process chain are presented.

In the recent years, rechargeable lithium-ion batteries have gained in importance for electronic devices and electric vehicles. Thus, research and development focuses on improving energy and power densities as well as durability of lithium-ion batteries. Especially for high energy and power densities, the electrode materials must possess high specific storage capacities and coulometric efficiencies. However, state-of-the-art anode and cathode electrode materials, e.g. graphite and LiFePO4 exhibit high coulometric efficiencies but rather low theoretical storage capacities (372 and 170 mAh/g, respectively). In the last decade silicon has become a promising anode material due to its high theoretical specific capacity of 3579 mAh/g at ambient temperature. However, this high specific storage capacity owing to host up to 3.75 lithium atoms per silicon atom leads to extreme volume expansion up to 280 % during lithiation, which results in pulverization and delamination of the electrode material after few cycles. Various approaches have been conducted to overcome these issues e.g. by using nano-sized active material or carbon coated silicon composite material. In addition to the materials science the electrode structure is of particular importance for the electrochemical performance. Electrode composition, binding mechanism due to the use of suitable binder polymers or particle size distribution of the active material are some exemplary parameters to stabilize the electrode structure and to handle such high mechanical stress during lithiation/delithiation. Here we present electrochemical investigations of high capacity and high efficiency graphene coated silicon nanocomposite based electrodes prepared by using a wet chemical doctor blade manufacturing process. This active material provides a capacity of >2000 mAh/g with efficiencies >99% over more than 500 cycles. Investigations focus on influence of the stability of the electrode structure by using impedance spectroscopy, scanning electron microscopy, confocal microscopy and estimation of the coating adhesion strength. Cyclic voltammetry and galvanostatic cycling will show the applicability of improved Si/C composite based electrodes compared to conventional graphite based electrodes for lithium-ion batteries both in half cells as well as full cells in combination with commercially available cathode material.

In order to optimize the electron transfer between the Li4Ti5O12-based active mass and the current collector, the surface of aluminum foil was modified either by alkaline etching or by a carbon coating. The as-modified aluminum foils were coated with an active mass of Li4Ti5O12 mixed with polyvinylidene fluoride, sodium carboxymethyl cellulose, or polyacrylic acid as binders. Untreated aluminum and copper foils served as reference current collectors. The corrosion reactions of aluminum foil with the applied binder solutions were studied and the electrode structure has been analyzed, depending on the binder. Finally, the electrochemical performance of the prepared electrodes was investigated. Based on these measurements, conclusions concerning the electrical contact between the different current collectors and the active masses were drawn. The energy density of the Li4Ti5O12 electrodes cast on carbon-coated aluminum foils was significantly increased, compared to the corresponding electrodes with a copper current collector.

A robust and electrochemically stable 3D nanoheterostructure consisting of Si nanoparticles (NPs), carbon nanotubes (CNTs) and reduced graphene oxide (rGO) is developed as an anode material (Si–CNT/rGO) for lithium-ion batteries (LIBs). It integrates the benefits from its three building blocks of Si NPs, CNTs, and rGO; Si NPs offer high capacity, CNTs act as a mechanical, electrically conductive support to connect Si NPs, and highly electrically conductive and flexible rGO provides a robust matrix with enough void space to accommodate the volume changes of Si NPs upon lithiation/delithiation and to simultaneously assure good electric contact. The composite material shows a high reversible capacity of 1665 mAh g−1 with good capacity retention of 88.6 % over 500 cycles when cycled at 0.5 C, that is, a 0.02 % capacity decay per cycle. The high-power capability is demonstrated at 10 C (16.2 A g−1) where 755 mAh g−1 are delivered, thus indicating promising characteristics of this material for high-performance LIBs.

A facile photothermal procedure for direct functionalization of carbon/polymer bipolar plate materials is demonstrated. Through irradiation with a microfocused beam of an Ar + -laser at λ = 514 nm in gaseous bromine and distinct laser powers and pulse lengths local bromination of the carbon/polymer material takes place. At a 1/ e spot diameter of 2.1 μm, functionalized surface areas with diameters down to 5 μm are fabricated. In complementary experiments large-area bromination is investigated using an ordinary tungsten lamp. For characterization contact angle goniometry, X-ray photoelectron spectroscopy and electron microscopy in conjunction with labeling techniques are employed. After irradiation bromine groups can easily be substituted by other chemical functionalities, e.g. azide and amine groups. This provides a facile approach in order to fabricate surface patterns and gradient structures with varying wetting characteristics. Mechanistic aspects and prospects of photothermal routines in micropatterning of carbon/polymer materials are discussed.

The reforming of natural gas to produce hydrogen for fuel cells is described, including the basic concepts (steam reforming or autothermal reforming) and the mechanisms of the chemical reactions. Experimental work has been done with a compact steam reformer, and a prototype of an experimental reactor for autothermal reforming was tested, both containing a Pt-catalyst on metallic substrate. Experimental results on the steam reforming system and a comparison of the steam reforming process with the autothermal process are given.

Direct methanol fuel cells (DMFCs) are attractive for several applications, however, at present, methanol crossover from the anode to the cathode appears to be a major limitation. For this reason, as one of the alternatives, membrane technology tries to obtain new methanol-impermeable polymer electrolytes. In this sense, it would be interesting to develop easy methods to check the new materials in relation to the methanol transport. In this work, a simple model is presented which permits to estimate easily the methanol diffusion coefficient of the membrane of a DMFC from open circuit voltage (OCV) measurements. The model has been checked in a DMFC using Nafion membranes as electrolyte.

Hydrogen generation for fuel cell systems by reforming technologies from various fuels is one of the main fields of investigation of the Fraunhofer ISE. Suitable fuels are, on the one hand, gaseous hydrocarbons like methane, propane but also, on the other hand, liquid hydrocarbons like gasoline and alcohols, e.g., ethanol as biogenic fuel. The goal is to develop compact systems for generation of hydrogen from fuel being suitable for small-scale membrane fuel cells. The most recent work is related to reforming according to the autothermal principle — fuel, air and steam is supplied to the reactor. Possible applications of such small-scale autothermal reformers are mobile systems and also miniature fuel cell as co-generation plant for decentralised electricity and heat generation. For small stand-alone systems without a connection to the natural gas grid liquid gas, a mixture of propane and butane is an appropriate fuel.

Oil and gas are raw materials—the availability of which is prognosticated to run short in the near future. The peak oil discussion is an example generally perceived as proof of this development to come.

A simple coating routine in order to tune the wettability of carbon/polymer bipolar plate materials is presented. Standard carbon/polypropylene composite materials as used for commercial bipolar plates for polymer-electrolyte-membrane fuel cell application are chemically modified via oxygen plasma activation and subsequent silanization using distinct precursor molecules including perfluorodecyltrichlorosilane and aminopropyltrimethoxysilane. For characterization of the samples contact angle measurements, infrared and Auger electron spectroscopy and scanning electron and atomic force microscopy are employed. Spectroscopic data provides direct evidence for successful functionalization of the substrates. Microscopic data reveals the inherent roughness of the micro-/nanostructured substrate surfaces. Depending on the particular silane precursor, the coating procedure yields hydrophilic and hydrophobic surfaces with static water contact angles ranging from 55° to 160°. The wettability of these substrates remains unchanged upon storage in clean air over a period of one year and more. Prospects of the coating procedure targeting the optimization of the water management in fuel cell applications are discussed.

The RSPFC is a battery-like hydrogen/oxygen system which offers the possibility of splitting water by electrolysis, storing the gases hydrogen and oxygen and regenerating electricity by the fuel cell process. The most outstanding feature is the use of only one energy conversion device for both processes, electrolysis and fuel cell operation. Membrane technology is the most suitable system for realization of this concept. Basic investigations concerning the best catalysts for the electrode reactions at electrode/membrane units have been carried out. The preparation of these units and the electrochemical characterization by half cell measurements and impedance measurements are reported as well as first experiences in reversibly operating small single cells.

Olivine, LiFePO4 is a promising cathode material for lithium-ion batteries due to its low cost, environmental acceptability and high stability. Its low electric conductivity prevented it for a long time from being used in large-scale applications. Decreasing its particle size along with carbon coating significantly improves electronic conductivity and lithium diffusion. With respect to the controlled formation of very small particles with large specific surface, gas-phase synthesis opens an economic and flexible route towards high-quality battery materials. Amorphous FePO4 was synthesized as precursor material for LiFePO4 by flame spray pyrolysis of a solution of iron acetylacetonate and tributyl phosphate in toluene. The pristine FePO4 with a specific surface from 126–218 m2 g−1 was post-processed to LiFePO4/C composite material via a solid-state reaction using Li2CO3 and glucose. The final olivine LiFePO4/C particles still showed a large specific surface of 24 m2 g−1 and were characterized using X-ray diffraction (XRD), electron microscopy, X-ray photoelectron spectrocopy (XPS) and elemental analysis. Electrochemical investigations of the final LiFePO4/C composites show reversible capacities of more than 145 mAh g−1 (about 115 mAh g−1 with respect to the total coating mass). The material supports high drain rates at 16 C while delivering 40 mAh g−1 and causes excellent cycle stability.

Segmented temperature measurements were performed to better understand the thermal behaviour and thermal interactions between the fluid-(gas)-phase and solid-phase temperature within a working high temperature polymer electrolyte membrane (HTPEM) fuel cell. Three types of flow-fields were studied, and the influence of temperature for no-load and load operating conditions was investigated. Tests were performed under various operating conditions, and the results demonstrate the utility of segmented temperature measurements. A significant difference in the temperature distribution was observed when the HTPEM fuel cell was operated with pure hydrogen and with hydrogen containing carbon monoxide. The findings may lead to improved HTPEM fuel cells and future middle temperature polymer electrolyte membrane (MTPEM) fuel cell designs.

High temperature polymer electrolyte membrane fuel cells (HT PEMFCs) offer tremendous flexibility when used as energy converters in stationary as well as mobile power devices. Coupling HT PEMFC stacks with fuel processors that use liquid as well as gaseous fuels to generate hydrogen rich gas is a promising prospect, which paves the way for a possible hydrogen economy. The current paper deals with the performance aspects of a 150 Wel HT PEMFC stack, which potentially could be coupled to (i) a natural gas reformer, (ii) a propane reformer, or (iii) a methanol reformer. A 12 cell HT PEMFC stack with a total active area of about 600 cm2 was operated in a test rack, and the results show that HT PEMFCs are principally suited for operation with reformates.

A review of the state-of-the-art of solid polymer fuel cell (SPFC) development is given. The international activities focus on cell performance and stack design, materials research and gas processing, depending on the application. The fastest progress is being made with respect to fuel cell development for transportation, but the specific advantages of SPFC make the system interesting for residential power supply systems, for on-site power production and also for small, portable power supplies.

Recent research concerning hydrogen technology focusses on membrane technology. Small electrolysers and fuel cells with high power density are attractive for many different applications such as transportation and energy storage for solar systems or other renewable energy sources. In order to lay the foundations of widespread applicatication, cost reduction must be achieved and a simple and reliable system must be designed. Various membrane/electrode units have been prepared and the results of electrolysis and fuel cell operation experiments are presented.

Results are reported on the flat band potential Vfb of the contact TiO2/CH3CN. The informations were taken from capacitance/voltage and photocurrent/voltage measurements. As electrolyte either pre-dried CH3CN or various mixtures of dried CH3CN with H2O were used. It was found that both the addition of H2O and illumination with band gap light affect Vfb considerably. – It could be shown that Vfb-values determined from photocurrent/potential measurements differ up to 2 V from values evaluated from capacitance/potential measurements taken on unilluminated electrodes. However, Vfb-values obtained from capacitance measurements on pre-illuminated electrodes agree well with data from photocurrent measurements. The results are discussed in terms of alterations of the inner Helmholtz plane. Finally, consequences of the observed Vfb shifts on the charge transfer process are outlined.