Advances in the Science and Engineering of Functional Materials 3rd Workshop between RWTH Aachen University and Seoul National University 30th & 31st October 2014 Institute of Physical Chemistry (IPC) RWTH Aachen University Aachen, Germany ii Financial assistance is gratefully acknowledged from International Office BK21PLUS SNU Materials Division for Educating Creative Global Leaders iii Thursday, 30.10. Morning Session 9.00 – 9.30 Prof. Doris Klee Vice-Rector for Human Resources Management and Development, RWTH Aachen University Greetings and Opening Prof. Ki-Bum Kim, Head of Department, Materials Science and Engineering, Seoul National University 9.30 – 10:00 Alexander Böker Nanoporous Ultra-thin Membranes formed via SelfAssembly of Protein-PolymerConjugates 10.00 – 10.30 Jeong-Yun Sun Tough Hydrogels & Stretchable Ionics 10.30 – 11.00 Coffee Break 11.00 – 11.30 Woong-Ryeol Yu New Electrospinning Nozzle to Improve Jet Stability and Its Application to Manufacture of Multi-layered Carbon Nanofibers 11.30 – 12.00 Martin Salinga Switching Kinetics in Phase change Materials 12.00 – 12.30 Young-Chang Joo Structure-property relationship of amorphous materials for electronic devices 12.30 – 14.00 Lunch iv Thursday, 30.10. Afternoon Session 14.00 – 14.30 Regina Dittmann From Defects to Future oxidebased resistive ReRAM 14.30 – 15.00 Miyoung Kim Formation of nano-filaments in a SrTiO3 thin film 15.00 – 15.30 Manfred Martin Bulk mixed ion electron conduction in amorphous gallium oxide causes memristive behavior 15.30 – 16.00 Coffee Break 16.00 – 16.30 Han-Ill Yoo Kinetic Unmixing and Decomposition of Ternary Oxides under Electric Fields 16.30 – 17.00 Marjana Lezaic Ab-initio Design of Multiferroic Materials 17.00 – 17.30 Seungwu Han Searching for functional oxides using high-throughput ab initio screening 17.40 – 18.00 Double degrees for Ph. D. students 19.30 Conference Dinner v Friday, 31.10. Morning Session 9.00 – 9.30 Doh-Yeon Kim Future; Sustainability and Asia 9.30 – 10.00 Ulrich Simon Electrical Characterization of Individual Inorganic Nanoparticles 10.00 – 10.30 Ki-Bum Kim Nanofabrication for BioInformation Technology 10.30 – 11.00 Coffee Break 11.00 – 11.30 Norbert H. Menzler Status of Anode-Supported Solid Oxide Fuel Cell Development at Forschungszentrum Jülich – Emphasis on Materials and Microstructure Development of Cells 11.30 – 12.00 Kisuk Kang Development of Advanced Materials for Li Rechargeable Batteries 12.00 – 12.30 Christoph Broeckmann Processing of Materials for Oxygen Transport Membranes 12.30 – 13.30 Lunch vi List of Participants Name Affiliation Email address Prof. Alexander Böker DWI - Leibniz Institute for Interactive Materials, Forckenbeckstrasse 50, D-52056 Aachen, Germany boker@dwi.rwth-aachen.de Prof. Christoph Broeckmann Institute for Materials Application in Mechanical Engineering, RWTH Aachen University, Augustinerbach 4, D-52062 Aachen, Germany c.broeckmann@iwm.rwthaachen.de PD Dr. Roger A. De Souza Institute of Physical Chemistry, RWTH Aachen University, Landoltweg 2, D-52074 Aachen, Germany desouza@pc.rwthaachen.de Prof. Regina Dittmann Peter Grünberg Institute (PGI-7), Forschungszentrum Jülich GmbH, Wilhelm-Johnen-Straße, D-52428 Jülich, Germany r.dittmann@fz-juelich.de Prof. Seungwu Han Department of Materials Science and Engineering, Mailstop 33-319, Seoul National University, Seoul, Korea hansw@snu.ac.kr Prof. YoungChang Joo Department of Materials Science and Engineering, Mailstop 33-311, Seoul National University, Seoul, Korea ycjoo@snu.ac.kr Prof. Kisuk Kang Department of Materials Science and Engineering, Mailstop 33-107, Seoul National University, Seoul, Korea matlgen1@snu.ac.kr Prof. Doh-Yeon Kim Department of Materials Science and Engineering, Mailstop 33-202, Seoul National University, Seoul, Korea dykim@snu.ac.kr Prof. Ki-Bum Kim Department of Materials Science and Engineering, Mailstop 131-108, Seoul National University, Seoul, Korea kibum@snu.ac.kr vii Prof. Miyoung Kim Department of Materials Science and Engineering, Mailstop 33-312, Seoul National University, Seoul, Korea mkim@snu.ac.kr Dr. Marjana Lezaic Peter Grünberg Institute (PGI-1), Forschungszentrum Jülich GmbH, Wilhelm-Johnen-Straße, D-52428 Jülich, Germany m.lezaic@fz-juelich.de Prof. Manfred Martin Institute of Physical Chemistry, RWTH Aachen University, Landoltweg 2, D-52074 Aachen, Germany martin@rwth-aachen.de Dr. Norbert H. Menzler Institute of Energy and Climate Research, Forschungszentrum Jülich GmbH, Wilhelm-Johnen-Straße, D-52428 Jülich, Germany n.h.menzler@fz-juelich.de Dr. Martin Salinga I.Institute of Physics (IA), RWTH Aachen University, Sommerfeldstr. 14, D-52074 Aachen, Germany martin.salinga@physik.rwthaachen.de PD Dr. Michael Schroeder Institute of Physical Chemistry, RWTH Aachen University, Landoltweg 2, D-52074 Aachen, Germany schroeder@rwth-aachen.de Prof. Ulrich Simon Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, D-52074 Aachen, Germany ulrich.simon@ac.rwthaachen.de Prof. Jeong-Yun Sun Department of Materials Science and Engineering, Mailstop 33-108, Seoul National University, Seoul, Korea jysun@snu.ac.kr Prof. Han-Ill Yoo Department of Materials Science and Engineering, Mailstop 33-106, Seoul National University, Seoul, Korea hiyoo@snu.ac.kr Prof. WoongRyeol Yu Department of Materials Science and Engineering, Mailstop 33-305, Seoul National University, Seoul, Korea woongryu@snu.ac.kr 1 Nanoporous Ultra-thin Membranes formed via Self-Assembly of Protein-Polymer-Conjugates Patrick van Rijn, Murat Tutus, Christine Kathrein, Nathalie C. Mougin, Hyunji Park, Christopher Hein, Marco P. Schürings, and Alexander Böker DWI - Leibniz-Institut für Interaktive Materialien, Lehrstuhl für Makromolekulare Materialien und Oberflächen, RWTH Aachen University, Aachen, Germany Self-assembled membranes offer a promising alternative for conventional membrane fabrication, especially in the field of nano-filtration. However, recent advances pushing the developments in self-assembled membranes towards thinner membranes with more selectivity are still limited with respect to active permeation area, stability and responsiveness. Here we introduce a new pore-making strategy which involves stimuli responsive protein-polymer conjugates self-assembled across a large area of 5 cm2 using drying-mediated interfacial self-assembly. Proteins are used as a sacrificial template which - upon denaturing - provide hydrophilic pores of identical size. The permeation is controlled by temperature switching below and above the lower critical solution temperature of the polymer. The membrane is flexible and easily assembled on porous supports. A high mass transport was measured and a size-selectivity of particles below 20 nm was determined, which is in very good agreement with the size of protein used. This approach diversifies membrane technology since various sizes and shapes of proteins can be used, in addition to different responsive polymers generating a platform for “smart” selfassembled membranes. References [1] N.C. Mougin, P. van Rijn, H. Park, A.H.E. Müller, A. Böker Adv. Funct. Mater. 2011, 21, 2470. [2] P. van Rijn, N.C. Mougin, D. Franke, H. Park, A. Böker Chem. Commun., 2011, 47, 8376. [3] P. van Rijn, N.C. Mougin, A. Böker Polymer, 2012, 53, 6045. [4] P. van Rijn, H. Park, K. Özlem Nazli, N.C. Mougin, A. Böker Langmuir, 2013, 29, 276. [5] P. van Rijn, M. Tutus, C. Kathrein, N.C. Mougin, H. Park, C. Hein, M.P. Schürings, A. Böker Adv. Funct. Mater. 2014, doi: 10.1002/adfm.201401825. 2 Tough Hydrogels & Stretchable Ionics Jeong-Yun Sun Department of Materials Science and Engineering, Seoul National University, Seoul, Korea Hydrogels are used as scaffolds for tissue engineering, vehicles for drug delivery, actuators for optics and fluidics, and model extracellular matrices for biological studies. The scope of hydrogel applications, however, is often severely limited by their mechanical behaviour. Most hydrogels do not exhibit high stretchability; for example, an alginate hydrogel ruptures when stretched to about 1.2 times its original length. Some synthetic elastic hydrogels have achieved stretches in the range 10– 20, but these values are markedly reduced in samples containing notches. Most hydrogels are brittle, with fracture energies of about 10 Jm-2, as compared to 1,000 Jm-2 for cartilage and 10,000 Jm-2 for natural rubbers. Intense efforts are devoted to synthesizing hydrogels with improved mechanical properties; certain synthetic gels have reached fracture energies of 100–1,000 Jm-2. We have reported the synthesis of a new hydrogel from polymers that form ionically and covalently crosslinked networks. Although such gels contain 90% water, they can be stretched beyond 20 times their initial length, and have fracture energies of 9,000 Jm-2. Even for samples containing notches, a stretch of 17 is demonstrated. We attribute the gels’ toughness to the synergy of two mechanisms: crack bridging by the network of covalent crosslinks, and hysteresis by unzipping the network of ionic crosslinks. Furthermore, the network of covalent crosslinks preserves the memory of the initial state, so that much of the large deformation is removed on unloading. The unzipped ionic crosslinks cause internal damage, but are healed by re-zipping. These gels serve as model systems to explore mechanisms of deformation and energy dissipation, and expand the scope of hydrogel applications. Furthermore, as a new application, we have proposed a class of devices enabled by hydrogel conductors that are highly stretchable, fully transparent to light of all colors, and capable of operation at frequencies beyond 10 kHz and voltages above 10 kV. We have created a transparent actuator that can generate large strains, and a transparent loudspeaker that produces sound over the entire audible range. The electromechanical transduction is achieved without electrochemical reactions. 3 New Electrospinning Nozzle to Improve Jet Stability and Its Application to Manufacture of Multi-layered Carbon Nanofibers Woong-Ryeol Yu Department of Materials Science and Engineering and Research Institute of Advanced Materials, Seoul National University, Seoul, Korea A new nozzle system for the efficient production of multi-layered nanofibers through electrospinning is reported. Developed a decade ago, the commonly used coaxial nozzle system consisting of two concentric cylindrical needles has remained unchanged, despite recent advances in multi-layered, multi-functional nanofibers. Here, we demonstrate a core-cut nozzle system, in which the exit pipe of the core nozzle is removed such that the core fluid can form an envelope inside the shell solution. This configuration effectively improves the coaxial electrospinning behavior of two fluids and significantly reduces the jet instability, which was proved by finite element simulation. The proposed electrospinning nozzle system was then used to fabricate bi-, tri-, and tetra-layered carbon nanofibers. 4 Switching kinetics in phase change materials Martin Salinga I. Physikalisches Institut IA, RWTH Aachen University, Aachen, Germany Phase change materials are essential ingredients for next-generation electronic memory devices and reconfigurable electronics for their ability to be switched between states with very different resistivity within nanoseconds upon electrical excitation, while being stable over many years otherwise. It is these materials’ characteristic combination of electronic excitability of their amorphous phase and their unconventional structural transformations that makes this seeming contradiction possible. Thorough experimental investigations of both phenomena allowed us to gain deeper insights into the fundamental properties of this family of materials. Recently the crystallization kinetics could be traced back to an extremely high fragility of the undercooled liquid phase. A comprehensive model including the quenching rate dependence of the glass formation and relaxation processes in the glass managed to explain the different experimental observations reported in literature. Our investigations of transient effects in electrical excitation of phase change materials concentrate on the changes around the threshold for resistivity breakdown in the amorphous phase. The discussion of the results from both studies give guidance to experimentalists and theoreticians aiming for a fundamental understanding of the physics of phase change materials. 5 Structure-property relationship of amorphous materials for electronic devices Young-Chang Joo Department of Materials Science and Engineering, Seoul National University, Seoul, Korea Amorphous materials have been actively applied in electronic devices, due to their unique properties originated from disordered atomic structure distinct from crystalline materials. However, such devices suffer from the reliability issues originated from their phase instability, and it is crucial to characterize and tune the phase stability for the development of stable devices. In this study, mechanical stress analysis was utilized to detect the structural changes and phase stability in amorphous films and to predict the device functionalities. The crystallization kinetics of the amorphous phase change materials were explored; crystallization temperature (Tx), glass transition temperature (Tg), super-cooled liquid region (Tx - Tg) of amorphous Ge2Sb2Te5 (GST) films doped with various elements. Besides, the viscosity and the fragility were also determined. Doping effects on the thermal stability and atomic mobility show successful matching with phase change RAM characteristics; data retention and SET speed, respectively. The novel in-situ measurement of mechanical stress and resistance were conducted to correlate two phenomena. Amorphous In-Ga-Zn-O (a-IGZO) is an active material for TFT, experiences phase instability originated from interfaces. Surface-to-volume ratios of the a-IGZO film were varied by thickness variation and the thickness dependence of the phase stability of a-IGZO are discussed. 6 From defects to future oxides-based resistive ReRAM Regina Dittmann Peter Grünberg Institute (PGI-7), Research Centre Jülich, Jülich, Germany Flash memories and DRAM are ubiquitous today. However, a potential leap beyond the limits of Flash (with respect to write speed, write energies) and DRAM (with respect to scalability, retention times) emerges from redox-based switching effects encountered in a large variety of metal oxides (ReRAM). Although first commercial memories based on Ta2O5 thin films are available since 2013, the microscopic details of the switching and failure mechanism are only rarely understood so far. Oxygen ion transport and redox reactions on the nanoscale provide the essential mechanisms. In contrast to most other applications of oxide thin films, point defects as well as extended defects promote the switching processes and their presence is prerequisite for a reliable device performance. The presentation will cover the current understanding of the microscopic switching processes and the role of defects extracted from a broad variety of spectroscopic investigations of resistively switching oxide devices. Furthermore, we will discuss its implications on the device performance such as switching time, switching power and retention time. 7 Formation of nano-filaments in a SrTiO3 thin film Miyoung Kim Department of Materials Science and Engineering, Seoul National University, Seoul, Korea Resistive switching memory (ReRAM) attracted considerable attention due to its scientific implications and technological potential for non-volatile memory and related applications. We investigate microstructures of a SrTiO3 thin film to elucidate atomistic origin of unipolar resistive switching, for which we employ in-situ transmission electron microscopy together with electron energy-loss spectroscopy. Interestingly, it is revealed that there exists preferred orientational relationship between the filaments and the neighboring SrTiO3 grains, which indicates that the filaments are generated in specific grain boundaries. Additionally, co-generation of Ruddlesden-Popper (RP) structure is often observed in the vicinity of the filament structure. Morphology and crystal structure of the filaments are further examined during repeated in-situ SET and RESET operation. This work provides insight on the evolution of nano-filaments in oxides. 8 Bulk mixed ion electron conduction in amorphous gallium oxide causes memristive behavior Yoshitaka Aoki,a Carsten Wiemann,b Vitaliy Feyer,b Hong-Seok Kim,c Claus Michael Schneider,b,d Han Ill-Yooc and Manfred Martina,c a Institute of Physical Chemistry, RWTH Aachen University and JARA-FIT, Aachen, Germany. b Peter Grünberg Institute (PGI-6) and JARA-FIT, Research Centre Jülich, Jülich, Germany. c Department of Materials Science and Engineering, Seoul National University, Seoul, Korea. d Fakultät für Physik and Center for Nanointegration Duisburg-Essen (CENIDE), Universität Duisburg-Essen, Duisburg, Germany. In thin films of mixed ionic electronic conductors sandwiched by two ion-blocking electrodes, the homogeneous migration of ions and their polarization will modify the electronic carrier distribution across the conductor, thereby enabling homogeneous resistive switching. Here we report non-filamentary memristive switching based on the bulk oxide ion conductivity of amorphous GaOx (x~1.1) thin films. We directly observe reversible enrichment and depletion of oxygen ions at the blocking electrodes responding to the bias polarity by using photoemission and transmission electron microscopies, proving that oxygen ion mobility causes memristive behaviour. The shape of the hysteresis I-V curves is tunable by the bias history, as found in the mathematically derived memristor model. This dynamical behaviour can be attributed to the coupled ion drift and diffusion motion and the oxygen concentration profile acting as a state function of the memristor. Y. Aoki et al., Nat. Commun. 5:3473 doi: 10.1038/ncomms4473 (2014) 9 Kinetic Unmixing and Decomposition of Ternary Oxides in Electric Fields Jakyu Chun,a Manfred Martina,b and Han-Ill Yooa a Department of Materials Science and Engineering, Seoul National University, Seoul, Korea b Institute of Physical Chemistry, RWTH Aachen University, Aachen, Germany A general expectation is that in a uniform oxygen activity atmosphere, cationelectrotransport induces a ternary or higher oxide, e.g., AB1+O3+, to kinetically unmix unless the electrochemical mobilities of, say, A2+and B4+ cations are identically equal, and eventually to decompose into the component oxides AO and BO 2 once the extent of unmixing exceeds the stability range of its nonmolecularity . It has, however, earlier been reported [Yoo et al., Appl. Phys. Lett., 2008, 92, 252103] that even a massive cation electrotransport induces BaTiO3 to neither unmix nor decompose even at a voltage far exceeding the so-called decomposition voltage Ud, a measure of the standard formation free energy of the oxide (| G f |=nFUd) in classic Gibbs sense. Here, we report that as expected, NiTiO3 unmixes at any voltage and even decomposes if the voltage applied exceeds seemingly a threshold value larger than Ud. We demonstrate experimentally that the electrochemical mobilities of Ni2+ and Ti4+ should be necessarily unequal for unmixing, Also, we show theoretically that equal cation mobilities appear to be a sufficiency for BaTiO3 only for a thermodynamic reason. The kinetic meaning of the decomposition voltage is elucidated in comparison with the thermodynamic decomposition voltage in the original Gibbs sense. o 10 Ab-initio Design of Multiferroic Materials Marjana Ležaić Peter Grünberg Institute, Research Centre Jülich, Jülich, Germany Multiferroic materials display a simultaneous ferroelectric and magnetic order and are currently one of the spots of high interest in spintronics investigations. The reasons are numerous possible applications such as 4-bit memory and a possibility of electric field controlled magnetization (or magnetic field controlled electric polarization). Designing novel multiferroics with predefined desired properties is not an easy task, due to an essential incompatibility of the physics driving the two functionalities, ferroelectricity and magnetism. In the few materials that do possess a non-zero net magnetisation along with a ferroelectric polarisation in a single phase, the problem usually encountered is the low magnetic ordering temperature. This talk will be dedicated to understanding the difficulties and to possible ways of circumventing them, within a framework of ab-initio multiferroics design [1]. Furthermore, some applications of both bulk and of multicomponent layered multiferroic systems will be discussed [2,3]. [1] Phys. Rev. B, 83, 024410 (2011) [2] Nature Materials 9, 649 (2010) [3] Phys. Rev. Lett. 111, 077601 (2013) 11 Searching for functional oxides using high-throughput ab initio screening Kanghoon Yim, Yong Youn, and Seungwu Han Department of Materials Science and Engineering, Seoul National University, Seoul, Korea In this talk, I will present our recent efforts to identify functional oxides appropriate for specific application targets, utilizing the high-throughput ab initio screening. First, we try to find candidate dielectric materials that can be used in next-generation memory (DRAM or FLASH) and logic (CPU) devices, based on the digital database of energy gap, dielectric constant, and defect formation energies for a large collection of binary and ternary oxides available on ICSD. Second, we try to identify ideal dopants for ZnO when the material is used for electronic or energy devices. For these ends, we develop a series of automation codes that can carry out ab initio computation of bulk and defect properties of oxides efficiently and reliably. 12 Future; Sustainability and Asia Doh-Yeon Kim Department of Materials Science and Engineering, Seoul National University, Seoul, Korea At the beginning of 20th century, the world population was 1.6 billions. It has been increased dramatically during last 100 years so that nowadays we are 7.3 billions. This means that overall situation for human-being has been greatly improved, and this is mainly due to the development of science and technology driven by Europeans. Particularly, the industrial revolution stemmed from the invention of steam engine has greatly changed the world. Why the industrial revolution happened in Europe(Britain) rather than in Asia(China)? And then, will Asia be remained as a follower rather than first-mover in future? In this talk, I’d like to discuss the sustainability of modern civilization and the future role of Asia for all human-being. 13 Electrical Characterization of Individual Inorganic Nanoparticles Ulrich Simon Institute of Inorganic Chemistry, RWTH Aachen University, Aachen, Germany Inorganic nanoparticles (NP) including metals, metal oxides, and chalcogenides exhibit size dependent electrical properties. This makes such NP promising for applications e.g. in energy conversion, information storage, or sensing devices. However, most of these applications rely on the integration of a multitude of NP instead of single ones. Thus, several applications utilize the integral properties of ensemble of NP, rather than the distinct properties of the individual nanoscale building blocks. In order to take full advantage of the nanoscale size for ultimate miniaturization, experimental techniques are required that allow analyzing the properties of individual particles in an environment that approaches the conditions to be applied for the desired application. Therefore we developed and evaluated methods which allow us to study the electrical properties of individual metal, metal oxide and chalcogenide NP either in a nanoelectrode (NE) configuration [1] or by means of a flexible nanomanipulator (NM) set-up [2]. In this report we will introduce our recent results on the charge transport properties of individual sub-20 metal NP in a lithographically fabricated NE and of sub-micron sized metal oxide and chalcogenide NP contacted in a NM set-up, which exhibit resistive switching properties and which therefore are considered promising for resistive memory devices. [1] M. Manheller, S. Karthäuser, R. Waser, K. Blech, U. Simon, J. Phys. Chem. C, 2012, 116, 20657-20665; N. Babajani, P. Kowalzik, R. Waser, M. Homberger, C. Kaulen, U. Simon, S. Karthäuser, J. Phys. Chem. C, 2013, 117 (42), 22002–22009 [2] J. Timper, K. Gutsmiedl, C. Wirges, J. Broda, M. Noyong, J. Mayer, T. Carell, U. Simon, Angew. Chem. Int. Ed., 2012, 51 (30), 7586-7588 14 Nanofabrication for Bio-Information Technology Ki-Bum Kim Department of Materials Science and Engineering, Seoul National University, Seoul, Korea The fabrication of nanometer scale features such as quantum dots and quantum wires in a controllable and economically viable manner is one of the essential requirements for the production of future ultra-high-density electronics, photonics, magnetic, and biological sensors and devices. In this talk, I will discuss a new method of patterning nanometer-scale periodic structures with much improved throughput by employing the various crystalline lattice images available in high resolution transmission electron microscopy (HRTEM) which is named as AIPEL (Atomic Image Projection Electron-beam Lithography). Then, I will change the subject to the nanopore fabrication by utilizing the same transmission electron microscope. The demonstration of single molecule sequencing with biological nanopores, most notably α-hemolysin protein that spontaneously embedded themselves in a lipid bilayer, greatly accelerates the work to mimic this structure in solid-state. Accordingly, various methods were proposed to form sub-10 nm, preferably down to 2 nm scale nanopore on the membrane structure utilizing either ion beam or electron beam perforation. These structures were interposed between cis- and trans-liquid chambers and successfully utilized to monitor the flow of DNA molecules by measuring the ionic current between cis- and trans-chambers. While these works presented interesting results, namely, demonstrating the transport of single stranded DNA through the nanopore when an electrical bias is applied, the scientific information one could harvest from these experiments is quite limited. Most importantly, the translocation time is too fast to obtain the information on the types of bases. In order to analyze the base types (namely, A, T, G, C), which is separated only 0.34 nm, it is important to design a structure where the translocation of DNA through the pore is well controlled. Recently, our group, in collaboration with the members of IBM, reported the formation of multiple nanopore structure by utilizing electron beam lithography and atomic layer deposition (ALD) with the pore size less than 10 nm. More importantly, this structure has built-in gate electrode, just like MOS transistors for semiconductor device, and can control the transport of ions. It is expected that this device can also be utilized to control the transport of DNA and other bio-molecules. 15 Status of Anode-Supported Solid Oxide Fuel Cell Development at Forschungszentrum Jülich – Emphasis on Materials and Microstructure Development of Cells Norbert H. Menzler Institute of Energy and Climate Research IEK-1, Research Centre Jülich, Jülich, Germany The presentation gives an overview about the status of anode-supported solid oxide fuel cell (ASC) development at Forschungszentrum Jülich. The ASC is based on a tape-cast Ni(O)-8YSZ support and screen printed functional layers like anode (Ni(O)/8YSZ), electrolyte (8YSZ), diffusion barrier (GDC) and mixed ionic-electronic conducting LSCF cathode. State-of-the-art single cells obtain current densities of approx. 1.3A/cm² at 0.7V and 700°C. In stack environment approx. 0.8A/cm² can be reached. By introducing thin-film electrolytes and barrier layers applied by e.g. solgel-technique or physical vapor deposition even higher current densities can be realized. In the past 10 years of development the focus has been lying firstly on choosing the best materials combinations with respect to single layer physical, mechanical and electrochemical characteristics but also on their interactions during manufacturing and operation. Subsequently, the layers micro-structures were optimized with respect to electrochemical functionality. Here parameters like particle size, porosity, thickness, layer integrity and so on play key roles to obtain high-power-density longterm stable cells. By optimizing all layers by means of chemistry and microstructure drastically enhanced current densities were reached. By doing so even 3A/cm² at 700°C and 0.7V are realistic. Besides cell optimization all other SOFC stack components like the steel for the bipolar plates, the glass-ceramic sealant, the metal protection layers and the cell contact materials have been optimized in house. Meanwhile Jülich operates the longest ever run planar stack which in August 2014 has reached an operation time of 7 years while degrading moderately with respect to loss of voltage. But the degradation of less than 1%/1000h is still too high for stationary applications (operation times 40-80,000h). By introducing a plasmasprayed protection layer onto the bipolar plates the degradation can be reduced to about 0.3%/1000h. Such kind of stack currently is running since 31,000h. Finally, in spring 2014 a 20kW el SOFC system which was developed, built and operated in Jülich has been shut down after ~ 7.000h of operation with natural gas/LNG and ambient air. With this system the applicability oft he Jülich SOFC stack design has been proven. 16 Development of Advanced Materials for Li Rechargeable Batteries Kisuk Kang Department of Material Science and Engineering, Seoul National University, Seoul, Korea Lithium rechargeable batteries have been widely used as key power sources for portable devices for the last couple of decades. Their high energy density and power have allowed the proliferation of ever more complex portable devices such as cellular phones, laptops and ipads. For larger scale applications, such as batteries in electric vehicles (EVs) or power tools or large energy storage systems (EESs), higher standards of the battery, especially in term of the rate (power) capability, energy density, cost-effectiveness and cycle stability are far more strictly required. However, current Li rechargeable battery technology has yet to improve significantly to meet those requirements. In this presentation, I will introduce our approaches to address these issues and some accomplishments that have been made in my research group. 17 Processing of Materials for Oxygen Transport Membranes Anke Kaletsch, Simone Herzog, Ewald Pfaff, Christoph Broeckmann Institute for Materials Application in Mechanical Engineering, RWTH Aachen University, Aachen, Germany Mixed ionic and electronic conducting (MIEC) materials like the perovskite Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF) are used for high temperature oxygen transport membrane (OTM). MIEC materials show selective oxygen conductibility at elevated temperatures of around 800 °C – 900 °C and can be used in several technical applications where oxygen is needed at a high temperature level, for example in the iron and steel industry, the chemical industry or for oxyfuel combustion in coal fired power plants. Different design concepts for membranes are going to be developed actually, based either on planar MIEC plates or tubular pipes. In both concepts the ceramic components need to be produced in a robust process that can be transferred easily to an industrial scale. In case of a planar design a tape casting process is developed. Tubes are produced by cold isostatic pressing (CIP) followed by sintering in air atmosphere. The membranes need to be integrated into the entire plant design, thus a gas- and vacuum tight joining technology is needed, usually between the ceramic membrane and connecting sleeves or frames made of metallic high temperature alloys. A special brazing technology, called reactive air brazing (RAB) has been developed for this purpose. Although MIEC materials mainly are optimized regarding high oxygen flux and high thermodynamic stability, a minimum mechanical strength is needed in order to survive mechanical load cases dominated by static forces, creep and thermal shocks. Therefore particular testing methods have been developed to characterize the mechanical properties of membrane materials.
© Copyright 2024