Symposium Organizers
Gehan Amaratunga University of Cambridge
Munichandraiah Nookala Indian Institute of Science
Lawrence G. Scanlon Air Force Research Laboratory
Endo Morinobu Shinshu University
Arokia Nathan University College London
BB1: Batteries I
Session Chairs
Gehan Amaratunga
Arokia Nathan
Monday PM, November 27, 2006
Republic A (Sheraton)
9:00 AM - BB1.1
Photonic Crystal Structures as a Basis for a Three-Dimensionally Interpenetrating Electrochemical Cell System.
Andreas Stein 1 , Justin Lytle 1 , Nicholas Ergang 1 , Kyu Lee 3 , William Smyrl 2
1 Department of Chemistry, University of Minnesota, Minneapolis, Minnesota, United States, 3 , Seoul National University, Seoul Korea (the Republic of), 2 Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis, Minnesota, United States
Show AbstractTemplating with colloidal crystals, arrays of close packed polymer spheres, is a general method of forming three-dimensionally ordered macroporous (3DOM) or inverse opal materials. The resulting structures consist of nanometer-thick walls that surround interconnected close-packed spherical voids with sub-micrometer diameters. Because of their periodic features with unit cell dimensions on the order of the wavelengths of UV-visible-IR light, inverse opals have generated significant interest as photonic crystals. Other applications, such as those involving reactivity of the skeleton (e.g., catalysis, biomaterials) can also benefit from the 3DOM structure. In the context of lithium ion batteries, the 3DOM architecture can lead to improved rate performance of individual electrodes. Here we employ a strategy involving multiple surface modification of conducting, monolithic 3DOM carbon to create a three-dimensionally interpenetrating cell with critical feature sizes on the scale of tens to hundreds of nanometers. The porous carbon was coated with an ultrathin, conformal layer of poly(phenylene oxide) by electro-oxidative deposition of phenolic monomers. The remaining void space was infiltrated with a vanadium alkoxide gel. The complete electrode structure was electrochemically lithiated and cycled multiple times. We demonstrate the ability to shuttle lithium ions between electrodes in this nano-/micro-structured cell, in which the interpenetrating electrode materials are electronically isolated. This design may be adaptable to battery, capacitor or sensor applications.
9:15 AM - BB1.2
Microfabricated Solid State Thin Film Lithium Batteries.
Raphael Salot 1 , Sami Oukassi 1 2 3 , Jean-Pierre Pereira-Ramos 2
1 , CEA, Grenoble France, 2 , CNRS, Thiais France, 3 , STM, Crolles France
Show AbstractThis work presents recent advances in the development and the integration of a solid state thin film battery, to work as a high voltage energy source for RF-MEMS powering. Micro-electro-mechanical systems require similarly miniaturized power sources. Up to day, Microgenerators are realized with mechanical masks, this method doesn’t allow dimensions below several decades of square mm of active area, and besides the whole process flow is done under controlled atmosphere so as to ensure materials chemical stability (mainly lithiated materials). Within this context, Microelectronics micro-fabrication procedures (photolithography, Reactive Ion Etching…) are used to reach both miniaturisation (100µmx100 µm targeted unit cell active area) and microelectronic IC technological compatibility. The whole process is realized in clean room environment. The thin film battery is composed of three active layers. First the positive electrode layer of crystalline vanadium pentoxide c-V2O5, the next level presents then the solid state electrolyte, a glassy ionic conducting material commonly known as “LiPON”. Finally, a negative electrode top level is realized by the evaporation of metallic lithium. The total stack thickness is of about 10 µm. A final wafer level packaging step is then realized to avoid reactivity with air and moisture. Specific attention will be put on the microfabrication processes developed for the positive electrode and the electrolyte (etching chemistry, resist stripping…). Several electrochemical characterizations (spectroscopic electrochemical impedance, charge-discharge cycling) were performed before and after micro-fabrication process steps so as to evaluate any possible effect on the electrochemical behaviour of the different studied layers
9:30 AM - BB1.3
Towards 3-D Battery Integration: Thermodynamic and Kinetic Properties of Lithium Intercalation in Silicon Thin Films.
Rogier Niessen 1 , Loic Baggetto 2 , Peter Notten 1 2
1 Philips Research, Philips Electronic NV, Eindhoven Netherlands, 2 Chemical Engineering, Eindhoven University of Technology, Eindhoven Netherlands
Show AbstractMicro batteries, both integrated monolithically and via a System-in-Package (SiP) approach, are expected to become more and more important in numerous small-sized devices, like medical implantables, biosensors, hearing aids, or autonomous network devices. Characteristic for these electronic applications is that they have to operate autonomously and reliably. Due to these requirements the thin film power source needs to be rechargeable, mechanically stable for a long period of time and have an extremely good cycling life. As the average energy consumption will be rather small, this opens up the possibility to integrate all solid-state rechargeable batteries, enabling a high degree of IC integration.It has been reported in the past that all-solid-state, Li-based, rechargeable batteries can be charged and discharged up to 10,000 times without failure. These thin-film batteries were, however, planarly structured, resulting in the fact that the geometric energy density of these devices is relatively low. By depositing the complete battery stack on a 3D etched substrate, obtained by either physical or wet-chemical etching, the effective energy and power density can be increased tremendously. Moreover, utilizing novel battery anode materials with a very high storage capacity comprising of thin film Silicon is especially beneficial.In order to determine to what degree these Silicon anodes impact the performance of 3D integrated batteries the electrochemical characteristics need to be determined very accurately. To this end the thermodynamic and kinetic properties of Silicon thin films are presented in detail. Employing a variety of electrochemical measurement tools, trends in various parameters will be shown depending on, among others, State-of-Charge (SoC) and cycling life of the Silicon layers. Some of these trends can be explained by phenomena like the substantial volume expansion of Silicon layers upon Li intercalation. Moreover, the impact of the crystallinity of the material on the thermodynamic and kinetic properties will be outlined.
9:45 AM - BB1.4
Development of Multifunctional Structural Composite Batteries.
James Snyder 1 , R. Carter 1 , E. Wong 1 , P. Nguyen 1 , E. Ngo 1 , K. Xu 2 , E. Wetzel 1
1 Materials Division, U.S. Army Research Laboratory, Aberdeen Proving Ground, Maryland, United States, 2 Directed Energy & Power Generation Division, U.S. Army Research Laboratory, Adelphi, Maryland, United States
Show AbstractThe weight and volume of conventional battery technologies greatly limits their performance in a range of mobile platforms. Significant research efforts are currently underway to reduce battery size and mass through improvements in energy density. A different approach is to integrate energy storage capability into load-bearing composites. These structural batteries could be used to replace conventional structural components, such as vehicle frame elements, with power-generating components. These structural batteries could enable significant system-level weight reductions if designed with sufficient structural and energy efficiency. To create a structural battery, load-bearing properties must be engineered into the battery electrodes, electrolyte, and/or packaging. Previous examples of structural batteries have focused on structural packaging. In this study, structural properties are being designed directly into the electrolyte and electrode materials. Novel electrode and electrolyte materials are being synthesized to optimize both energy storage and load-bearing capabilities, and the components are being integrated using scalable, cost-effective composite processing techniques. The current structural battery design utilizes carbon fiber fabrics as anodes, cathode-coated metal meshes, a fiberglass separator to ensure electrical isolation of the electrode layers, and an interpenetrating structural solid polymer electrolyte binding the components. The precise cathode composition and processing route are being optimized for high electrochemical capacity, electrical conductivity, rechargeability, and mechanical robustness. The style, orientation, and architecture of the fabrics are being systematically investigated to provide optimal structural and electrochemical performance. The polymer electrolyte is being developed to transfer load to the fibers while providing ion transport between electrodes. Our current electrolyte research focuses on polymerized vinyl ester derivatives of poly(ethylene glycol) (PEG). Varying the proportions, architecture, functionalities, and combination of the vinyl ester / PEG constituents has allowed for a wide range of tailorable structural and electrolytic properties. Addition of nanofillers further enhances the mechanical and even electrochemical properties. Our results show that it is possible to engineer polymer electrolytes with both ion conductivity and structural capacity. The liquid resin monomer complexed with lithium salt allows for traditional structural composite processing approaches, such as fabric pre-impregnation or vacuum assisted resin transfer molding, followed by thermal cure. This processing route is scalable and amenable to complex part shapes, and the resulting fully processed battery composites have demonstrated electrochemical charging and discharging cycles as well as reasonable composite structural properties.
10:00 AM - **BB1.5
An Oxygen Electrode and Crystalline Polymer Electrolytes for Rechargeable Lithium Batteries.
Aurelie Debart 1 , Yuri Andreev 1 , Takeshi Ogasawara 1 2 , Chuhong Zhang 1 , Jianli Bao 1 , Graham Armstrong 1 , Peter Bruce 1
1 Chemisty, University of St Andrews, St Andrews United Kingdom, 2 Mobile Energy Company, SANYO Electric Co., Ltd., Hyogo Japan
Show AbstractA leap forward in the performance of rechargeable lithium batteries is required to meet the demands of new markets for energy storage, especially to address global warming. Materials research holds the key to such advances but not by linear development of new electrodes and electrolytes. New approaches and new concepts are required. Two such approaches will be described.LiCoO2 has been a dominant cathode in rechargeable lithium batteries since their introduction in 1991. However it can store only 140 mAhg-1 (0.5Li/Co). The LiCoO2 cathode is the greatest obstacle limiting the energy storage of the rechargeable lithium battery. Research effort worldwide on lithium intercalation electrodes to replace LiCoO2 can only hope to increase their capacity by a factor of two. By replacing the lithium intercalation cathode with a porous carbon electrode containing a catalyst, oxygen from the air can react with Li+ and e– in the cell to form lithium oxide. The capacity to store charge increases from around 140 mAhg-1 for LiCoO2 to 1200-1800 mAhg-1 for the oxygen electrode, representing a leap forward in energy storage. The reservoir for oxygen is of course infinite. The device may be regarded as a lithium battery/fuel cell hybrid. The chemistry is quite different from the air electrode in an aqueous battery. Recently we have shown that the lithium oxide formed on discharge is decomposed on charging and that cycling may be sustained, with practical capacities exceeding 600 mAhg-1 after some 50 cycles. Results will be presented concerning the processes that accompany charging, as well as the various factors influencing the capacity and cyclability of the rechargeable lithium/air cell. The replacement of the non-aqueous lithium electrolyte in rechargeable lithium batteries by a true solid polymer electrolyte would represent a significant advance, permitting the fabrication of all-solid-state batteries with higher energy density, increased safety and rugged construction. After some 20 years of effort on amorphous polymer electrolytes they have not achieved a sufficient level of conductivity for many applications. Crystalline polymer electrolytes were believed for many years to be insulators. Recently we have shown that simple crystalline polymer electrolytes (polymer:salt complexes) such as poly(ethylene oxide)6:LiXF6, where X equals P, As, Sb, can conduct. We shall describe how these polymer:salt complexes may be modified in a variety of ways in order to raise the conductivity of the crystalline polymer electrolytes by up to two orders of magnitude, demonstrating the potential that such materials have for further advancement towards application.
10:30 AM - BB1.6
Three-Dimensional Battery Architectures.
Debra Rolison 1 3 , Jeffrey Long 1 , Bruce Dunn 2 , Henry White 3
1 Surface Chemistry, Naval Research Laboratory, Washington, District of Columbia, United States, 3 Chemistry, University of Utah, Salt Lake City, Utah, United States, 2 Materials Science & Engineering, UCLA, Los Angeles, California, United States
Show AbstractTo power devices with limited real estate, such as microelectromechanical systems (MEMS) and distributed autonomous sensors (such as dust motes), while maintaining a small areal footprint, batteries must somehow make good use of thickness. Only recently has research focused on improving battery performance by reconfiguring the electrode materials currently employed in 2-D batteries into 3-D architectures [1,2,3]. Three-dimensional configurations offer a means to keep transport distances short and yet provide enough material such that the batteries can power MEMS and other small-scale devices for extended periods of time, usually at an areal footprint of 1 J/mm2. This class of battery architectures should also maximize power and energy density. A defining characteristic of 3-D batteries is that transport between electrodes remains one-dimensional (or nearly so) at the microscopic level, while the electrodes are configured in complex geometries (i.e., nonplanar) in order to increase the energy density of the cell within the footprint area. Three-dimensional designs offer the opportunity to achieve milliwatt-hour energies in cubic millimeter packages and, more importantly, with square millimeter footprints. The design rules as derived from experiment and modeling of prototype 3-D battery architectures will be discussed.[1] R.W. Hart, H.S. White, B. Dunn, D.R. Rolison, Electrochem. Commun. 5 (2003) 120.[2] J.W. Long, B. Dunn, D.R. Rolison, H.S. White, Chem. Rev. 104 (2004) 4463.[3] M. Nathan, D. Golodnitsky, V. Yufit, E. Strauss, T. Ripenbein, I. Shechtman, S. Menkin, E. Peled, J. Microelectromech. Syst. 14 (2005) 879.
10:45 AM - BB1.7
Laser Printed Solid-State Rechargeable Li-ion Microbatteries.
Alberto Pique 1 , Heungsoo Kim 1 , Ray Auyeung 1
1 Materials Science & Technology Division, Naval Research Laboratory, Washington, District of Columbia, United States
Show AbstractThe trend for developing increasingly smaller and more autonomous microelectronic devices has not yet been matched by power sources with correspondingly reduced volumes. This need has gone unfulfilled due to the difficulties of depositing and processing at low temperatures complex battery materials into limited-dimensional architectures. At the Naval Research Laboratory we are investigating the fabrication of microbatteries using a laser printing technique called laser direct-write (LDW). LDW techniques are non-lithographic processes that allow the deposition of patterns of complex material systems onto virtually any type of surface and requiring low processing temperatures. For the development of solid-state Li-ion rechargeable microbattery systems, the laser printed anode and cathode layers are highly porous, thus allowing the deposition of thick electrodes (~ 100 micrometers) with low internal resistance. The LiCoO2 cathode and carbon anode electrodes are laser printed onto metallic current collectors and separated by a laser-cut porous membrane impregnated with a gel polymer electrolyte in order to produce mm size scale solid-state rechargeable Li-ion cells. The resulting microbatteries exhibit specific capacities of 130 mAh/g and discharge capacities in excess of 1.2 mAh/cm2. This presentation will describe the use of LDW process for the fabrication and rapid prototyping of rechargeable Li-ion microbatteries with various form factors ideally suited for mobile electronic systems.This work was supported by the Office of Naval Research.
11:30 AM - **BB1.8
Prospecting for a Counterpart of Moore's Law for Rechargeable Batteries.
K.m. Abraham 1
1 , E-KEM Sciences, Needham, Massachusetts, United States
Show AbstractAdvances in microelectronics guided by Moore’s Law have enabled the proliferation of portable consumer products such as laptop computers, cell phones and personal digital assistants. The last two decades have also seen impressive advances in rechargeable battery technologies although it is generally recognized that their progress has been slower than the pace set by microelectronics. The question arises if we can formulate a counterpart of Moore’s Law for guiding the rapid progress of rechargeable battery technologies. A brief review of rechargeable batteries, particularly lithium-ion batteries, will be made with emphasis on recent advances in materials and performance of practical batteries. The requirements of electrode and electrolyte materials and cell engineering to improve the energy and power of Li-ion batteries will be discussed. The energy density of rechargeable lithium batteries have increased from about 200 Wh/liter in the middle nineteen eighties to more than 500 Wh/liter recently for lithium-ion batteries. Very high power capability of lithium-ion batteries have been demonstrated with discharge rates as high as the 100C rate in systems utilizing liquid electrolytes. The prospect for creating a counterpart of Moore’s Law for rechargeable batteries depends on gaining a clear understanding of the factors governing the energy, power and rechargeability of practical batteries. Modest advances in energy density and significant advances in power density can be made through battery engineering whereas significant advances in energy density and cycle life rest with discovering new electrode materials and optimally engineering them. A benchmark law may be formulated to guide the former whereas the latter may just hinge on serendipity.
12:00 PM - BB1.9
Microstructural Design of Rechargeable Lithium Ion Batteries for High Power Density Applications.
R. Edwin Garcia 1 , Yet-Ming Chiang 2
1 Materials Engineering, Purdue University, West Lafayette, Indiana, United States, 2 Materials Science and Engineering, MIT, Cambridge, Massachusetts, United States
Show Abstract12:15 PM - BB1.10
Electrophoretically Assembling Batteries into Small Spaces.
Ryan Wartena 1 , Yet-Ming Chiang 1
1 Department of Material Science and Engineering, MIT, Cambridge, Massachusetts, United States
Show Abstract12:30 PM - **BB1.11
Recent Trends in Lithium Ion Batteries for Mobile Energy Storage.
M Stanley Whittingham 1
1 Chemistry and Materials, SUNY, Binghamton, New York, United States
Show AbstractThe last five years have seen dramatic advances in lithium-ion battery technology in all components of the cell. The cathode has expanded from lithium cobalt oxide to mixed nickel-manganese-cobalt compounds as well as simple iron phosphates. In the former each transition metal plays a critical role, as does the initial lithium content as in Li1+x(NiyMnyCo1-2y)1-xO2. Careful control of the synthesis conditions allows the precise positioning of the nickel and lithium ions; this is even more the case for y = 0.5 where a number of ordered structures are possible. In the phosphate class of materials, it is now possible to form them by low temperature methods with excellent electrochemical behavior, and control the particle size and vary the transition metal content. Possibilities for replacing the carbonaceous anodes are also now becoming available. This recent work will be discussed together with some future possibilities. This work is supported by the US Department of Energy, Office of FreedomCAR and Vehicle Technologies through the BATT program at LBNL.
BB2: Batteries II
Session Chairs
Munichandraiah Nookala
Lawrence Scanlon
Monday PM, November 27, 2006
Republic A (Sheraton)
2:30 PM - **BB2.1
Micro- and Nano-instrument Power.
Vassili Karanassios 1
1 , University of Waterloo, Waterloo, Ontario, Canada
Show AbstractThe power of micro- and nano-instruments that can be used on-site (where they are needed the most), that have improved figures-of-merit and that are smaller, cheaper, smarter and faster (at producing results) than their conventional-size, tethered-to-a-wall-socket counterparts is intuitively obvious. But where will such an instrument get its electrical power from? This is not evident when considering that such an instrument is designed to operate in remote or inaccessible locations. Consider, for example a pill-size spectrometer that transmits high resolution fluorescence images of biological tissue (for cancer diagnosis) as it travels through the gastro intestinal tract. Where would such a spectrometer get its electrical power? This is not naturally apparent. In this presentation, the paradigm shifts required to integrate electrical power into micro- and nano-instruments (and ideally, to make the intuitively obvious naturally apparent) will be explored.
BB3: Fuel Cells
Session Chairs
Munichandraiah Nookala
Lawrence Scanlon
Monday PM, November 27, 2006
Republic A (Sheraton)
3:00 PM - **BB3.1
Perspectives On The Mobile Energy Storage Systems Using Hydrogen Adsorption In Novel Nano-Composite Materials.
Renju Zacharia 1 , Sang Woon Hwang 1 , A. Stephan 1 , Kee Suk Nahm 1
1 , Chonbuk National University, Jeonju Korea (the Republic of)
Show AbstractCommercial realization and success of hydrogen-based mobile energy storage systems ultimately depend on the development of solid-state hydrogen storage systems that effectively store and release hydrogen at ambient pressure and temperature conditions. Last few years have witnessed the emergence of a broad spectrum of novel nanostructured materials that reversibly adsorb hydrogen under ambience of temperature and moderate pressures. They diverge from nanocrystalline intermetallic systems based on prototypical hydrogen adsorbing alloys to the state-of-the-art nanotube-nanometal composites. Though, the experimental studies pertaining to above systems are limited and in the rudimentary phase, various theoretical modelling anticipates their remarkable hydrogen storage capacity. However, the predicted high storage capacity is confined only to some selected local configurations of these materials. Thus, it remains, as an experimental challenge to confirm their predicted high storage capacities. If experimentally confirmed, nanocrystalline metals and nantoube composites open up an effective way to engineer the hydrogen adsorption for mobile energy storage.Here, we review the emerging hydrogen storage technologies based on novel nanostructured materials, such as nanocrystalline metallic and intermetallic systems, and nanometal-functionalized carbon nanotube composites. The promising hydrogen adsorption characterisitics of these composite materials are illustrated in our latest results on the Ti- and Pt-decorated multiwalled carbon nanotubes. Isothermal hydrogen storage studies of carbon nanotubes doped with these metals performed at a pressure of 28 atm and 25 °C suggest an enhancement by a factor of 6 when compared to the storage capacity of pristine un-doped samples. The significant enhancement in the reverisble hydrogen storage capacity observed in our studies can be partially accounted for by considering the unique hybridization effects and spill-over effect in nanometal-nanotube composites.
4:30 PM - BB3.2
Modeling Platinum Loss in PEM Fuel Cell Cathodes.
Edward Holby 1 , Dane Morgan 1 , Yang Shao-Horn 2
1 Materials Science and Engineering Program, University of Wisconsin-Madison, Madison , Wisconsin, United States, 2 , Massachusetts Institute of Technology, Cambridge, Massachusetts, United States
Show AbstractLoss of electrochemically active surface area (ECA) in the carbon-supported platinum electrocatalyst cathode is a key issue in meeting automotive cost efficiency and durability standards for polymer electrolyte membrane (PEM) fuel cells.1 A previous experimental study2 has shown that Ostwald ripening of platinum nanoparticles and dissolution and precipitation of aqueous platinum ions off of the carbon support, triggered by crossover hydrogen from the anode, are the dominant mechanisms for ECA loss. By adapting a numerical model put forth by Darling and Meyers,3 the time evolution of particle size distributions (PSDs) and their associated ECAs under PEM fuel cell conditions are simulated. This simulation takes into account the effects of temperature, voltage, concentration of aqueous platinum ions, platinum oxide formation on the particles and hydrogen crossover current density. We examine a range of PSDs with similar initial surface area. The ECA loss is significantly different in form and total magnitude for each of the PSDs. It is also found that the hydrogen crossover current density can have a large effect on the extent of Ostwald ripening and Pt dissolution. These results indicate that the initial Pt PSD can have an important impact on the long-term durability of PEM fuel cells.
1. H. A. Gasteiger, S. S. Kocha, B. Sompalli, F. T. Wagner, Applied Catalysis B: Environmental 56, 9-35 (2005).
2. P. J. Ferreira, G.J. la O’, Y. Shao-Horn, D. Morgan, R. Makharia, S. Kocha and H. A. Gasteiger, J. Electrochem. Soc. 152, A2256-A2271 (2005).
3. R. M. Darling and J. P. Meyers, J. Electrochem. Soc. 150, A1523-A1527 (2003).
4:45 PM - BB3.3
Steam Reforming of Propane over Nickel Aluminate Catalysts
Hong He 1 , Jackie Ying 1
1 Chemical Engineering Department, Massachusetts Institute of Technology, Cambridge, Massachusetts, United States
Show AbstractNew nickel aluminate catalysts were developed for steam reforming process to generate hydrogen for fuel cell applications. Nanocrystalline nickel aluminates with various Ni/Al ratios were prepared by chemical co-precipitation. For the steam reforming of propane, nanocrystalline catalyst with Ni/Al ratio of 1.10 provided the highest catalytic activity. Nickel aluminate catalyst was further impregnated with various metal promoters to improve the low-temperature catalytic activity and resistance against coking. Due to the higher reducibility and active surface area obtained with the introduction of Re, low-temperature activity was effectively enhanced with this promoter. Coke formation was found to be significantly inhibited by the use of V promoter, without sacrificing the catalytic activity. The combination of Re and V promoters gave rise to the optimal system with high catalytic activity and coking resistance at high temperatures. Key words: steam reforming, propane, nickel aluminate, rhenium, vanadium
5:00 PM - BB3.4
Proton Conducting Membranes Based on SPEEK/SiSPPSU Blend.
Maria Luisa Di Vona 1 , Debora Marani 1 2 , Enrico Traversa 1 , Silvia Licoccia 1 , Philippe Knauth 2
1 Scienze e Tecnologie Chimiche, University of Rome Tor Vergata, Rome Italy, 2 MADIREL (UMR 6121 CNRS), Université de Provence Centre St Jérôme, Marseille France
Show Abstract5:15 PM - BB3.5
Characterization of Nickel and Cobalt catalysts for Steam Reforming of Methanol in Microreactors.
Debasish Kuila 1 , Krithi Shetty 1 , Shihuai Zhao 1 , Chris Marshall 2
1 IfM/Chemistry, Louisiana Tech University, Ruston, Louisiana, United States, 2 , Argonne National Lab, Chicago, Illinois, United States
Show Abstract5:30 PM - BB3.6
Synthesis and Methane Combustion of Nanostructured Yttria-Zirconia Ceramics Composite.
Jianyi Cui 1 , Jackie Ying 3 2
1 Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts, United States, 3 Chemical Engineering, Massachusetts Institute of Techonology, Cambridge, Massachusetts, United States, 2 , Institute of Bioengineering and Nanotechnology, The Nanos Singapore
Show Abstract5:45 PM - BB3.7
Characteristics of Au, Pt, Fe, and Ni Multi-metallic Nanoparticle Catalyst Systems.
Derrick Mott 1 , Andrew Smith 1 , Jeffrey Galkowski 1 , Jin Luo 1 , Chuan-Jian Zhong 1
1 Chemistry, State Univ. of New York at Binghamton, Binghamton, New York, United States
Show AbstractThe understanding of the surface properties of platinum-based multimetallic alloy nanoparticles is essential for exploiting their unique catalytic properties. This presentation reports findings of an investigation to determine the surface catalytic properties of platinum, gold, iron, and nickel alloyed nanoparticles. Platinum based alloy nanoparticles of 2-5 nm sizes with controlled multi-metallic compositions were studied as a model system. The nanoparticles were assembled on silica and carbon supporting materials, and thermally treated at controlled conditions. The spectroscopic characteristics for the CO stretching bands on the nanoparticle catalysts treated under different temperatures were compared with those of the monometallic nanoparticle counterparts. The findings correlate well with the electronic effect due to the d-band shift on the alloy nanoparticle surface, which is also consistent with the alloy properties of our platinum based nanocrystals. MOR electrocatalysis was used to further study the nanoparticle systems and shows an interesting correlation to the FTIR data. The results indicate that the unique alloys containing Pt, Au, Fe, and Ni elements are indeed potentially powerful catalysts for energy storage and power devices. Implications of the findings to the understanding of the mechanistic details into the synergistic properties of the platinum-based multi-metallic nanoparticle catalysts will also be discussed.
BB4: Poster Session: Energy Storage Devices for Mobile Energy
Session Chairs
Ghassan Jabbour
Kee Suk Nahm
Tuesday AM, November 28, 2006
Exhibition Hall D (Hynes)
9:00 PM - BB4.1
Carbon Embedded and -Supported Platinum-Clusters made by Flame Synthesis.
Frank Ernst 1 , Robert Buchel 1 , Reto Strobel 1 , Sotiris Pratsinis 1
1 Particle Technology Laboratory, ETH Zurich, Zurich Switzerland
Show Abstract9:00 PM - BB4.10
Characterization Of Aluminum Anode Thin Films On Various Substrates For Thin Film Battery
Arun Patil 1 , Dong Wook Shin 2 1 , Ji-Won Choi 1 , Seok-Jin Yoon 1 , Yong Soo Cho 2
1 Thin Film Materials Research Center, Korea Institute of Science and Technology, Seoul Korea (the Republic of), 2 Department of Materials Science and Engineering, Yonsei University, Seoul Korea (the Republic of)
Show Abstract9:00 PM - BB4.11
Modeling and Fabrication of MEMS Piezoeletric Vibration Energy Harvesters.
Woo Sik Kim 1 , Anna Mracek 1 , Brian Wardle 1
1 Aeronautics and Astronautics, MIT, Cambridge, Massachusetts, United States
Show Abstract9:00 PM - BB4.13
Nanocatalysts for Fischer-Tropsch Synthesis to Higher Alkanes Using an Array of Microreactors.
Debasish Kuila 1 , Shirish Mehta 1 , Shihuai Zhao 1 , Upali Siriwardane 1
1 IfM/Chemistry, Louisiana Tech University, Ruston, Louisiana, United States
Show Abstract9:00 PM - BB4.14
Acid-functionalized Carbon Nanotube-Nafion Composite Membrane for Direct Methanol Fuel Cell Application.
Jingyu Hyeon-Lee 1 , Myungsup Jung 1 , Seokgwang Doo 1
1 Energy and Materials Research Laboratory, Samsung Advanced Institute of Technology, Suwon Korea (the Republic of)
Show Abstract9:00 PM - BB4.15
Size Control, Characterization and Hydrogenation Studies of Fuel Cell Nanocatalysts.
Anatoly Frenkel 1 , Sarah Azran 1 , Bursky-Tammam Nina 1 , Gabriel Cwilich 1 , Eliot Deutsch 1 , Elie Horowitz 1 , Nathan Hould 2 , Leah Kanner 1 , Daniel Lowenstein 1 , Adam Mayerhoff 1 , Yardanna Platt 1 , Miriam Rafailovich 2 , Sidney Schechet 1 , Michelle Simpser 1 , Dina Turetsky 1 , David Wermuth 1 , Juan Zhou 2 , Sijia Zhao 2 , Fredy Zypman 1
1 Physics, Yeshiva University, New York, New York, United States, 2 Materials Science , Stony Brook University, Stony Brook, New York, United States
Show Abstract9:00 PM - BB4.16
Temperature Dependence Study of Gas Permeability in Metal Doped Composite Polymeric Membranes.
Yogesh Vijay 1 , A. Jain 1 , N. Acharya 1 , Kamlendra Awasthi 1 , Vaibhav Kulshrestha 1
1 Department of Physics, University of Rajasthan, Jaipur India
Show Abstract9:00 PM - BB4.2
Demonstration of a Novel Alkaline Battery Cathode Material: Periodate Salts.
Stuart Licht 1 , Xingwen Yu 1
1 , University of Massachusetts Boston, Boston, Massachusetts, United States
Show Abstract Periodates are the highest valent state form of iodine compounds, and have been used as strong oxidants in organic synthesis and quantitative titrimetric determination of a variety of reducing agents. We report a new alkaline battery chemistry using this heptavalent iodine alkaline salt as a cathode material. Commercially available potassium periodate and sodium periodate are used for this demonstration. An unusual alkaline solubility of KIO4 in KOH solution is observed, and a mechanism is proposed for this behavior in which potassium cation and hydroxide complex with KIO4 to form insoluble periodates at high KOH concentrations. Both potassium periodate and sodium periodate will be shown to be very stable in KOH solution. Low solubility, high stability and compatibility with alkaline electrolyte are attractive characteristics for electrochemical storage. The theoretical cathodic storage capacity of KIO4 and NaIO4 is determined based on the 2 electron reaction: IO4- + H2O + 2e- → IO3- + 2OH-. For KIO4, the theoretical capacity is (2×96485/230)/3.6=233mAh/g, for NaIO4, theoretical capacity is (2×96485/214)/3.6=250mAh/g. Primary periodate batteries are studied using a Zn anode, and a KIO4 (or NaIO4) cathode in a coin cell configuration. The open circuit potential of the cell is 1.4-1.5 V. The cathode is efficiently used during discharge and, over 95% of the theoretical intrinsic capacity is observed during discharge. Using reversible metal hydride as the anode, secondary periodate batteries, and the charge reversibility of the alkaline periodate couple, are also being probed. An excellent rechargeable performance of the periodate (for both KIO4 and NaIO4) cathode is observed. The effective depth of discharge approaches 100% at the first 20 cycles.
9:00 PM - BB4.3
Synthesis and Analysis of Ag2FeO4 Fe(VI) Ferrate Super-iron Cathodes.
Stuart Licht 1 , Lan Yang 1
1 Chemistry , University of Massachusetts , Boston , Massachusetts, United States
Show Abstract9:00 PM - BB4.4
Structural, Magnetic and Electrochemical Properties of the Spinel LiMn2-yCoyO4 Nanosized Powders.
Noureddine Amdouni 1 , Francois Gendron 2 , Alain Mauger 3 , Christian Julien 4
1 PCMS, Universite de Tunis, Tunis Tunisia, 2 Institut des NanoSciences de Paris, Universite P & M Curie, Paris France, 3 MIPPU, CNRS, Paris France, 4 Institut des NanoSciences de Paris, Universite P & M Curie, Paris France
Show AbstractWe present the synthesis, characterization and electrode behaviour of LiMn2-yCoyO4 (0≤y≤0) spinel oxides prepared by the wet-chemitry via the carboxylic acid route. The phase evolution was studied as a function of the cobalt substitution and the modification on the intercalation and deintercalation of Li ions. Characterization methods include TG-DTA, XRD, SEM, Raman and FTIR. LiMn2 yCoyO4 samples crystallise with the cubic spinel-like structure (Fd3m S.G.). Raman scattering and Fourier transform infrared vibrational spectroscopies indicate that the vibrational mode frequencies and relative intensities of the bands are sensitive to the covalency of the (Co,Mn)-O bonds. MEB micrographs show that the particle size of the LiMn2 yCoyO4 powders ranges in the submicronic domain with a narrow grain-size distribution. Magnetic susceptibility and electron spin resonance measurements show the compositional dependence of the magnetic parameters, i.e. Curie temperature, Curie-Weiss constant and Néel temperature, when Mn is substituted by Co.The overall electrochemical capacity of LiMn2-yCoyO4 oxides have been reduced due to the 3d6 metal substitution, however, a more stable charge-discharge cycling performances have been observed when electrodes are charged up to 4.3 V as compared to the performance of the native oxide. For such a cut-off voltage, the charge capacity of the Li//LiMn2-yCoyO4 cell is ca. 118 mAh/g. Differences and similarities between LiMn2O4 and Co-substituted oxides are discussed therefrom.
9:00 PM - BB4.5
Electrochemical Features of Li-Ni-Mn-Co Oxides.
Ashraf Abdel-Ghany 1 , Karim Zaghib 2 , Francois Gendron 3 , Alain Mauger 4 , Ahmed Eid 5 , Ahmed Hashem 6 , Christian Julien 7
1 INSP, Universite P & M Curie, Paris France, 2 , IREQ, Varennes, Quebec, Canada, 3 INSP, Universite P & M Curie, Paris France, 4 MIPPU, CNRS, Paris France, 5 , National Research Center, Ghiza Egypt, 6 , National Research Center, Ghiza Egypt, 7 Institu des NanoSciences de Paris, Universite P & M Curie, Paris France
Show AbstractLithium-ion batteries are emerging as the prime power sources for portable electronics due to their high energy density. These cells currently use the layered LiCoO2 electrode material which delivers only 50% of the theoretical capacity (273 mAh/g) in the 4-volt range. The limitation in utilization has been attributed to chemical instabilities which can be suppressed on going from LiCoO2 to LiCoxNiyMnzO2. Among the mixed-cation oxides, LiCo0.2Ni0.8O2, LiNi0.5Mn0.3O2, and LiCo0.33Ni0.33Mn0.33O2 have been identified to have better chemical stability, better cyclability and rate capability. These compounds satisfy two rules. First, the sum of the cation occupations on the 3b sites of space group R-3m in the transition-metal layers equals one. Second, the sum of the cation oxidation state times the cation occupation must equal three [1]. Here we report the electrochemical behavior of Li cells using various lithium transition metal oxides. The Li-Ni-Mn-Co oxides were synthesized by wet chemistry through oxalic acid assisted sol-gel method. Materials have been characterized by XRD, FTIR, and magnetometry. Electrochemical cells with the configuration LiNixMnyCozO2/LiPF6-EC-DEC/Li cells were tested at various C-rate discharge currents [2]. The effective magnetic moment of LiNi0.33Mn0.33Co0.33O2, μeff =2.86 μB, is consistent with the theoretical value 3.93 μB calculated from the spin-only of Ni2+, Mn4+ and Co3+. Consequently, as the effective moment for the (Ni2+, Mn4+ and Co3+) cations differs from 4.56 μB calculated from the spin-only of the (Ni3+, Mn3+ and Co3+) cations in the low-spin configuration, it is conclusively demonstrated that the oxidation states of Co, Ni and Mn in LTM⅓O are determined. LTM⅓O exhibits a ferromagnetic (FM) behavior in the low-temperature region (T<30 K). The Curie temperature corresponding to the departure from the FM behaviour is estimated to be Tc=32 K. The FM interaction is clearly observed for LTM⅓O where the 3b and 3a sites are randomly occupied by a small fraction of Ni2+, Mn4+ and Co3+. The voltage profiles for Li//LiNi0.75Mn0.25O2 and Li//LiNi0.4Mn0.4Co0.2O2 cells at discharge rate C/5. These cells show very smooth discharge curves with an average voltage near 3.80 V. The first cycle irreversible capacity loss for the LiNi0.75Mn0.25O2 electrode is 20 mAh/g while 10 mAh/g for the LiNi0.4Mn0.4Co0.2O2 cell. Electrochemical features of LiNixMnyCozO2 layered oxides with various concentration of cobalt in the range z=0.0-0.5 are presented and discussed in relation with the local structure of the electrode materials.References[1] Z. Lu, D.D. McNeil, J.R. Dahn, ESSL 4, A200 (2001).[2] A. Abdel-Ghany, K. Zaghib, C.M. Julien, in: Portable and Emergency Energy Sources, ed. by Z. Stoynov and D. Vladikova, Marin Dynov Publishing House, Sofia 2006, p. 1.
9:00 PM - BB4.6
Long-Term Stability of Primary Film Battery for Radio Frequency Identification(RFID) Tag and Ubiquitous Sensor Node.
Young-Gi Lee 1 , Junho Yeo 2 , Cheol Sig Pyo 3 , Kwangseuk Kyhm 4 , Kuk Young Cho 5 , Kwang Sun Ryu 1
1 Ionics Devices Team , Electronics & Telecommunications Research Institute(ETRI), Daejeon Korea (the Republic of), 2 RFID System Research Team, Electronics & Telecommunications Research Institute(ETRI), Daejeon Korea (the Republic of), 3 RFID/USN Research Group, Electronics & Telecommunications Research Institute(ETRI), Daejeon Korea (the Republic of), 4 Research Center for Dielectric & Advanced Matter Physics, School of Physics, Pusan National University, Pusan Korea (the Republic of), 5 Division of Advanced Materials Engineering, Kongju National University, Kongju, Chungnam, Korea (the Republic of)
Show AbstractPrimary battery has existed for over 100 years and it is a convenient source of power for portable electric and electronic devices. In the 1970s, a film type primary battery was first innovated by Polaroid, that is, P-80 Leclanché film battery having an electrode area of approximately 5.1cm by 5.1cm and an inclusion type of film cell within the camer-film pack. Up to recently, the worldwide trend in electronics, automation, communication, and health-care products is moving towards smaller, smarter, thinner, flexible and mass-produced devices. This development is creating a growing need for low-cost thin and flexible microelectronic solutions including micro-power sources that are not subject to size or design constraints. In the 1990s, Power Paper has developed a breakthrough technology platform that enables the mass production of low-cost, thin and flexible energy cells capable of powering a host of applications, especially for a battery-assisted RFID, namely, Power ID. Its core technology is a process that enables the printing of caseless, thin, flexible energy cells on a polymer film substrate, not on metal current collector, by means of a simple mass-printing technology. However, these caseless film batteries have some drawbacks in shelf life and self-discharge. Under prolonged period over 25°C or when exposed to dry atmosphere for a long time, the aqueous electrolytes easily dry out and the internal resistance increases little by little. In addition, the open circuit voltage gradually decreases in their storing due to the self-discharge. In this study, we have introduced a variety of hydrogel polymers and newly developed electrolyte solutions to enhance the long-term stability of film battery for good shelf life. We also have tried to systematically optimize a polymer film thickness and composition for safe packaging and better current collecting ability.
9:00 PM - BB4.7
Solid Oxide Fuel Cells in Unmanned Undersea Vehicle Applications.
Louis Carreiro 1 , A. Burke 1
1 , Naval Undersea Warfare Center, Newport, Rhode Island, United States
Show Abstract9:00 PM - BB4.8
Modeling of the Thermal Behavior of a Lithium-polymer Battery.
Ui Seong Kim 1 , Say Hoon Jeon 1 , Chee Burm Shin 1 , Hyeon-Taik Hong 1 , Chi-Su Kim 2
1 Chemical Engineering, Ajou University, Suwon Korea (the Republic of), 2 Battery R&D Center, VK Corporation, Pyeongtaek Korea (the Republic of)
Show Abstract9:00 PM - BB4.9
Thermoelectric Power Devices Based on InN Thin Films.
Takayuki Matsumoto 1 , Shigeo Yamaguchi 1 2 , Atsushi Yamamoto 3
1 EEIE, Kanagawa University, Yokohama Japan, 2 High-Tech Research Center, Kanagawa University, Yokomaha Japan, 3 Energy Technology Research Institute, AIST, Tsukuba Japan
Show Abstract
Symposium Organizers
Gehan Amaratunga University of Cambridge
Munichandraiah Nookala Indian Institute of Science
Lawrence G. Scanlon Air Force Research Laboratory
Endo Morinobu Shinshu University
Arokia Nathan University College London
BB5: Cathodes and Anodes
Session Chairs
Peter Bruce
Vassili Karanassios
Tuesday AM, November 28, 2006
Republic A (Sheraton)
9:30 AM - BB5.1
Iron Phosphates as Cathodes of Lithium-Ion Batteries.
Shijun Wang 1 , M. Stanley Whittingham 1
1 Materials Science, SUNY at Binghamton, Binghamton, New York, United States
Show AbstractOur study focuses on optimizing the parameters of hydrothermal synthesis to produce iron phosphates for lithium batteries, with an emphasis on pure LiFePO4 with olivine structure and compounds containing a higher iron:phosphate ratio. Lithium iron phosphate (LiFePO4) is a promising cathode candidate for lithium ion batteries due to its high theoretical capacity, environmentally benign and the low cost of starting materials. Well crystallized LiFePO4 can be successfully synthesized at the temperature above 150 °C. The addition of a reducing agent, such as hydrazine, is essential to minimize the oxidation of ferrous (Fe2+) to ferric (Fe3+) in the final compound. The morphology of LiFePO4 is highly dependent on the pH of the initial solution. We are also interested in the lipscombite iron phosphates with general formula of Fe2-y○y(PO4)(OH)3-3y(H2O)3y-2 (○ = vacancy). It has “log-like” structure formed by Fe-O octahedral chains. The chains are partially occupied by the Fe3+ sites, and these iron atoms and some of the vacancies can be substituted by other cations. The protons may be ion-exchanged for lithium. This work is being supported by the DOE, Office of FreedomCAR, through the BATT program.
9:45 AM - BB5.2
Investigation of Li-Ion Intercalation Properties of Tunnel-Structured Manganese Oxides.
Malgorzata Gulbinska 1 , Weina Li 2 , Vincent Crisostomo 2 , Steven Suib 2 3
1 Lithion, Inc., Yardney Technical Products, Inc., Pawcatuck, Connecticut, United States, 2 Chemistry, University of Connecticut, Storrs, Connecticut, United States, 3 Institute of Materials Science, University of Connecticut, Storrs, Connecticut, United States
Show AbstractIn this study, manganese oxides with one-dimensional arrays of tunnels were synthesized by a variety of synthetic methods (e.g. reflux, hydrothermal, microwave-field assisted) and tested for lithium-ion intercalation properties. The effect of tunnel opening dimensions (i.e. 2 × 2, 3 × 3 edge-sharing MnO6 octahedra) on the structural stability upon cycling in secondary lithium-ion batteries was investigated. Isomorphous substitution of higher-valency ions into manganese oxide frameworks (e.g. V5+ ions) was studied in terms of cycling stability and intercalation voltage properties. Structural properties and morphology of synthesized materials were characterized by XRD and FESEM, respectively. Manganese oxide materials were investigated as cathodes in Li-ion cathode half-cells.In the discussed family of manganese oxides, MnO6 octahedra share corners and form the tunnel openings (e.g. 2 × 2, in the synthetic cryptomelane structure, KMn8O16 × nH2O). Structural and electrochemical studies of α-MnO2 (dehydrated cryptomelane), stabilized with Li2O present in the tunnels instead of the K+ ions and H2O were performed by C. S. Johnson et al. Pistoia and Antonini described the electrochemical behavior of selected polymorphs of MnO2, such as α-, β-, γ-MnO2. Ohzuku et al. investigated the effects of various stabilizing cations (K+, NH4+, and Rb+,) on Li+, intercalation within the 2 × 2 tunnels of α-MnO2. In this work, we report the effect of high-valency ion substitution into the cryptomelane-type and related structures on their lithium-ion intercalation properties. Very few previous studies have attempted the incorporation of transition metal cations into the framework of manganese oxides. In this study, V5+ ions were substituted for Mn4+ in the mixed valence (Mn4+/Mn3+) manganese oxide framework. When tested in Li-ion batteries, vanadium-doped cathode materials exhibited flat discharge profiles that shifted towards higher voltages, from 2.39 V at about 50% depth of discharge for an un-doped material, through 2.56 V for 3.5% of doped vanadium, to 2.60 V for 6.3% vanadium. Vanadium ion was increasingly doped into the manganese oxide framework (3.5%-6.3%) without significant changes in discharge capacity values (~107-117 mAh/g). The observed increase in Li+ intercalation voltage, accompanied by the apparent lack of capacity loss on vanadium incorporation can be of practical importance in attempts to increase the operating voltage of manganese oxide-based cathode materials for lithium-ion batteries.
10:00 AM - **BB5.3
High Performance of Lithium Iron Phosphates for HEV with Quality Control made by Magnetometry.
Christian Julien 1 , Karim Zaghib 2 , Alain Mauger 3 , Francois Gendron 4
1 Institut des NanoSciences de Paris, Universite P & M Curie, Paris France, 2 , Institut de Recherche d'Hydro-Québec, Varennes, Quebec, Canada, 3 MIPPU, CNRS, Paris France, 4 Institut des NanoSciences de Paris, Universite P & M Curie, Paris France
Show Abstract10:45 AM - BB5.5
Atomic-Scale Studies of the LiFePO4 Olivine-Type Battery Material: Defects, Dopants and Surface Structures.
M.Saiful Islam 1 , Craig Fisher 1 , Peter Slater 2
1 Chemistry, University of Bath, Bath United Kingdom, 2 Chemistry, University of Surrey, Guildford United Kingdom
Show Abstract11:30 AM - BB5.6
Comparison of Structure and Physical Properties of High- and Low-Rate Olivine Cathodes for Lithium-ion Batteries.
Nonglak Meethong 1 , Hsiao-Ying Huang 1 , Scott Speakman 2 , Craig Carter 1 , Yet-Ming Chiang 1
1 Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts, United States, 2 Center for Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts, United States
Show AbstractA wide variety of mobile electronic devices now have increased performance due to incorporation of high energy density lithium-ion batteries. A new goal for portable power is the realization of safe and durable high power batteries to meet the demands of applications such as power tools and hybrid electric vehicles. While certain lithium metal phosphate olivines have been shown to be promising, not all olivines demonstrate beneficial properties. In this presentation we will correlate results from electrochemical tests, structural analysis, and electron microscopy that together clarify the structural and chemical features distinguishing high rate from low rate olivines.
11:45 AM - BB5.7
First-principles Modeling of Thermal Stability of Cathode Materials in Li-ion Batteries.
Lei Wang 1 , Thomas Maxisch 1 , Gerbrand Ceder 1
1 Materials Science and Engineering, Massachusetts Institute of Techonology, Cambridge, Massachusetts, United States
Show Abstract12:30 PM - BB5.9
Synthesis, Structure, and Electrochemical Properties of Li4Ti5O12.
Chintalapalle Ramana 1 , Satoshi Utsunomiya 1 , Udo Becker 1 , Rodney Ewing 1 2 , Karim Zaghib 3 , Christian Julien 4
1 Geological Sciences, University of Michigan, Ann Arbor, Michigan, United States, 2 Department of Materials Science and Engineering, University of Michigan, Ann Arbor, Michigan, United States, 3 , Institut de Recherches d'Hydro-Québec, Varennes, Quebec, Canada, 4 Institut des Nano-Sciences de Paris, Université Pierre et Marie Curie, Paris France
Show Abstract12:45 PM - BB5.10
Structural and Compositional Properties of Nanocrystalline Si-Cr Alloy Anodes for Thin Film Battery
Arun Patil 1 , Dong Wook Shin 2 1 , Ji-Won Choi 1 , Seok-Jin Yoon 1
1 Thin Film Materials Research Center, Korea Institute of Science and Technology, Seoul Korea (the Republic of), 2 Department of Materials Science and Engineering, Yonsei University, Seoul Korea (the Republic of)
Show AbstractBB6: Energy Conversion
Session Chairs
Tuesday PM, November 28, 2006
Republic A (Sheraton)
2:30 PM - **BB6.1
Semi-transparent Amorphous Silicon Solar Cells on Inexpensive Plastic Substrates.
Arun Madan 1 2
1 , MV Systems, Inc., Golden, Colorado, United States, 2 Dept. of Metallurgical and Materials Engineering, Colorado School of Mines, Golden , Colorado, United States
Show Abstract3:00 PM - **BB6.2
Flexible Organic Photovoltaics.
Ghassan Jabbour 1
1 Dept. of Chemical and Materials Engineering, Arizona State University, Tempe, Arizona, United States
Show Abstract3:30 PM - BB6.3
Microstructural Effects of Thermoelectric Nanowire Composites
Mara Howell 1 , R. Edwin Garcia 1 , Timothy Sands 1 2
1 School of Materials Engineering, Purdue University, West Lafayette, Indiana, United States, 2 School of Electrical and Computer Engineering, Purdue University, West Lafayette, Indiana, United States
Show AbstractThermoelectric materials offer exciting promise for harvesting useful electricity from waste heat; however, most current thermoelectric devices offer low power conversion efficiencies and exhibit low thermoelectric figures of merit. Improvements in material selection, material processing, and device design are needed to further advance the thermoelectric technology and make it a viable option for energy generation. Although thin film Bismuth Telluride (Bi2Te3) is often the thermoelectric material chosen for cooling and power generation applications, nanowire arrays offer distinct advantages, and are easily fabricated using an electro-deposition process and porous anodic alumina (PAA). Additionally, process parameters can control several features of interest, such as the nanowire diameter and texture. The texture of nanowire grains is of particular interest, as the high crystal anisotropy of Bi2Te3 leads to anisotropic material properties. As a result, the nanowire texture is expected to have a significant affect on the composite’s thermoelectric performance and figure of merit, ZT. By studying the effect of grain orientation on the thermoelectric performance of the composite, an optimum orientation can be determined for the Bi2Te3 nanowire grains. Other microstructural features of interest include grain size, grain shape, and the thickness and properties of the grain boundaries. The effect of the microstructural features on the performance and ZT of thermoelectric nanowire composites was studied by using a computational model and resolving the nanowire microstructure. The results can be used to design a nanowire composite with optimal efficiency.
3:45 PM - BB6.4
Mechanical-to-electrical Energy Conversion of Thin-film Piezoelectric Membrane Laminates for Micropower Generation.
Dylan Morris 1 , Leland Weiss 2 , Cecilia Richards 2 , Robert Richards 2 , David Bahr 2
1 Center for Materials Research, Washington State University, Pullman, WA, Washington, United States, 2 Mechanical and Materials Engineering, Washington State University, Pullman, Washington, United States
Show AbstractBB7: Capacitors
Session Chairs
Tuesday PM, November 28, 2006
Republic A (Sheraton)
4:30 PM - BB7.1
Electrochemical Supercapacitor Studies of Nano Structured MnO2.
Munichandraiah Nookala 1 , Devaraj Sankar 1
1 Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore, Karnataka, India
Show AbstractAn electrochemical supercapacitor is a charge (or energy) storage device, which can withstand to higher power discharge compared to a battery, and deliver higher energy compare to a conventional electrostatic and electrolytic capacitor[1]. The most widely studied materials for supercapacitors include (i) carbaneous materials, (ii) conducting polymers and (iii) transition metal oxides. Among different transition metal oxides, amorphous hydrous RuO2 has a high specific capacitance (~760 F g-1) due to solid-state pseudo Faradaic reaction. However, high cost, low porosity and rapid decrease of power density at high charge/discharge rates are disadvantages for using RuO2.xH2O in practical supercapacitors. In recent years, attention has been paid on hydrous manganese oxide as it is inexpensive, its raw materials are abundant in nature, it is environmentally friendly and also it is widely used in batteries. However, maximum specific capacitance reported for hydrous MnO2 is 240 F g-1 at the loading level of 0.4 – 0.5 mg cm-2 [2]. But, 1370 F g-1 is expected for MnO2 based on charge storage mechanism reported recently [3. Decreasing the particle size is considered to be a significant approach to enhance material utilization and thus specific capacitance. In the present study, nanoparticles of MnO2 were prepared in a microemulsion medium and electrochemical characterization studies pertaining to supercapacitor properties were performed. The oxide particles were found to have hexagonal shape of about 50 nm or nano-rod depending on the temperature at which MnO2 was annealed. Specific capacitance values as high as 297 F g-1 were obtained. TEM image of the as-prepared MnO2 is showed that the particles have hexagonal shape of 50 nm diameter. Cyclic voltammograms of MnO2 electrodes at sweep rates up to 100 mV s?1 have rectangular shape due to nano particles of MnO2. The specific capacitance (SC) was calculated using equation: SC = I / (u m), where u is sweep rate used for recording cyclic voltammogram and m is the mass of active material [4]. The electrodes of the as prepared a-MnO2 nano particles were subjected to galvanostatic charge-discharge cycling between 0 and 1 V vs SCE in 0.1 M Na2SO4 aqueous electrolyte at several current densities (c.d.). Discharge SC obtained is 296.9 F g-1. This value is much higher than what is reported in the literature. Results of these studies and the effect of annealing will be presented.References:[1] B. E. Conway, ‘Electrochemical Supercapacitors’, Kluwer Academic Publishers/Plenum Press, New York (1999).[2] J. K. Chang and W. T. Tsai, J. Electrochem. Soc., 150, A1333 (2003).[3] M. Toupin, T. Brousse and D. Belanger, Chem. Mater., 16, 3184 (2004).[4] S. Devaraj and N. Munichandraiah, Electrochem. Solid-State Lett., 8, A373 (2005).
4:45 PM - BB7.2
Activated Carbons for High Power Energy Storage: Below the Surface of Non-Faradaic Reactions.
Prabeer Barpanda 1 2 , Glenn Amatucci 1 2
1 Materials Science and Engineering, Rutgers University, Piscataway, New Jersey, United States, 2 Energy Storage Research group, , New Jersey Technology Centre,, North Brunswick,, New Jersey, United States
Show Abstract5:00 PM - BB7.3
Novel Nanoporous Carbon Derived from Coal Tar Pitch/polyethylene Glycol Diacid Blends as Electrodes for Ultracapacitors.
Ramakrishnan Rajagopalan 1 , Keith Perez 2 , Henry Foley 1 2
1 Materials Research Institute, The Pennsylvania State University, University Park, Pennsylvania, United States, 2 Chemical Engineering, The Pennsylvania State University, University Park, Pennsylvania, United States
Show Abstract5:15 PM - BB7.4
Mesoporous Carbon Materials as Electrodes for Electrochemical Double-Layer Capacitor.
Sea Park 1 , Chengdu Liang 2 , Sheng Dai 2 , Nancy Dudney 1 , David DePaoli 3
1 Material Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee, United States, 2 Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee, United States, 3 Nuclear Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee, United States
Show Abstract5:30 PM - BB7.5
On the Fly Modifications of electrochemical Materials During Direct-write Deposition for Energy Storage Applications.
Nicholas Kattamis 1 2 , Christina Peabody 1 2 , Craig Arnold 1 2
1 Mechanical and Aerospace Engineering, Princeton University, Princeton, New Jersey, United States, 2 Princeton Institute for Science and Technology of Materials, Princeton University, Princeton, New Jersey, United States
Show Abstract5:45 PM - BB7.6
Development of Nano-Micro-Macro-Structured Porous Nickel Electrodes for use in Supercapacitors.
Jason Manning 1 2 , Roger Campbell 1 , Brenda O'Neil 1 , Leigh McKenzie 1 , Renee Woo 2 , Martin Bakker 1 2 , George Havrilla 3
1 Center for Materials for Information Technology, The University of Alabama, Tuscaloosa, Alabama, United States, 2 The Department of Chemistry, The University of Alabama, Tuscaloosa, Alabama, United States, 3 , Los Alamos National Laboratory, Los Alamos, New Mexico, United States
Show AbstractThe extremely high surface areas required for supercapacitors has limited the use of metal based electrodes, despite the other advantages such electrodes might have. Self-assembling surfactants and block co-polymers can be used as templates to produce nanostructured thin films that readily give 60-140 fold increases in surface area on both planar and three-dimensional substrates. However, even when relatively high surface area porous metal substrates such as nickel foam are used as a starting point, the resultant material still has surface area density well short of that available in other types of materials. Micro-emulsions offer a method of generating microstructure that bridges the gap between the 100 micron scale structures of foamed metals and the 10-50 nm scale structure of self-assembling block co-polymers. Electrodeposition of nickel and cobalt from micro-emulsions of Tween surfactants gives rise to structure on the 0.1-10 micron length scale. The scale of the microstructure is strongly influenced by the metal ion concentration and the potential at which the electrodeposition. The nature of the metal ion also strongly effects the ease with which the microstructure can be generated and the distribution of the microstructured film on foamed nickel electrodes. For microstructured nickel films ten fold surface area increases can be readily achieved. The microstructured films are expected to be compatible with a number of the nanostructuring methods to yield cumulative surface area increases of 1000-2000 fold.
Symposium Organizers
Gehan Amaratunga University of Cambridge
Munichandraiah Nookala Indian Institute of Science
Lawrence G. Scanlon Air Force Research Laboratory
Endo Morinobu Shinshu University
Arokia Nathan University College London
BB8/AA7: Joint Session: Solid State Ionics for Mobile Energy
Session Chairs
Rosa Palacin
Stanley Whittingham
Wednesday AM, November 29, 2006
Republic B (Sheraton)
9:30 AM - **BB8.1/AA7.1
Enabling Aspects of Metal Halide Nanocompositesfor Reversible Energy Storage.
Glenn Amatucci 1 , Fadwa Badway 1 , Nathalie Pereira 1 , Wei Tong 1 , Irene Plitz 1 , Jafar Al-Sharab 1 , Frederick Cosandey 1 , Adam Skrzypczak 1 , John Gural 1
1 Energy Storage Research Group, Department of Materials Science and Engineering, Rutgers, the State University of New Jersey, North Brunswick, New Jersey, United States
Show Abstract10:00 AM - BB8.2/AA7.2
A Study on the LiMn2O4 Cathodes with Mesh-like Structures for Li Secondary Batteries.
Min Park 1 , Dong-Hoon Chung 1 , Bong-Kwan Shin 1 , Seung-Ki Joo 1
1 School pf Material Science and Engineering, Seoul National University, Seoul Korea (the Republic of)
Show Abstract10:15 AM - BB8.3/AA7.3
Nanosized Amorphous Materials as Anodes for Lithium Batteries.
Quan Fan 1 , M. Stanley Whittingham 1
1 Department of Chemistry, State University of New York at Binghamton, Binghamton, New York, United States
Show Abstract10:30 AM - BB8.4/AA7.4
Macroporous Silicon Inverse Opals as Electrodes for Lithium-Ion Secondary Batteries.
Alexei Esmanski 1 , Geoffrey Ozin 1
1 Chemistry, University of Toronto, Toronto, Ontario, Canada
Show AbstractColloidal crystal templating methods are among the “hottest” areas in materials science today. Three-dimensional macroporous ordered structures (“opals” and “inverse opals”) can be produced by these methods on a large scale. Although a principal area of research for materials with opal and inverse opal morphologies is that of photonic crystals, a few investigations have examined the possibility of using these structures as gas sensors, catalysts and battery electrodes.Specifically, there are several potential advantages of lithium-ion battery electrodes, based on inverse opal structures. High electrode-electrolyte interfacial surface area and easier access to the bulk of electrode, as well as reduced lithium diffusion length allow for the use of batteries at higher discharge rates [1]. Highly open hierarchical structures also provide better mechanical stability to volume swings during battery cycling.The theoretical capacity of silicon for lithium insertion at room temperature is 3579mAh/g (Li15Si4 phase) [2]. For comparison, the theoretical capacity of graphite, the material of choice in modern state-of-the-art lithium-ion batteries, is only 372mAh/g. This makes silicon one of the most promising anode materials despite its relatively low electronic conductivity and lithium diffusion rates.In this study, opal films (10–40 μm thick) of monodisperse silica nanospheres were fabricated by the evaporation induced self-assembly method [3]. These templates were uniformly infiltrated with amorphous silicon via chemical vapor deposition, with subsequent removal of the silica template [4]. The structural/electrochemical property relationships of silicon inverse colloidal crystal films have been investigated and compared to traditional negative electrode materials, so as to outline the main benefits of the inverse opal hierarchical structure. Electrochemical cycling of silicon inverse opal films demonstrated their good cycling ability, high lithium insertion capacity approaching the theoretical value and excellent coulombic efficiency. Electron microscopy studies confirmed that the open hierarchical structure is maintained during lithium insertion-deinsertion and revealed interesting morphological changes occurring in the system during cycling.References:1. J. S. Sakamoto, B. Dunn, J. Mater. Chem., 2002, 12, 28592. M. N.Obrovac, L. Christensen, El-Chem. Solid-State Lett., 2004, 7, A933. P. Jiang, J. F. Bertone, K. S. Hwang, V. L. Colvin, Chem. Mater., 1999, 11, 21324. A. Blanco, E. Chomski, S. Grabtchak, M. Ibisate, S. John, S. W. Leonard, C. Lopez, F. Messeguer, H. Miguez, J. P. Mondia, G. A, Ozin, O. Toader, H. M. van Driel, Nature, 2000, 405, 437
10:45 AM - BB8.5/AA7.5
Preparation and Characterization of ALD TiN Thin Films on Lithium Titanate Spinel (Li4Ti5O12) for Lithium Ion Battery Applications.
Mark Snyder 1 , Boris Ravdel 4 , Joseph DiCarlo 4 , M. Wheeler 1 , Carl Tripp 2 3 , William DeSisto 1 3
1 Chemical & Biological Engineering, University of Maine, Orono, Maine, United States, 4 , Lithion Corp., Pawcatuck, Connecticut, United States, 2 Chemistry, University of Maine, Orono, Maine, United States, 3 Laboratory for Surface Science & Technology (LASST), University of Maine, Orono, Maine, United States
Show AbstractLithium titanate spinel (Li4Ti5O12) has received an increasing level of attention over the last five years as a nanopowder lithium-ion battery anode. Nanopowder electrodes may provide a higher energy density than currently available. Applying a thin film that is both conducting and chemically inert to harmful reactions with the solvent/electrolyte may enhance battery cycle life. We are investigating thin TiN films on Li4Ti5O12 prepared by atomic layer deposition (ALD) and have characterized their properties, including their influence, on Li-ion battery performance. ALD consists of sequential deposition of self-terminating, surface layer half-reactions (an “A step” and “B step”) and has the potential to uniformly coat irregular surfaces like nanoparticles. To gain a basic understanding of the mechanism of thin film formation on a powder surface, modification of a silica powder surface with TiCl4 (step A) and NH3 (step B) to form a TiN thin film has been performed and characterized in situ with FTIR. Six layers were deposited at 400 C. IR spectra of a TiClx-terminated surface after step A, and an NH-terminated surface after step B were obtained. Insight was gained on causes of incomplete surface film coverage. ALD thin films have been deposited on Li4Ti5O12 as well. Thin films of 200 to 1000 layers were deposited at temperatures from 400 to 600 C. A 200-layer film deposited at 500 C had an estimated thickness of 6 nm on a particle of about 50 nm in length. Nitrogen analysis and transmission electron microscopy were used to verify the presence of nitrogen and formation of a thin film, respectively, on Li4Ti5O12. Modifying the powder with an ALD thin film coating produced a powder that maintained charge longer with shorter transient periods during cyclic voltammetry. It also held a more consistent charge capacity over varying discharge rates in coin cell testing than unmodified Li4Ti5O12. Furthermore, the surface of the spinel nanopowder has been studied under vacuum and at varying temperatures with diffuse reflectance infrared Fourier transform spectroscopy revealing surface hydroxyls, carbonates and water. Several probe molecules have been used to determine the presence of acid/base sites and explore potential methods of bonding with thin film precursors. Pyridine bonded with the surface at Lewis acid sites. No evidence of Brönsted acid sites were observed. Hexamethyldisilazane formed Ti-O-Si bonds. Both of these reactions proceeded at room temperature and 400 C.
11:30 AM - **BB8.6/AA7.6
Nanostructured Catalysts for Portable Fuel Cells Applications.
Vincenzo Antonucci 1 , Vincenzo Baglio 1 , Alessandra Di Blasi 1 , Alessandro Stassi 1 , Claudia D'Urso 1 , Antonino Arico' 1
1 Energy and Transport, CNR-ITAE, Messina Italy
Show AbstractStationary and automotive fuel cells (FC) devices are expected to play an important role for the sustainable energy generation in the next years. Significant interest is also addressed to small portable fuel cells that possibly will find market application before large-size FC systems. The potential market for portable fuel cell systems deals with remote and micro-distributed electrical energy generation including mobile phones, lap-top computers, energy supply for weather stations, medical devices, auxiliary power units (APU) etc. The main advantages of such systems rely on the high energy density of liquid fuels such as methanol and ethanol, long-life-time, easy recycle and low emission of pollutants in the environment. The CNR-ITAE Istitute is involved in European and National projects with the aim to develop nanostructured catalyst for portable direct methanol and ethanol fuel cells. The target for DMFC/DEFC devices for portable application is to work at relatively low temperatures and atmospheric pressure with high efficiency and performance. The effective operation at this low temperature is particularly challenging and requires innovation in different aspects of materials and system development. In particular to address the poor reaction kinetics at the anode, high surface area catalysts composed of nanosised noble metal particles need to be developed and investigated for operation at low temperatures starting from sub-ambient to 60 °C. Although, one of the main drawback of DMFC systems i.e. the methanol cross-over through the membrane is strongly depressed by the decrease of the operating temperature, this constraint affects the cathode performance even at low temperature by causing a mixed potential and poisoning of the cathode surface. Accordingly, it is strongly necessary to develop methanol /ethanol tolerant cathode catalysts with suitable activity at low temperature. Also in this case, a proper catalytic activity for achieving portable fuel cells performance targets is assured by noble metal catalyst properly modified with transition metals capable of reducing the adsorption of alcohols on the cathode surface. The activity presented in this communication deals with both anode and cathode catalysts synthesised by a low–temperature colloidal route characterised by high concentration of metallic phase on carbon black and particle size smaller than 3 nm. The structure and morphology of the catalysts has been investigated and these properties have been correlated with the electrochemical activity and tolerance to methanol poisoning.
12:00 PM - BB8.7/AA7.7
Synthesis of Bimetallic and Trimetallic Alloy Nanoparticles as Catalysts in Fuel Cells.
Peter Njoki 1 , Jin Luo 1 , Bilal Khan 1 , Suprav Mishra 1 , Ravishanker Sujakumar 1 , Chuan-Jian Zhong 1
1 Chemistry, State Univ. of New York at Binghamton, Binghamton, New York, United States
Show Abstract12:15 PM - BB8.8/AA7.8
Passive Air Breathing Fuel Cells For Portable Applications: What are the Limits to Cathode Performance?
Ryan O'Hayre 1 2 , Tibor Fabian 2 , Shawn Litster 2 , Fritz Prinz 2 , Juan Santiago 2
1 Metallurgical and Materials Engineering, Colorado School of Mines, Golden, Colorado, United States, 2 Mechanical Engineering, Stanford University, Stanford, California, United States
Show Abstract12:30 PM - BB8.9/AA7.9
Direct-Write Microfabrication of Single-Chamber Solid Oxide Fuel Cells with Interdigitated Electrodes.
Melanie Kuhn 1 , Teko Napporn 2 , Michel Meunier 2 , Daniel Therriault 1 , Srikar Vengallatore 3
1 Department of Mechanical Engineering, Ecole Polytechnique de Montreal, Montreal, Quebec, Canada, 2 Department of Engineering Physics, Ecole Polytechnique de Montreal, Montreal, Quebec, Canada, 3 Department of Mechanical Engineering, McGill University, Montreal, Quebec, Canada
Show AbstractMiniaturized single-chamber solid-oxide fuel cells (SC-SOFC) are a promising class of devices for portable power generation required in the operation of distributed networks of microelectromechanical systems (MEMS) in harsh environments. The single-face configuration, which consists of interdigitated (comb-like) array of electrodes on an yttria-stabilized zirconia (YSZ) electrolyte substrate, is of particular interest because of the ease of high-temperature microfluidic packaging and integration with MEMS. The primary design consideration for this configuration is the minimization of electrode widths and inter-electrode spacings to dimensions on the order of a few micrometers. This is necessary to minimize polarization resistance and increase fuel cell efficiency. Achieving these geometries using standard microfabrication methods is difficult because of the thickness, porosity, and complex chemistries of the electrodes. Here, we report the development of an innovative and rapid method for manufacturing SC-SOFCs with interdigitated electrodes using robot-controlled direct-writing. The main steps consist of: (i) formation of inks (or suspensions) using anode (NiO-YSZ) and cathode (lanthanum strontium manganite) powders, (ii) pressure-driven extrusion of inks through a micronozzle using a robot-controlled platform, and (iii) sequential sintering to form the fuel cell. The first-generation SC-SOFC device, with electrode widths of 130 μm and inter-electrode spacing of 300 μm, has been manufactured using direct-write microfabrication. The electrodes have been extensively characterized using electron microscopy and x-ray diffraction to assess porosity and to confirm phase identity. The primary process parameters in this approach are the particle size and size distribution, rheological properties of the suspension, extrusion pressure, nozzle size, stage velocity, and sintering conditions. As the first step in the development of detailed process-structure-performance correlations for the fuel cells, we have studied the effects of extrusion pressure (in the range 30-40 bar) and stage velocity (in the range 0.2-2.0 mm/s) on the geometry and size of electrodes, for fixed suspension viscosity and nozzle diameter. An optimal combination of speed and pressure has been identified and catalogued in the form of process maps. Similarly, the particle size distribution of the anode and cathode powders is found to have a significant effect on the microstructure, especially porosity, of the sintered electrodes. The implications of these results for the design of the next generation of SC-SOFC, with reduced electrode dimensions and improved electrochemical performance, will be discussed.
12:45 PM - BB8.10/AA7.10
Materials and Design Study for Micromachined Solid Oxide Fuel Cells Membranes.
Samuel Rey-Mermet 1 , Paul Muralt 1
1 STI-IMX-LC, Ecole Polytechnique Fédérale de Lausanne, Lausanne Switzerland
Show AbstractIn this work we studied materials design and processes for the realization of a micro SOFC entirely based on silicon MEMS technology. As electrolyte materials, ceria doped gadolinia Ce0.8Gd0.2O2-x (CGO) and zirconia stabilized with yttria Zr 0.92Y0.08O2-x (YSZ) were investigated in the form of 0.2 to 2 μm thick films deposited by reactive magnetron sputtering. X-rays diffraction patterns and scanning electron microscopy show that both types of films exhibit a crystalline columnar structure. Predominant texture are are (111) for CGO and (101) for YSZ. The ionic conductivities measured by DC and AC techniques matched well with the literature values. For the CGO thin films, the conductivity of the film perpendicular to the substrate was slightly smaller (1.8 S/m at 700°C in air) than the conductivity in the plane of the film (2 S/m at 700°C in air) proving that there was no short through the grain boundaries. The activation energies for ionic conduction were measured as 0.51-0.58 eV for CGO films and are thus slightly smaller than the bulk ceramics values. The ionic conductivity of the YSZ thin film in reducing conditions at 500°C amounts to 35 S/m in reducing atmosphere at 900°C, with an activation energy of 0.21 eV. Stress analysis made by curvature measurements show that a thermal treatment of the CGO films reduces the compressive stress after deposition. This heat treatment reorganizes or removes the oxygen vacancies in the film leading to a change of the strain. Free standing 200 nm thick CGO membranes of 500 μm diameter were realized. These membranes are too fragile for application in real conditions. A supporting nickel grid was developed giving mechanical stability up to at least 550°C. The electrochemically deposited nickel grid is applied on the anode side and serves as a current collector at the same time. With this design, it is possible to fabricate 1 μm thin free standing membranes with a diameter of 5 mm. The grid is composed of hexagonal cells with a diagonal of 100 μm and a line width of 10 μm. The anode is made of porous Ni-CGO co-sputtered by reactive magnetron sputtering using a nickel and a CGO target. The anode has a total conductivity of 5000 S/cm in argon atmosphere. The cathode of cobalt doped lanthanum perovskite La0.32Sr0.68CoO3 (LSC) is also deposited by reactive magnetron sputtering. A dense and thin LSC film covers the entire cell surface and has a conductivity of 80 S/cm at 600°C in air. A platinum current collector mesh is also deposited on the LSC to increase the electronic conductivity of the cathode. In this work we realized large, mechanically stable fuel cell membranes and developed materials by sputtering with sufficient properties for applications.