Nanomaterials for Solid State Hydrogen Storage

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1 Nanomaterials for Solid State Hydrogen Storage

2 Fuel Cells and Hydrogen Energy Series Editor: Narottam P. Bansal NASA Glenn Research Center Cleveland, OH Aims and Scope of the Series During the last couple of decades, notable developments have taken place in the science and technology of fuel cells and hydrogen energy. Most of the knowledge developed in this field is contained in individual journal articles, conference proceedings, research reports, etc. Our goal in developing this series is to organize this information and make it easily available to scientists, engineers, technologists, designers, technical managers and graduate students. The book series is focused to ensure that those who are interested in this subject can find the information quickly and easily without having to search through the whole literature. The series includes all aspects of the materials, science, engineering, manufacturing, modeling, and applications. Fuel reforming and processing; sensors for hydrogen, hydrocarbons and other gases will also be covered within the scope of this series. A number of volumes edited/authored by internationally respected researchers from various countries are planned for publication during the next few years. Titles in this series Nanomaterials for Solid State Hydrogen Storage R.A. Varin, T. Czujko, and Z. S. Wronski ISBN , 2009 Modeling Solid Oxide Fuel Cells: Methods, Procedures and Techniques R. Bove and S. Ubertini, eds. ISBN , 2008

3 Robert A.Varin Tomasz Czujko Zbigniew S. Wronski Nanomaterials for Solid State Hydrogen Storage

4 Robert A. Varin Tomasz Czujko University of Waterloo University of Waterloo Department of Mechanical Department of Mechanical and Mechatronics Engineering and Mechatronics Engineering 200 University Ave. W 200 University Ave. W Waterloo, Ontario Waterloo, Ontario Canada N2L 3G1 Canada N2L 3G1 Zbigniew S. Wronski CANMET Energy Technology Centre Hydrogen Fuel Cells and Transportation Energy Natural Resources Canada 1 Haanel Drive Ottawa, Ontario Canada K1A 1M1 ISBN: e-isbn: DOI: / Library of Congress Control Number: Springer Science+Business Media, LLC 2009 All rights reserved. This work may not be translated or copied in whole or in part without the written permission of the publisher (Springer Science+Business Media, LLC, 233 Spring Street, New York, NY 10013, USA), except for brief excerpts in connection with reviews or scholarly analysis. Use in connection with any form of information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed is forbidden. The use in this publication of trade names, trademarks, service marks, and similar terms, even if they are not identified as such, is not to be taken as an expression of opinion as to whether or not they are subject to proprietary rights. Printed on acid-free paper springer.com

5 Preface Although hydrogen as a chemical element has been known to the humankind and used in various capacities for a very long time, only in the past 15 years its importance to the world population as an energy vector has gradually emerged. A long-term reliance of humanity on the energy derived solely from fossil fuels, such as coal in the nineteenth and crude oil and natural gas in the twentieth century, has led to a number of new challenges facing all of us in the twenty-first century, such as sharp reduction in the world crude oil and eventually coal supply, global warming and following climate changes due to the release of growing amounts of greenhouse gas CO 2, and poor urban air quality. Hydrogen is essentially the only viable remedy for the growing world energy problems. Hydrogen is a very attractive alternative energy vector for replacing fossil fuel-based economy. The future Hydrogen Economy offers a potential solution to satisfying the global energy requirements while reducing (and eventually eliminating) carbon dioxide and other greenhouse gas emissions and improving energy security. Hydrogen is ubiquitous, clean, efficient, and can be produced directly from sunlight and water by biological organisms and using semiconductor-based systems similar to photovoltaics. Hydrogen can also be produced indirectly via thermal processing of biomass or fossil fuels where the development of advanced technological processes combined with a CO 2 sequestration is emerging. However, this rosy picture, as it usually happens in a real life, is marred by a number of obstacles which must be overcome before the Hydrogen Economy becomes a reality. One of these obstacles is safe and efficient storage of hydrogen particularly for mobile/automotive applications where hydrogen gas will be supplied to fuel cells that, in turn, will power the transport vehicles in a clean, inexpensive, safe, and efficient manner. From all possible solutions to hydrogen storage the one which relies upon storage in solid media (hydrides) is the most attractive one. The fast emerging nanoscience/nanotechnology will allow fabricating nanomaterials for solid-state hydrogen storage that can, in a long run, revolutionize hydrogen storage. This book is our modest contribution to this innovative area of hydrogen storage. Wherever possible we tried to illustrate the hydrogen storage behavior by our own results. In Chap. 1, we introduce the reader to the motivation for the transformation to the Hydrogen Economy. In a number of following sections/subsections, we v

6 vi Preface provide a comprehensive synchronic history of development of hydrides and nanomaterials including the existing fabrication methods with a special emphasis on ball (mechanical) milling in high-energy mills. Important hydride properties and experimental techniques for assessing hydrogen storage behavior are also discussed. In Chap. 2, we review hydrogen storage properties of selected simple metal and intermetallic hydrides with the most emphasis on magnesium hydride (MgH 2 ) which now can be treated as a model hydride whose hydrogen storage properties in nanostructured form can be used as a benchmark for comparing the properties of other hydrides. Chapter 3 brings a thorough review of the properties of complex hydrides whose high volumetric and gravimetric capacities make them most attractive for the vehicular solid-state hydrogen storage in transportation. Chapter 4 provides information on carbons and nanocarbons as alternative means of hydrogen storage to solid hydrides. This includes diamond and nanodiamond, graphene, ordered graphites and nanographites, disordered and active carbons, fullerenes, carbon nanotubes, and other nanoshapes. Chapter 5 is a sort of an executive summary where we provide a critical assessment of the present state of knowledge and make predictions for the future developments. Waterloo, ON Waterloo, ON Ottawa, ON Robert A. Varin Tomasz Czujko Zbigniew S. Wronski

7 Contents 1 Introduction Motivation: The Hydrogen Economy Brief, Synchronic History of Development of Hydrides and Nanomaterials Early Investigations of Metal Hydrogen Systems and Hydrides Early Routes to Nanomaterials Historical Development of Classical Hydrogen Storage AB 5 Alloys Historical Development of Interstitial Hydrides in Other Intermetallic Systems Historical Development of Nanophase AB 2 Intermetallic Hydrides New Routes to Nanomaterials: Mechanical Alloying and Mechanochemical Activation Historical Development of Lightweight Metal Hydrides and Hydride Complexes Early Studies of Noninterstitial Transition Metal Ternary Hydrides Toward Chemical/Complex Hydrides Historical Development of Nanocarbons and Carbon Nanotubes New Materials and Techniques Nanoprocessing in Solid State in High-Energy Ball Mills Processes for the Synthesis of Nanostructured Materials Milling Processes and Equipment Nanoprocessing Methods and Mechanisms Mechanical Milling Mechanical Alloying vii

8 viii Contents Mechanochemical Activation Mechanochemical Synthesis (Mechanosynthesis) of Nanohydrides Mechanical Amorphization Important Hydride Properties and Experimental Techniques Thermodynamics Pressure Composition Temperature (PCT) Properties Calculation of Activation Energy PCT and Kinetic Curves Determination by Volumetric Method in a Sieverts-Type Apparatus Microstructural Characterization of Ball-Milled Hydrides Weight Percent of a Hydride Phase and Hydrogen by DSC Method References Simple Metal and Intermetallic Hydrides Mg/MgH Crystallographic and Material Characteristics Hydrogen Storage Characteristics of Commercial Mg and MgH Absorption Desorption Hydrogen Storage Characteristics of Mechanically (Ball) Milled MgH Microstructural Evolution During Milling and Subsequent Cycling of Commercial MgH 2 Powders Hydrogen Absorption of Ball-milled Commercial MgH 2 Powders Hydrogen Desorption of Ball-milled Commercial MgH 2 Powders Hydrogen Storage Characteristics of MgH 2 Synthesized by Reactive Mechanical (Ball) Milling of Mg Aging Effects in Stored MgH 2 Powders Other Methods of Synthesis of Nanostructured MgH 2 than Ball Milling MgH 2 with Catalytic Additives Mg/MgH 2 Metals and Intermetallics Desorption in Vacuum Desorption at Atmospheric Pressure of Hydrogen Mg/MgH 2 Metal Oxides Mg/MgH 2 Carbon/ Graphite and Carbon Nanotubes

9 Contents ix 2.3 Other Metal Hydrides Containing Mg AlH Other Metal and Intermetallic-based Hydrides: New Developments Metal Hydrides Rare-Earth AB 5 Compounds Titanium Iron AB Compounds Titanium and Zirconium AB 2 Compounds Other Novel Intermetallic Hydrides References Complex Hydrides Ternary Transition Metal Complex Hydrides Mg 2 NiH Mg 2 FeH Mg 2 CoH Alanates NaAlH LiAlH Mg(AlH 4 ) 2 and Ca(AlH 4 ) Amides Metal Borohydrides Destabilization of High Desorption Temperature Hydrides by (Nano)Compositing MgH 2 LiAlH 4 Composite System MgH 2 NaAlH 4 Composite System MgH 2 NaBH 4 Composite System References Carbons and Nanocarbons Diamond and Nanodiamonds Graphene, Ordered Graphite, and Nanographites Graphene In-Plane σ and Out-of-Plane π Bonding Van der Walls Interplanar and Intermolecular Interactions Physisorption of Hydrogen on Carbons Chemisorption of Hydrogen on Carbons Graphitic Nanofibers, Whiskers, and Polyhedral Crystals Graphite Disordered and Active Carbons Disordered Graphites and Mechanically-Activated Carbons

10 x Contents Active Carbons and Chemically Activated Carbons Amorphous Carbon Highly Ordered Fullerenes, Carbon Nanotubes, and Carbon Nanohorns Fullerenes and Hydrofullerenes Carbon Nanotubes Carbon Nanohorns Nanostructured Carbon Shells and Carbon Onions References Summary Metal/Intermetallic Hydrides Complex Hydrides Nanocarbons and Others Index

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SpringerBriefs in Mathematics For further volumes: http://www.springer.com/series/10030 George A. Anastassiou Advances on Fractional Inequalities 123 George A. Anastassiou Department of Mathematical Sciences