PNNL-25234 PNNL Development and Analysis of Material-Based Hydrogen Storage Systems for the Hydrogen Storage Engineering Center of Excellence February 2016 K Brooks E Rönnebro K Alvine K Simmons K Johnson M Weimar K Klymyshyn M Westman R Pires DISCLAIMER This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor Battelle Memorial Institute, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. 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(9/2003) PNNL-25234 PNNL Development and Analysis of Material-Based Hydrogen Storage Systems for the Hydrogen Storage Engineering Center of Excellence K Brooks E Rönnebro K Alvine K Simmons K Johnson M Weimar K Klymyshyn M Westman R Pires February 2016 Prepared for U.S. Department of Energy Energy Efficiency and Renewable Energy Office of Fuel Cell Technology Pacific Northwest National Laboratory Richland, Washington 99352 Executive Summary The Hydrogen Storage Engineering Center of Excellence is a team of universities, industrial corporations, and federal laboratories with the mandate to develop lower-pressure, materials-based, hydrogen storage systems for hydrogen fuel cell light-duty vehicles. Although not engaged in the development of new hydrogen storage materials themselves, it is an engineering center that addresses engineering challenges associated with the currently available hydrogen storage materials. Three material-based approaches to hydrogen storage are being researched: 1) chemical hydrogen storage materials 2) cryo-adsorbents, and 3) metal hydrides. The U.S. Department of Energy through its USDRIVE program has established storage system targets to ensure that light-duty vehicles using these technologies have driving ranges comparable to currently available vehicles while meeting commercial performance, cost, and reliability requirements. Specific target values are provided for specific years to help guide the system development. The targets include gravimetric and volumetric density, cost, operating temperatures and pressures, charging and discharging rates, transient behavior, and safety. As a member of this Center, Pacific Northwest National Laboratory (PNNL) has been involved in the design and evaluation of systems developed with each of these three hydrogen storage materials. The scope of PNNL’s efforts in the development of chemical hydrogen storage materials includes the following five major tasks as delineated below: Develop storage system designs that are amenable to vehicle applications. The goal of these storage systems is to meet the DOE Technical Targets for light-duty vehicles. Collect the key properties of the storage materials that are required to develop these system designs. Such things as thermodynamic characteristics, reaction kinetics, and transport properties were measured. Develop models that predict the system’s performance in a vehicle and allow the storage system to be appropriately sized to meet a set of drive cycles. Perform experimental work to guide the system design of individual components and ultimately validate the storage system models. Develop system costs for production ranges between 10,000 and 500,000 units for the most viable systems developed. The cost estimates were developed using both top-down and a bottom-up approaches. Work on chemical hydrogen storage materials was performed in both Phase I and Phase II. DOE determined not to continue work with chemical hydrogen storage materials in Phase III. The PNNL Phase-I work focused on the development of a storage system using solid ammonia borane as the storage material in the form of a powder or pellet. The PNNL Phase-II work focused on development of a chemical hydrogen storage material using slurry material. Rather than focusing only on slurry forms of ammonia borane, it included the evaluation of a slurry form of alane as well. Both phases included development of system designs, measurements of key properties, model development, validation testing, and cost modeling. The scope of PNNL’s efforts in the development of cryo-adsorbent materials includes the following five major tasks as delineated below: Design and assess the types of tanks that can be used for cryo-adsorbent materials. Assist in the down-selection of the tank type based on gravimetric and volumetric density, cost, and compatibility. Develop a method to cool the outer wall of the tank and reduce the refueling time and hydrogen required for refueling. iii Identify and consolidate, if possible, the balance of plant components for the target designs to meet performance targets, and reduce system mass, volume, and cost. Develop system costs for production ranges between 10,000 and 500,000 units for the most viable systems developed. The cost estimates were developed using both top-down and a bottom-up approaches. Identify system components that are chemically and physically compatible with the conditions of the cryo-adsorbent system. In the case of cryo-adsorbents materials, the work performed in Phase I continued into Phase II and III with no significant change in scope. In Phase I, PNNL began the development of the Tankinator code that provides estimates of mass, volume, and material cost for Type I, III, and IV tanks. Further refinements were performed in Phase II. Modification of the balance of plant components and the cost estimates for the cryo-adsorbent systems were initiated in Phase I and completed in Phase III. Phase III included work in the development of the liquid nitrogen (LN2) cooled-wall tank concept accelerates the cooling process and minimizes the amount of cold hydrogen required during refueling. In Phase II, tensile and dynamic mechanical analysis tests performed on potential tank liner materials at cryogenic temperatures. This work was continued in Phase III with cryogenic compression tests being performed with polymers saturated with high-pressure (5000 psi) hydrogen. The scope of PNNL’s efforts in the development of metal hydrides was much smaller than the other two areas and included two tasks as delineated below: Identify and consolidate, if possible, the balance of plant components for the target designs to meet performance targets, and reduce system mass, volume, and cost. Develop system costs for production ranges between 10,000 and 500,000 units for one metal hydride-based system. As with the other materials, the cost estimates were developed using both top-down and a bottom-up approaches. The metal hydride materials work did not continue beyond Phase I as a result of their low gravimetric density. As a result, the systems designs described here are not as well developed. iv Acknowledgments This material is based upon work supported by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Fuel Cell Technologies. The authors would like to thank all members of the Hydrogen Storage Engineering Center of Excellence for stimulating discussions and Jesse Adams, Ned Stetson, and Bob Bowman for their outstanding support. v Acronyms and Abbreviations AB ammonia borane AFA anti-foaming agents BOP balance of plant CAD computer-aided design CH chemical hydride CHS chemical hydrogen storage CHCoE Chemical Hydride Center of Excellence CNG compressed natural gas COMSOL® interactive computer modeling program for solving coupled partial differential equations in one or more physical domains simultaneously CRF capital recovery factor DMA dynamic mechanical analysis DOE U.S. Department of Energy EAB elongation at break ECTFE ethylene chlorotrifluoroethylene ENG enhanced natural graphite EPDM ethylene propylene diene monomer ETFE ethylene tetrafluoroethylene CSA Canadian Standards Association FCRF fixed capital recovery factor FEP fluorinated ethylene propylene GGE gallons of gasoline equivalent HDPE high-density polyethylene HSECoE Hydrogen Storage Engineering Center of Excellence HT P-alkyl aromatics HTR synthetic hydrocarbons vii KJMA Kolmagorov-Johnson-Mehl-Avrami LANL Los Alamos National Laboratory LDPE low-density polyethylene MATI Modular Adsorbent Tank Insert MC methyl cellulose MEPS MEPS North American Steel MLVSI multilayer vacuum super insulation MOF