Engineering Hydrogen Storage Systems

Increased research into the chemistry, physics and material science of hydrogen cycling compounds has led to the rapid growth of solid-phase hydrogen-storage options. The operating conditions of these new options span a wide range: system temperature can be as low as 70K or over 600K, system pressure varies from less than 100kPa to 35MPa, and heat loads can be moderate or can be measured in megawatts. While the intense focus placed on storage materials has been appropriate, there is also a need for research in engineering, specifically in containment, heat transfer, and controls. The DOE’s recently proposed engineering center of expertise underscores the growing understanding that engineering research will play a role in the success of advanced hydrogen storage systems. Engineering a hydrogen system will minimally require containment of the storage media and control of the hydrogenation and dehydrogenation processes, but an elegant system design will compensate for the storage media’s weaker aspects and capitalize on its strengths. To achieve such a complete solution, the storage tank must be designed to work with the media, the vehicle packaging, the power-plant, and the power-plant’s control system. In some cases there are synergies available that increase the efficiency of both subsystems simultaneously. In addition, system designers will need to make the hard choices needed to convert a technically feasible concept into a commercially successful product. Materials cost, assembly cost, and end of life costs will all shape the final design of a viable hydrogen storage system. Once again there is a critical role for engineering research, in this case into lower cost and higher performance engineering materials. Each form of hydrogen storage has its own, unique, challenges and opportunities for the system designer. These differing requirements stem directly from the properties of the storage media. Aside from physical containment of compressed or liquefied hydrogen, most storage media can be assigned to one of four major categories, chemical storage, metal hydrides, complex hydrides, or physisorption. Specific needs of each technology are discussed below. Physisorption systems currently operate at 77K with very fast kinetics and good gravimetric capacity; and as such, special engineering challenges center on controlling heat transfer. Excellent MLVSI is available, its cost is high and it is not readily applied to complex shape in a mass manufacture setting. Additionally, while the heat of adsorption on most physisorbents is a relatively modest 6–10kJ/mol H2, this heat must be moved up a 200K gradient. Physisorpion systems are also challenged on density. Consequently, methods for reducing the cost of producing and assembling compact, high-quality insulation, tank design to minimize heat transfer while maintaining manufacturability, improved methods of heat transfer to and from the storage media, and controls to optimize filling are areas of profitable research. It may be noted that the first two areas would also contribute to improvement of liquid hydrogen tanks. Metal hydrides are currently nearest application in the form of high pressure metal hydride tanks because of their reduced volume relative to compressed gas tanks of the same capacity and pressure. These systems typically use simple pressure controls, and have enthalpies of roughly 20kJ/mol H2 and plateau pressures of at most a few MPa. During filling, temperatures must be high enough to ensure fast kinetics, but kept low enough that the thermodynamically set plateau pressure is well below the filling pressure. To accomplish this balance the heat transfer system must handle on the order of 300kW during the 5 minute fill of a 10kg tank. These systems are also challenged on mass and the cost of the media. High value areas for research include: heat transfer inside a 35MPa rated pressure vessel, light and strong tank construction materials with reduced cost, and metals or other materials that do not embrittle in the presence of high pressure hydrogen when operated below ∼400K. The latter two topics would also have a beneficial impact on compressed gas hydrogen storage systems, the current “system to beat”. Complex hydrides frequently have high hydrogen capacity but also an enthalpy of adsorption >30kJ/mol H2, a hydrogen release temperature >370K, and in many cases multiple steps of adsorption/desorption with slow kinetics in at least one of the steps. Most complex hydrides are thermal insulators in the hydrided form. From an engineering perspective, improved methods and designs for cost effective heat transfer to the storage media in a 5 to 10MPa vessel is of significant interest, as are materials that resist embrittlement at pressures below 10MPa and temperatures below 500K. Chemical hydrides produce heat when releasing hydrogen; in some systems this can be managed with air cooling of the reactor, but in other systems that may not be possible. In general, chemical hydrides must be removed from the vehicle and regenerated off-board. They are challenged on durability and recycling energy. Engineering research of interest in these systems centers around maintaining the spent fuel in a state suitable for rapid removal while minimizing system mass, and on developing highly efficient recycling plant designs that make the most of heat from exothermic steps. While the designs of each category of storage tank will differ with the material properties, two common engineering research thrusts stand out, heat transfer and structural materials. In addition, control strategies are important to all advanced storage systems, though they will vary significantly from system to system. Chemical systems need controls primarily to match hydrogen supply to power-plant demand, including shut down. High pressure metal hydride systems will need control during filling to maintain an appropriately low plateau pressure. Complex hydrides will need control for optimal filling and release of hydrogen from materials with multi-step reactions. Even the relatively simple compressed-gas tanks require control strategies during refill. Heat transfer systems will modulate performance and directly impact cost. While issues such as thermal conductivity may not be as great as anticipated, the heat transfer system still impacts gravimetric efficiency, volumetric efficiency and cost. These are three key factors to commercial viability, so any research that improves performance or reduces cost is important. Recent work in the DOE FreedomCAR program indicates that some 14% of the system mass may be attributed to heat transfer in complex hydride systems. If this system is made to withstand 100 bar at 450K the material cost will be a meaningful portion of the total tank cost. Improvements to the basic shell and tube structures that can reduce the total mass of heat transfer equipment while maintaining good global and local temperature control are needed. Reducing the mass and cost of the materials of construction would also benefit all systems. Much has been made of the need to reduce the cost of carbon fiber in compressed tanks and new processes are being investigated. Further progress is likely to benefit any composite tank, not just compressed gas tanks. In a like fashion, all tanks have metal parts. Today those parts are made from expensive alloys, such as A286. If other structural materials could be proven suitable for tank construction there would be a direct cost benefit to all tank systems. Finally there is a need to match the system to the storage material and the power-plant. Recent work has shown there are strong effects of material properties on system performance, not only because of the material, but also because the material properties drive the tank design to be more or less efficient. Filling of a hydride tank provides an excellent example. A five minute or less fill time is desirable. Hydrogen will be supplied as a gas, perhaps at a fixed pressure and temperature. The kinetics of the hydride will dictate how fast hydrogen can be absorbed, and the thermodynamics will determine if hydrogen can be absorbed at all; both properties are temperature dependent. The temperature will depend on how fast heat is generated by absorption and how fast heat can be added or removed by the system. If the design system and material properties are not both well suited to this filling scenario the actual amount of hydrogen stored could be significantly less than the capacity of the system. Controls may play an important role as well, by altering the coolant temperature and flow, and the gas temperature and pressure, a better fill is likely. Similar strategies have already been demonstrated for compressed gas systems. Matching system capabilities to power-plant needs is also important. Supplying the demanded fuel in transients and start up are obvious requirements that both the tank system and material must be design to meet. But there are opportunities too. If the power-plant heat can be used to release hydrogen, then the efficiency of vehicle increases greatly. This efficiency comes not only from preventing hydrogen losses from supplying heat to the media, but also from the power-plant cooling that occurs. To reap this benefit, it will be important to have elegant control strategies that avoid unwanted feedback between the power-plant and the fuel system. Hydrogen fueled vehicles are making tremendous strides, as can be seen by the number and increasing market readiness of vehicles in technology validation programs. Research that improves the effectiveness and reduces the costs of heat transfer systems, tank construction materials, and control systems will play a key role in preparing advanced hydrogen storage systems to be a part of this transportation revolution.Copyright © 2007 by ASME