Dynamics of cryogenic hydrogen storage in insulated pressure vessels for automotive applications

A dynamic model is used to characterize cryogenic H₂ storage in an insulated pressure vessel that can flexibly hold liquid H₂ and compressed H₂ at 350 bar. A double-flow refueling device is needed to ensure that the tank can be consistently refueled to its theoretical capacity regardless of the initial conditions. Liquid H₂ charged into the tank is stored as supercritical fluid if the initial tank temperature is >120 K and as a subcooled liquid if it is <100 K. An in-tank heater is needed to maintain the tank pressure above the minimum delivery pressure. Even if H₂ is stored as a supercritical fluid, liquid H₂ will form as H₂ is withdrawn and will further transform to a two-phase mixture and ultimately to a superheated gas. The recoverable fraction of the total stored inventory depends on the minimum H₂ delivery pressure and the power rating of the heater. The dormancy of cryogenic H₂ is a function of the maximum allowable pressure and the pressure of stored H₂; the evaporative losses cannot deplete H₂ from the tank beyond 64% of the theoretical storage capacity.     

On-board and Off-board performance of hydrogen storage options for light-duty vehicles

Leading physical and materials-based hydrogen storage options are evaluated for their potential to meet the vehicular targets for gravimetric and volumetric capacity, cost, efficiency, durability and operability, fuel purity, and environmental health and safety. Our analyses show that hydrogen stored as a compressed gas at 350–700 bar in Type III or Type IV tanks cannot meet the near-term volumetric target of 28 g/L. The problems of dormancy and hydrogen loss with conventional liquid H₂ storage can be mitigated by deploying pressure-bearing insulated tanks. Alane (AlH₃) is an attractive hydrogen carrier if it can be prepared and used as a slurry with >50% solids loading and an appropriate volume-exchange tank is developed. Regenerating AlH₃ is a major problem, however, since it is metastable and it cannot be directly formed by reacting the spent Al with H₂. We have evaluated two sorption-based hydrogen storage systems, one using AX-21, a high surface-area superactivated carbon, and the other using MOF-177, a metal-organic framework material. Releasing hydrogen by hydrolysis of sodium borohydride presents difficult chemical, thermal and water management issues, and regenerating NaBH₄ by converting B–O bonds is energy intensive. We have evaluated the option of using organic liquid carriers, such as n-ethylcarbazole, which can be dehydrogenated thermolytically on-board a vehicle and rehydrogenated efficiently in a central plant by established methods and processes. While ammonia borane has a high hydrogen content, a solvent that keeps it in a liquid state needs to be found, and developing an AB regeneration scheme that is practical, economical and efficient remains a major challenge.     

Thermodynamic analysis of filling compressed gaseous hydrogen storage tanks

This paper reports a thermodynamic analysis of filling a fuel tank with compressed gaseous hydrogen. The analysis is based on energy and exergy methods. A parametric study is performed to investigate the effect of initial conditions on the exergy destruction and exergy efficiency of filling processes. The transient filling process is studied to determine the temperature and pressure changes inside the storage tank during filling.     

Enhanced dormancy due to para-to-ortho hydrogen conversion in insulated cryogenic pressure vessels for automotive applications

A dynamic model has been developed to characterize dormancy and hydrogen loss from an insulated cryogenic pressure vessel that is filled with 99.79%-para liquid hydrogen to reach supercritical conditions. The model considers the thermodynamics and kinetics of the endothermic para-to-ortho conversion that occurs when the stored H₂ heats after the vessel is exposed to ambient conditions for an extended time. The thermal, thermodynamic, and kinetic aspects of the model were validated against experimental data obtained on a 151-L tank designed for service at nominal pressures up to 350 bar. Depending on the initial pressure, temperature, amount of H₂, and the rate of heat gain from the ambient, the endothermic para-to-ortho conversion can extend the loss-free dormancy time by up to 85%. Under conditions in which the endothermic conversion does not materially affect dormancy, it can still significantly reduce the H₂ loss rate and it can even introduce a secondary dormancy period.     

High-density automotive hydrogen storage with cryogenic capable pressure vessels

LLNL is developing cryogenic capable pressure vessels with thermal endurance 5–10 times greater than conventional liquid hydrogen (LH₂) tanks that can eliminate evaporative losses in routine usage of (L)H₂ automobiles. In a joint effort BMW is working on a proof of concept for a first automotive cryo-compressed hydrogen storage system that can fulfill automotive requirements on system performance, life cycle, safety and cost. Cryogenic pressure vessels can be fueled with ambient temperature compressed gaseous hydrogen (CGH₂), LH₂ or cryogenic hydrogen at elevated supercritical pressure (cryo-compressed hydrogen, CcH₂). When filled with LH₂ or CcH₂, these vessels contain 2–3 times more fuel than conventional ambient temperature compressed H₂ vessels. LLNL has demonstrated fueling with LH₂ onboard two vehicles. The generation 2 vessel, installed onboard an H₂-powered Toyota Prius and fueled with LH₂ demonstrated the longest unrefueled driving distance and the longest cryogenic H₂ hold time without evaporative losses. A third generation vessel will be installed, reducing weight and volume by minimizing insulation thickness while still providing acceptable thermal endurance. Based on its long experience with cryogenic hydrogen storage, BMW has developed its cryo-compressed hydrogen storage concept, which is now undergoing a thorough system and component validation to prove compliance with automotive requirements before it can be demonstrated in a BMW test vehicle.     

A comparative analysis of the cryo-compression and cryo-adsorption hydrogen storage methods

While conventional low-pressure LH₂ dewars have existed for decades, advanced methods of cryogenic hydrogen storage have recently been developed. These advanced methods are cryo-compression and cryo-adsorption hydrogen storage, which operate best in the temperature range 30–100 K. We present a comparative analysis of both approaches for cryogenic hydrogen storage, examining how pressure and/or sorbent materials are used to effectively increase onboard H₂ density and dormancy. We start by reviewing some basic aspects of LH₂ properties and conventional means of storing it. From there we describe the cryo-compression and cryo-adsorption hydrogen storage methods, and then explore the relationship between them, clarifying the materials science and physics of the two approaches in trying to solve the same hydrogen storage task (∼5–8 kg H₂, typical of light duty vehicles). Assuming that the balance of plant and the available volume for the storage system in the vehicle are identical for both approaches, the comparison focuses on how the respective storage capacities, vessel weight and dormancy vary as a function of temperature, pressure and type of cryo-adsorption material (especially, powder MOF-5 and MIL-101). By performing a comparative analysis, we clarify the science of each approach individually, identify the regimes where the attributes of each can be maximized, elucidate the properties of these systems during refueling, and probe the possible benefits of a combined “hybrid” system with both cryo-adsorption and cryo-compression phenomena operating at the same time. In addition the relationships found between onboard H₂ capacity, pressure vessel and/or sorbent mass and dormancy as a function of rated pressure, type of sorbent material and fueling conditions are useful as general designing guidelines in future engineering efforts using these two hydrogen storage approaches.     

Technical assessment of compressed hydrogen storage tank systems for automotive applications

The performance and cost of compressed hydrogen storage tank systems has been assessed and compared to the U.S. Department of Energy (DOE) 2010, 2015, and ultimate targets for automotive applications. The on-board performance and high-volume manufacturing cost were determined for compressed hydrogen tanks with design pressures of 350 bar (∼5000 psi) and 700 bar (∼10,000 psi) capable of storing 5.6 kg of usable hydrogen. The off-board performance and cost of delivering compressed hydrogen was determined for hydrogen produced by central steam methane reforming (SMR). The main conclusions of the assessment are that the 350-bar compressed storage system has the potential to meet the 2010 and 2015 targets for system gravimetric capacity but will not likely meet any of the system targets for volumetric capacity or cost, given our base case assumptions. The 700-bar compressed storage system has the potential to meet only the 2010 target for system gravimetric capacity and is not likely to meet any of the system targets for volumetric capacity or cost, despite the fact that its volumetric capacity is much higher than that of the 350-bar system. Both the 350-bar and 700-bar systems come close to meeting the Well-to-Tank (WTT) efficiency target, but fall short by about 5%.     

Delivery of cold hydrogen in glass fiber composite pressure vessels

We are proposing to minimize hydrogen delivery cost through utilization of glass fiber tube trailers at 200 K and 70 MPa to produce a synergistic combination of container characteristics with properties of hydrogen gas: (1) hydrogen cooled to 200 K is ∼35% more compact for a small increase in theoretical storage energy (exergy); and (2) these cold temperatures (200 K) strengthen glass fibers by as much as 50%, expanding trailer capacity without the use of much more costly carbon fiber composite vessels.     

Large-scale compressed hydrogen storage as part of renewable electricity storage systems

Storing energy in the form of hydrogen is a promising green alternative. Thus, there is a high interest to analyze the status quo of the different storage options. This paper focuses on the large-scale compressed hydrogen storage options with respect to three categories: storage vessels, geological storage, and other underground storage alternatives. In this study, we investigated a wide variety of compressed hydrogen storage technologies, discussing in fair detail their theory of operation, potential, and challenges. The analysis confirms that a techno-economic chain analysis is required to evaluate the viability of one storage option over another for a case by case. Some of the discussed technologies are immature; however, this does not rule out these technologies; rather, it portrays the research opportunities in the field and the foreseen potential of these technologies. Furthermore, we see that hydrogen would have a significant role in balancing intermittent renewable electricity production.     

Technical assessment of cryo-compressed hydrogen storage tank systems for automotive applications

On-board and off-board performance and cost of cryo-compressed hydrogen storage are assessed and compared to the targets for automotive applications. The on-board performance of the system and high-volume manufacturing cost were determined for liquid hydrogen refueling with a single-flow nozzle and a pump that delivers liquid H₂ to the insulated cryogenic tank capable of being pressurized to 272 atm. The off-board performance and cost of delivering liquid hydrogen were determined for two scenarios in which hydrogen is produced by central steam methane reforming (SMR) or by central electrolysis. The main conclusions are that the cryo-compressed storage system has the potential of meeting the ultimate target for system gravimetric capacity, mid-term target for system volumetric capacity, and the target for hydrogen loss during dormancy under certain conditions of minimum daily driving. However, the high-volume manufacturing cost and the fuel cost for the SMR hydrogen production scenario are, respectively, 2–4 and 1.6–2.4 times the current targets, and the well-to-tank efficiency is well short of the 60% target specified for off-board regenerable materials.     

Three-dimensional modeling and simulation of hydrogen absorption in metal hydride hydrogen storage vessels

In this paper, a three-dimensional hydrogen absorption model is developed to precisely study the hydrogen absorption reaction and resultant heat and mass transport phenomena in metal hydride hydrogen storage vessels. The 3D model is first experimentally validated against the temperature evolution data available in the literature. In addition to model validation, the detailed 3D simulation results show that at the initial absorption stage, the vessel temperature and H/M ratio distributions are uniform throughout the entire vessel, indicating that hydrogen absorption is very efficient early during the hydriding process; thus, the local cooling effect is not influential. On the other hand, non-uniform distributions are predicted at the subsequent absorption stage, which is mainly due to differential degrees of cooling between the vessel wall and core regions. In addition, a parametric study is carried out for various designs and hydrogen feed pressures. This numerical study provides a fundamental understanding of the detailed heat and mass transfer phenomena during the hydrogen absorption process and further indicates that efficient design of the storage vessel and cooling system is critical to achieve rapid hydrogen charging performance.     

Fatigue life evaluation of high pressure hydrogen storage vessel

By combining the micromechanics and continuum damage mechanics, a theoretical model is proposed to perform the fatigue evaluation of high pressure hydrogen storage vessel under cyclic internal pressure, which concentrates on the fatigue properties of the aluminum liner. Results show that the fatigue lifetime of vessel relates to the finite element mesh size, crack density and ratio in an element, cyclic loading amplitude and stress status at the liner. Effects of the mesh size and crack density on the fatigue lifetime of vessel are discussed. In addition, numerical results are also compared with those by experiments.     

Multi-mode hydrogen storage in nanocontainers

Hydrogen can be stored in containers or in materials (in molecular or atomic forms). The atomic form can further exist as multiple phases. Molecular hydrogen can be adsorbed on the surface or can be present inside the material. By invoking multiple modes of hydrogen storage, we establish a paradigm shift in the philosophy of hydrogen storage. Using a novel strategy of storage of molecular hydrogen in metal (Pd) nanocontainers, we observe that 18% hydrogen is in molecular form. Interestingly, this is achieved at 25 °C and 1 atm pressure; which is in contrast to storage in MOFs and carbonaceous materials like nanotubes. Enhancement in storage capacity as compared to Pd nanocrystals of the same mass is observed (36% increase at 1 atm & 25 °C), along with fast kinetics (0.5 wt% hydrogen absorption in 5 s). A new mechanism for hydrogen storage involving the dual catalytic role of Pd is established.     

Analysis of multi-layered thick-walled filament-wound hydrogen storage vessels

In this paper a three-dimensional elasticity analysis on multi-layered thick-walled filament-wound hydrogen storage vessels is outlined. An exact solution to stresses of the metal liner and each anisotropic layer is presented, based on Lekhnitskii's theory and the generalized plane strain assumption. The governing equation for determining the radial displacement of the hydrogen vessel is derived and the stresses in the cylindrical coordinates are then obtained. The matrix equation that determines the integration coefficients of the governing equation is formulated by considering the boundary and interface conditions. The normal and in-plane shear stresses and the twisting rate of the vessel are calculated for various thicknesses of the aluminum liner; the results are then compared to those presented by Xia et al. It is shown that the addition of the liner significantly reduces the stress magnitude of the hydrogen vessel; this stress magnitude decreases as the liner thickness increases. The results also revealed that the twisting effect is reduced by increasing the liner thickness. The ratio of hoop-to-axial stress is no longer a constant through the vessel wall and varies within the wall thickness. In addition, various combinations of anisotropic composites and isotropic liner materials are here examined to pinpoint preferable material combinations that lead to a lower equivalent stress level of the liner and higher strength reserve of the composite laminate.     

Cryo-adsorptive hydrogen storage on activated carbon. I: Thermodynamic analysis of adsorption vessels and comparison with liquid and compressed gas hydrogen storage

This paper presents a thermodynamic analysis of cryo-adsorption vessels for hydrogen storage. The analysis is carried out with an unsteady lumped model and gives a global assessment of the behavior of the storage system during operation (discharge), dormancy and filling. The adsorbent used is superactivated carbon AX-21™. Cryogenic hydrogen storage, either by compression or adsorption, takes advantage of the effect of temperature on the storage density. In order to store 4.1 kg H₂ in 100 L, a pressure of 750 bar at 298 K is necessary, but only 150 bar at 77 K. The pressure is further reduced to 60 bar if the container is filled with pellets of activated carbon [7]. However, adsorption vessels are submitted to intrinsic thermal effects which considerably influence their dynamic behavior and due to which thermal management is required for smooth operation. In this analysis, among energy balances for filling and discharge processes, the influence of the intrinsic thermal effects during vessel operation is presented. Hydrogen losses during normal operation as well as during long periods of inactivity are also considered. The results are compared to those obtained in low-pressure and high-pressure insulated LH₂ and CH₂ tanks.     

Investigations of AB5-type hydrogen storage materials with enhanced hydrogen storage capacity

The present study deals with investigations on synthesis, characterization and hydrogenation behavior of the MmNi₅-type hydrogen storage alloys Mm_0.9Ca_0.1Ni_4.9−xFe_xAl_0.1 (x = 0, 0.1, 0.2 and 0.3). All the alloys are synthesized by radio frequency induction melting following the composite pellet route. The X-ray diffraction pattern of dehydrogenated alloy without iron, detects peaks corresponding to calcium hydride, which are absent in the XRD pattern of the alloy with iron. The hydrogenation behavior is monitored by means of activation curves, absorption-desorption pressure-composition isotherms, hysteresis factors and desorption kinetic curves. The substitution of Iron at the place of nickel in the alloys Mm_0.9Ca_0.1Ni_4.9−xFe_xAl_0.1 (x = 0, 0.1, 0.2 and 0.3) gives an increase in the hydrogen storage capacity as 1.82, 1.90, 2.2 and 1.95 wt% corresponding to x = 0, 0.1, 0.2 and 0.3 respectively. The correlation between structural characteristics and hydrogenation behavior is described and discussed.     

The potential for avoiding hydrogen release from cryogenic pressure vessels after vacuum insulation failure

This paper presents an analysis of vacuum insulation failure in an automotive cryogenic pressure vessel (also known as cryo-compressed vessel) storing hydrogen. Vacuum insulation failure increases heat transfer into cryogenic vessels by about a factor of 100, potentially leading to rapid pressurization and venting of the cryogen to avoid exceeding maximum allowable working pressure (MAWP). Hydrogen release to the environment may be dangerous, especially if the vehicle is located in a closed space (e.g. a garage or tunnel) at the moment of insulation failure. We therefore consider utilization of the hydrogen in the vehicle fuel cell and dissipation of the electricity by operating vehicle accessories or electric resistances as an alternative to releasing hydrogen to the environment. We consider two strategies: initiating hydrogen extraction immediately after vacuum insulation failure or waiting until maximum operating pressure is reached before extraction. The results indicate that cryogenic pressure vessels have thermodynamic advantages that enable slowing down hydrogen release to moderate levels that can be consumed in the fuel cell and dissipated in vehicle accessories supplemented by electric resistances, even in the worst case when the insulation fails at the moment when the vessel stores hydrogen near its maximum density (70 g/L at 300 bar). The two proposed strategies are therefore feasible, and the best alternative can be chosen based on economic and/or implementation constraints.