Thermodynamic analysis of the para-to-ortho hydrogen conversion in cryo-compressed hydrogen vessels for automotive applications

Cryo-compressed hydrogen storage has potential applications in fuel-cell vehicles due to its large storing density and thermal endurance. The dormancy of storage can be extended when considering the endothermic conversion of para-to-ortho hydrogen. In present study, a thermodynamic model is established to analyze the effect of the conversion in a cryogenic pressure vessel. The influence of the parameters such as the filling density, initial temperature and initial ortho hydrogen fraction is studied. It is demonstrated that different “transition pressures” for the vessels exist for different filling densities. The conversion can carry out sufficiently and the dormancy can be extended significantly when the designed release pressure of the vessel matches with the transition pressure. The heat of absorption increases with the initial o-H₂ fraction, whereas the peak of conversion rate occurs earlier for the vessel with a large initial o-H₂ fraction. The dormancy can be extended by 163% for the vessel with filling density of 70 kg/m³. The investigations on the effect of the para-to-ortho hydrogen conversion can provide useful guideline for the design of cryo-compressed hydrogen vessels.     

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.     

Improving small unmanned aerial vehicle flight endurance with cryo-compressed hydrogen vessels

Detailed analysis indicates that substantial increases (22–43%) in flight endurance of small unmanned aerial vehicles (UAVs) powered by liquid hydrogen (LH₂) are possible by increasing the maximum allowable pressure of the cryogenic storage vessel beyond the critical point to contain evaporated hydrogen (H₂) and mitigate vent losses to the environment. Taking an existing UAV (US Naval Research Laboratory's “Ion Tiger”) as a baseline, we consider the effect of increasing Dewar maximum allowable pressure on flight endurance, under two different scenarios. In Case 1, the weight of the H₂ storage system (including H₂) is kept equal to the baseline design to maintain flight conditions unchanged. In Case 2, the external volume of the Dewar is kept equal to the baseline design, and the weight of the Dewar (and UAV) increases when the maximum allowable pressure increases, with the result that the propulsion power for the heavier UAV increases.The results are favorable. Although the modified Dewars have smaller inner volume (Case 1) or greater weight (Case 2) than the original Ion Tiger, flight endurance increases by 22% (Case 1) and 43% (Case 2), because the large H₂ vent losses (39%) of the original design are reduced to only 1.6% (Case 1) and 1% (Case 2). The much higher utilization efficiency of the H₂ stored in these modified Dewars compensates for their volume and weight disadvantages, resulting in UAVs with superior endurance.     

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.     

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.     

Thermodynamic analysis of low-temperature and high-pressure (cryo-compressed) hydrogen storage processes cooled by mixed-refrigerants

Cryo-compressed hydrogen (CcH₂) is a promising hydrogen storage method with merits of high density with low power consumption. Thermodynamic analysis and comparison of several CcH₂ processes are conducted in this paper, under hydrogen storage conditions of 10–100 MPa at 60–100 K. Mixed-refrigerant J-T (MRJT), nitrogen/neon reverse Brayton (RBC) and hydrogen expansion are employed for cooling hydrogen, respectively. Combined CcH₂ processes such as MRJT + neon-RBC are proposed to reach higher CcH₂ density at lower temperatures (<80 K). It was indicated that the specific power consumptions (SPC) of MRJT processes are obviously lower than those of nitrogen/neon-RBC or hydrogen expansion processes. For a typical storage condition of 50 MPa at 80 K, MRJT CcH₂ process could achieve hydrogen density of 71.59 kg m^?3, above liquid hydrogen. While its SPC of 6.42 kWh kg^?1 is about 40% lower than current dual-pressure Claude hydrogen liquefaction processes (10.85 kWh kg^?1).     

The design and optimization of a cryogenic compressed hydrogen refueling process

Cryo-compressed hydrogen storage has excellent volume and mass hydrogen storage density, which is the most likely way to meet the storage requirements proposed by United States Department of Energy（DOE）. This paper contributes to propose and analyze a new cryogenic compressed hydrogen refueling station. The new type of low temperature and high-pressure hydrogenation station system can effectively reduce the problems such as too high liquefaction work when using liquid hydrogen as the gas source, the need to heat and regenerate to release hydrogen, and the damage of thermal stress on the storage tank during the filling process, so as to reduce the release of hydrogen and ensure the non-destructive filling of hydrogen. This paper focuses on the study of precooling process in filling. By establishing a heat transfer model, the dynamic trend of tank temperature with time in the precooling process of low-temperature and high-pressure hydrogen storage tank under constant pressure is studied. Two analysis methods are used to provide theoretical basis for the selection of inlet diameter of hydrogen storage tank. Through comparative analysis of the advantages and disadvantages of the two analysis methods, it is concluded that the analysis method of constant mass flow is more suitable for the selection in practical applications. According to it, the recommended diameter of the storage tank at the initial temperature of 300 K, 200 K and 100 K is selected, which are all 15 mm. It is further proved that the calculation method can meet the different storage tank states of hydrogen fuel cell vehicles when selecting the pipe diameter.     

The fill density of automotive cryo-compressed hydrogen vessels

Cryo-compressed hydrogen storage promises to deliver highest system storage density leading to fundamental cost and safety advantages. However, cryogenic vessels are complex systems, continuously drifting in thermodynamic space depending on use patterns, insulation performance, vessel characteristics, liquid hydrogen pump performance, and para-H₂ to ortho-H₂ conversion. This paper shows a comprehensive evaluation of all factors affecting cryogenic vessel fill density, in an effort to evaluate system performance vs. operational parameters over a broad range of conditions. The results confirm previous experiments and models indicating that cryogenic vessels have maximum fill density of all available storage technologies, and fill density is most sensitive to daily driving distance and insulation performance. It is finally predicted that para-H₂ to ortho-H₂ conversion will affect most automobiles, increasing fill density by up to 5.3%. In a future world dominated by cryogenic H₂ fueled vehicles, para-H₂ to ortho-H₂ conversion inside the vessel will be the closest contact an average person will have with quantum mechanics outside of consumer electronics.     

Performance analysis of vapor-cooled shield insulation integrated with para-ortho hydrogen conversion for liquid hydrogen tanks

A composite thermal insulation system consisting of variable-density multi-layer insulation (VDMLI) and vapor-cooled shields (VCS) integrated with para-ortho hydrogen (P-O) conversion is proposed for long-term storage of liquid hydrogen. High-performance thermal insulation is realized by minimizing the thermal losses via the VDMLI design and fully recovering the cold energy released from the sensible heat and P-O conversion of the vented gas. Effects of different design considerations on the thermal insulation performance are studied. The results show that the maximum reduction of the heat leak with multiple VCSs can reach 79.9% compared to that without VCS. The heat leak with one VCS is reduced by 61.1%, and further reduced by 11.6% after adding catalysts. It is found that the deterioration of the insulation performance has an almost linear relationship with catalytic efficiency. A unified criterion with relative optimization efficiency is finally proposed to evaluate the improvement of the VCS number.     

Analysis of multilayered carbon fiber winding of cryo-compressed hydrogen storage vessel

In order to meet the hydrogen storage requirements of fuel cell vehicles, and improve the storage density of hydrogen, a cryo-compressed hydrogen storage method was proposed. The performance of cryo-compressed hydrogen storage vessel was analyzed in this paper. Based on the classical laminate theory and heat transfer solution, the stress and displacement of carbon fiber were precisely calculated to guarantee the cryo-compressed vessel severing in the cryogenic condition. Subsequently, the Tsai-Wu failure criterion was used to judge the failure of carbon fiber reinforced plastics layers. The stacking sequence, winding angle, comparison of the vessel's performance at room temperature and low temperature were conducted. The numerical results showed that the properties of storage vessel decreased at cryogenic condition, and the thickness of carbon fiber at cryogenic temperature at least increased by 47.06% than that at the room temperature. Mainly influence of low temperature on the cryo-compressed vessel were concentrated on the hoop stress of helical winding and the axial stress of hoop winding. For the vessel design, it is achievable to increase these two parts by using higher strength resin materials.     

Modeling the effects of loading scenario and thermal expansion coefficient on potential failure of cryo-compressed hydrogen vessels

A multiscale thermomechanical model for a simplified Type-3 cryogenic, compressed-hydrogen (H₂) storage vessel is described in this paper. The model accounts for the temperature-dependent elastic-plastic behavior of the vessel's carbon/epoxy composite overwrap and aluminum alloy liner. The homogenized thermo-elastic-plastic behavior for the individual laminae of the vessel layup is obtained using an incremental Eshelby-Mori-Tanaka approach associated with a micromechanical failure criterion to predict laminar failure while a standard elastic-plastic constitutive model is used to describe the behavior of the typical aluminum alloy assumed for the liner. The vessel's response to external loadings is modeled using a finite element method. Four loading scenarios, representing four thermomechanical cycles applied to the vessel, are analyzed to evaluate constituent and laminar stresses as well as the associated failure criterion during the cycle according to these scenarios. The model can provide helpful guidance to mitigate thermal stresses by selecting a suitable loading scenario, optimizing the layup, and tailoring the thermomechanical properties of the resin matrix.     

Supply system of cryo-compressed hydrogen for fuel cell stacks on heavy duty trucks

The work presents the design and analysis of a novel cryo-compressed hydrogen (CCH₂) supply system. It aims to storage CCH₂ (around 20 MPa and 20 K), but supply hydrogen under suitable conditions (0.16 MPa and 338 K) for fuel cell stacks. Generally, thermal waste of fuel cell occupies nearly half of the entire outcome and cannot be applied for truck driving. But in this system, original wasted energy can be reused to heat cool hydrogen, which relieves the heat burden of cooling device. This process is carefully designed and demonstrated for a 25-ton heavy duty truck. Mass flow rate in the specified CCH₂ system is verified by theoretical calculating. Also, negative throttling effect of hydrogen is carefully considered for comprehensive utilization. At last, different efficiency of cryogenic heat exchangers are compared to explore the characteristics of energy consumption.     

Experiment of cryo-compressed (90-MPa) hydrogen leakage diffusion

To improve safety regulations for fuel cell vehicles and hydrogen infrastructures, experiments on cryo-compressed hydrogen leakage diffusion were conducted. The experimental apparatus can supply 90 MPa hydrogen at various temperature conditions (50 K–300 K) at a maximum flow rate of 100 kg/h. The hydrogen leakage flow rate was measured using pinhole nozzles with different outlet diameters (0.2 mm, 0.4 mm, 0.7 mm, and 1 mm). It was confirmed that the hydrogen leakage flow rate increases as the supply temperature decreases. To evaluate the hydrogen flow rate including the cryogenic condition, the orifice equation for liquid was found to be appropriate. The orifice flow coefficient converged to a constant value of 0.6 on the high-density condition side. The hydrogen concentration distribution was measured by injecting high-pressure hydrogen from the 0.2-mm pinhole for 10 min under a constant pressure/temperature condition. The axial hydrogen concentration distribution obtained by the ambient temperature (～300 K) hydrogen injection test well agreed with the experimental formula based on previous research studies. In addition, as the hydrogen injection temperature decreased, it was found that the hydrogen concentration increased, and an empirical formula of the 1% concentration distance for the cryogenic hydrogen system was newly presented. Additional tests were conducted using pinholes of different diameters, and a 1% concentration distance was confirmed to be proportional to the hydrogen leakage flow rate to the 0.5th power.     

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.     

Supercritical cryo-compressed hydrogen storage for fuel cell electric buses

Liquid hydrogen (LH₂) truck delivery and storage at dispensing sites is likely to play an important role in an emerging H₂ infrastructure. We analyzed the performance of single phase, supercritical, on-board cryo-compressed hydrogen storage (CcH₂) with commercially-available LH₂ pump enabled single-flow refueling for application to fuel cell electric buses (FCEB). We conducted finite-element stress analyses of Type 3 CcH₂ tanks using ABAQUS for carbon fiber requirement and Fe-Safe for fatigue life. The results from these analyses indicate that, from the standpoint of weight, volume and cost, 2-mm 316 stainless steel liner is preferred to aluminium 6061 alloy in meeting the required 15,000 charge-discharge cycles for 350–700 bar storage pressures. Compared to the Type 3, 350 bar, ambient-temperature H₂ storage systems in current demonstration FCEBs, 500-bar CcH₂ storage system is projected to achieve 91% improvement in gravimetric capacity, 175% improvement in volumetric capacity, 46% reduction in carbon fiber composite mass, and 21% lower system cost, while exceeding >7 day loss-free dormancy with initially 85%-full H₂ tank.     

Evaluation on the harm effects of accidental releases from cryo-compressed hydrogen tank for fuel cell cars

Cryogenic compressed hydrogen tank may open new possibilities for onboard storage due to its high energy density and acceptable thermal endurance. As promising hydrogen storage for commercial use, its hazards need comprehensive investigation. This paper studies the consequences of accidental hydrogen releases from cryo-compressed storage and evaluates the cold effects, thermal effects, and overpressure and missile effects. Two typical storage conditions for a fuel cell car are considered, including driving condition and quasi-venting condition after a long-term of parking. Results show that flash fire and vapor cloud explosion can be considered as the leading consequences. Without ignition, catastrophic rupture may be more dangerous than leakages but with ignition the results may vary for different release diameters. For leakages, quasi-venting condition may be more dangerous than driving condition. However, for catastrophic rupture, the results may be not uniformed but depend on whether and when the hydrogen is ignited. Moreover, the influences of wind velocity and atmospheric pressure are also investigated.     

Vehicular storage of hydrogen in insulated pressure vessels

This paper describes an alternative technology for storing hydrogen fuel onboard vehicles. Insulated pressure vessels are cryogenic capable vessels that can accept cryogenic liquid hydrogen, cryogenic compressed gas or compressed hydrogen gas at ambient temperature. Insulated pressure vessels offer advantages over conventional storage approaches. Insulated pressure vessels are more compact and require less carbon fiber than compressed hydrogen vessels. They have lower evaporative losses than liquid hydrogen tanks, and are lighter than metal hydrides.

The paper outlines the advantages of insulated pressure vessels and describes the experimental and analytical work conducted to verify that insulated pressure vessels can be safely used for vehicular hydrogen storage. Insulated pressure vessels have successfully completed a series of certification tests. A series of tests have been selected as a starting point toward developing a certification procedure. An insulated pressure vessel has been installed in a hydrogen fueled truck and tested over a six month period.     

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.     

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.     

Performances comparison of adsorption hydrogen storage tanks at a wide temperature and pressure zone

Large-scale application of hydrogen requires safe, reliable and efficient storage technologies. Among the existing hydrogen storage technologies, cryo-compressed hydrogen (CcH₂) storage has the advantages of high hydrogen storage density, low energy consumption and no ortho-para hydrogen conversion. But it still needs higher hydrogen storage pressure when reaching higher hydrogen storage density. In order to reduce hydrogen storage pressure and improve storage density, solid adsorption technology is introduced in CcH₂. Activated carbon and metal-organic framework materials (MOFs) are employed as adsorbents in this paper. The gravimetric/volumetric hydrogen storage capacities of different adsorption tanks are studied and compared with the hydrogen storage conditions of 1–55 MPa at 77–298 K. The results show that the hydrogen storage density of CcH₂ combined with adsorption is higher than that of pure adsorption hydrogen storage, and the storage pressure is lower than that of pure CcH₂ under the same hydrogen storage capacity. And the combination of two hydrogen storage technologies can achieve a high hydrogen storage capacity equivalent to that of liquid hydrogen at a lower pressure.