Cold hydrogen delivery in glass fiber composite pressure vessels: Analysis,manufacture and testing

This paper describes Lawrence Livermore National Laboratory (LLNL) and Spencer Composites Corporation (SCC) efforts in demonstrating an innovative approach to hydrogen delivery. This approach minimizes hydrogen delivery cost through utilization of glass fiber pressure vessels at 200 K and 70 MPa to produce a synergistic combination of container characteristics and 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.     

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.     

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.     

High pressure hydrogen fires

Within the scope of the French national project DRIVE and European project HyPER, high pressure jet flames of hydrogen were produced and instrumented.The experimental technique and measurement strategy are presented. Many aspects are original developments like the direct measurement of the mass flow rate by weighing continuously the hydrogen container, the image processing to extract the flame geometry, the heat flux measurement device, the thermocouples arrangement…Flames were observed from 900 bar down to 1 bar with orifices ranging from 1 to 3 mm. An original set of data is now available about the main flame characteristics and about some thermodynamic aspects of hydrogen releases under high pressure.A brief comparison of some available models is presented.     

Safety approach for composite pressure vessels for road transport of hydrogen. Part 1: Acceptable probability of failure and hydrogen mass

Hydrogen is a promising alternative for current energy carriers. Compressed gas cylinders are the storage systems closest to the commercialization of hydrogen in vehicles. The safety factors in current standards are seen as restrictive for further growth and competitiveness of hydrogen infrastructure. A probabilistic approach can be employed in order to give a rational background to the safety factors. However, an acceptable probability of failure needs to be estimated before calculating the safety factors. The discussion of determining the acceptable probability must include the mass of hydrogen since this determines the consequences of an accident. It is concluded that an annual probability of failure of 10⁻⁷ would be appropriate for small pressure vessels containing a few kilograms of hydrogen. Larger pressure vessels of a few hundred kilograms or more should be designed for an annual probability 10⁻⁸.     

In-situ diffraction techniques for studying hydrogen storage materials under high hydrogen pressure

Diffraction-based methods offer unique advantages for elucidating the pathways by which materials absorb and desorb hydrogen, especially when a phase change or the formation of new compounds is involved. In this case, the hydriding reaction may be followed via the changing crystallography of the phases involved in response to a change in temperature or hydrogen pressure. By using a fast diffractometer, the reaction kinetics may also be correlated to environmental conditions and the degree of completion of the reaction. In this paper we consider and model quantitatively the essential elements of a successful in-situ diffraction experiment with neutrons or X-rays under hydrogen pressures up to several kilobars: a gas manifold to accurately measure hydrogen uptake; a pressure cell designed for maximum detected intensity; means to exclude scattering arising in the cell as much as possible; methodology to correct for attenuation and subtract background intensity from the cell and environment.     

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.     

Acoustic emission-based damage characterization of 70 MPa type IV hydrogen composite pressure vessels during hydraulic tests

This paper aims to characterize the damage mechanisms of 70 MPa Type IV hydrogen composite pressure vessels using the acoustic emission (AE) method. First, AE signals were captured during the 0–105 MPa and 0–158 MPa hydraulic tests of two vessels using multi-step loading method. Second, the AE feature parameters in time-domain and frequency-domain such as amplitude, frequency, and energy are studied. A multi-parameter statistical analysis (MPSA) method based on empirical mode decomposition (EMD) and K-means algorithm is performed to cluster AE events for the vessels. Intrinsic mode functions (IMFs) are decomposed by EMD and three IMFs with high frequency are chosen to reconstruct the feature parameters and provide signal pre-processing for K-means clustering analysis. Based on the relationship between AE features and damage modes, three main clusters with separate amplitude, absolute energy, and energy are correlated to matrix cracking, fiber/matrix debonding, and fiber breakage damage mechanisms. Besides, the effectiveness of MPSA method for signal classification is validated by principal component analysis (PCA) and fast Fourier transformation (FFT) method. Finally, the AE feature parameters such as amplitude and counts to peak for the three main damage modes are studied for the hydraulic proof tests and the burst tests to explore the damage evolution behaviors of the vessels with pressure increasing. Results show that AE method can be reliably used to characterize damage evolution mechanisms in composite pressure vessels.     

Storage of cryo-compressed hydrogen in flexible glass capillaries

We present the results of the theoretical calculations and the corresponding experiments with compressed hydrogen storage in flexible glass capillaries both at room and liquid nitrogen temperatures. It was demonstrated that the strength of produced quartz capillaries can be high enough to withstand the internal hydrogen pressure up to 233 MPa and capillary vessels can have relatively high volumetric and gravimetric capacity.     

Raman spectroscopy study of molecular hydrogen solubility in water at high pressure

We have measured the Raman spectra of gaseous molecular hydrogen dissolved in liquid water at room temperature and as a function of pressure. Vibrational spectra of molecular hydrogen have been clearly detected. Band intensities and profiles have been carefully measured using, for calibration purposes, the water OH stretching band. From the measured intensities of the Raman band, we have obtained the behavior of hydrogen concentration in the liquid water, as a function of the gas partial pressure. The observed behavior is presented and compared to Henry’s law predictions. Additionally, we present a detailed analysis of the spectral band features from which important information on the interaction of hydrogen with water molecules could be derived.     

Safety criteria for the transport of hydrogen in permanently mounted composite pressure vessels

The recent growth of the net of hydrogen fuelling stations increases the demands to transport compressed hydrogen on road by battery vehicles or tube-trailers, both in composite pressure vessels. As a transport regulation, the ADR is applicable in Europe and adjoined regions, and is used for national transport in the EU. This regulation provides requirements based on the behaviour of each individual pressure vessel, regardless of the pressure of the transported hydrogen and relevant consequences resulting from generally possible worst case scenarios such as sudden rupture. In 2012, the BAM (German Federal Institute for Materials Research and Testing) introduced consequence-dependent requirements and established them in national transport requirements concerning the “UN service life checks” etc. to consider the transported volume and pressure of gases. This results in a requirement that becomes more restrictive as the product of pressure and volume increases. In the studies presented here, the safety measures for hydrogen road transport are identified and reviewed through a number of safety measures from countries including Japan, the USA and China. Subsequently, the failure consequences of using trailer vehicles, the related risk and the chance are evaluated. A benefit-related risk criterion is suggested to add to regulations and to be defined as a safety goal in standards for hydrogen transport vehicles and for mounted pressure vessels. Finally, an idea is given for generating probabilistic safety data and for highly efficient evaluation without a significant increase of effort.     

Hydrogen storage properties of nanostructured MgH2/TiH2 composite prepared by ball milling under high hydrogen pressure

Nanostructured MgH₂/0.1TiH₂ composite was synthesized directly from Mg and Ti metal by ball milling under an initial hydrogen pressure of 30 MPa. The synthesized composite shows interesting hydrogen storage properties. The desorption temperature is more than 100 °C lower compared to commercial MgH₂ from TG-DSC measurements. After desorption, the composite sample absorbs hydrogen at 100 °C to a capacity of 4 mass% in 4 h and may even absorb hydrogen at 40 °C. The improved properties are due to the catalyst and nanostructure introduced during high pressure ball milling. From the PCI results at 269, 280, 289 and 301 °C, the enthalpy change and entropy change during the desorption can be determined according to the van’t Hoff equation. The values for the MgH₂/0.1TiH₂ nano-composite system are 77.4 kJ mol⁻¹ H₂ and 137.5 J K⁻¹ mol⁻¹ H₂, respectively. These values are in agreement with those obtained for a commercial MgH₂ system measured under the same conditions. Nanostructure and catalyst may greatly improve the kinetics, but do not change the thermodynamics of the materials.     

Analysis of millisecond collision of composite high pressure hydrogen storage cylinder

For vehicle-mounted high-pressure hydrogen storage cylinders, impact resistance is an important indicator. This work aims at building a model of 70 MPa composite fully wound Ⅳ cylinder around T800 carbon fiber material, investigating the law of transient changes in the body of the bottle under different velocity impacts and the source of risk of bursting. Through millisecond impact analysis, the energy transfer path and transformation trend inside the cylinder are obtained. Meanwhile, it was found that there was a clear pattern of positive correlation between the tensile and compressive stresses generated by the difference between the internal pressure of the bottle and the impact pressure. The final results show that after the impact, the failure occurred firstly at the inner wall of the fiber corresponding to the impact point, and the fiber damage spreads in all directions. The thickness of the failure pavement increases from the inside to the outside.     

The cold high-pressure approach to hydrogen delivery

In view of the very expensive and wasteful nature of today's approaches to H₂ delivery, we explore the possibility of transporting cold (200 K) high pressure (875 bar) H₂ in thermally insulated trailers and dispensing H₂ directly from the trailer, with the potential to eliminate station compressor, cascade, and refrigerator, leading to major reductions in station complexity, maintenance, electricity consumption, and cost, while improving functionality by enabling essentially unlimited back to back refuels, and improving safety due to reduced H₂ expansion energy at low temperature.Detailed techno-economic analysis shows promise for substantial delivery cost reductions through cold high pressure H₂ dispensed directly from the trailer. Results indicate that: (1) Terminal operations for cold high pressure H₂ delivery are $0.32/kg H₂ more expensive than for 350 bar compressed gas delivery (today's lowest cost H₂ delivery technology) due to higher level of pressurization (to 1000 bar) and chilling needs (to 165 K). (2) Trailer cost drops slightly ($0.73 vs. $0.81/kg H₂ for a 350 bar trailer) due to increased capacity (1035 kg H₂ delivered vs. 700 kg) compensating for increased capital cost ($906,900 for cold high pressure H₂ vs. $634,000 for 350 bar trailer). (3) Cold hydrogen delivery presents major advantages in fueling station cost, reduced from $1.27 to $0.46/kg H₂ due to elimination of major system components: compressor, cascade, and chiller. (4) Total compression cost (terminal + station) drops from $0.92/kg H₂ ($0.32 terminal and $0.60 station) for 350 bar trailers to $0.55/kg H₂ (all at the terminal) for cold high pressure H2. (5) Elimination of small-scale station compressors is the main contributor to reduced delivery cost due to their inefficiency, capital expense, and maintenance needs. In summary, total delivery cost reduction vs. 350 bar trailer equals $0.58/kg H₂ (from $2.96 to 2.38/kg H₂), equivalent to 24% of the total delivery cost. This large cost advantage will improve the economics of H₂ vehicles facilitating the transition to a future of zero emission transportation.     

Facile production of optically active hollow glass microspheres for photo-induced outgassing of stored hydrogen

Illumination of engineered hollow glass microspheres with near-infrared light is used to rapidly release stored gases, in particular hydrogen. Photo-induced outgassing of hydrogen is made possible by introducing optically active dopants into the glass such as cobalt. Recycled amber glass frit coated with polypropylene glycol and cobalt sulfate is converted into hollow glass microspheres with a simple, low-cost flame spraying method. Hollow glass microspheres made by this process release hydrogen more quickly when illuminated versus traditional outgassing with a heated oven. A simple model is proposed for engineering the geometry of the hollow glass microspheres.     

Safety approach for composite pressure vessels for road transport of hydrogen. Part 2: Safety factors and test requirements

Composite pressure vessels for transporting hydrogen on roads are a promising and efficient solution for supplying refueling stations. The safety factors of current ISO design standards are perceived as being restrictive for design. In this paper, new safety factors are calculated based on a probabilistic approach and by extending the methods used in the DNV Offshore standard DNV-OS-C501 “Composite Components”. Short-term and long-term conditions are addressed.     

Theoretical model and experimental analysis of a high pressure PEM water electrolyser for hydrogen production

This work aims at analysing the performances of a prototype of a high pressure Polymer Electrolyte Membrane water electrolyser.     

Hydrogen release from a high pressure gaseous hydrogen reservoir in case of a small leak

The dynamic blow-down process of a high pressure gaseous hydrogen (GH₂) reservoir in case of a small leak is a complex process involving a chain of distinct flow regimes and gas states. This paper presents models to predict the hydrogen concentration and velocity field in the vicinity of a postulated small leak. An isentropic expansion model with a real gas equation of state for normal hydrogen is used to calculate the time dependent gas state in the reservoir and at the leak. The subsequent gas expansion to 0.1 MPa is predicted with a zero-dimensional model. The gas conditions after expansion serve as input to a newly developed integral model for a round free turbulent H₂-jet into ambient air. Predictions are made for the blow-down of hydrogen reservoirs with 10, 30 and 100 MPa initial pressure. A normalized hydrogen concentration field in the free jet is presented which allows for a given leak scenario the prediction of the axial and radial range of flammable H₂-air mixtures.     

Empirical profiling of cold hydrogen plumes formed from venting of LH2 storage vessels

Liquid hydrogen (LH₂) storage is viewed as a viable approach to assure sufficient hydrogen capacity at commercial fuelling stations. Presently, LH₂ is produced at remote facilities and then transported to the end-use site by road vehicles (i.e., LH₂ tanker trucks). Venting of hydrogen to depressurize the transport storage tank is a routine part of the LH₂ delivery and site transfer process. The behavior of cold hydrogen plumes has not been well characterized because of the sparsity of empirical field data, which can lead to overly conservative safety requirements. Committee members of the National Fire Protection Association (NFPA) Standard 2 [1] formed the Hydrogen Storage Safety Task Group, which consists of hydrogen producers, safety experts, and computational fluid dynamics modellers, has identified the lack of understanding of hydrogen dispersion during LH₂ venting of storage vessels as a critical gap for establishing safety distances at LH₂ facilities, especially commercial hydrogen fuelling stations. To address this need, the National Renewable Energy Laboratory Sensor Laboratory, in collaboration with the NFPA Hydrogen Storage Task Group, developed a prototype Cold Hydrogen Plume Analyzer to empirically characterize the hydrogen plume formed during LH₂ storage tank venting. The prototype analyzer was field deployed during an actual LH₂ venting process. Critical findings included:

• •Hydrogen above the lower flammable limit (LFL) was detected as much as 2 m lower than the release point, which is not predicted by existing models.
• •Personal monitors detected hydrogen at ground level, although at levels below the LFL.
• •A small but inconsistent correlation was found between oxygen depletion and the hydrogen concentration.
• •A negligible to non-existent correlation was found between in-situ temperature measurements and the hydrogen concentration.

The prototype analyzer is being upgraded for enhanced metrological capabilities, including improved real-time spatial and temporal profiling of hydrogen plumes and tracking of prevailing weather conditions. Additional deployments are planned to monitor plume behavior under different wind, humidity, and temperature conditions. The data will be shared with the Hydrogen Storage Task Group and ultimately will be used support theoretical models and code requirements prescribed in NFPA 2.