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Hydrogen Storage High-Capacity Hydrogen Storage for Portable Power Fundamental Hydrogen Interactions for the Development of Advanced Hydrogen Storage Materials Hydrogen for Thermal Energy Storage Leveraging the reversible reaction of hydrogen with metals for long duration energy storage
Hydrogen-powered locomotives may present an alternative to diesel for achieving transportation-related decarbonization, energy security, and resilience goals. As an emerging technology, hydrogen locomotives may not have adequate representation in current safety codes and standards. NFPA 2 and other appropriate codes and standards were reviewed to identify technical gaps in the code for hydrogen rail defueling, refueling, maintenance, and storage. Several technical gaps pertaining to setback distances, allowable quantities, ventilation rates, and grounding have been identified. Fueling requirements can be informed by road vehicle standards but may need to be revised for larger quantity hydrogen locomotive systems. Since there are no hydrogen-specific locomotive design and safety standards, some aspects of diesel-based locomotive standards may apply. CGA G- 5.5 currently provides the most guidance on height, placement, orientation, and design of vent systems, while other standards emphasize the importance of shielding vent stacks and provide requirements for orientation of their discharge.
Studies that examine the combined effects of hydrogen and rail loading environments in the context of hydrogen embrittlement of steels have not been performed. Large-scale hydrogen storage requires either gaseous hydrogen stored in pressure vessels and tubing or liquid hydrogen in cryogenic, insulated tanks. Since the focus of this study is on steels, we examine the influence of hydrogen on stainless steel used for high pressure tubing and cryogenic tanks and Cr-Mo steel liners used in gaseous pressure vessels. Literature studies show that despite hydrogen degradation, these steels can be used effectively and safely if the stresses are managed. The shock and vibration environment on railcars present unique environments where stresses and loading rates can be high. A literature review was conducted to understand the accelerations experienced in rail by examining instrumented railcars of nuclear fuel casks. Hydrogen studies were examined that focused on steel pressure hardware with an emphasis on fatigue, fast loading rates, and low temperatures. A simplified fatigue assessment was performed to examine design cycles for three different hydrogen components: stainless steel tubing, stainless steel cryogenic tanks, and gaseous pressure vessels. The assessments were idealized and used bounding cases of accelerations in both normal rail conditions and coupling events. In normal shock and vibration environments when accelerations were less than 2 g, infinite design life was calculated. In extreme shock or coupling environments, finite design life was calculated which was shown to be dependent on unsupported lengths of pressure components. It was shown that adjusting the unsupported length can reduce the bending stress thereby increasing design life.
The use of hydrogen as a clean and renewable energy source is increasing rapidly for both vehicle and stationary applications. There are safety concerns for the locations in which hydrogen is made, used, and transported (i.e., pipelines and tanker trucks). Sensors are needed to comply with safety regulations and to enable a smooth and safe rollout of hydrogen as an alternative energy. However, hydrogen sensors do not yet exist that have the combined features of small size and low power for easy deployment coupled with high-volume manufacturability and low cost. This is necessary to accommodate the emerging fixed and mobile markets while retaining critical metrological metrics, including measurement range, detection limits, selectivity, fast response, stability, and long lifetime. An amperometric gas sensor for hydrogen (AGS) has been developed using an innovative manufacturing method. The sensor was designed using scalable fabrication strategies based on “Printed Electronics” (PE) methodology which are compatible with large-scale production. Prototype sensors were batch fabricated with multiple individual elements on a substrate compatible in size with a standard 8-inch wafer to enable high-volume, low-cost manufacturing, thereby leveraging PE and semiconductor fabrication infrastructure. This novel AGS was instrumented with control circuitry and evaluated for hydrogen detection in the range of 0–5000 ppmv H2 in air. Specific performance evaluations included assessment of the sensor measurement range, repeatability, and selectivity.
Thermoplastic polymers are required to perform unfailingly under stringent conditions of changing pressures (35 MPa to 70 MPa) and temperatures (-40°C to +85°C) in storage and fueling operations. Although diffusivity in glassy polymers appear to be an order of magnitude lower than elastomers, polymer microstructural attributes such as degree of crystallinity and presence of polar and non-polar groups on the main chain with and without branching can play a substantial role in influencing their behaviors in hydrogen environments. In the work described here, the effect of high-pressure hydrogen cycling on PEEK, PTFE, PA11, HDPE, POM (and different commercial grades of these polymers) under ambient and cold (-40°C) conditions is addressed. Ex-situ characterization for polymer changes included density measurements for impact of hydrogen retention, hardness changes using nanoindentation, storage modulus and glass transition changes using dynamic mechanical and thermal analysis (DMTA), degree of crystallization with Differential Scanning Calorimetry (DSC) and tensile testing following ASTM D412. In other evaluations, solid-state nuclear magnetic resonance (NMR), attenuated total reflectance Fourier transform infra-red spectroscopy (ATRFTIR), X-ray diffraction (XRD), and X-ray CT results are presented. The overall impact of these evaluations is to establish a technical basis for the behaviors of common thermoplastics in cycling hydrogen environments under ambient and cold temperatures while establishing the relationship between polymer structure-based properties and hydrogen transport effects.
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This data release provides estimates of hydrogens economic potential for possible hydrogen applications and production technologies by geographic location for various scenarios, as described in "The Technical and Economic Potential of the H2@Scale Concept within the United States". We define the economic potential as the quantity of hydrogen at an equilibrium price at which suppliers are willing to sell and consumers are willing to buy the same quantity of hydrogen.
Fluorocarbon-based rubber (FKM) compounds are typically utilized in the aeronautical industry due to its exceptional chemical and thermal resistance and recently has drawn significant interest from the hydrogen community for various hydrogen applications, but there exists little data evaluating its hydrogen compatibility. In this paper, a formulated FKM compound was exposed to ultrahigh hydrogen pressure (90 MPa) and analyzed by attenuated total reflectance Fourier-transform infrared (ATR-FTIR) spectroscopy and crosslinking densities by solvent swelling measurement. ATR-FTIR spectroscopic data demonstrated that high-pressure hydrogen not only caused cleavages in polymer backbone and cross linkages, but also induced additional degradation of FKM compounds by breaking intermolecular hydrogen bonding between carboxylic acids, which were produced during rubber molding and post curing processes. This hydrogen pressure-driven degradation was significantly higher towards the core of the material than at the surface due to its weaker bonding between polymers and fillers.
Safe practices in the production, storage, distribution, and use of hydrogen are essential for the widespread acceptance of hydrogen and fuel cell technologies. A significant safety incident could damage public perception of hydrogen and fuel cells. Recent incidents involving multi-cylinder hydrogen transport vehicles in the United States have brought attention to the potential impacts of mobile hydrogen storage and transportation. Road transportation of bulk gaseous hydrogen presents unique hazards that can be very different from those for stationary equipment, and new equipment developers may have less experience and expertise than seasoned gas providers. In response to the aforementioned incidents, and in support of hydrogen and fuel cell activities in California specifically, the Hydrogen Safety Panel (HSP) has investigated the safety of mobile hydrogen and fuel cell applications (mobile auxiliary/emergency fuel cell power units, mobile fuelers, multi-cylinder transport vehicles, unmanned aircraft power supplies, and mobile hydrogen generators). The HSP examined the applications, requirements, and performance of mobile applications that are being used extensively outside of California to understand how safety considerations are applied. This report discusses the results of the HSP’s evaluation of hydrogen and fuel cell mobile applications along with recommendations to address relevant safety issues.
The application of hydrogen as an energy carrier has been expanding into industrial and transportation sectors enabling sustainable energy resources and providing a zero-emission energy infrastructure. The hydrogen supply infrastructure includes processes from production and storage, to transportation and distribution, to end use. Each portion of the hydrogen supply infrastructure is regulated by international, federal, state, and local entities. Regulations are enforced by entities which provide guidance and updates as necessary. While energy sources such as natural gas are currently regulated via the Code of Federal Regulations and United States Code, there might be some ambiguity as to which regulations are applicable to hydrogen and where regulatory gaps may exist. This report contains an overview of the regulations that apply to hydrogen, and those that may indirectly cover hydrogen as an energy carrier participating in a sustainable zero emission global energy system. As part of this effort, the infrastructure of hydrogen systems and regulation enforcement entities are defined, and a visual map and reference table are developed. This regulatory map and table can be used to identify the boundaries of federal oversight for each component of the hydrogen supply value chain which includes production, storage, distribution, and use.
The hydrogen infrastructure involves hydrogen production, storage and delivery for utilization with clean energy applications. Hydrogen ingress into structural materials can be detrimental due to corrosion and embrittlement. To enable safe operation in applications that need protection from hydrogen isotopes, this review article summarizes most recent advances in materials design and performance characterization of barrier coatings to prevent hydrogen isotopes’ absorption ingress and permeation. Barriers are crucial to prevent hydride formation and unwanted hydrogen effects to increase safety, materials’ lifetime and reduce cost for applications within nuclear and renewable energy. The coating may be applied on a material that requires protection from hydrogen pick-up, transport and hydride formation in hydrogen storage containers, in pipelines, spent nuclear fuel storage or in nuclear reactors. While existing, commercial coatings that have been much in use may be satisfactory for various applications, it is desirable to evaluate whether alternative coating concepts can provide a greater resistance to hydrogen isotope permeation along with other improved properties, such as mechanical strength and thermal resistance. The information presented here is focusing on recent findings within the past 5–7 years of promising hydrogen barriers including oxides, nitrides, carbon, carbide, MAX-phases and metals and their mechanical strength, hydrogen pick-up, radiation resistance and coating manufacturing techniques. A brief introduction to hydrogen permeation is provided. Knowledge gaps were identified to provide guidance for material’s research prospects.
Hydrogen utilization in clean energy technologies is challenged by limited storage and transport within materials, owing to the complex hydrogen kinetics at interfaces [1]. Understanding these interfacial mechanisms at the nanoscale is crucial for developing improved materials for hydrogen applications, particularly proton-conducting fuel cells (PCFCs). Vertically aligned nanocomposites (VANs) grown by pulsed laser deposition (PLD) offer a unique platform for investigating the interfacial effects on hydrogen transport due to their well-defined interfaces parallel to the direction of charge transport [2-4]. To investigate hydrogen transport, the two phases within the VANs were chosen as BaZr 0.9 Y 0.1 O 3-x (BZY), a known proton conductor, and Pr 0.1 Ce 0.9 O 2-x (PCO), a mixed ionic-electronic conductor [5]. This PCO-BZY VANs architecture allows the investigation of how the interface between a proton conductor and a mixed conductor influences hydrogen transport. However, because of the small size of hydrogen, it is difficult to discern the nature of its interactions with interfaces from bulk measurements at the macroscale, thus necessitating nanoscale measurements [6]. Electron energy loss spectroscopy (EELS) allows for nanometer-resolution probing of the local atomic structure and chemistry at the BZY/PCO interface. In this study, plan-view analysis of PCO-BZY VANs films was employed to characterize the structure and phase distribution of the VANs and investigate the interface between the nanostructures. The films were imaged using scanning electron microscopy (SEM) in the Hitachi S-4800 SEM, collecting secondary electron images using mixed upper and lower detectors. Then, plan-view transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM) EELS were employed using a JEOL ARM300 microscope operated at 300kV with a Gatan K3 GIF Continuum detector to study the distribution of the BZY and PCO phases through the film. As a result, spectrum images were acquired at a dispersion of 0.18eV per channel and denoised afterward by principal component analysis (PCA) method.
Relevance: Detection is recognized as a critical element for hydrogen facility safety design and supports risk mitigation. Detection methodologies will support validation of H2 behavior research. Hydrogen point sensors play a critical role for safety and process monitoring, but other methodologies can be developed. Approach: NREL Sensor Laboratory tests and verifies sensor performance for manufacturers, developers, end-users, regulatory agencies and SDOs/CDOs NREL deployment activity supports regulatory requirement verification, hydrogen behavior models, and method development for use by stakeholders. Accomplishments and Progress: NREL's R&D accomplishments have supported developers, industry, and SDOs by providing sensor performance and deployment expertise not otherwise available. Development of alternative detection strategies for hydrogen applications have been initiated. HyWAM and advanced detection methodologies deployments at H2@Scale Facilities are being implemented. Collaborations: Collaboration with government laboratories, universities, private organizations and regulatory agencies has leveraged the NREL Sensor Laboratory's success in advancing hydrogen safety sensors and process control. Proposed Future Work: NREL will support hydrogen deployment by the proper implementation of hydrogen sensors and advanced detection strategies. NREL will continue to support science-based codes and standards. This effort will be guided by the needs of the hydrogen community.
Cerium oxide (ceria) has found a wide variety of applications in catalysis including as a catalyst, a modifier, or a support, largely thanks to its robust redox properties and versatile acid-base function. While it is often utilized for oxidation reactions, ceria has recently attracted intense research interest for its unusual ability to selectively hydrogenate alkynes to alkenes. The intriguing hydrogenation ability of ceria has sparked renewed research efforts to understand how pure ceria works as a hydrogenation catalyst. In this review, recent advances in both experimental and computational studies of ceria are summarized, focusing on the interaction of ceria with H 2 and in hydrogenation reactions. Significant insights from various studies including in situ spectroscopy/microscopy and theoretic modeling of ceria in hydrogen-involved reactions are discussed, which shed light on the origin of the hydrogenation ability of ceria and the reaction mechanisms involved in ceria-catalyzed alkyne hydrogenation. Ways to further improve both the mechanistic understanding and catalytic performance of ceria-based materials for hydrogenation reactions are proposed at the end in the summary and outlook section.
The maritime industry is investigating a number of fuel options for reducing emissions, including liquefied natural gas (LNG), biofuels, and electrical drive systems powered by batteries and/or hydrogen-fueled fuel cells. Hydrogen-fueled ships offer the potential to significantly reduce, if not eliminate, regulated and unregulated pollutants in maritime applications. Argonne National Laboratory conducted preliminary comparisons of the total cost of ownership (TCO) of several classes of ships to determine how fuel cell technology compares to the current diesel technology, what advancements are needed for hydrogen fuel cell technology to be competitive in the future, and what applications may be appropriate for introducing fuel cells into the maritime industry. These studies included feeder container ships, harbor tugboats, river pushboats, and auto/passenger ferries. For this study, TCO was defined to include the cost of fuel, propulsion system, and fuel storage system, the levelized cost of propulsion/auxiliary engines, and the cost of annual maintenance and consumables. It did not include the cost of the vessel frame or other components, aside from the propulsion system, that the fuel cell and diesel ships have in common. A 10% internal rate of return (IRR) was applied to the initial capital investment and an installation cost factor of 20% was applied to the capital cost. The capital cost of each component (e.g., engine, fuel tank, motor, etc.) was amortized over a period of 20 years, except for the fuel cell system, which was amortized over 6 or 10 years depending on ship class. The initial comparisons for container ships indicate that fuel costs are by far the dominant contributor to the TCO. With the current low cost of low-sulfur marine gasoil (LSMGO) and relatively high cost of hydrogen, it is difficult for hydrogen to compete with LSMGO in container ship applications. The large energy demand for container ships also favors the use of the higher volumetric energy density LSMGO fuel, especially for longer voyages. The space required to store enough hydrogen for the same journey is larger than that needed to store diesel fuels and can reduce the available cargo carrying and revenue generating space available on the ship.
Herein, we report MXene-filled epoxy-based vitrimeric nanocomposites featuring a semi-interpenetrating network (S-IPN) to develop a hydrogen gas (H 2 ) barrier coating with self-healing characteristics for compressed H 2 storage applications. The reversible epoxy network was formed by synthesizing linear epoxy chains with pendent bis-hydroxyl groups using amino diol, which were then crosslinked with 1,4-benzenediboronic acid to generate dynamic boronic ester linkages. To achieve the S-IPN-type molecular arrangement, the epoxy chains were in situ crosslinked in the presence of poly(ethylene-co-vinyl alcohol) (EVOH), giving rise to a self-healing network (EEP) with a healing efficiency of 87%. Into the S-IPN vitrimer (EEP), a 2D platelet-type nanofiller MXene was incorporated to introduce a tortuous path for H 2 gas diffusion along with improved mechanical properties. The nanocomposite coating was applied to nylon 6 liner material, which is conventionally used in all-composite H 2 storage vessels. Further, the application of a 2 wt% MXene/EEP nanocomposite coating showed a permeability coefficient of 0.062 cm 3 mm m -2 d -1 atm -1 exhibiting ~96% reduction in gas permeability compared to uncoated nylon 6. The same nanocomposite exhibited a healing efficiency of 79%. Increasing the MXene loading to 10 wt% further reduced the permeability coefficient to 0.002 cm 3 mm m -2 d -1 atm -1 ; however, the healing efficiency decreased due to restricted chain mobility. In essence, the current work highlights the potential of vitrimeric S-IPN nanocomposite coatings for H 2 gas-barrier applications, enhancing safety and performance.
Phenomenological CALPHAD (CALculation of PHAse Diagrams) models, widely used for multicomponent materials, often contain a considerable number of parameters and require fitting using data from a relatively small number of experimental measurements or theoretical calculations. Sometimes these parameters are introduced for the purpose of improving model fits but without clear physical justification, which leads to overparametrized models with poor generalization performance. Automated approaches for optimal model selection based on the available data therefore become critical. Here, in this work, a least absolute shrinkage and selection operator (LASSO)-based approach is developed for model selection by leveraging the linearity of the CALPHAD model with respect to its parameters to convert the model selection and fitting to a LASSO minimization problem. We demonstrate its utility for thermodynamic modeling of thermochemical hydrogen (TCH) production materials using lanthanum strontium manganite (LSM) as an example. Various TCH-relevant properties, including oxygen stoichiometry as a function of oxygen partial pressure, enthalpy of reduction, and entropy of reduction, are successfully predicted with reasonable accuracy using a minimal set of model parameters. Importantly, the model selection and fitting involve minimal human decision; it can therefore be applied to high-throughput DFT defect calculations and yield efficient workflows for TCH material modeling and optimization.