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Results for “High Pressure Hydrogen Storage”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Effect of hydrogen on tensile properties of 304L stainless steel at cryogenic temperatures

Safe and efficient hydrogen storage and distribution are key attributes to realizing hydrogen as an alternative energy carrier. To this end, cryogenic liquid and cryo-compressed gaseous hydrogen are considered high energy density alternatives to ambient temperature gas. However, these alternatives have significant material demands to overcome extreme temperature (20 K) and pressure (700 bar) as well as hydrogen effects. Austenitic stainless steels are widely used for cryogenic pressure vessels owing to relatively high ductility even at 4 K. However, the influence of hydrogen on mechanical properties at cryogenic temperatures has rarely been studied. In this study, the tensile properties of 304L austenitic stainless steel with internal hydrogen were evaluated at 20 K, 77 K, and 113 K. Test specimens were saturated with internal hydrogen to concentration of 140 wtppm in a high pressure environment at elevated temperature, a process called thermal precharging. While lower temperature in known to increase strength properties and reduced elongation at fracture, the presence of internal hydrogen increased both strength and elongation at fracture, but reduced ductility. Magnetic evaluation of the uniformly strained region of the test specimens suggest that hydrogen mitigates the strain-induced transformation to a’-martensite. Brittle fracture features and secondary cracking indicative of hydrogen embrittlement were observed on the fracture surfaces of hydrogen-precharged specimens, which is consistent with the loss of ductility.

Merkel, Daniel R.↗
DOE OSTI2020

Structural Implications of Interfacial Hydrogen Bonding in Hydrated Wyoming-Montmorillonite Clay

Montmorillonite (MMT) clay - a layered porous nanomaterial used as seals in engineered waste containment barriers for spent nuclear fuel - adopts discrete hydration/swelling states depending upon surrounding water and ion activities and confining pressure. The structure of nanoconfined water and charge-balancing counterions in the clay mineral interlayers dictate the swelling and mechanical behavior of MMT, so a molecular model for this clay with high structural fidelity is required to accurately predict the reliability of long-term nuclear waste storage. Here, we present a molecular model for MMT that is based on high resolution transmission electron microscopy of Wyoming-MMT single crystals. Imaging data unambiguously show a cis-vacant arrangement of structural hydroxyl groups in the octahedral sheet, whereas existing molecular models assume a centrosymmetric trans-vacant configuration for MMT. Furthermore, using atomistic simulations, we find that the cis-vacant arrangement of structural hydroxyl groups significantly affects the structure of adsorbed water yielding a larger population of hydrogen bonds with bridging oxygens on the tetrahedral sheet and weak hydrogen bonding between the hydroxyl groups in the octahedral sheet and water in the clay mineral interlayers. As a result, water adsorbed in the interlayer is more "ice-like", with stronger ordering and lower density, although the diffusivity of the interlayer species is not significantly diminished. Our improved structural model for MMT provides insight into the energetics of water adsorption, which ultimately dictates its pore- to macro-scale swelling, transport, and fracture properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Balancing volumetric and gravimetric uptake in highly porous materials for clean energy

A huge challenge facing scientists is the development of adsorbent materials that exhibit ultrahigh porosity but maintain balance between gravimetric and volumetric surface areas for the onboard storage of hydrogen and methane gas—alternatives to conventional fossil fuels. Here we report the simulation-motivated synthesis of ultraporous metal–organic frameworks (MOFs) based on metal trinuclear clusters, namely, NU-1501-M (M = Al or Fe). Relative to other ultraporous MOFs, NU-1501-Al exhibits concurrently a high gravimetric Brunauer–Emmett–Teller (BET) area of 7310 m 2 g -1 and a volumetric BET area of 2060 m 2 cm -3 while satisfying the four BET consistency criteria. The high porosity and surface area of this MOF yielded impressive gravimetric and volumetric storage performances for hydrogen and methane: NU-1501-Al surpasses the gravimetric methane storage U.S. Department of Energy target (0.5 g g -1 ) with an uptake of 0.66 g g -1 [262 cm 3 (standard temperature and pressure, STP) cm -3 ] at 100 bar/270 K and a 5- to 100-bar working capacity of 0.60 g g -1 [238 cm 3 (STP) cm -3 ] at 270 K; it also shows one of the best deliverable hydrogen capacities (14.0 weight %, 46.2 g liter -1 ) under a combined temperature and pressure swing (77 K/100 bar → 160 K/5 bar).

Science & Technology - Other Topics↗
DOE OSTI2022

Electrochemical CO2 conversion to formic acid through the Andora Process

Electrochemical utilization or conversion of CO2 can be used to convert waste CO2 into targeted high-value and cost-effective commercial products. Conventional processes for CO2 conversion to fuel sources are challenging and expensive due to their requirement for high temperatures and pressures. Electrochemically, a catalyst can be used at a fixed applied potential to reduce CO2 to form a desired product with less competition at modest operating conditions. Formic acid (FA) has recently become a product of interest for CO2 conversion due to its potential for hydrogen storage and fuel cell applications. Electrochemically, FA is produced through a direct two-electron transfer process involving CO2 with a proton source, requiring less energy input and fewer reaction steps than traditional processes. However, there remain significant obstacles for the broader-scale implementation of CO2 on the market, including competition with unwanted CO and H, the presence of molecular oxygen, and stability of the electrocatalyst. In order to overcome some of these challenges, a new continuous flow Andora Process was developed consisting of two separate cells to decouple electrochemical reduction of the charge carrier with the FA production via an engineered catalyst. Recent experimental results show that with appropriate design changes and operating conditions to the flow system, FA production above 500 mM can be achieved along with efficiencies above 80%. TEA and LCA assessments of the Andora Process show a potential for the reduction in the GWP potential and cost saving compared to the current comparative formic acid production process.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2026

Hydrophobic Metal–Organic Frameworks Enable Superior High-Pressure Ammonia Storage through Geometric Design

Hydrophobic metal–organic frameworks (MOFs) are typically overlooked for ammonia storage due to weak host–guest interactions. Here, we demonstrate that four structurally analogous aluminum-based MOFs exhibit a counterintuitive behavior whereby framework geometry, rather than ligand hydrophilicity, determines high-pressure NH 3 adsorption performance. The hydrophobic CAU-23 achieved an exceptional capacity matching hydrophilic analogs despite its poor low-pressure uptake. This pressure-dependent enhancement stems from the unique 4-cis-4-trans geometry of CAU-23 compared to the purely cis arrangement of MIL-160 and KMF-1 and the alternating cis-trans configuration of MOF-303. Critically, CAU-23 retained 95% capacity over three high-pressure cycles, whereas hydrophilic MOFs suffered 39–46% irreversible losses due to strong NH 3 -framework interactions that compromise structural integrity. Grand canonical Monte Carlo simulations reveal that high pressure enables NH 3 clustering through intermolecular hydrogen bonding, bypassing the need for strong host–guest interactions. High-pressure powder X-ray diffraction measurements confirm the exceptional mechanical resilience of CAU-23, showing complete structural recovery upon decompression despite exhibiting the highest pressure sensitivity among the studied MOFs. An extended analog, HE-CAU-23, validates this design principle with further enhanced capacity. Furthermore, these findings reveal a paradigm shift toward hydrophobic MOFs with optimized geometry for high-performance and regenerable gas storage applications.

MOFs↗
DOE OSTI2024

Nano-enhanced solid-state hydrogen storage: Balancing discovery and pragmatism for future energy solutions

Nanomaterials have revolutionized the battery industry by enhancing energy storage capacities and charging speeds, and their application in hydrogen (H 2 ) storage likewise holds strong potential, though with distinct challenges and mechanisms. H 2 is a crucial future zero-carbon energy vector given its high gravimetric energy density, which far exceeds that of liquid hydrocarbons. However, its low volumetric energy density in gaseous form currently requires storage under high pressure or at low temperature. This review critically examines the current and prospective landscapes of solid-state H 2 storage technologies, with a focus on pragmatic integration of advanced materials such as metal-organic frameworks (MOFs), magnesium-based hybrids, and novel sorbents into future energy networks. These materials, enhanced by nanotechnology, could significantly improve the efficiency and capacity of H 2 storage systems by optimizing H 2 adsorption at the nanoscale and improving the kinetics of H 2 uptake and release. We discuss various H 2 storage mechanisms—physisorption, chemisorption, and the Kubas interaction—analyzing their impact on the energy efficiency and scalability of storage solutions. The review also addresses the potential of “smart MOFs”, single-atom catalyst-doped metal hydrides, MXenes and entropy-driven alloys to enhance the performance and broaden the application range of H 2 storage systems, stressing the need for innovative materials and system integration to satisfy future energy demands. High-throughput screening, combined with machine learning algorithms, is noted as a promising approach to identify patterns and predict the behavior of novel materials under various conditions, significantly reducing the time and cost associated with experimental trials. In closing, we discuss the increasing involvement of various companies in solid-state H 2 storage, particularly in prototype vehicles, from a techno-economic perspective. In conclusion, this forward-looking perspective underscores the necessity for ongoing material innovation and system optimization to meet the stringent energy demands and ambitious sustainability targets increasingly in demand.

25 ENERGY STORAGE↗
DOE OSTI2020

A Mechanical Test Frame for Property Evaluations at Cryogenic Temperature

On-board storage of hydrogen fuel has been designated as a limiting factor in the advancement of fuel cell technologies in the automotive industry. The use of cryo-compressed Type III pressure vessels presents one option to overcome this barrier. These multi-material vessels will be expected to perform at high pressure and extreme low temperatures, which creates a complex engineering design challenge. Many materials exhibit highly temperature-dependent properties, which must be considered for the efficient design of cryo-compressed pressure vessels. Complicating this issue, mechanical property data at cryogenic temperatures is sparse. This technical paper provides a description of a test apparatus commissioned specifically to help address this shortcoming. A mechanical test frame was retrofitted with a continuous flow cryostat capable to evaluate various mechanical properties throughout a broad temperature range of 25 °C to -269 °C with a load limit of 10 kN. An investigation of the thermomechanical properties of an epoxy resin was carried out as a demonstration.

Mechanical characterization, cryogenic pressure ve↗
DOE OSTI2021

Development of an Advanced Hydrogen Energy Storage System using Aerogel in a Cryogenic Flux Capacitor (CFC)

The Cryogenic Flux Capacitor (CFC) is a cold, dense fluid storage core with integrated design features that afford the designer flexibility and provide new possibilities for the storage and discharge of energy. The stored energy, in this case, is represented by hydrogen physically bonded within the nanoscale pores within the aerogel composite blanket material, and the process of bonding or debonding is governed by principles of physical adsorption (physisorption) and thermodynamics. The large surface area afforded by the nanoporous aerogel (~1,000 m2/g) allows for storage densities close to, or in some cases exceeding, that of normal boiling point liquids. Its performance easily exceeds what can be achieved via ambient temperature, high-pressure gas storage for an equivalent volume. CFC storage is predicted to be easily scalable, is constructed from readily available commercial materials, lends itself to a range of pressure applications, and is geometry insensitive. They can also be used in modular designs, affording even more flexibility for potential deployment. In addition to the aerogel adsorbent within the blanket material, a CFC includes thermally-conductive membrane layered with the aerogel, which acts as a large-area, quick-response thermal management system. The system conducts heat throughout the volume to discharge the unit quickly. This same thermal management system can also be connected to a refrigeration system, or cold fluid such as liquid nitrogen (LN2), to facilitate the charging up of the CFC. The charging and discharging can be performed as fast or as slow as desired by controlling the cooling or heating supplied to the CFC.

08 HYDROGEN↗
DOE OSTI2020

Dispersion of cryogenic hydrogen through high-aspect ratio nozzles

Liquid hydrogen is increasingly being used as a delivery and storage medium for stations that provide compressed gaseous hydrogen for fuel cell electric vehicles. In efforts to provide scientific justification for separation distances for liquid hydrogen infrastructure in fire codes, the dispersion characteristics of cryogenic hydrogen jets (50–64 K) from high aspect ratio nozzles have been measured at 3 and 5 bar abs stagnation pressures. These nozzles are more characteristic of unintended leaks, which would be expected to be cracks, rather than conventional round nozzles. Spontaneous Raman scattering was used to measure the concentration and temperature field along the major and minor axes. Within the field of interrogation, the axis-switching phenomena was not observed, but rather a self-similar Gaussian-profile flow regime similar to room temperature or cryogenic hydrogen releases through round nozzles. The concentration decay rate and half-widths for the planar cryogenic jets were found to be nominally equivalent to that of round nozzle cryogenic hydrogen jets indicating a similar flammable envelope. The results from these experiments will be used to validate models for cryogenic hydrogen dispersion that will be used for simulations of alternative scenarios and quantitative risk assessment.

08 HYDROGEN↗
DOE OSTI2021

Defying Thermodynamics: Stabilization of Alane Within Covalent Triazine Frameworks for Reversible Hydrogen Storage

The highly unfavorable thermodynamics of direct aluminum hydrogenation can be overcome by stabilizing alane within a nanoporous bipyridine-functionalized covalent triazine framework (AlH 3 @CTF-bipyridine). This material and the counterpart AlH 3 @CTF-biphenyl rapidly desorb H 2 between 95 and 154°C, with desorption complete at 250°C. Sieverts measurements, 27 Al MAS NMR and 27 Al{ 1 H} REDOR experiments, and computational spectroscopy reveal that AlH 3 @CTF-bipyridine dehydrogenation is reversible at 60°C under 700 bar hydrogen, >10 times lower pressure than that required to hydrogenate bulk aluminum. DFT calculations and EPR measurements support an unconventional mechanism whereby strong AlH 3 binding to bipyridine results in single-electron transfer to form AlH 2 (AlH 3 ) n clusters. Here the resulting size-dependent charge redistribution alters the dehydrogenation/rehydrogenation thermochemistry, suggesting a novel strategy to enable reversibility in high-capacity metal hydrides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Linking the Spin Transition of Ferric Iron in δ‐(Al,Fe)OOH to Water Storage in the Lower Mantle

As the most massive geochemical reservoir, the lower mantle affects the Earth's budget of volatile elements, including hydrogen or H 2 O. The properties of minerals in the lower mantle are further affected by changes in the electronic configurations of iron cations, that is, by spin transitions. The feedback between spin transitions and potential storage of H 2 O in solid hydrous phases in the lower mantle, however, remains unexplored. By combining high‐pressure nuclear resonant inelastic X‐ray scattering and high‐pressure high‐temperature X‐ray diffraction experiments, we constrained the thermal equation of state of δ‐(Al,Fe)OOH, a member of the phase H solid solution. Based on the derived thermal equation of state of δ‐(Al,Fe)OOH and the underlying thermodynamic model, we calculate the excess Gibbs free energy that arises from the spin transition of ferric iron in this compound and evaluate the effect on phase equilibria. The results of our analysis show that the spin transition of ferric iron in phase H may significantly reduce the thermodynamic activity and hence the concentration of H 2 O in a coexisting hydrous melt. As a consequence, nominally anhydrous minerals of the lower mantle may become dehydrated in the presence of phase H. Our analysis further suggests that, under certain conditions, the spin transition may expand the thermal stability of Fe 3+ ‐bearing phase H and create a geochemical link between the storage of H 2 O in phase H and ferric iron in the lower mantle.

Buchen, Johannes [Univ. of Bayreuth (Germany); Cal↗
DOE OSTI2024

Modeling Approach for the Aluminum-clad Dry Storage Pilot using HFIR Fuel

To confirm that the dry storage of aluminum-clad research reactor spent nuclear fuel (ASNF) will remain within the safety envelope after applied drying schemes and that the resulting evolution of the gas space composition, temperature, and pressure conditions are understood, a dry storage pilot project is being established. The pilot will incorporate an instrumented lid for discrete interval or for on-demand gas composition and temperature monitoring of two DOE Standard Canisters (DSCs) loaded with three High Flux Isotope Reactor (HFIR) inner cores per DSC. Each DSC would be subjected to a separate alternative candidate drying scheme. Canisters will undergo 1 to 5 years of monitoring, including internal temperature and gas sampling to track pressure and composition changes. This report outlines the approach for modeling the ASNF-in-canister behavior in terms of evolving gas space conditions for the ASNF dry storage pilot using HFIR fuel. The ASNF has an adherent surface oxyhydroxide layer comprised of boehmite/bayerite that generates hydrogen when subjected to irradiation. Three-dimensional multi-physics computational fluid dynamics simulations will be executed to compute the thermal field within the DSC and provide inputs to a chemical model employed to compute pressure buildup as hydrogen is generated in the system. Implemented in Cantera, the chemical model solves gas phase and aluminum oxyhydroxide surface-mediated radiolysis reactions. Gas phase reactions are sourced from Wittman and Hanson (2015), whereas surface-mediated reactions are incorporated by fitting experimental data using an optimization algorithm (Abboud, 2023). Water radiolysis reactions from Wren and Ball (2001) are adopted with modifications as described in Abboud (2023c). Understanding the effect of the hydrogen buildup over time is important for long-term storage safety considerations. Modeling results will include the canister pressure, temperature, and composition evolution from the initial helium backfill with the addition of radiolytically-evolved chemical species (e.g., hydrogen and oxygen). The specific HFIR cores for the pilot program have not yet been selected, and the overall design is still in development. The CFD-chemical model used for this work will be based on prior models with necessary updates to allow for improved accuracy and efficiency. The experimental data obtained from the HFIR demonstration will be used to improve and validate the computational models to predict the ASNF-in-canister behavior.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Metal hydride composition-derived parameters as machine learning features for material design and H 2 storage

Though hydrogen is a promising energy carrier for a green future, many challenges persist. One is the difficulty in engineering storage solutions, with metal hydrides being a leading contender among solid-state strategies. To facilitate efficient searching of candidate materials, ridge regression, simple decision trees, random forest ensembles, and gradient boosting ensembles were employed to predict the energy of formation, with the random forest ensemble resulting in the lowest test set error. First, two public databases, Materials Project and HydPark, were searched for metal hydrides. Feature engineering was performed before the models were developed, resulting in electronegativity, density, atomic density, d-character, f-character, band gap, hydrogen weight fraction, magnetization, temperature, and pressure being retained. The models were then benchmarked by the lowest test error before a random forest ensemble was used to populate entries missing energy of formation. Furthermore, all were then scored by hydrogen storage capacity and energy of formation suitability. Readily available features including several derived from only the chemical formula which were found to be highly predictive. and so are promising for high-throughput screening of arbitrary novel hydride formulations and blends for thermodynamic feasibility.

25 ENERGY STORAGE↗
DOE OSTI2021

Energy Arbitrage: Comparison of Options for use with LWR Nuclear Power Plants

Arbitrage is the opportunistic buying and selling of a commodity during local pricing valleys and peaks respectively to maximize economic value. This report evaluates options for energy arbitrage integrated with existing light water reactor (LWR) nuclear power plants (NPPs) where nuclear energy could be stored in a variety of forms and later recovered to generate electrical power during periods when grid electricity demand and pricing are high. The forms of energy storage examined in this report include the potential value of batteries, hydrogen, and thermal energy storage for coupling with nuclear power. Various large demand response options are also analyzed, including the production of liquid nitrogen via air separation and liquefaction, liquefaction of hydrogen, compressed hydrogen, and the cryogenic capture of CO2. Demand response refers to dispatchable loads that can cycle up or down depending on-grid electricity demand to aid in balancing the grid. Large demand response options could dispatch to aid nuclear power stations in avoiding power turndowns by providing an alternate disposition for electrical energy by producing marketable products (e.g., liquid nitrogen, hydrogen, or captured CO2). Static conditions were chosen and analyzed in this report for each option. Dynamic operation or optimization of energy arbitrage or demand response are out of scope for this report. The analysis is based on storage systems with discharge capacities of 500 MW for which various durations of storage and costs of charging (electricity cost) are examined. While the value of thermal energy to an industrial user for flexible plant operations has been previously proven as a business case, this report evaluates costs of hydrogen energy storage and leading thermal energy storage options, and large demand response loads that could be integrated with LWRs in comparison to utility-scale battery storage for use of off-peak nuclear energy. Compilation of this information will be used by the Idaho National Laboratory (INL) RAVEN/HERON systems integration and economics tool to evaluate thermal energy dispatch to industrial users. Relative ranking of energy storage options was done using a levelized cost of storage (LCOS) metric which calculates a rough breakeven cost for the system, taking into account the capital and operating costs as well as the revenue from arbitrage. Table ES1 below shows the LCOS for each of the energy storage options considered. First, in the table, lithium iron (Fe) phosphate batteries are listed as the base case for comparison against the other options. Next is hydrogen storage where most of the hydrogen analyses assumed the hydrogen to be produced using solid oxide electrolytic cell (SOEC) high temperature steam electrolysis (HTSE). The others used existing models of polymer electrolyte membrane (PEM) low temperature electrolysis to produce hydrogen. HTSE performance parameters and costs were taken from existing INL models. Various means were assumed to convert the hydrogen to electricity, including PEM fuel cells (FCs) and a gas turbine mixed in a 30 vol% mixture with natural gas. Physical storage (pressure vessels) and geological storage (natural underground features) were used to store the hydrogen as noted. Geological storage is more economical, but the locations are limited because of the requirement for pre-existing geological formations that will support storage. Thermal energy storage (TES) options were also analyzed including electro-thermal energy storage (ETES) and four different liquid sensible heat TES storage media as noted (Hitec, Hitec XL, Therminol-66, and Dowtherm A). The ETES process considered was modified using existing public documentation on an Echogen process and uses a separate supercritical CO2 charge and discharge cycle with sand as the heat storage media.

25 ENERGY STORAGE↗
DOE OSTI2025

Risk assessment of wellbore leakage during underground hydrogen storage

The expansion of renewable energy sources would require large-scale energy storage options to overcome the intermittent nature of these sources. Underground hydrogen storage (UHS) in depleted hydrocarbon reservoirs offers a scalable and practical energy storage solution. These reservoirs are chosen for their availability and large capacity, but the unique properties of hydrogen raise concerns about potential leakage pathways, particularly through wellbores. In this study, we develop and apply, for the first time, reduced-order models (ROMs) specifically designed for efficient leakage risk prediction in UHS systems operating in depleted hydrocarbon reservoirs. Using 3,000 high-fidelity simulation scenarios, we examine the influence of 11 key parameters, including reservoir and aquifer depths, wellbore permeability and porosity, initial saturations of water, oil and gas fractions (hydrogen, light, intermediate, and heavy hydrocarbons), reservoir pressure multiplier, and the aquifer-to-reservoir volume ratio, to simulate leakage behavior over a 1,000-year timescale. We train ROMs using a two-step classification-regression approach, achieving R 2 values exceeding 99 % across all targets. These ROMs effectively capture the leakage evolution and identify critical controls of leakage, guiding the design of mitigation strategies. Results indicate that gas leakage occurs in about 27 % of scenarios as early as five years post-operation, reaching volumes of up to 106 ft3. Oil leakage is less frequent (~17 %) and typically begins decades later. Our findings also show that hydrogen often migrates first, owing to its smaller molecular size and higher buoyancy, followed by heavier hydrocarbons. Over time, these heavier components contribute significantly to the total leaked volume, reinforcing the need for targeted monitoring and remediation strategies. Our analysis highlights that deeper storage reservoirs, shallower aquifers, and low-permeability wellbores significantly reduce leakage risks. In conclusion, this work offers a robust framework for risk-informed UHS deployment, supporting energy security through reliable large-scale hydrogen storage while safeguarding environmental integrity.

08 HYDROGEN↗
DOE OSTI2020

Feasibility of TEMPO-functionalized imidazolium, ammonium and pyridinium salts as redox-active carriers in ethaline deep eutectic solvent for energy storage

The discovery of electrolytes that have low vapor pressures and high solubility towards redox active species with an ability to undergo multiple electron transfer reactions is a challenge to realize in large-scale energy storage. In this work, we investigate the feasibility of (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) derived halide salts as redox active species in ethaline (1 : 2 ethylene glycol : choline chloride), a deep eutectic solvent (DES). Hydrogen bonding and electrostatic interactions achieved by the functionalization of TEMPO are shown to improve solubility in ethaline. This is the first study evaluating the physical properties and electrochemical behavior of the newly synthesized TEMPO-salts in ethaline providing insight into the impact of chemical functionality on the utility of these redox active species in DESs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

A study on texture stability and the biaxial creep behavior of as-hydrided CWSR Zircaloy-4 cladding at the effective stresses from 55 MPa to 65 MPa and temperatures from 300°C to 400°C

The creep rupture of high burnup used nuclear fuel (> 45 GWD/MTU) cladding is regarded as one of the failure mechanisms during long-term dry storage. A high amount of zirconium hydride in the cladding matrix would degrade the mechanical properties of the cladding especially leading to delayed hydride cracking. To better understand the influence of zirconium hydride on the biaxial thermal creep performance and the crystalline texture stability of Zircaloy-4 cladding, the pressurized tube technique is applied to test the durability of the as-hydrided material. Tests were performed on as-received Zircaloy-4 tubular specimens as well as-hydrided ones with targeted 300 wt parts per million (wppm) or 750 wppm hydrogen. The biaxial creep experiments were conducted at temperatures from 300 degrees C to 400 degrees C and at equivalent stresses at mid-wall from 55 MPa to 65 MPa. The hydridation process prior to creep tests induces the formation of FCC delta-hydride platelets along the circumferential direction of the tube. This alignment and phase structure of hydride show no significant change after biaxial creep tests. The creep strain-rate negatively depends on the hydrogen content. The synchrotron wide-angle X-ray diffraction (WAXD) technique and electron backscatter diffraction (EBSD) analysis were applied for the study of the crystallographic orientation relationship. zirconium-to-hydride grain orientation follows Shoji-Nishiyama crystallographic relationship. This relationship is stable before and after creep deformation. These results of creep performance and texture stability of Zircaloy-4 claddings can help support the design basis of interim and long-term dry storage facilities.

creep↗
DOE OSTI2021

Defying Thermodynamics: Stabilization of Alane Within Covalent Triazine Frameworks for Reversible Hydrogen Storage

Metastable metal hydrides such as AlH 3 have many attractive features as hydrogen storage media, but generally require complex reaction schemes for regeneration following H 2 release. Here in this paper, we demonstrate that the highly unfavorable thermodynamics of direct aluminum hydrogenation can be overcome by stabilizing alane within a nanoporous bipyridine-functionalized Covalent Triazine Framework (AlH 3 @CTF-bipyridine). This material and the counterpart AlH 3 @CTF-biphenyl rapidly desorb H 2 between 95 and 154 °C, with desorption complete at 250 °C. Sieverts measurements, 27 Al MAS NMR and 27 Al{ 1 H} REDOR experiments, and computational spectroscopy reveal that AlH 3 @CTF-bipyridine dehydrogenation is reversible at 60 °C under 700 bar hydrogen, >10 times lower pressure than that required to hydrogenate bulk aluminum. DFT calculations and EPR measurements support an unconventional mechanism whereby strong AlH 3 binding to bipyridine results in single-electron transfer to form AlH 2 (AlH 3 ) n clusters. The resulting size-dependent charge redistribution alters the dehydrogenation/rehydrogenation thermochemistry, suggesting a novel strategy to enable reversibility in high-capacity metal hydrides.

Coordination Chemistry↗