Degradation Behavior of LaNi(sub 4.8)Sn(sub 0.2)H(sub x) during Thermal Cycling
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Degradation Thermal Cycling alloys exposed to hydr↗
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Crystallographic Study of LaNi(sub 5-x)SN(sub x) (0.2,x,0.5) Compounds and Theri Hydrides
The structural properties of tin substituted LaNi5 compounds and corresponding deuteries have been investigated by single crystal X-ray and neutron power diffraction.
Sn AB5 Hydrides neutron diffraction single crystal↗
Defect Equilibria from First Principles: From Widegap Oxides to Topological Semimetals
Materials functionality and performance is rarely determined by the ideal crystal alone but is usually affected by formation of imperfections and the solution of impurities. In some applications, such as solar thermochemical hydrogen generation, defect formation is the fundamentally enabling mechanism of the desired functionality. In other cases, such as Cd3As2 topological semimetals, unintentional self-doping presents an obstacle to the access to the unique electronic properties. In either case, a quantitative understanding of the relevant defect mechanism is essential for developing design strategies. This presentation will touch upon numerous aspects in the computational simulation of defect equilibria, including non-equilibrium design strategies, the coupling of solid state and gas-phase reactions, dopant-defect and defect-defect interactions, both attractive and repulsive, the accuracy of total energy functionals and electronic structure methods, and the role of the shape of the density of states for the charge balance condition and Fermi level position, as well as machine-learning prediction of defect energies (1). Specific materials systems include Ga2O3 (2), Cd3As2 (3), and (Sr,Ce)MnO3 (4). (1) M.D. Witman, A. Goyal, T. Ogitsu, A.H. McDaniel, S. Lany, Nat. Comput. Sci. 3, 675 (2023). (2) A. Goyal, A. Zakutayev, V. Stevanovic, S. Lany, J. Appl. Phys. 129, 245704 (2021). (3) C. Brooks, M. van Schilfgaarde, D. Pashov, J.N. Nelson, K. Alberi, D.S. Dessau, S. Lany, Phys. Rev. B 107, 224110 (2023). (4) A. Goyal, M.D. Sanders, R.P. O'Hayre, S. Lany, PRX Energy 3, 013008 (2024).
CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS,M↗
Computational Approaches for Clean Energy Materials
Currently, 80% of the global final energy consumption occurs in form of fuels and only 20% as electricity. On the other hand, renewable energy additions come almost exclusively in the form of electricity (dominantly photovoltaics and wind). Thus, a successful energy transition will require enormous growth in renewables, sufficient to convert excess electricity into fuels, as well as the development of non-electricity based solar fuel technologies. As much as photovoltaic capacities have grown over the past 20 years, it is far from clear that current technologies and materials are up to the task to grow from here by yet another factor 100 until 2050. Therefore, sustained research efforts on emerging inorganic semiconductors for solar electricity and fuels are essential for facing the double challenge of climate change and energy security. Computational materials science can make important contributions, guiding and supporting research activities through both materials search and discovery and through detailed studies that help to develop a mechanistic understanding of materials performance and bottlenecks. This presentation will highlight three recent computational projects with relevance for photovoltaics and solar fuels (1) Defect graph neural networks (dGNN) for materials discovery in solar thermochemical hydrogen (STCH) [1]. The dGNN approach facilitates broad and fast materials screening for defect properties. (2) Modeling highly off-stoichiometric systems by evaluating the free energy of defect interaction [2]. This approach allows quantitative prediction of H2 production in complex STCH oxides. (3) First-principles atomic structure prediction for interfaces [3]. This work showed how an atomically thin CdCl2 interlayer phase enables in principle ideal electron transport across the incommensurate SnO2/CdTe interface. [1] M.D. Witman, A. Goyal, T. Ogitsu, A.H. McDaniel, S. Lany, Nat. Comput. Sci. (2023). https://doi.org/10.1038/s43588-023-00495-2. [2] A. Goyal, M.D. Sanders, R.P. O'Hayre, S. Lany, PRX Energy 3, 013008 (2024). https://doi.org/10.1103/PRXEnergy.3.013008. [3] A. Sharan, M. Nardone, D. Krasikov, N. Singh, S. Lany, Appl. Phys. Rev. 9, 041411 (2022). https://doi.org/10.1063/5.0104008.
density functional theory↗
germs-lab/LAMPS-miscanthus-microbiome
Data and analysis to accompany our submitted paper characterizing the LAMPS Miscanthus Microbiome comparing 16S rRNA gene DNA sequencing of Miscanthus in a staggered-start experiment. Authors for this analysis include Fernando Igne Rocha, Lanying Ma, and Adina Howe.
Igne Rocha, Fernando↗
Heterostructural Rocksalt-Wurtzite Interfaces
Data and code accompanying the following publication: Sharad Mahatara and Stephan Lany, "Heterostructural interface engineering for ultrawide gap nitrides from first principles: TaC/AlN and TaC/GaN rocksalt-wurtzite interfaces," Physical Review Applied 22, 054044 (2024). https://doi.org/10.1103/PhysRevApplied.22.054044
36 MATERIALS SCIENCE↗
Metal hydrides: a historical perspective
Metal hydrides are known for their outstanding performance as materials for hydrogen storage and processing. These materials find applications for short- and long-term energy storage, compression and supply of hydrogen gas, thermal energy storage, as electrodes and electrolytes in rechargeable batteries, for the microstructural optimisation of functional materials, in thin film technologies, as catalysts, getters and in many other uses. After the discovery of the first binary metal hydrides back in the 19th century, their studies covered all possible binary M-H systems and expanded rapidly into the field of ternary hydrides following the recognition of the excellent hydrogen storage performance of LaNi 5 - and TiFe-based materials, which operate efficiently at room temperature and at near-ambient H 2 pressures. This review aims to provide an overview of the early works, as well as selected recent results on various classes of metal hydrides. It also covers the recent activities from the major contributing countries and continents, including USA, Europe, Japan, China and Australia. These studies relate to achieving the hydrogen storage systems goals set by the Department of Energy in the United States which inspired the research activities at the national and international level, through execution of the tasks on hydrogen-based energy storage managed by the International Energy Agency. The review is prepared by international experts in the field and covers the most important past developments and also presents the recent achievements in the field.
08 HYDROGEN↗
Flux Growth of Cerium Nickel Gallides Studied by In Situ Neutron Diffraction
In this work, reactions of cerium and nickel in excess molten gallium were monitored by neutron diffraction during heating and cooling. The formation of binary intermediates CeGa 2 and Ni 2 Ga 3 was observed during heating. During cooling of the molten mixture from 900 °C, precipitation of BaAl 4 -type CeNi 0.74 Ga 3.26 occurred at 850 °C. Upon cooling to 650 °C, this compound reacted in the flux to form Ce 2 NiGa 10 and then Ce 2 NiGa 12 , the latter of which persisted to room temperature. Making use of this information, subsequent reactions were quenched at 750 °C to isolate crystals of CeNi 0.74 Ga 3.26 for further study. Similar reactions replacing Ce with La and quenching above 750 °C yielded LaNi 0.35 Ga 3.65 crystals. Magnetic susceptibility studies on CeNi 0.74 Ga 3.26 indicate that the cerium is trivalent; the Ce 3+ moments undergo a strongly anisotropic ferromagnetic ordering with moment perpendicular to the c axis below 7 K. Heat capacity data show little evidence of heavy fermion behavior. Resistivity measurements show that both LaNi0.35Ga3.65 and CeNi 0.74 Ga 3.26 exhibit metallic behavior. Density of states calculations support this and indicate that Ni/Ga mixing in the compound stabilizes the structure.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Mixed conductive composites for ‘Low-Temperature’ thermo-chemical CO 2 splitting and syngas generation
An effective strategy to design platinum group metal (PGM) free redox catalysts for “low temperature” CO 2 splitting followed with methane partial oxidation was proposed and validated. Composites of mixed ionic-electronic conductive (MIEC) oxides were found to be highly effective at relatively low temperatures (600–750 °C). Specifically, perovskite structured LaNi 0.35 Fe 0.65 O 3 and rock salt structured Ce 0.85 Gd 0.1 Cu 0.05 O 2–δ , as two compatible yet structurally distinct MIEC oxides, were integrated into composite redox catalyst particles. Resulting from the synergistic effect of the two MIEC phases, 90% CO 2 to CO conversion was demonstrated at 750 °C. Up to 90% methane conversion with 96% CO selectivity was also achieved in the methane POx step. The redox catalysts were characterized in detail to illustrate the underlying mechanisms for the synergistic effects. Electrical conductivity relaxation (ECR) measurements indicated significantly lowered activation energy for lattice oxygen (O 2– ) migration (0.43 eV). The enhanced oxygen migration in turn led to reversible exsolution of active transition metal nanoparticles (Ni–Fe alloy) from the mixed oxide, serving as active sites for methane activation while further enhancing lattice oxygen exchange, as confirmed by in situ X-ray diffraction and transmission electron microscopy. In conclusion, the composite redox catalysts demonstrate superior redox activity, coke resistance, and long term redox stability, making them potentially suitable for CO 2 utilization and methane partial oxidation under a hybrid redox process scheme.
03 NATURAL GAS↗
Design of lightweight BCC multi-principal element alloys with enhanced hydrogen storage using a machine learning-driven genetic algorithm
Body-centered cubic (BCC) based multi-principal element alloy (MPEA) hydrides have demonstrated significant potential for compact and efficient hydrogen storage. In this work, we first leverage machine learning (ML) models to predict the hydrogen affinity, storage capacity and phase stability of BCC MPEAs, creating a unique hydrogen-to-metal (H/M) predictor for materials with unprecedented performance. We developed a metaheuristic optimizer high-throughput framework by interfacing ML models with a genetic algorithm for the accelerated search of {Mg, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo} based lightweight BCC MPEAs with improved hydrogen storage characteristics. We report five new MPEAs with a predicted gravimetric hydrogen storage capacity of around 3.5 wt% or more, including Cr 0.09 Mg 0.73 Ti 0.18 (4.25 wt% H) and Cr 0.21 Nb 0.11 Ti 0.35 V 0.33 (3.5 wt% H). The electronic structure of the top-performing composition, Cr 0.09 Mg 0.73 Ti 0.18 , was analyzed using density functional theory (DFT) to understand the reasons for its improved hydrogen storage properties compared to TiFe (1.90 wt% H), LaNi 5 (1.37 wt% H) or BCC MPEAs like TiVNbCr (3.70 wt% H). Temperature-dependent molecular dynamics (MD) studies were further performed on optimized BCC MPEAs to qualitatively study hydrogen mobility and analyze the effect of different elemental composition on bulk hydrogen diffusion. Our findings demonstrate how a ML assisted genetic algorithm framework can be used for efficient search of stable, lightweight and cost-effective MPEAs while minimizing the need for expensive ab initio calculations.
DFT↗
Defect-mediated metastability and carrier lifetimes in polycrystalline (Ag,Cu)(In,Ga)Se 2 absorber materials
Using a combination of optical and electrical measurements, we develop a model for metastable defects in Ag-alloyed Cu(In,Ga)Se 2 , one of the leading thin film photovoltaic materials. By controlling the pre-selenization conditions of the back contact prior to the growth of polycrystalline (Ag,Cu)(In,Ga)Se 2 absorbers and subsequently exposing them to various stresses (light soaking and dark-heat), we explore in this paper the nature and role of metastable defects on the electro-optical and photovoltaic performance of high-efficiency solar cell materials and devices. Positron annihilation spectroscopy indicates that dark-heat exposure results in an increase in the concentration of the selenium–copper divacancy complex (V Se –V Cu ), attributed to depassivation of donor defects. Deep-level optical spectroscopy finds a corresponding increase of a defect at Ev+0.98 eV, and deep-level transient spectroscopy suggests that this increase is accompanied by a decrease in the concentration of mid-bandgap recombination centers. Time-resolved photoluminescence excitation spectroscopy data are consistent with the presence of the V Se –V Cu divacancy complex, which may act as a shallow trap for the minority carriers. Light-soaking experiments are consistent with the V Se –V Cu optical cycle proposed by Lany and Zunger, resulting in the conversion of shallow traps into recombination states that limit the effective minority carrier recombination time (and the associated carrier diffusion length) and an increase in the doping density that limits carrier extraction in photovoltaic devices.
14 SOLAR ENERGY↗
Hydride Bed Helium-3 Recovery and Partial Regeneration
Savannah River Tritium Enterprise has used LaNi 4.25 Al 0.75 (LANA75) hydride beds to store hydrogen isotopes for over two decades. A benefit of using LANA75 is that the 3He generated from tritium decay is retained in the hydride material, allowing the hydride beds to deliver high-purity product gas. A disadvantage is that the 3He accumulates in the LANA75 material over time, which forms a heel that cannot be removed under normal operating conditions. The heel traps hydrogen in the bed, slowly reducing the operational capacity of the bed as the heel grows. Eventually, the 3 He begins to release from the material, preventing the delivery of high-purity product. The hydride beds are replaced when (1) operational capacity is reduced such that it is impactive to routine operations, and/or (2) product purity is not maintained due to 3 He release.Several beds were operated beyond their design life. One of these beds was selected to undergo heating beyond its normal operating temperature to evaluate the possibility of removing a portion of the hydrogen and helium heel to improve bed function until a replacement could take place. This bake-out removed a portion of the hydrogen and helium heel, and preliminary data indicate that bake-outs may partially regenerate the beds. The bed’s performance will continue to be monitored, and additional bake-outs will likely be performed. Performing bake-outs results in increasing the recovery of 3 He, more efficient end-of-life activities (such as isotopic exchange), and extension of the useful service life of the bed.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Thermal Stability Testing of LANA.75
Savannah River Site has used the metal hydride LaNi 4.25 Al 0.75 (LANA.75) in the Tritium Facilities for over two decades. LANA.75 beds store significant quantities of tritium but have a limited service life due to the radiolytic decay of tritium to 3He within the metal matrix. It has been shown that the isotherm performance of a tritium-aged LANA.75 sample can be restored by heating under vacuum. Additional investigation is needed to ensure there are no unexpected changes to the hydride before this technique is employed in full-scale beds in the Tritium Facilities. In addition, it is necessary to verify the regenerable behavior and thermal stability of LANA.75 on a small scale prior to it being implemented on a large scale. In this work, a non-tritiated bench-scale LANA.75 sample was held at 750°C under vacuum for 200 h to simulate exposure to multiple restoration evolutions. Hydride isotherm performance, chemical composition, crystallinity, and morphology are compared between the pre-restorative and post-restorative testing samples. No significant changes were observed in composition or crystallinity. Comparison of pre-anneal and post-anneal isotherms showed that performance improved rather than deteriorated during the evolution. Scanning electron microscopy analysis showed small growths on the particle surface after exposure to regeneration conditions. Additional testing will be required to determine the cause of these growths.
08 HYDROGEN↗
Simulated Aging of Metal Tritides by Ball Milling Induced Gas Incorporation
The study of tritium aging effects on materials requires a significant time commitment as a consequence of its 12.3-year half-life, making developmental studies prohibitively difficult and expensive. However, detailed knowledge of long-term aging effects is critical to the development of structural and storage materials for future fusion reactor technologies. As a result, multiple approaches to simulated aging effects have been investigated. Here, we report a method of simulated tritium aging achieved though the incorporation of trapped gases via high-energy ball milling of LaNi 4.25 Al 0.75 alloy storage material. Experimental results verify the presence of trapped gases by a combination of temperature programmed desorption and LECO chemical analysis. Following gas incorporation, we find that many of the degraded hydrogen sorption properties found in aged storage materials are reproduced by the ball milled powders.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
Microscopic characterization of the magnetic properties of the itinerant antiferromagnet La 2 Ni 7 by La 139 NMR/NQR measurements
In this study, 139 La nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) measurements have been performed to investigate the magnetic properties of the itinerant magnet La 2 Ni 7 , which shows a series of antiferromagnetic (AFM) phase transitions at T N1 = 61 K, T N2 = 56 K, and T N3 = 42 K under zero magnetic field. Two distinct La NMR signals were observed due to the two crystallographically inequivalent La sites in La 2 Ni 7 (La1 and La2 in the La 2 Ni 4 and the LaNi 5 subunits of the La 2 Ni 7 unit cell, respectively). From the 139 La NQR spectrum in the AFM state below T N3 , the AFM state was revealed to be a commensurate state where Ni-ordered moments align along the crystalline c axis. Owing to the two different La sites, we were able to estimate the average values of the Ni-ordered moments (0.09 – 0.10 μB / Ni and 0.17 μB / Ni around La1 and La2, respectively) from 139 La NMR spectrum measurements in the AFM state below T N3 , suggesting a nonuniform distribution of the Ni-ordered moments in the AFM state. In contrast, a more uniform distribution of the Ni-ordered moments in the saturated paramagnetic state induced by the application of high magnetic fields is observed. The temperature dependence of the sublattice magnetization measured by the internal magnetic induction at the La2 site in the AFM state was reproduced by a local-moment model better than the self-consistent renormalization (SCR) theory for weak itinerant antiferromagnets. Given the small Ni-ordered moments in the magnetically ordered state, our results suggest that La 2 Ni 7 has characteristics of both itinerant nature and localized nature in its magnetism. With this in mind, it is noteworthy that the temperature dependence of nuclear spin-relaxation rates (1/T 1 ) in the paramagnetic state above T N1 measured at zero magnetic field can be explained qualitatively by both the SCR theory and the local-moment model.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
SR19021 Tritium Aging of Regenerated LANA.75 (Final Project Report)
The Savannah River Tritium Enterprise (SRTE) has used the metal hydride LaNi 4.25 Al 0.75 (LANA.75) in the Tritium Facilities for over two decades. The objective of this project was to expand upon the understanding of LANA.75 regeneration. Three distinct scopes were identified: monitor tritium aging of the single sample regenerated, regenerate a second tritium-aged sample, and perform thermal stability testing on a non-tritiated sample of LANA.75.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
SR19021 Tritium Aging of Regenerated LANA.75 (Final Project Report)
The Savannah River Tritium Enterprise (SRTE) has used the metal hydride LaNi 4.25 Al 0.75 (LANA.75) in the Tritium Facilities for over two decades. LANA.75 beds store significant quantities of tritium but have a limited service life due to the radiolytic decay of tritium to He-3 within the metal matrix. It has been shown that heating tritium-aged LANA.75 under vacuum can reverse tritium aging effects, eliminating the heel of trapped hydrogen, and restoring the reversible capacity. Additional investigation is needed to ensure there are no unexpected changes to the hydride before this restoration technique is employed in full scale beds in the Tritium Facilities. This project was to be comprised of three distinct scopes: obtain tritium aging data on the sample regenerated in 2018, regenerate a tritium-aged sample at 600 °C, and perform thermal stability testing on a non-tritiated sample. Isotherms were collected on the previously regenerated sample after approximately two years of tritium aging. Isotherms were collected at 80, 100, and 120 °C. As expected, there was a decrease in the plateau pressure, an increase in plateau slope, and a portion of the “heel” of tritium trapped in the metal had been reestablished. Unexpectedly, it appeared that the plateau had shortened at the higher tritium to metal ratios as well. This is typically seen in older samples. The second scope, to regenerate a second tritium-aged LANA.75 sample, was not completed. A Task Technical and Quality Assurance Plan was written and approved, a high temperature test cell was fabricated, several pre-job briefs were held, and the hydride sample was passivated with air. Despite these successes, the hydride sample was not recovered from the legacy test cell. The third scope was to perform thermal stability testing on a “cold” LANA.75 sample. A non-tritiated sample of LANA.75 was held at 750 °C under vacuum for 200 hours to simulate exposure to multiple regeneration evolutions. Hydride isotherm performance, chemical composition, crystallinity, particle size, and morphology are compared between the pre- and post-regeneration samples. No significant changes were observed in composition, crystallinity, or particle size. Comparison of before and after isotherms showed that performance improved rather than deteriorated during the evolution. Scanning Electron Microscopy (SEM) analysis showed small growths on the particle surface after exposure to regeneration conditions. Additional testing will be required to determine the cause of these growths.
07 ISOTOPE AND RADIATION SOURCES↗
(abstract) Development of Sorbent Bed Assembly for a Periodic 10K Solid Hydrogen Cryocooler
A closed-cycle 10K sorption cryocooler is being fabricated for microgravity testing during a future space shuttle mission. A critical component of this cryogenic refrigerator is the metal hydride sorbent bed assembly (SBA). The SBA uses hydrides which absorb hydrogen gas at low pressure, (i.e., about 0.25 MPa from liquid hydrogen at 25K and below 0.2 kPa from solid hydrogen near 10K) and subsequently delivers hydrogen at nearly 10 MPa to a storage reservoir to repeat the Joule-Thomson (J-T) expansion process. The SBA includes three independent hydride beds where two contain LaNi(sub 4.8)Sn(sub 0.2) alloy and the third ZrNi. Detailed descriptions will be given for the three beds, which have specialized design features to enhance performance at each step of operation. In particular, two beds must rapidly absorb hydrogen in order for the J-T cold stage to reach 10K within two minutes from a 65K holding temperature. Performance characterization results will be compared to model analyses of the SBA.
applications microgravity↗