Graphene oxide/metal nanocrystal multilaminates as the atomic limit for safe and selective hydrogen storage.

PubMed

Cho, Eun Seon; Ruminski, Anne M; Aloni, Shaul; Liu, Yi-Sheng; Guo, Jinghua; Urban, Jeffrey J

2016-02-23

Interest in hydrogen fuel is growing for automotive applications; however, safe, dense, solid-state hydrogen storage remains a formidable scientific challenge. Metal hydrides offer ample storage capacity and do not require cryogens or exceedingly high pressures for operation. However, hydrides have largely been abandoned because of oxidative instability and sluggish kinetics. We report a new, environmentally stable hydrogen storage material constructed of Mg nanocrystals encapsulated by atomically thin and gas-selective reduced graphene oxide (rGO) sheets. This material, protected from oxygen and moisture by the rGO layers, exhibits exceptionally dense hydrogen storage (6.5 wt% and 0.105 kg H2 per litre in the total composite). As rGO is atomically thin, this approach minimizes inactive mass in the composite, while also providing a kinetic enhancement to hydrogen sorption performance. These multilaminates of rGO-Mg are able to deliver exceptionally dense hydrogen storage and provide a material platform for harnessing the attributes of sensitive nanomaterials in demanding environments.

Sequential desorption energy of hydrogen from nickel clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Deepika,; Kumar, Rakesh, E-mail: rakesh@iitrpr.ac.in; R, Kamal Raj.

2015-06-24

We report reversible Hydrogen adsorption on Nickel clusters, which act as a catalyst for solid state storage of Hydrogen on a substrate. First-principles technique is employed to investigate the maximum number of chemically adsorbed Hydrogen molecules on Nickel cluster. We observe a maximum of four Hydrogen molecules adsorbed per Nickel atom, but the average Hydrogen molecules adsorbed per Nickel atom decrease with cluster size. The dissociative chemisorption energy per Hydrogen molecule and sequential desorption energy per Hydrogen atom on Nickel cluster is found to decrease with number of adsorbed Hydrogen molecules, which on optimization may help in economical storage andmore » regeneration of Hydrogen as a clean energy carrier.« less

Graphene oxide/metal nanocrystal multilaminates as the atomic limit for safe and selective hydrogen storage

DOE PAGES

Cho, Eun Seon; Ruminski, Anne M.; Aloni, Shaul; ...

2016-02-23

Interest in hydrogen fuel is growing for automotive applications; however, safe, dense, solid-state hydrogen storage remains a formidable scientific challenge. Metal hydrides offer ample storage capacity and do not require cryogens or exceedingly high pressures for operation. However, hydrides have largely been abandoned because of oxidative instability and sluggish kinetics. We report a new, environmentally stable hydrogen storage material constructed of Mg nanocrystals encapsulated by atomically thin and gas-selective reduced graphene oxide (rGO) sheets. This material, protected from oxygen and moisture by the rGO layers, exhibits exceptionally dense hydrogen storage (6.5 wt% and 0.105 kg H 2 per litre inmore » the total composite). As rGO is atomically thin, this approach minimizes inactive mass in the composite, while also providing a kinetic enhancement to hydrogen sorption performance. In conclusion, these multilaminates of rGO-Mg are able to deliver exceptionally dense hydrogen storage and provide a material platform for harnessing the attributes of sensitive nanomaterials in demanding environments.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cho, Eun Seon; Ruminski, Anne M.; Aloni, Shaul

Interest in hydrogen fuel is growing for automotive applications; however, safe, dense, solid-state hydrogen storage remains a formidable scientific challenge. Metal hydrides offer ample storage capacity and do not require cryogens or exceedingly high pressures for operation. However, hydrides have largely been abandoned because of oxidative instability and sluggish kinetics. We report a new, environmentally stable hydrogen storage material constructed of Mg nanocrystals encapsulated by atomically thin and gas-selective reduced graphene oxide (rGO) sheets. This material, protected from oxygen and moisture by the rGO layers, exhibits exceptionally dense hydrogen storage (6.5 wt% and 0.105 kg H 2 per litre inmore » the total composite). As rGO is atomically thin, this approach minimizes inactive mass in the composite, while also providing a kinetic enhancement to hydrogen sorption performance. In conclusion, these multilaminates of rGO-Mg are able to deliver exceptionally dense hydrogen storage and provide a material platform for harnessing the attributes of sensitive nanomaterials in demanding environments.« less

Synthesis of polyetherimide / halloysite nanotubes (PEI/HNTs) based nanocomposite membrane towards hydrogen storage

NASA Astrophysics Data System (ADS)

Muthu, R. Naresh; Rajashabala, S.; Kannan, R.

2018-04-01

Even though hydrogen is considered as green and clean energy sources of future, the blooming of hydrogen economy mainly relies on the development of safe and efficient hydrogen storage medium. The present work is aimed at the synthesis and characterization of polyetherimide/acid treated halloysite nanotubes (PEI/A-HNTs) nanocomposite membranes for solid state hydrogen storage medium, where phase inversion technique was adopted for the synthesis of nanocomposite membrane. The synthesized PEI/A-HNTs nanocomposite membranes were characterized by XRD, FTIR, SEM, EDX, CHNS elemental analysis and TGA. Hydrogenation studies were performed using a Sievert's-like hydrogenation setup. The important conclusions arrived from the present work are the PEI/A-HNTs nanocomposite membranes have better performance with a maximum hydrogen storage capacity of 3.6 wt% at 100 °C than pristine PEI. The adsorbed hydrogen possesses the average binding energy of 0.31 eV which lies in the recommended range of US- DOE 2020 targets. Hence it is expected that the PEI/A-HNTs nanocomposite membranes may have bright extent in the scenario of hydrogen fuel cell applications.

Hydrogen sorption characteristics of nanostructured Pd–10Rh processed by cryomilling

DOE PAGES

Yang, Nancy; Yee, Joshua K.; Zhang, Zhihui; ...

2014-10-03

Palladium and its alloys are model systems for studying solid-state storage of hydrogen. Mechanical milling is commonly used to process complex powder systems for solid-state hydrogen storage; however, milling can also be used to evolve nanostructured powder to modify hydrogen sorption characteristics. In the present study, cryomilling (mechanical attrition milling in a cryogenic liquid) is used to produce nanostructured palladium-rhodium alloy powder. Characterization of the cryomilled Pd-10Rh using electron microscopy, X-ray diffraction, and surface area analysis reveals that (i) particle morphology evolves from spherical to flattened disk-like particles; while the (ii) crystallite size decreases from several microns to less thanmore » 100 nm and (iii) dislocation density increases with increased cryomilling time. Hydrogen absorption and desorption isotherms as well as the time scales for absorption were measured for cryomilled Pd-10Rh, and correlated with observed microstructural changes induced by the cryomilling process. In short, as the microstructure of the Pd-10Rh alloy is refined by cryomilling: (i) the maximum hydrogen concentration in the α-phase increases, (ii) the pressure plateau becomes flatter, and (iii) the equilibrium hydrogen capacity at 760 Torr increases. In addition, the rate of hydrogen absorption was reduced by an order of magnitude compared to non-cryomilled (atomized) powder.« less

Combining computation and experiment to accelerate the discovery of new hydrogen storage materials

NASA Astrophysics Data System (ADS)

Siegel, Donald

2009-03-01

The potential of emerging technologies such as fuel cells (FCs) and photovoltaics for environmentally-benign power generation has sparked renewed interest in the development of novel materials for high density energy storage. For applications in the transportation sector, the demands placed upon energy storage media are especially stringent, as a potential replacement for fossil-fuel-powered internal combustion engines -- namely, the proton exchange membrane FC -- utilizes hydrogen as a fuel. Although hydrogen has about three times the energy density of gasoline by weight, its volumetric energy density (even at 700 bar) is roughly a factor of six smaller. Consequently, the safe and efficient storage of hydrogen has been identified as one of the key materials-based challenges to realizing a transition to FC vehicles. This talk will present an overview of recent efforts at Ford aimed at developing new materials for reversible, solid state hydrogen storage. A tight coupling between first-principles modeling and experiments has greatly accelerated our efforts, and several examples illustrating the benefits of this approach will be presented.

Solid-state structures and properties of scandium hydride; hydrogen storage and switchable mirrors application

NASA Astrophysics Data System (ADS)

Khodja, Khadidja; Bouhadda, Youcef; Seddik, Larbi; Benyelloul, Kamel

2016-05-01

First-principles calculation has been performed on the rare earth hydride ScH2 for hydrogen storage and switchable mirror applications, using the pseudo-potentials and plane waves based on the density-functional theory (DFT). The electronic and structural properties are studied within both local-density and generalized gradient approximations for exchange energy. The formation energy and the optical properties have been investigated and discussed. Our calculated results are generally in good agreement with theoretical and experimental data. Contribution to the topical issue "Materials for Energy Harvesting, Conversion and Storage (ICOME 2015) - Elected submissions", edited by Jean-Michel Nunzi, Rachid Bennacer and Mohammed El Ganaoui

Solid Aluminum Borohydrides for Prospective Hydrogen Storage.

PubMed

Dovgaliuk, Iurii; Safin, Damir A; Tumanov, Nikolay A; Morelle, Fabrice; Moulai, Adel; Černý, Radovan; Łodziana, Zbigniew; Devillers, Michel; Filinchuk, Yaroslav

2017-12-08

Metal borohydrides are intensively researched as high-capacity hydrogen storage materials. Aluminum is a cheap, light, and abundant element and Al 3+ can serve as a template for reversible dehydrogenation. However, Al(BH 4 ) 3 , containing 16.9 wt % of hydrogen, has a low boiling point, is explosive on air and has poor storage stability. A new family of mixed-cation borohydrides M[Al(BH 4 ) 4 ], which are all solid under ambient conditions, show diverse thermal decomposition behaviors: Al(BH 4 ) 3 is released for M=Li + or Na + , whereas heavier derivatives evolve hydrogen and diborane. NH 4 [Al(BH 4 ) 4 ], containing both protic and hydridic hydrogen, has the lowest decomposition temperature of 35 °C and yields Al(BH 4 ) 3 ⋅NHBH and hydrogen. The decomposition temperatures, correlated with the cations' ionic potential, show that M[Al(BH 4 ) 4 ] species are in the most practical stability window. This family of solids, with convenient and versatile properties, puts aluminum borohydride chemistry in the mainstream of hydrogen storage research, for example, for the development of reactive hydride composites with increased hydrogen content. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-assembled air-stable magnesium hydride embedded in 3-D activated carbon for reversible hydrogen storage.

PubMed

Shinde, S S; Kim, Dong-Hyung; Yu, Jin-Young; Lee, Jung-Ho

2017-06-01

The rational design of stable, inexpensive catalysts with excellent hydrogen dynamics and sorption characteristics under realistic environments for reversible hydrogen storage remains a great challenge. Here, we present a simple and scalable strategy to fabricate a monodispersed, air-stable, magnesium hydride embedded in three-dimensional activated carbon with periodic synchronization of transition metals (MHCH). The high surface area, homogeneous distribution of MgH 2 nanoparticles, excellent thermal stability, high energy density, steric confinement by carbon, and robust architecture of the catalyst resulted in a noticeable enhancement of the hydrogen storage performance. The resulting MHCH-5 exhibited outstanding hydrogen storage performance, better than that of most reported Mg-based hydrides, with a high storage density of 6.63 wt% H 2 , a rapid kinetics loading in <5 min at 180 °C, superior reversibility, and excellent long-term cycling stability over ∼435 h. The significant reduction of the enthalpy and activation energy observed in the MHCH-5 demonstrated enhancement of the kinetics of de-/hydrogenation compared to that of commercial MgH 2 . The origin of the intrinsic hydrogen thermodynamics was elucidated via solid state 1 H NMR. This work presents a readily scaled-up strategy towards the design of realistic catalysts with superior functionality and stability for applications in reversible hydrogen storage, lithium ion batteries, and fuel cells.

Multiply Surface-Functionalized Nanoporous Carbon for Vehicular Hydrogen Storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pfeifer, Peter; Gillespie, Andrew; Stalla, David

The purpose of the project “Multiply Surface-Functionalized Nanoporous Carbon for Vehicular Hydrogen Storage” is the development of materials that store hydrogen (H 2) by adsorption in quantities and at conditions that outperform current compressed-gas H 2 storage systems for electric power generation from hydrogen fuel cells (HFCs). Prominent areas of interest for HFCs are light-duty vehicles (“hydrogen cars”) and replacement of batteries with HFC systems in a wide spectrum of applications, ranging from forklifts to unmanned areal vehicles to portable power sources. State-of-the-art compressed H 2 tanks operate at pressures between 350 and 700 bar at ambient temperature and storemore » 3-4 percent of H 2 by weight (wt%) and less than 25 grams of H 2 per liter (g/L) of tank volume. Thus, the purpose of the project is to engineer adsorbents that achieve storage capacities better than compressed H 2 at pressures less than 350 bar. Adsorption holds H 2 molecules as a high-density film on the surface of a solid at low pressure, by virtue of attractive surface-gas interactions. At a given pressure, the density of the adsorbed film is the higher the stronger the binding of the molecules to the surface is (high binding energies). Thus, critical for high storage capacities are high surface areas, high binding energies, and low void fractions (high void fractions, such as in interstitial space between adsorbent particles, “waste” storage volume by holding hydrogen as non-adsorbed gas). Coexistence of high surface area and low void fraction makes the ideal adsorbent a nanoporous monolith, with pores wide enough to hold high-density hydrogen films, narrow enough to minimize storage as non-adsorbed gas, and thin walls between pores to minimize the volume occupied by solid instead of hydrogen. A monolith can be machined to fit into a rectangular tank (low pressure, conformable tank), cylindrical tank (high pressure), or other tank shape without any waste of volume.« less

Mesoscale Modeling of Kinetic Phase Behaviors in Mg-B-H (Subcontract Report)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, H.; Thornton, K.; Wood, B. C.

Storage of hydrogen on board vehicles is one of the critical enabling technologies for creating hydrogenfueled transportation systems that can reduce oil dependency and mitigate the long-term effects of fossil fuels on climate change. Stakeholders in developing hydrogen infrastructure are currently focused on highpressure storage at 350 bar and 700 bar, in part because no viable solid-phase storage material has emerged. Nevertheless, solid-state materials, including high-density hydrides, remain of interest because of their unique potential to meet all DOE targets and deliver hydrogen at lower pressures and higher on-board densities. A successful solution would significantly reduce costs and ensure themore » economic viability of a U.S. hydrogen infrastructure. The Mg(BH 4) 2-MgB 2 system represents a highly promising solution because of its reasonable reaction enthalpy, high intrinsic capacity, and demonstrated reversibility, yet suffers from poor reaction kinetics. This subcontract aims to deliver a phase-field model for the kinetics of the evolution of the relevant phases within the Mg-B-H system during hydrogenation and dehydrogenation. This model will be used within a broader theory, synthesis, and characterization framework to study the properties of geometry-selected nanoparticles of pristine and doped MgB 2/Mg(BH 4) 2 with two aims: (1) understand the intrinsic limitations in (de)hydrogenation; (2) devise strategies for improving thermodynamics and kinetics through nanostructuring.« less

Blending materials composed of boron, nitrogen and carbon to transform approaches to liquid hydrogen stores

DOE Office of Scientific and Technical Information (OSTI.GOV)

Whittemore, Sean M.; Bowden, Mark; Karkamkar, Abhijeet

2015-12-02

Energy storage remains a key challenge for the advancement of fuel cell applications. Because of this, hydrogen has garnered much research attention for its potential as an energy carrier. This can be attributed to its abundance from non-petroleum sources, and its energy conversion efficiency. Our group, among others, has been studying the use of ammonia borane as a chemical hydrogen storage material for the past several years. Ammonia borane (AB, NH3BH3), a solid state complex composed of the light weight main group elements of nitrogen and boron, is isoelectronic with ethane and as such is an attractive hydrogen storage materialmore » with a high gravimetric capacity of H2 (19.6 wt%). However, the widespread use of AB as a chemical hydrogen storage material has been stalled by some undesirable properties and reactivity. Most notably, AB is a solid and this presents compatibility issues with the existing liquid fuel infrastructure. The thermal release of H2 from AB also results in the formation of volatile impurities (borazine and ammonia) that are detrimental to operation of the fuel cell. Additionally, the major products in the spent fuel are polyborazylene and amine borane oligomers that present challenges in regenerating AB. This research was funded by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy. The Pacific Northwest National Laboratory is operated by Battelle for DOE.« less

The reactivity of sodium alanates with O[2], H[2]O, and CO[2] : an investigation of complex metal hydride contamination in the context of automotive systems.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dedrick, Daniel E.; Bradshaw, Robert W.; Behrens, Richard, Jr.

2007-08-01

Safe and efficient hydrogen storage is a significant challenge inhibiting the use of hydrogen as a primary energy carrier. Although energy storage performance properties are critical to the success of solid-state hydrogen storage systems, operator and user safety is of highest importance when designing and implementing consumer products. As researchers are now integrating high energy density solid materials into hydrogen storage systems, quantification of the hazards associated with the operation and handling of these materials becomes imperative. The experimental effort presented in this paper focuses on identifying the hazards associated with producing, storing, and handling sodium alanates, and thus allowingmore » for the development and implementation of hazard mitigation procedures. The chemical changes of sodium alanates associated with exposure to oxygen and water vapor have been characterized by thermal decomposition analysis using simultaneous thermogravimetric modulated beam mass spectrometry (STMBMS) and X-ray diffraction methods. Partial oxidation of sodium alanates, an alkali metal complex hydride, results in destabilization of the remaining hydrogen-containing material. At temperatures below 70 C, reaction of sodium alanate with water generates potentially combustible mixtures of H{sub 2} and O{sub 2}. In addition to identifying the reaction hazards associated with the oxidation of alkali-metal containing complex hydrides, potential treatment methods are identified that chemically stabilize the oxidized material and reduce the hazard associated with handling the contaminated metal hydrides.« less

Nanomaterials for renewable energy production and storage.

PubMed

Chen, Xiaobo; Li, Can; Grätzel, Michaël; Kostecki, Robert; Mao, Samuel S

2012-12-07

Over the past decades, there have been many projections on the future depletion of the fossil fuel reserves on earth as well as the rapid increase in green-house gas emissions. There is clearly an urgent need for the development of renewable energy technologies. On a different frontier, growth and manipulation of materials on the nanometer scale have progressed at a fast pace. Selected recent and significant advances in the development of nanomaterials for renewable energy applications are reviewed here, and special emphases are given to the studies of solar-driven photocatalytic hydrogen production, electricity generation with dye-sensitized solar cells, solid-state hydrogen storage, and electric energy storage with lithium ion rechargeable batteries.

System for operating solid oxide fuel cell generator on diesel fuel

NASA Technical Reports Server (NTRS)

Singh, Prabhu (Inventor); George, Raymond A. (Inventor)

1997-01-01

A system is provided for operating a solid oxide fuel cell generator on diesel fuel. The system includes a hydrodesulfurizer which reduces the sulfur content of commercial and military grade diesel fuel to an acceptable level. Hydrogen which has been previously separated from the process stream is mixed with diesel fuel at low pressure. The diesel/hydrogen mixture is then pressurized and introduced into the hydrodesulfurizer. The hydrodesulfurizer comprises a metal oxide such as ZnO which reacts with hydrogen sulfide in the presence of a metal catalyst to form a metal sulfide and water. After desulfurization, the diesel fuel is reformed and delivered to a hydrogen separator which removes most of the hydrogen from the reformed fuel prior to introduction into a solid oxide fuel cell generator. The separated hydrogen is then selectively delivered to the diesel/hydrogen mixer or to a hydrogen storage unit. The hydrogen storage unit preferably comprises a metal hydride which stores hydrogen in solid form at low pressure. Hydrogen may be discharged from the metal hydride to the diesel/hydrogen mixture at low pressure upon demand, particularly during start-up and shut-down of the system.

Composition design for Laves phase-related body-centered cubic-V solid solution alloys with large hydrogen storage capacities.

PubMed

Wang, H B; Wang, Q; Dong, C; Yuan, L; Xu, F; Sun, L X

2008-03-19

This paper analyzes the characteristics of alloy compositions with large hydrogen storage capacities in Laves phase-related body-centered cubic (bcc) solid solution alloy systems using the cluster line approach. Since a dense-packed icosahedral cluster A(6)B(7) characterizes the local structure of AB(2) Laves phases, in an A-B-C ternary system, such as Ti-Cr (Mn, Fe)-V, where A-B forms AB(2) Laves phases while A-C and B-C tend to form solid solutions, a cluster line A(6)B(7)-C is constructed by linking A(6)B(7) to C. The alloy compositions with large hydrogen storage capacities are generally located near this line and are approximately expressed with the cluster-plus-glue-atom model. The cluster line alloys (Ti(6)Cr(7))(100-x)V(x) (x = 2.5-70 at.%) exhibit different structures and hence different hydrogen storage capacities with increasing V content. The alloys (Ti(6)Cr(7))(95)V(5) and Ti(30)Cr(40)V(30) with bcc solid solution structure satisfy the cluster-plus-glue-atom model.

Feasibility analysis of a hydrogen backup power system for Russian telecom market

NASA Astrophysics Data System (ADS)

Borzenko, V. I.; Dunikov, D. O.

2017-11-01

We performed feasibility analysis of 10 kW hydrogen backup power system (H2BS) consisting of a water electrolyzer, a metal hydride hydrogen storage and a fuel cell. Capital investments in H2BS are mostly determined by the costs of the PEM electrolyzer, the fuel cell and solid state hydrogen storage materials, for single unit or small series manufacture the cost of AB5-type intermetallic compound can reach 50% of total system cost. Today the capital investments in H2BS are 3 times higher than in conventional lead-acid system of the same capacity. Wide distribution of fuel cell hydrogen vehicles, development of hydrogen infrastructure, and mass production of hydrogen power systems will for sure lower capital investments in fuel cell backup power. Operational expenditures for H2BS is only 15% from the expenditures for lead acid systems, and after 4-5 years of exploitation the total cost of ownership will become lower than for batteries.

Direct Evidence for Solid-like Hydrogen in a Nanoporous Carbon Hydrogen Storage Material at Supercritical Temperatures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ting, Valeska P.; Ramirez-Cuesta, Anibal J.; Bimbo, Nuno

Here in this paper we report direct physical evidence that confinement of molecular hydrogen (H 2) in an optimized nanoporous carbon results in accumulation of hydrogen with characteristics commensurate with solid H 2 at temperatures up to 67 K above the liquid vapor critical temperature of bulk H 2. This extreme densification is attributed to confinement of 112 molecules in the optimally sized micropores, and occurs at pressures as low as 0.02 MPa. The quantities of contained, solid-like H 2 increased with pressure and were directly evaluated using in situ inelastic neutron scattering and confirmed by analysis of gas sorptionmore » isotherms. The demonstration of the existence of solid-like H 2 challenges the existing assumption that supercritical hydrogen confined in nanopores has an upper limit of liquid H 2 density. Thus, this insight offers opportunities for the development of more accurate models for the evaluation and design of nanoporous materials for high capacity adsorptive hydrogen storage.« less

Direct Evidence for Solid-like Hydrogen in a Nanoporous Carbon Hydrogen Storage Material at Supercritical Temperatures

DOE PAGES

Ting, Valeska P.; Ramirez-Cuesta, Anibal J.; Bimbo, Nuno; ...

2015-07-14

Here in this paper we report direct physical evidence that confinement of molecular hydrogen (H 2) in an optimized nanoporous carbon results in accumulation of hydrogen with characteristics commensurate with solid H 2 at temperatures up to 67 K above the liquid vapor critical temperature of bulk H 2. This extreme densification is attributed to confinement of 112 molecules in the optimally sized micropores, and occurs at pressures as low as 0.02 MPa. The quantities of contained, solid-like H 2 increased with pressure and were directly evaluated using in situ inelastic neutron scattering and confirmed by analysis of gas sorptionmore » isotherms. The demonstration of the existence of solid-like H 2 challenges the existing assumption that supercritical hydrogen confined in nanopores has an upper limit of liquid H 2 density. Thus, this insight offers opportunities for the development of more accurate models for the evaluation and design of nanoporous materials for high capacity adsorptive hydrogen storage.« less

Chemical bonding analysis on amphoteric hydrogen - alkaline earth ammine borohydrides

NASA Astrophysics Data System (ADS)

Kiruthika, S.; Ravindran, P.

2018-04-01

Usually the ions in solid are in the positive oxidation states or in the negative oxidation state depending upon the chemical environment. It is highly unusual for an ion having both positive as well as negative oxidation state in a particular compound. Structural analysis suggest that the alkaline earth ammine borohydrides (AABH) with the chemical formula M (BH4)2(NH3)2 (M = Mg, Ca, or Sr) where hydrogen is present in +1 and -1 oxidation states. In order to understand the oxidation states of hydrogen and also the character of chemical bond present in AABH we have made charge density, electron localization function, Born effective charge, Bader effective charge, and density of states analyses using result from the density functional calculations. Our detailed analyses show that hydrogen is in amphoteric behavior with hydrogen closer to boron is in negative oxidation state and that closer to nitrogen is in the positive oxidation state. Due to the presence of finite covalent bonding between the consitutents in AABH the oxidation state of hydrogen is non-interger value. The confirmation of the presence of amphtoric behavior of hydrogen in AABH has implication in hydrogen storage applications.

Combined on-board hydride slurry storage and reactor system and process for hydrogen-powered vehicles and devices

DOEpatents

Brooks, Kriston P; Holladay, Jamelyn D; Simmons, Kevin L; Herling, Darrell R

2014-11-18

An on-board hydride storage system and process are described. The system includes a slurry storage system that includes a slurry reactor and a variable concentration slurry. In one preferred configuration, the storage system stores a slurry containing a hydride storage material in a carrier fluid at a first concentration of hydride solids. The slurry reactor receives the slurry containing a second concentration of the hydride storage material and releases hydrogen as a fuel to hydrogen-power devices and vehicles.

High temperature solid oxide regenerative fuel cell for solar photovoltaic energy storage

NASA Technical Reports Server (NTRS)

Bents, David J.

1987-01-01

A hydrogen-oxygen regenerative fuel cell energy storage system based on high temperature solid oxide fuel cell technology is discussed which has application to darkside energy storage for solar photovoltaics. The forward and reverse operating cycles are described, and heat flow, mass, and energy balance data are presented to characterize the system's performance and the variation of performance with changing reactant storage pressure. The present system weighs less than nickel hydrogen battery systems after 0.7 darkside operation, and it maintains a specific weight advantage over radioisotope generators for discharge periods up to 72 hours.

High temperature solid oxide regenerative fuel cell for solar photovoltaic energy storage

NASA Astrophysics Data System (ADS)

Bents, David J.

A hydrogen-oxygen regenerative fuel cell energy storage system based on high temperature solid oxide fuel cell technology is discussed which has application to darkside energy storage for solar photovoltaics. The forward and reverse operating cycles are described, and heat flow, mass, and energy balance data are presented to characterize the system's performance and the variation of performance with changing reactant storage pressure. The present system weighs less than nickel hydrogen battery systems after 0.7 darkside operation, and it maintains a specific weight advantage over radioisotope generators for discharge periods up to 72 hours.

Hydrogen generation from deliquescence of ammonia borane using Ni-Co/r-GO catalyst

NASA Astrophysics Data System (ADS)

Chou, Chang-Chen; Chen, Bing-Hung

2015-10-01

Hydrogen generation from the catalyzed deliquescence/hydrolysis of ammonia borane (AB) using the Ni-Co catalyst supported on the graphene oxide (Ni-Co/r-GO catalyst) under the conditions of limited water supply was studied with the molar feed ratio of water to ammonia borane (denoted as H2O/AB) at 2.02, 3.97 and 5.93, respectively. The conversion efficiency of ammonia borane to hydrogen was estimated both from the cumulative volume of the hydrogen gas generated and the conversion of boron chemistry in the hydrolysates analyzed by the solid-state 11B NMR. The conversion efficiency of ammonia borane could reach nearly 100% under excess water dosage, that is, H2O/AB = 3.97 and 5.93. Notably, the hydrogen storage capacity could reach as high as 6.5 wt.% in the case with H2O/AB = 2.02. The hydrolysates of ammonia borane in the presence of Ni-Co/r-GO catalyst were mainly the mixture of boric acid and metaborate according to XRD, FT-IR and solid-state 11B NMR analyses.

Japan's Sunshine Project

NASA Astrophysics Data System (ADS)

1992-07-01

A summary report is given on the results of hydrogen energy research and development achieved during 1991 under the Sunshine Project. In hydrogen manufacturing, regenerative cells that can also generate power as fuel cells were discussed by using solid macromolecular electrolytic films for the case where no electrolysis is carried out with water electrolysis. Yttria stabilized zirconia (YSZ), an oxide solid electrolyte was used for the basic research on high-temperature steam electrolysis. Compositions of hydrogen storage alloys and their deterioration mechanisms were investigated to develop hydrogen transportation and storage technologies. High-density hydrides were searched, and fluidization due to paraffin was discussed. Electrode materials and forming technologies were discussed to develop a hydrogen to power conversion system using hydrogen storage alloys as reversible electrodes. Hydrogen-oxygen combustion was studied in terms of reactive theories, and so was the control of ignition and combustion using ultraviolet ray ignition plasma. Studies were made on hydrogen brittlement in welds on materials in hydrogen utilization and its preventive measures. Surveys were given on technical movements and development problems in high-efficiency, pollution-free hydrogen combustion turbines.

Materials Engineering and Scale Up of Fluid Phase Chemical Hydrogen Storage for Automotive Applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Westman, Matthew P.; Chun, Jaehun; Choi, Young Joon

Among candidates for chemical hydrogen storage in PEM fuel cell automotive applications, ammonia borane (AB, NH3BH3) is considered to be one of the most promising materials due to its high hydrogen content of 14-16 wt% below 200°C and high volumetric density. In our previous paper, we selected AB in silicone oil as a role model for a slurry hydrogen storage system. Materials engineering properties were optimized by increasing solid loading by using an ultra-sonic process. In this paper, we proceeded to scale up to liter size batches with solid loadings up to 50 wt% (8 wt% H2) with dynamic viscositiesmore » less than 1000cP at 25°C. The use of a non-ionic surfactant, Triton X-15, shows significant promise in controlling the level of foaming produced during the thermal dehydrogenation of the AB. Through the development of new and efficient processing techniques and the ability to adequately control the foaming, stable homogenous slurries of high solid loading have been demonstrated as a viable hydrogen delivery source.« less

Chemical hydrogen storage material property guidelines for automotive applications

NASA Astrophysics Data System (ADS)

Semelsberger, Troy A.; Brooks, Kriston P.

2015-04-01

Chemical hydrogen storage is the sought after hydrogen storage media for automotive applications because of the expected low pressure operation (<20 atm), moderate temperature operation (<200 °C), system gravimetric capacities (>0.05 kg H2/kgsystem), and system volumetric capacities (>0.05 kg H2/Lsystem). Currently, the primary shortcomings of chemical hydrogen storage are regeneration efficiency, fuel cost and fuel phase (i.e., solid or slurry phase). Understanding the required material properties to meet the DOE Technical Targets for Onboard Hydrogen Storage Systems is a critical knowledge gap in the hydrogen storage research community. This study presents a set of fluid-phase chemical hydrogen storage material property guidelines for automotive applications meeting the 2017 DOE technical targets. Viable material properties were determined using a boiler-plate automotive system design. The fluid-phase chemical hydrogen storage media considered in this study were neat liquids, solutions, and non-settling homogeneous slurries. Material properties examined include kinetics, heats of reaction, fuel-cell impurities, gravimetric and volumetric hydrogen storage capacities, and regeneration efficiency. The material properties, although not exhaustive, are an essential first step in identifying viable chemical hydrogen storage material properties-and most important, their implications on system mass, system volume and system performance.

Hydrogen generation systems utilizing sodium silicide and sodium silica gel materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wallace, Andrew P.; Melack, John M.; Lefenfeld, Michael

Systems, devices, and methods combine reactant materials and aqueous solutions to generate hydrogen. The reactant materials can sodium silicide or sodium silica gel. The hydrogen generation devices are used in fuels cells and other industrial applications. One system combines cooling, pumping, water storage, and other devices to sense and control reactions between reactant materials and aqueous solutions to generate hydrogen. Multiple inlets of varied placement geometries deliver aqueous solution to the reaction. The reactant materials and aqueous solution are churned to control the state of the reaction. The aqueous solution can be recycled and returned to the reaction. One systemmore » operates over a range of temperatures and pressures and includes a hydrogen separator, a heat removal mechanism, and state of reaction control devices. The systems, devices, and methods of generating hydrogen provide thermally stable solids, near-instant reaction with the aqueous solutions, and a non-toxic liquid by-product.« less

Hydrogen generation systems utilizing sodium silicide and sodium silica gel materials

DOEpatents

Wallace, Andrew P.; Melack, John M.; Lefenfeld, Michael

2015-07-14

Systems, devices, and methods combine reactant materials and aqueous solutions to generate hydrogen. The reactant materials can sodium silicide or sodium silica gel. The hydrogen generation devices are used in fuels cells and other industrial applications. One system combines cooling, pumping, water storage, and other devices to sense and control reactions between reactant materials and aqueous solutions to generate hydrogen. Multiple inlets of varied placement geometries deliver aqueous solution to the reaction. The reactant materials and aqueous solution are churned to control the state of the reaction. The aqueous solution can be recycled and returned to the reaction. One system operates over a range of temperatures and pressures and includes a hydrogen separator, a heat removal mechanism, and state of reaction control devices. The systems, devices, and methods of generating hydrogen provide thermally stable solids, near-instant reaction with the aqueous solutions, and a non-toxic liquid by-product.

High H⁻ ionic conductivity in barium hydride.

PubMed

Verbraeken, Maarten C; Cheung, Chaksum; Suard, Emmanuelle; Irvine, John T S

2015-01-01

With hydrogen being seen as a key renewable energy vector, the search for materials exhibiting fast hydrogen transport becomes ever more important. Not only do hydrogen storage materials require high mobility of hydrogen in the solid state, but the efficiency of electrochemical devices is also largely determined by fast ionic transport. Although the heavy alkaline-earth hydrides are of limited interest for their hydrogen storage potential, owing to low gravimetric densities, their ionic nature may prove useful in new electrochemical applications, especially as an ionically conducting electrolyte material. Here we show that barium hydride shows fast pure ionic transport of hydride ions (H(-)) in the high-temperature, high-symmetry phase. Although some conductivity studies have been reported on related materials previously, the nature of the charge carriers has not been determined. BaH2 gives rise to hydride ion conductivity of 0.2 S cm(-1) at 630 °C. This is an order of magnitude larger than that of state-of-the-art proton-conducting perovskites or oxide ion conductors at this temperature. These results suggest that the alkaline-earth hydrides form an important new family of materials, with potential use in a number of applications, such as separation membranes, electrochemical reactors and so on.

Hydrogen storage systems based on magnesium hydride: from laboratory tests to fuel cell integration

NASA Astrophysics Data System (ADS)

de Rango, P.; Marty, P.; Fruchart, D.

2016-02-01

The paper reviews the state of the art of hydrogen storage systems based on magnesium hydride, emphasizing the role of thermal management, whose effectiveness depends on the effective thermal conductivity of the hydride, but also depends of other limiting factors such as wall contact resistance and convective exchanges with the heat transfer fluid. For daily cycles, the use of phase change material to store the heat of reaction appears to be the most effective solution. The integration with fuel cells (1 kWe proton exchange membrane fuel cell and solid oxide fuel cell) highlights the dynamic behaviour of these systems, which is related to the thermodynamic properties of MgH2. This allows for "self-adaptive" systems that do not require control of the hydrogen flow rate at the inlet of the fuel cell.

Large Scale Production of Densified Hydrogen Using Integrated Refrigeration and Storage

NASA Technical Reports Server (NTRS)

Notardonato, William U.; Swanger, Adam Michael; Jumper, Kevin M.; Fesmire, James E.; Tomsik, Thomas M.; Johnson, Wesley L.

2017-01-01

Recent demonstration of advanced liquid hydrogen storage techniques using Integrated Refrigeration and Storage (IRAS) technology at NASA Kennedy Space Center led to the production of large quantities of solid densified liquid and slush hydrogen in a 125,000 L tank. Production of densified hydrogen was performed at three different liquid levels and LH2 temperatures were measured by twenty silicon diode temperature sensors. System energy balances and solid mass fractions are calculated. Experimental data reveal hydrogen temperatures dropped well below the triple point during testing (up to 1 K), and were continuing to trend downward prior to system shutdown. Sub-triple point temperatures were seen to evolve in a time dependent manner along the length of the horizontal, cylindrical vessel. Twenty silicon diode temperature sensors were recorded over approximately one month for testing at two different fill levels (33 67). The phenomenon, observed at both two fill levels, is described and presented detailed and explained herein., and The implications of using IRAS for energy storage, propellant densification, and future cryofuel systems are discussed.

Porous polymeric materials for hydrogen storage

DOEpatents

Yu, Luping [Hoffman Estates, IL; Liu, Di-Jia [Naperville, IL; Yuan, Shengwen [Chicago, IL; Yang, Junbing [Westmont, IL

2011-12-13

Porous polymers, tribenzohexazatriphenylene, poly-9,9'-spirobifluorene, poly-tetraphenyl methane and their derivatives for storage of H.sub.2 prepared through a chemical synthesis method. The porous polymers have high specific surface area and narrow pore size distribution. Hydrogen uptake measurements conducted for these polymers determined a higher hydrogen storage capacity at the ambient temperature over that of the benchmark materials. The method of preparing such polymers, includes oxidatively activating solids by CO.sub.2/steam oxidation and supercritical water treatment.

Porous polymeric materials for hydrogen storage

DOEpatents

Yu, Luping; Liu, Di-Jia; Yuan, Shengwen; Yang, Junbing

2013-04-02

A porous polymer, poly-9,9'-spirobifluorene and its derivatives for storage of H.sub.2 are prepared through a chemical synthesis method. The porous polymers have high specific surface area and narrow pore size distribution. Hydrogen uptake measurements conducted for these polymers determined a higher hydrogen storage capacity at the ambient temperature over that of the benchmark materials. The method of preparing such polymers, includes oxidatively activating solids by CO.sub.2/steam oxidation and supercritical water treatment.

Enhanced Hydrogen Storage Properties and Reversibility of LiBH4 Confined in Two-Dimensional Ti3C2.

PubMed

Zang, Lei; Sun, Weiyi; Liu, Song; Huang, Yike; Yuan, Huatang; Tao, Zhanliang; Wang, Yijing

2018-05-30

LiBH 4 is of particular interest as one of the most promising materials for solid-state hydrogen storage. Herein, LiBH 4 is confined into a novel two-dimensional layered Ti 3 C 2 MXene through a facile impregnation method for the first time to improve its hydrogen storage performance. The initial desorption temperature of LiBH 4 is significantly reduced, and the de-/rehydrogenation kinetics are remarkably enhanced. It is found that the initial desorption temperature of LiBH 4 @2Ti 3 C 2 hybrid decreases to 172.6 °C and releases 9.6 wt % hydrogen at 380 °C within 1 h, whereas pristine LiBH 4 only releases 3.2 wt % hydrogen under identical conditions. More importantly, the dehydrogenated products can partially rehydrogenate at 300 °C and under 95 bar H 2 . The nanoconfined effect caused by unique layered structure of Ti 3 C 2 can hinder the particles growth and agglomeration of LiBH 4 . Meanwhile, Ti 3 C 2 could possess superior effect to destabilize LiBH 4 . The synergetic effect of destabilization and nanoconfinement contributes to the remarkably lowered desorption temperature and improved de-/rehydrogenation kinetics.

Chemical hydrogen storage material property guidelines for automotive applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Semelsberger, Troy; Brooks, Kriston P.

2015-04-01

Chemical hydrogen storage is the sought after hydrogen storage media for automotive applications because of the expected low pressure operation (<20 atm), moderate temperature operation (<200 C), system gravimetric capacities (>0.05 kg H2/kg system), and system volumetric capacities (>0.05 kg H2/L system). Currently, the primary shortcomings of chemical hydrogen storage are regeneration efficiency, fuel cost and fuel phase (i.e., solid or slurry phase). Understanding the required material properties to meet the DOE Technical Targets for Onboard Hydrogen Storage Systems is a critical knowledge gap in the hydrogen storage research community. This study presents a set of fluid-phase chemical hydrogen storagemore » material property guidelines for automotive applications meeting the 2017 DOE technical targets. Viable material properties were determined using a boiler-plate automotive system design. The fluid phase chemical hydrogen storage media considered in this study were neat liquids, solutions, and non-settling homogeneous slurries. Material properties examined include kinetics, heats of reaction, fuel-cell impurities, gravimetric and volumetric hydrogen storage capacities, and regeneration efficiency. The material properties, although not exhaustive, are an essential first step in identifying viable chemical hydrogen storage material propertiesdand most important, their implications on system mass, system volume and system performance.« less

Architecture and method for a burst buffer using flash technology

DOEpatents

Tzelnic, Percy; Faibish, Sorin; Gupta, Uday K.; Bent, John; Grider, Gary Alan; Chen, Hsing-bung

2016-03-15

A parallel supercomputing cluster includes compute nodes interconnected in a mesh of data links for executing an MPI job, and solid-state storage nodes each linked to a respective group of the compute nodes for receiving checkpoint data from the respective compute nodes, and magnetic disk storage linked to each of the solid-state storage nodes for asynchronous migration of the checkpoint data from the solid-state storage nodes to the magnetic disk storage. Each solid-state storage node presents a file system interface to the MPI job, and multiple MPI processes of the MPI job write the checkpoint data to a shared file in the solid-state storage in a strided fashion, and the solid-state storage node asynchronously migrates the checkpoint data from the shared file in the solid-state storage to the magnetic disk storage and writes the checkpoint data to the magnetic disk storage in a sequential fashion.

Temperature- and composition-dependent hydrogen diffusivity in palladium from statistically-averaged molecular dynamics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Xiaowang; Heo, Tae Wook; Wood, Brandon C.

Solid-state hydrogen storage materials undergo complex phase transformations whose kinetics is often limited by hydrogen diffusion. Among metal hydrides, palladium hydride undergoes a diffusional phase transformation upon hydrogen uptake, during which the hydrogen diffusivity varies with hydrogen composition and temperature. Here we perform robust statistically-averaged molecular dynamics simulations to obtain a well-converged analytical expression for hydrogen diffusivity in bulk palladium that is valid throughout all stages of the reaction. Our studies confirm significant dependence of the diffusivity on composition and temperature that elucidate key trends in the available experimental measurements. Whereas at low hydrogen compositions, a single process dominates, atmore » high hydrogen compositions, diffusion is found to exhibit behavior consistent with multiple hopping barriers. Further analysis, supported by nudged elastic band computations, suggests that the multi-barrier diffusion can be interpreted as two distinct mechanisms corresponding to hydrogen-rich and hydrogen-poor local environments.« less

Temperature- and composition-dependent hydrogen diffusivity in palladium from statistically-averaged molecular dynamics

DOE PAGES

Zhou, Xiaowang; Heo, Tae Wook; Wood, Brandon C.; ...

2018-03-09

Solid-state hydrogen storage materials undergo complex phase transformations whose kinetics is often limited by hydrogen diffusion. Among metal hydrides, palladium hydride undergoes a diffusional phase transformation upon hydrogen uptake, during which the hydrogen diffusivity varies with hydrogen composition and temperature. Here we perform robust statistically-averaged molecular dynamics simulations to obtain a well-converged analytical expression for hydrogen diffusivity in bulk palladium that is valid throughout all stages of the reaction. Our studies confirm significant dependence of the diffusivity on composition and temperature that elucidate key trends in the available experimental measurements. Whereas at low hydrogen compositions, a single process dominates, atmore » high hydrogen compositions, diffusion is found to exhibit behavior consistent with multiple hopping barriers. Further analysis, supported by nudged elastic band computations, suggests that the multi-barrier diffusion can be interpreted as two distinct mechanisms corresponding to hydrogen-rich and hydrogen-poor local environments.« less

Predicting protein aggregation during storage in lyophilized solids using solid state amide hydrogen/deuterium exchange with mass spectrometric analysis (ssHDX-MS).

PubMed

Moorthy, Balakrishnan S; Schultz, Steven G; Kim, Sherry G; Topp, Elizabeth M

2014-06-02

Solid state amide hydrogen/deuterium exchange with mass spectrometric analysis (ssHDX-MS) was used to assess the conformation of myoglobin (Mb) in lyophilized formulations, and the results correlated with the extent of aggregation during storage. Mb was colyophilized with sucrose (1:1 or 1:8 w/w), mannitol (1:1 w/w), or NaCl (1:1 w/w) or in the absence of excipients. Immediately after lyophilization, samples of each formulation were analyzed by ssHDX-MS and Fourier transform infrared spectroscopy (FTIR) to assess Mb conformation, and by dynamic light scattering (DLS) and size exclusion chromatography (SEC) to determine the extent of aggregation. The remaining samples were then placed on stability at 25 °C and 60% RH or 40 °C and 75% RH for up to 1 year, withdrawn at intervals, and analyzed for aggregate content by SEC and DLS. In ssHDX-MS of samples immediately after lyophilization (t = 0), Mb was less deuterated in solids containing sucrose (1:1 and 1:8 w/w) than in those containing mannitol (1:1 w/w), NaCl (1:1 w/w), or Mb alone. Deuterium uptake kinetics and peptide mass envelopes also indicated greater Mb structural perturbation in mannitol, NaCl, or Mb-alone samples at t = 0. The extent of deuterium incorporation and kinetic parameters related to rapidly and slowly exchanging amide pools (Nfast, Nslow), measured at t = 0, were highly correlated with the extent of aggregation on storage as measured by SEC. In contrast, the extent of aggregation was weakly correlated with FTIR band intensity and peak position measured at t = 0. The results support the use of ssHDX-MS as a formulation screening tool in developing lyophilized protein drug products.

Advancement of Systems Designs and Key Engineering Technologies for Materials Based Hydrogen Storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

van Hassel, Bart A.

UTRC lead the development of the Simulink Framework model that enables a comparison of different hydrogen storage systems on a common basis. The Simulink Framework model was disseminated on the www.HSECoE.org website that is hosted by NREL. UTRC contributed to a better understanding of the safety aspects of the proposed hydrogen storage systems. UTRC also participated in the Failure Mode and Effect Analysis of both the chemical- and the adsorbent-based hydrogen storage system during Phase 2 of the Hydrogen Storage Engineering Center of Excellence. UTRC designed a hydrogen storage system with a reversible metal hydride material in a compacted formmore » for light-duty vehicles with a 5.6 kg H2 storage capacity, giving it a 300 miles range. It contains a heat exchanger that enables efficient cooling of the metal hydride material during hydrogen absorption in order to meet the 3.3 minute refueling time target. It has been shown through computation that the kinetics of hydrogen absorption of Ti-catalyzed NaAlH4 was ultimately limiting the rate of hydrogen absorption to 85% of the material capacity in 3.3 minutes. An inverse analysis was performed in order to determine the material property requirements in order for a metal hydride based hydrogen storage system to meet the DOE targets. Work on metal hydride storage systems was halted after the Phase 1 to Phase 2 review due to the lack of metal hydride materials with the required material properties. UTRC contributed to the design of a chemical hydrogen storage system by developing an adsorbent for removing the impurity ammonia from the hydrogen gas, by developing a system to meter the transport of Ammonia Borane (AB) powder to a thermolysis reactor, and by developing a gas-liquid-separator (GLS) for the separation of hydrogen gas from AB slurry in silicone oil. Stripping impurities from hydrogen gas is essential for a long life of the fuel cell system on board of a vehicle. Work on solid transport of AB was halted after the Phase 1 to Phase 2 review in favor of studying the slurry-form of AB as it appeared to be difficult to transport a solid form of AB through the thermolysis reactor. UTRC demonstrated the operation of a compact GLS in the laboratory at a scale that would be required for the actual automotive application. The GLS met the targets for weight and volume. UTRC also reported about the unresolved issue associated with the high vapor pressure of fluids that could be used for making a slurry-form of AB. Work on the GLS was halted after the Phase 2 to Phase 3 review as the off-board regeneration efficiency of the spent AB was below the DOE target of 60%. UTRC contributed to the design of an adsorbent-based hydrogen storage system through measurements of the thermal conductivity of a compacted form of Metal Organic Framework (MOF) number 5 and through the development and sizing of a particulate filter. Thermal conductivity is important for the design of the modular adsorbent tank insert (MATI), as developed by Oregon State University (OSU), in order to enable a rapid refueling process. Stringent hydrogen quality requirements can only be met with an efficient particulate filtration system. UTRC developed a method to size the particulate filter by taking into account the effect of the pressure drop on the hydrogen adsorption process in the tank. UTRC raised awareness about the potential use of materials-based H2 storage systems in applications outside the traditional light-duty vehicle market segment by presenting at several conferences about niche application opportunities in Unmanned Aerial Vehicles (UAV), Autonomous Underwater Vehicles (AUV), portable power and others.« less

The Fuel Cell Powered Club Car Carryall

NASA Technical Reports Server (NTRS)

Eichenberg, Dennis J.

2005-01-01

The NASA Glenn Research Center initiated development of the Fuel Cell Powered Club Car Carryall as a way to reduce pollution in industrial settings, reduce fossil fuel consumption and reduce operating costs for transportation systems. The Club Car Carryall provides an inexpensive approach to advance the state of the art in electric vehicle technology in a practical application. The project transfers space technology to terrestrial use via non-traditional partners, and provides power system data valuable for future aeronautics and space applications. The work was done under the Hybrid Power Management (HPM) Program. The Carryall is a state of the art, dedicated, electric utility vehicle. Hydrogen powered proton exchange membrane (PEM) fuel cells are the primary power source. Ultracapacitors were used for energy storage as long life, maintenance free operation, and excellent low temperature performance is essential. Metal hydride hydrogen storage was used to store hydrogen in a safe and efficient low-pressure solid form. The report concludes that the Fuel Cell Powered Club Car Carryall can provide excellent performance, and that the implementation of fuel cells in conjunction with ultracapacitors in the power system can provide significant reliability and performance improvements.

High temperature solid oxide regenerative fuel cell for solar photovoltaic energy storage

NASA Technical Reports Server (NTRS)

Bents, David J.

1987-01-01

A hydrogen-oxygen regenerative fuel cell (RFC) energy storage system based on high temperature solid oxide fuel cell (SOFC) technology is described. The reactants are stored as gases in lightweight insulated pressure vessels. The product water is stored as a liquid in saturated equilibrium with the fuel gas. The system functions as a secondary battery and is applicable to darkside energy storage for solar photovoltaics.

Mechanochemical activation and synthesis of nanomaterials for hydrogen storage and conversion in electrochemical power sources.

PubMed

Wronski, Zbigniew S; Varin, Robert A; Czujko, Tom

2009-07-01

In this study we discuss a process of mechanical activation employed in place of chemical or thermal activation to improve the mobility and reactivity of hydrogen atoms and ions in nanomaterials for energy applications: rechargeable batteries and hydrogen storage for fuel cell systems. Two materials are discussed. Both are used or intended for use in power sources. One is nickel hydroxide, Ni(OH)2, which converts to oxyhydroxide in the positive Ni electrode of rechargeable metal hydride batteries. The other is a complex hydride, Mg(AIH4)2, intended for use in reversible, solid-state hydrogen storage for fuel cells. The feature shared by these unlikely materials (hydroxide and hydride) is a sheet-like hexagonal crystal structure. The mechanical activation was conducted in high-energy ball mills. We discuss and demonstrate that the mechanical excitation of atoms and ions imparted on these powders stems from the same class of phenomena. These are (i) proliferation of structural defects, in particular stacking faults in a sheet-like structure of hexagonal crystals, and (ii) possible fragmentation of a faulted structure into a mosaic of layered nanocrystals. The hydrogen atoms bonded in such nanocrystals may be inserted and abstracted more easily from OH- hydroxyl group in Ni(OH)2 and AlH4- hydride complex in Mg(AlH4)2 during hydrogen charge and discharge reactions. However, the effects of mechanical excitation imparted on these powders are different. While the Ni(OH)2 powder is greatly activated for cycling in batteries, the Mg(AlH4)2 complex hydride phase is greatly destabilized for use in reversible hydrogen storage. Such a "synchronic" view of the structure-property relationship in respect to materials involved in hydrogen energy storage and conversion is supported in experiments employing X-ray diffraction (XRD), differential scanning calorimetry (DSC) and direct imaging of the structure with a high-resolution transmission-electron microscope (HREM), as well as in property characterization.

Preparation and characterization of azithromycin--Aerosil 200 solid dispersions with enhanced physical stability.

PubMed

Li, Xuechao; Peng, Huanhuan; Tian, Bin; Gou, Jingxin; Yao, Qing; Tao, Xiaoguang; He, Haibing; Zhang, Yu; Tang, Xing; Cai, Cuifang

2015-01-01

The main purpose of this study was to investigate the feasibility of azithromycin (AZI)--Aerosil 200 solid dispersions specifically with high stability under accelerated condition (40 °C/75% RH). Ball milling (BM) and hot-melt extrusion (HME) were used to prepare AZI solid dispersions. The physical properties of solid dispersions were evaluated by differential scanning calorimetry (DSC), scanning electron microscopy (SEM), powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA). For solid dispersions prepared with both methods, no crystalline of AZI was detected (except for AZI: Aerosil 200=75:25) by DSC or PXRD, indicating the amorphous state of AZI in solid dispersions. The FT-IR results demonstrated the loss of crystallization water and the formation of hydrogen bonds between Aerosil 200 and AZI during the preparation of solid dispersions. After 4 weeks storage under accelerated condition, the degree of crystallinity of AZI increased in solid dispersions prepared by BM, whereas for solid dispersions containing AZI, Aerosil 200 and glyceryl behenate (GB) prepared by HME, no crystalline of AZI was identified. This high stability can be attributed to the hydrophobic properties of GB and the presence of hydrogen bonds. Based on the above results, it is inferred the protection of hydrogen bonds between AZI and Aerosil 200 formed during preparation process effectively inhibited the recrystallization of AZI and improved the physical stability of amorphous AZI in the presence of Aerosil 200. Copyright © 2015 Elsevier B.V. All rights reserved.

Predicting Protein Aggregation during Storage in Lyophilized Solids Using Solid State Amide Hydrogen/Deuterium Exchange with Mass Spectrometric Analysis (ssHDX-MS)

PubMed Central

2015-01-01

Solid state amide hydrogen/deuterium exchange with mass spectrometric analysis (ssHDX-MS) was used to assess the conformation of myoglobin (Mb) in lyophilized formulations, and the results correlated with the extent of aggregation during storage. Mb was colyophilized with sucrose (1:1 or 1:8 w/w), mannitol (1:1 w/w), or NaCl (1:1 w/w) or in the absence of excipients. Immediately after lyophilization, samples of each formulation were analyzed by ssHDX-MS and Fourier transform infrared spectroscopy (FTIR) to assess Mb conformation, and by dynamic light scattering (DLS) and size exclusion chromatography (SEC) to determine the extent of aggregation. The remaining samples were then placed on stability at 25 °C and 60% RH or 40 °C and 75% RH for up to 1 year, withdrawn at intervals, and analyzed for aggregate content by SEC and DLS. In ssHDX-MS of samples immediately after lyophilization (t = 0), Mb was less deuterated in solids containing sucrose (1:1 and 1:8 w/w) than in those containing mannitol (1:1 w/w), NaCl (1:1 w/w), or Mb alone. Deuterium uptake kinetics and peptide mass envelopes also indicated greater Mb structural perturbation in mannitol, NaCl, or Mb-alone samples at t = 0. The extent of deuterium incorporation and kinetic parameters related to rapidly and slowly exchanging amide pools (Nfast, Nslow), measured at t = 0, were highly correlated with the extent of aggregation on storage as measured by SEC. In contrast, the extent of aggregation was weakly correlated with FTIR band intensity and peak position measured at t = 0. The results support the use of ssHDX-MS as a formulation screening tool in developing lyophilized protein drug products. PMID:24816133

ENVIRONMENTAL REACTIVITY OF SOLID STATE HYDRIDE MATERIALS: MODELING AND TESTING FOR AIR AND WATER EXPOSURE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anton, D.; James, C.; Cortes-Concepcion, J.

2010-05-18

To make commercially acceptable condensed phase hydrogen storage systems, it is important to understand quantitatively the risks involved in using these materials. A rigorous set of environmental reactivity tests have been developed based on modified testing procedures codified by the United Nations for the transportation of dangerous goods. Potential hydrogen storage material, 2LiBH4{center_dot}MgH2 and NH3BH3, have been tested using these modified procedures to evaluate the relative risks of these materials coming in contact with the environment in hypothetical accident scenarios. It is apparent that an ignition event will only occur if both a flammable concentration of hydrogen and sufficient thermalmore » energy were available to ignite the hydrogen gas mixture. In order to predict hydride behavior for hypothesized accident scenarios, an idealized finite element model was developed for dispersed hydride from a breached system. Empirical thermodynamic calculations based on precise calorimetric experiments were performed in order to quantify the energy and hydrogen release rates and to quantify the reaction products resulting from water and air exposure. Both thermal and compositional predictions were made with identification of potential ignition event scenarios.« less

Increasing hydrogen storage capacity using tetrahydrofuran.

PubMed

Sugahara, Takeshi; Haag, Joanna C; Prasad, Pinnelli S R; Warntjes, Ashleigh A; Sloan, E Dendy; Sum, Amadeu K; Koh, Carolyn A

2009-10-21

Hydrogen hydrates with tetrahydrofuran (THF) as a promoter molecule are investigated to probe critical unresolved observations regarding cage occupancy and storage capacity. We adopted a new preparation method, mixing solid powdered THF with ice and pressurizing with hydrogen at 70 MPa and 255 +/- 2 K (these formation conditions are insufficient to form pure hydrogen hydrates). All results from Raman microprobe spectroscopy, powder X-ray diffraction, and gas volumetric analysis show a strong dependence of hydrogen storage capacity on THF composition. Contrary to numerous recent reports that claim it is impossible to store H(2) in large cages with promoters, this work shows that, below a THF mole fraction of 0.01, H(2) molecules can occupy the large cages of the THF+H(2) structure II hydrate. As a result, by manipulating the promoter THF content, the hydrogen storage capacity was increased to approximately 3.4 wt % in the THF+H(2) hydrate system. This study shows the tuning effect may be used and developed for future science and practical applications.

Apparatus and methods for storing and releasing hydrogen

DOEpatents

Heung, Leung K.

2001-01-01

A rechargeable device that stores and discharges hydrogen is described. The device stores hydrogen in a solid form and supplies hydrogen as a gas when needed. The solid storage medium may be metal hydride in a ground particle form that avoids the need for compaction or other treatment. Dividers partition a container into separate chambers, each provided with a matrix, formed from an appropriate material like a thermally-conductive aluminum foam, which forms a number of cells. For proper chamber size, the ratio of chamber length to container diameter should be between about 0.5 and 2. Metal hydride particles (or other hydrogen storage medium) may be placed within the cells, which help prevent excessive particle settling. The container is provided with a hydrogen transfer port through which hydrogen gas passes upon either discharging from or charging of the metal hydride particles. A filter may be placed within the port to allow hydrogen to flow but prevent particles from escaping. A heat transferring surface is formed by, for instance, a channel that is thermally coupled with the aluminum foam. Fluid flows through the channel to deliver or remove heat during the respective hydrogen discharging or charging processes.

Apparatus and methods for storing and releasing hydrogen

DOEpatents

Heung, Leung K.

2000-01-01

A rechargeable device that stores and discharges hydrogen is described. The device stores hydrogen in a solid form and supplies hydrogen as a gas when needed. The solid storage medium may be metal hydride in a ground particle form that avoids the need for compaction or other treatment. Dividers partition a container into separate chambers, each provided with a matrix, formed from an appropriate material like a thermally-conductive aluminum foam, which forms a number of cells. For proper chamber size, the ratio of chamber length to container diameter should be between about 0.5 and 2. Metal hydride particles (or other hydrogen storage medium) may be placed within the cells, which help prevent excessive particle settling. The container is provided with a hydrogen transfer port through which hydrogen gas passes upon either discharging from or charging of the metal hydride particles. A filter may be placed within the port to allow hydrogen to flow but prevent particles from escaping. A heat transferring surface is formed by, for instance, a channel that is thermally coupled with the aluminum foam. Fluid flows through the channel to deliver or remove heat during the respective hydrogen discharging or charging processes.

Predicting New Materials for Hydrogen Storage Application

PubMed Central

Vajeeston, Ponniah; Ravindran, Ponniah; Fjellvåg, Helmer

2009-01-01

Knowledge about the ground-state crystal structure is a prerequisite for the rational understanding of solid-state properties of new materials. To act as an efficient energy carrier, hydrogen should be absorbed and desorbed in materials easily and in high quantities. Owing to the complexity in structural arrangements and difficulties involved in establishing hydrogen positions by x-ray diffraction methods, the structural information of hydrides are very limited compared to other classes of materials (like oxides, intermetallics, etc.). This can be overcome by conducting computational simulations combined with selected experimental study which can save environment, money, and man power. The predicting capability of first-principles density functional theory (DFT) is already well recognized and in many cases structural and thermodynamic properties of single/multi component system are predicted. This review will focus on possible new classes of materials those have high hydrogen content, demonstrate the ability of DFT to predict crystal structure, and search for potential meta-stable phases. Stabilization of such meta-stable phases is also discussed.

The numerical approach adopted in toba computer code for mass and heat transfer dynamic analysis of metal hydride hydrogen storage beds

DOE Office of Scientific and Technical Information (OSTI.GOV)

El Osery, I.A.

1983-12-01

Modelling studies of metal hydride hydrogen storage beds is a part of an extensive R and D program conducted in Egypt on hydrogen energy. In this context two computer programs; namely RET and RET1; have been developed. In RET computer program, a cylindrical conduction bed model is considered and an approximate analytical solution is used for solution of the associated mass and heat transfer problem. This problem is solved in RET1 computer program numerically allowing more flexibility in operating conditions but still limited to cylindrical configuration with only two alternatives for heat exchange; either fluid is passing through tubes imbeddedmore » in the solid alloy matrix or solid rods are surrounded by annular fluid tubes. The present computer code TOBA is more flexible and realistic. It performs the mass and heat transfer dynamic analysis of metal hydride storage beds using a variety of geometrical and operating alternatives.« less

Carbon Dioxide-Free Hydrogen Production with Integrated Hydrogen Separation and Storage.

PubMed

Dürr, Stefan; Müller, Michael; Jorschick, Holger; Helmin, Marta; Bösmann, Andreas; Palkovits, Regina; Wasserscheid, Peter

2017-01-10

An integration of CO 2 -free hydrogen generation through methane decomposition coupled with hydrogen/methane separation and chemical hydrogen storage through liquid organic hydrogen carrier (LOHC) systems is demonstrated. A potential, very interesting application is the upgrading of stranded gas, for example, gas from a remote gas field or associated gas from off-shore oil drilling. Stranded gas can be effectively converted in a catalytic process by methane decomposition into solid carbon and a hydrogen/methane mixture that can be directly fed to a hydrogenation unit to load a LOHC with hydrogen. This allows for a straight-forward separation of hydrogen from CH 4 and conversion of hydrogen to a hydrogen-rich LOHC material. Both, the hydrogen-rich LOHC material and the generated carbon on metal can easily be transported to destinations of further industrial use by established transport systems, like ships or trucks. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of storage conditions on the recrystallization of drugs in solid dispersions with crospovidone.

PubMed

Shibata, Yusuke; Fujii, Makiko; Suzuki, Ayako; Koizumi, Naoya; Kanada, Ken; Yamada, Masaki; Watanabe, Yoshiteru

2014-06-01

The physical stability of amorphous solid dispersions (SDs) is influenced by their storage conditions. The goal of this work was to investigate the factors affecting the recrystallization of drugs in SDs after storage under conditions of high temperature and high humidity. SDs of three drugs (dipyridamole, nifedipine and indomethacin) with different functional groups (amino, carbonyl and hydroxyl) and onset times for crystallization of the amorphous state were prepared using crospovidone (CrosPVP). All of the drugs in the SDs remained in an amorphous state at 25 °C/50% relative humidity (RH) in closed glass bottles for at least six months. Under conditions of high temperature (40 °C/75%RH/closed and 60 °C/open), differences in interactions between the hydrogen bond donors of the drugs and the amide carbonyl group of CrosPVP are essential factors for recrystallization of the drugs in the SDs. On the other hand, under condition of high humidity (40 °C/75%RH/open), in addition to the difference in the interaction between the drug and CrosPVP, the rate of increase in moisture content affects their recrystallization in SDs.

Synthesis and Engineering Materials Properties of Fluid Phase Chemical Hydrogen Storage Materials for Automotive Applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choi, Young Joon; Westman, Matthew P.; Karkamkar, Abhijeet J.

Among candidates for chemical hydrogen storage in PEM fuel cell automotive applications, ammonia borane (AB, NH3BH3) is considered to be one of the most promising materials due to its high practical hydrogen content of 14-16 wt%. This material is selected as a surrogate chemical for a hydrogen storage system. For easier transition to the existing infrastructure, a fluid phase hydrogen storage material is very attractive and thus, we investigated the engineering materials properties of AB in liquid carriers for a chemical hydrogen storage slurry system. Slurries composed of AB and high temperature liquids were prepared by mechanical milling and sonicationmore » in order to obtain stable and fluidic properties. Volumetric gas burette system was adopted to observe the kinetics of the H2 release reactions of the AB slurry and neat AB. Viscometry and microscopy were employed to further characterize slurries engineering properties. Using a tip-sonication method we have produced AB/silicone fluid slurries at solid loadings up to 40wt% (6.5wt% H2) with viscosities less than 500cP at 25°C.« less

Combining plasma gasification and solid oxide cell technologies in advanced power plants for waste to energy and electric energy storage applications.

PubMed

Perna, Alessandra; Minutillo, Mariagiovanna; Lubrano Lavadera, Antonio; Jannelli, Elio

2018-03-01

The waste to energy (WtE) facilities and the renewable energy storage systems have a strategic role in the promotion of the "eco-innovation", an emerging priority in the European Union. This paper aims to propose advanced plant configurations in which waste to energy plants and electric energy storage systems from intermittent renewable sources are combined for obtaining more efficient and clean energy solutions in accordance with the "eco-innovation" approach. The advanced plant configurations consist of an electric energy storage (EES) section based on a solid oxide electrolyzer (SOEC), a waste gasification section based on the plasma technology and a power generation section based on a solid oxide fuel cell (SOFC). The plant configurations differ for the utilization of electrolytic hydrogen and oxygen in the plasma gasification section and in the power generation section. In the first plant configuration IAPGFC (Integrated Air Plasma Gasification Fuel Cell), the renewable oxygen enriches the air stream, that is used as plasma gas in the gasification section, and the renewable hydrogen is used to enrich the anodic stream of the SOFC in the power generation section. In the second plant configuration IHPGFC (Integrated Hydrogen Plasma Gasification Fuel Cell) the renewable hydrogen is used as plasma gas in the plasma gasification section, and the renewable oxygen is used to enrich the cathodic stream of the SOFC in the power generation section. The analysis has been carried out by using numerical models for predicting and comparing the systems performances in terms of electric efficiency and capability in realizing the waste to energy and the electric energy storage of renewable sources. Results have highlighted that the electric efficiency is very high for all configurations (35-45%) and, thanks to the combination with the waste to energy technology, the storage efficiencies are very attractive (in the range 72-92%). Copyright © 2017 Elsevier Ltd. All rights reserved.

Large scale production of densified hydrogen to the triple point and below

NASA Astrophysics Data System (ADS)

Swanger, A. M.; Notardonato, W. U.; E Fesmire, J.; Jumper, K. M.; Johnson, W. L.; Tomsik, T. M.

2017-12-01

Recent demonstration of advanced liquid hydrogen storage techniques using Integrated Refrigeration and Storage technology at NASA Kennedy Space Center led to the production of large quantities of densified liquid and slush hydrogen in a 125,000 L tank. Production of densified hydrogen was performed at three different liquid levels and LH2 temperatures were measured by twenty silicon diode temperature sensors. Overall densification performance of the system is explored, and solid mass fractions are calculated. Experimental data reveal hydrogen temperatures dropped well below the triple point during testing, and were continuing to trend downward prior to system shutdown. Sub-triple point temperatures were seen to evolve in a time dependent manner along the length of the horizontal, cylindrical vessel. The phenomenon, observed at two fill levels, is detailed herein. The implications of using IRAS for energy storage, propellant densification, and future cryofuel systems are discussed.

Large Scale Production of Densified Hydrogen to the Triple Point and Below

NASA Technical Reports Server (NTRS)

Swanger, A. M.; Notardonato, W. U.; Fesmire, J. E.; Jumper, K. M.; Johnson, W. L.; Tomsik, T. M.

2017-01-01

Recent demonstration of advanced liquid hydrogen storage techniques using Integrated Refrigeration and Storage technology at NASA Kennedy Space Center led to the production of large quantities of densified liquid and slush hydrogen in a 125,000 L tank. Production of densified hydrogen was performed at three different liquid levels and LH2 temperatures were measured by twenty silicon diode temperature sensors. Overall densification performance of the system is explored, and solid mass fractions are calculated. Experimental data reveal hydrogen temperatures dropped well below the triple point during testing, and were continuing to trend downward prior to system shutdown. Sub-triple point temperatures were seen to evolve in a time dependent manner along the length of the horizontal, cylindrical vessel. The phenomenon, observed at two fill levels, is detailed herein. The implications of using IRAS for energy storage, propellant densification, and future cryofuel systems are discussed.

Interaction of Hydrogen with MOF-5.

PubMed

Bordiga, Silvia; Vitillo, Jenny G; Ricchiardi, Gabriele; Regli, Laura; Cocina, Donato; Zecchina, Adriano; Arstad, Bjørnar; Bjørgen, Morten; Hafizovic, Jasmina; Lillerud, Karl Petter

2005-10-06

Hydrogen storage is among the most demanding challenges in the hydrogen-based energy cycle. One proposed strategy for hydrogen storage is based on physisorption on high surface area solids such as metal-organic frameworks (MOFs). Within this class of materials, MOF-5 has been the first structure studied for hydrogen storage. The IR spectroscopy of adsorbed H2 performed at 15 K and ab initio calculations show that the adsorptive properties of this material are mainly due to dispersive interactions with the internal wall structure and to weak electrostatic forces associated with O13Zn4 clusters. Calculated and measured binding enthalpies are between 2.26 and 3.5 kJ/mol, in agreement with the H2 rotational barriers reported in the literature. A minority of binding sites with higher adsorption enthalpy (7.4 kJ/mol) is also observed. These species are probably associated with OH groups on the external surfaces present as termini of the microcrystals.

Center for Hydrogen Storage.

DOT National Transportation Integrated Search

2013-06-01

The main goals of this project were to (1) Establish a Center for Hydrogen Storage Research at Delaware State University for the preparation and characterization of selected complex metal hydrides and the determination their suitability for hydrogen ...

Potential low cost, safe, high efficiency propellant for future space program

NASA Astrophysics Data System (ADS)

Zhou, D.

2005-03-01

Mixtures of nanometer or micrometer sized carbon powder suspended in hydrogen and methane/hydrogen mixtures are proposed as candidates for low cost, high efficiency propellants for future space programs. While liquid hydrogen has low weight and high heat of combustion per unit mass, because of the low mass density the heat of combustion per unit volume is low, and the liquid hydrogen storage container must be large. The proposed propellants can produce higher gross heat combustion with small volume with trade off of some weight increase. Liquid hydrogen can serve as the fluid component of the propellant in the mixtures and thus used by current rocket engine designs. For example, for the same volume a mixture of 5% methane and 95% hydrogen, can lead to an increase in the gross heat of combustion by about 10% and an increase in the Isp (specific impulse) by 21% compared to a pure liquid hydrogen propellant. At liquid hydrogen temperatures of 20.3 K, methane will be in solid state, and must be formed as fine granules (or slush) to satisfy the requirement of liquid propellant engines.

Charge induced enhancement of adsorption for hydrogen storage materials

NASA Astrophysics Data System (ADS)

Sun, Xiang

2009-12-01

The rising concerns about environmental pollution and global warming have facilitated research interest in hydrogen energy as an alternative energy source. To apply hydrogen for transportations, several issues have to be solved, within which hydrogen storage is the most critical problem. Lots of materials and devices have been developed; however, none is able to meet the DOE storage target. The primary issue for hydrogen physisorption is a weak interaction between hydrogen and the surface of solid materials, resulting negligible adsorption at room temperature. To solve this issue, there is a need to increase the interaction between the hydrogen molecules and adsorbent surface. In this study, intrinsic electric dipole is investigated to enhance the adsorption energy. The results from the computer simulation of single ionic compounds with hydrogen molecules to form hydrogen clusters showed that electrical charge of substances plays an important role in generation of attractive interaction with hydrogen molecules. In order to further examine the effects of static interaction on hydrogen adsorption, activated carbon with a large surface area was impregnated with various ionic salts including LiCl, NaCl, KCl, KBr, and NiCl2 and their performance for hydrogen storage was evaluated by using a volumetric method. Corresponding computer simulations have been carried out by using DFT (Density Functional Theory) method combined with point charge arrays. Both experimental and computational results prove that the adsorption capacity of hydrogen and its interaction with the solid materials increased with electrical dipole moment. Besides the intrinsic dipole, an externally applied electric field could be another means to enhance hydrogen adsorption. Hydrogen adsorption under an applied electric field was examined by using porous nickel foil as electrodes. Electrical signals showed that adsorption capacity increased with the increasing of gas pressure and external electric voltage. Direct measurement of the amount of hydrogen adsorption was also carried out with porous nickel oxides and magnesium oxides using the piezoelectric material PMN-PT as the charge supplier due to the pressure. The adsorption enhancement from the PMN-PT generated charges is obvious at hydrogen pressure between 0 and 60 bars, where the hydrogen uptake is increased at about 35% for nickel oxide and 25% for magnesium oxide. Computer simulation reveals that under the external electric field, the electron cloud of hydrogen molecules is pulled over to the adsorbent site and can overlap with the adsorbent electrons, which in turn enhances the adsorption energy. Experiments were also carried out to examine the effects of hydrogen spillover with charge induced enhancement. The results show that the overall storage capacity in nickel oxide increased remarkably by a factor of 4.

SISGR - Hydrogen Caged in Carbon-Exploration of Novel Carbon-Hydrogen Interactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lueking, Angela; Badding, John; Crespi, Vinent

Hydrogen trapped in a carbon cage, captured through repulsive interactions, is a novel concept in hydrogen storage. Trapping hydrogen via repulsive interactions borrows an idea from macroscale hydrogen storage (i.e. compressed gas storage tanks) and reapplies these concepts on the nanoscale in specially designed molecular containers. Under extreme conditions of pressure, hydrogen solubility in carbon materials is expected to increase and carbon is expected to restructure to minimize volume via a mixed sp2/sp3 hydrogenated state. Thermodynamics dictate that pre-formed C-H structures will rearrange with increased pressure, yet the final carbon-hydrogen interactions may be dependent upon the mechanism by which hydrogenmore » is introduced. Gas “trapping” is meant to denote gas present in a solid in a high density, adsorbed-like state, when the external pressure is much less than that necessary to provide a comparable fluid density. Trapping thus denotes a kinetically metastable state rather than thermodynamic equilibrium. This project probed mechanochemical means to polymerize select hydrocarbons in the presence of gases, in an attempt to form localized carbon cages that trap gases via repulsive interactions. Aromatic, polyaromatic, and hydroaromatic molecules expected to undergo cyclo-addition reactions were polymerized at high (~GPa) pressures to form extended hydrogenated amorphous carbon networks. Notably, aromatics with a pre-existing internal free volume (such as Triptycene) appeared to retain an internal porosity upon application of pressure. However, a high photoluminescence background after polymerization precluded in situ identification of trapped gases. No spectroscopic evidence was found after depressurization that would be indicative of pockets of trapped gases in a localized high-pressure environment. Control studies suggested this measurement may be insensitive to gases at low pressure. Similarly, no spectral fingerprint was found for gas-imbued spherical carbon nanoshells, even after chemical “capping” of the gas-imbued nanoshells to limit gas diffusivity. Subsequently, spectral probes of gas vibrational modes adsorbed in various carbon nanostructures (including activated carbons, single-wall carbon nanotubes, polymers of intrinsic microporosity (PIMs), and UV-irradiated PIMs with decreased pore size) were found only at high pressure. The vibrational mode of the adsorbed film became perturbed in high density films, and the perturbation was sensitive to surface functional groups, pore size, and pore dimension. Experimental results were corroborated with first-principle modeling using density functional theory. Development of semi-empirical correlations that relate the spectral features to pore dimension, geometry, and chemical potential of the adsorbed film are on-going.« less

The TMI regenerable solid oxide fuel cell

NASA Technical Reports Server (NTRS)

Cable, Thomas L.

1995-01-01

Energy storage and production in space requires rugged, reliable hardware which minimizes weight, volume, and maintenance while maximizing power output and usable energy storage. These systems generally consist of photovoltaic solar arrays which operate during sunlight cycles to provide system power and regenerate fuel (hydrogen) via water electrolysis; during dark cycles, hydrogen is converted by the fuel cell into system. The currently preferred configuration uses two separate systems (fuel cell and electrolyzer) in conjunction with photovoltaic cells. Fuel cell/electrolyzer system simplicity, reliability, and power-to-weight and power-to-volume ratios could be greatly improved if both power production (fuel cell) and power storage (electrolysis) functions can be integrated into a single unit. The Technology Management, Inc. (TMI), solid oxide fuel cell-based system offers the opportunity to both integrate fuel cell and electrolyzer functions into one unit and potentially simplify system requirements. Based an the TMI solid oxide fuel cell (SOPC) technology, the TMI integrated fuel cell/electrolyzer utilizes innovative gas storage and operational concepts and operates like a rechargeable 'hydrogen-oxygen battery'. Preliminary research has been completed on improved H2/H2O electrode (SOFC anode/electrolyzer cathode) materials for solid oxide, regenerative fuel cells. Improved H2/H2O electrode materials showed improved cell performance in both fuel cell and electrolysis modes in reversible cell tests. ln reversible fuel cell/electrolyzer mode, regenerative fuel cell efficiencies (ratio of power out (fuel cell mode) to power in (electrolyzer model)) improved from 50 percent (using conventional electrode materials) to over 80 percent. The new materials will allow the TMI SOFC system to operate as both the electrolyzer and fuel cell in a single unit. Preliminary system designs have also been developed which indicate the technical feasibility of using the TMI SOFC technology for space applications with high energy storage efficiencies and high specific energy. Development of small space systems would also have potential dual-use, terrestrial applications.

The TMI regenerable solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Cable, Thomas L.

1995-04-01

Energy storage and production in space requires rugged, reliable hardware which minimizes weight, volume, and maintenance while maximizing power output and usable energy storage. These systems generally consist of photovoltaic solar arrays which operate during sunlight cycles to provide system power and regenerate fuel (hydrogen) via water electrolysis; during dark cycles, hydrogen is converted by the fuel cell into system. The currently preferred configuration uses two separate systems (fuel cell and electrolyzer) in conjunction with photovoltaic cells. Fuel cell/electrolyzer system simplicity, reliability, and power-to-weight and power-to-volume ratios could be greatly improved if both power production (fuel cell) and power storage (electrolysis) functions can be integrated into a single unit. The Technology Management, Inc. (TMI), solid oxide fuel cell-based system offers the opportunity to both integrate fuel cell and electrolyzer functions into one unit and potentially simplify system requirements. Based an the TMI solid oxide fuel cell (SOPC) technology, the TMI integrated fuel cell/electrolyzer utilizes innovative gas storage and operational concepts and operates like a rechargeable 'hydrogen-oxygen battery'. Preliminary research has been completed on improved H2/H2O electrode (SOFC anode/electrolyzer cathode) materials for solid oxide, regenerative fuel cells. Improved H2/H2O electrode materials showed improved cell performance in both fuel cell and electrolysis modes in reversible cell tests. ln reversible fuel cell/electrolyzer mode, regenerative fuel cell efficiencies (ratio of power out (fuel cell mode) to power in (electrolyzer model)) improved from 50 percent (using conventional electrode materials) to over 80 percent. The new materials will allow the TMI SOFC system to operate as both the electrolyzer and fuel cell in a single unit. Preliminary system designs have also been developed which indicate the technical feasibility of using the TMI SOFC technology for space applications with high energy storage efficiencies and high specific energy. Development of small space systems would also have potential dual-use, terrestrial applications.

Probing hydrogen bonding in cocrystals and amorphous dispersions using (14)N-(1)H HMQC solid-state NMR.

PubMed

Tatton, Andrew S; Pham, Tran N; Vogt, Frederick G; Iuga, Dinu; Edwards, Andrew J; Brown, Steven P

2013-03-04

Cocrystals and amorphous solid dispersions have generated interest in the pharmaceutical industry as an alternative to more established solid delivery forms. The identification of intermolecular hydrogen bonding interactions in a nicotinamide palmitic acid cocrystal and a 50% w/w acetaminophen-polyvinylpyrrolidone solid dispersion are reported using advanced solid-state magic-angle spinning (MAS) NMR methods. The application of a novel (14)N-(1)H HMQC experiment, where coherence transfer is achieved via through-space couplings, is shown to identify specific hydrogen bonding motifs. Additionally, (1)H isotropic chemical shifts and (14)N electric field gradient (EFG) parameters, both accessible from (14)N-(1)H HMQC experiments, are shown to be sensitive to changes in hydrogen bonding geometry. Numerous indicators of molecular association are accessible from this experiment, including NH cross-peaks occurring from intermolecular hydrogen bonds and changes in proton chemical shifts or electric field gradient parameters. First-principles calculations using the GIPAW approach that yield accurate estimates of isotropic chemical shifts, and EFG parameters were used to assist in assignment. It is envisaged that (14)N-(1)H HMQC solid state NMR experiments could become a valuable screening technique of solid delivery forms in the pharmaceutical industry.

Development of spray-dried co-precipitate of amorphous celecoxib containing storage and compression stabilizers.

PubMed

Dhumal, Ravindra S; Shimpi, Shamkant L; Paradkar, Anant R

2007-09-01

The purpose of this study was to obtain an amorphous system with minimum unit operations that will prevent recrystallization of amorphous drugs since preparation, during processing (compression) and further storage. Amorphous celecoxib, solid dispersion (SD) of celecoxib with polyvinyl pyrrollidone (PVP) and co-precipitate with PVP and carrageenan (CAR) in different ratios were prepared by the spray drying technique and compressed into tablets. Saturation solubility and dissolution studies were performed to differentiate performance after processing. Differential scanning calorimetry and X-ray powder difraction revealed the amorphous form of celecoxib, whereas infrared spectroscopy revealed hydrogen bonding between celecoxib and PVP. The dissolution profile of the solid dispersion and co-precipitate improved compared to celecoxib and amorphous celecoxib. Amorphous celecoxib was not stable on storage whereas the solid dispersion and co-precipitate powders were stable for 3 months. Tablets of the solid dispersion of celecoxib with PVP and physical mixture with PVP and carrageenan showed better resistance to recrystallization than amorphous celecoxib during compression but recrystallized on storage. However, tablets of co-precipitate with PVP and carageenan showed no evidence of crystallinity during stability studies with comparable dissolution profiles. This extraordinary stability of spray-dried co-precipitate tablets may be attributed to the cushioning action provided by the viscoelastic polymer CAR and hydrogen bonding interaction between celecoxib and PVP. The present study demonstrates the synergistic effect of combining two types of stabilizers, PVP and CAR, on the stability of amorphous drug during compression and storage as compared to their effect when used alone.

Effects of magnesium-based hydrogen storage materials on the thermal decomposition, burning rate, and explosive heat of ammonium perchlorate-based composite solid propellant.

PubMed

Liu, Leili; Li, Jie; Zhang, Lingyao; Tian, Siyu

2018-01-15

MgH 2 , Mg 2 NiH 4 , and Mg 2 CuH 3 were prepared, and their structure and hydrogen storage properties were determined through X-ray photoelectron spectroscopy and thermal analyzer. The effects of MgH 2 , Mg 2 NiH 4 , and Mg 2 CuH 3 on the thermal decomposition, burning rate, and explosive heat of ammonium perchlorate-based composite solid propellant were subsequently studied. Results indicated that MgH 2 , Mg 2 NiH 4 , and Mg 2 CuH 3 can decrease the thermal decomposition peak temperature and increase the total released heat of decomposition. These compounds can improve the effect of thermal decomposition of the propellant. The burning rates of the propellant increased using Mg-based hydrogen storage materials as promoter. The burning rates of the propellant also increased using MgH 2 instead of Al in the propellant, but its explosive heat was not enlarged. Nonetheless, the combustion heat of MgH 2 was higher than that of Al. A possible mechanism was thus proposed. Copyright © 2017. Published by Elsevier B.V.

Control of both particle and pore size in nanoporous palladium alloy powders

DOE PAGES

Jones, Christopher G.; Cappillino, Patrick J.; Stavila, Vitalie; ...

2014-07-15

Energy storage materials often involve chemical reactions with bulk solids. Porosity within the solids can enhance reaction rates. The porosity can be either within or between individual particles of the material. Greater control of the size and uniformity of both types of pore should lead to enhancements of charging and discharging rates in energy storage systems. Furthermore, to control both particle and pore size in nanoporous palladium (Pd)-based hydrogen storage materials, first we created uniformly sized copper particles of about 1 μm diameter by the reduction of copper sulfate with ascorbic acid. In turn, these were used as reducing agentsmore » for tetrachloropalladate in the presence of a block copolymer surfactant. The copper reductant particles are geometrically self-limiting, so the resulting Pd particles are of similar size. The surfactant induces formation of 10 nm-scale pores within the particles. Some residual copper is alloyed with the Pd, reducing hydrogen storage capacity; use of a more reactive Pd salt can mitigate this. The reaction is conveniently performed in gram-scale batches.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Long, Jeffrey R.

The design and characterization of new materials for hydrogen storage is an important area of research, as the ability to store hydrogen at lower pressures and higher temperatures than currently feasible would lower operating costs for small hydrogen fuel cell vehicles. In particular, metal-organic frameworks (MOFs) represent promising materials for use in storing hydrogen in this capacity. MOFs are highly porous, three-dimensional crystalline solids that are formed via linkages between metal ions (e.g., iron, nickel, and zinc) and organic molecules. MOFs can store hydrogen via strong adsorptive interactions between the gas molecules and the pores of the framework, providing amore » high surface area for gas adsorption and thus the opportunity to store hydrogen at significantly lower pressures than with current technologies. By lowering the energy required for hydrogen storage, these materials hold promise in rendering hydrogen a more viable fuel for motor vehicles, which is a highly desirable outcome given the clean nature of hydrogen fuel cells (water is the only byproduct of combustion) and the current state of global climate change resulting from the combustion of fossil fuels. The work presented in this report is the result of collaborative efforts between researchers at Lawrence Berkeley National Lab (LBNL), the National Institute of Standards and Technology (NIST), and General Motors Corporation (GM) to discover novel MOFs promising for H 2 storage and characterize their properties. Described herein are several new framework systems with improved gravimetric and volumetric capacity to strongly bind H 2 at temperatures relevant for vehicle storage. These materials were rigorously characterized using neutron diffraction, to determine the precise binding locations of hydrogen within the frameworks, and high-pressure H 2 adsorption measurements, to provide a comprehensive picture of H 2 adsorption at all relevant pressures. A rigorous understanding of experimental findings was further achieved via first-principles electronic structure calculations, which also supported synthetic efforts through predictions of additional novel frameworks with promising properties for vehicular H 2 storage. The results of the computational efforts also helped to elucidate the fundamental principles governing the interaction of H 2 with the frameworks, and in particular with exposed metal sites in the pores of these materials. Significant accomplishments from this project include the discovery of a metal-organic framework with a high H 2 binding enthalpy and volumetric capacity at 25 °C and 100 bar, which surpasses the metrics of any other known metal-organic framework. Additionally this material was designed to be extremely cost effective compared to most comparable adsorbents, which is imperative for eventual real-world applications. Progress toward synthesizing new frameworks containing multiple open coordination sites is also discussed, and appears to be the most promising future direction for hydrogen storage in these porous materials.« less

Influence of storage, heat treatment, and solids composition on the bleaching of whey with hydrogen peroxide.

PubMed

Li, Xiaomeng E; Campbell, Rachel E; Fox, Aaron J; Gerard, Patrick D; Drake, MaryAnne

2012-07-01

The residual annatto colorant in liquid whey is bleached to provide a desired neutral color in dried whey ingredients. This study evaluated the influence of starter culture, whey solids and composition, and spray drying on bleaching efficacy. Cheddar cheese whey with annatto was manufactured with starter culture or by addition of lactic acid and rennet. Pasteurized fat-separated whey was ultrafiltered (retentate) and spray dried to 34% whey protein concentrate (WPC34). Aliquots were bleached at 60 °C for 1 h (hydrogen peroxide, 250 ppm), before pasteurization, after pasteurization, after storage at 3 °C and after freezing at -20 °C. Aliquots of retentate were bleached analogously immediately and after storage at 3 or -20 °C. Freshly spray dried WPC34 was rehydrated to 9% (w/w) solids and bleached. In a final experiment, pasteurized fat-separated whey was ultrafiltered and spray dried to WPC34 and WPC80. The WPC34 and WPC80 retentates were diluted to 7 or 9% solids (w/w) and bleached at 50 °C for 1 h. Freshly spray-dried WPC34 and WPC80 were rehydrated to 9 or 12% solids and bleached. Bleaching efficacy was measured by extraction and quantification of norbixin. Each experiment was replicated 3 times. Starter culture, fat separation, or pasteurization did not impact bleaching efficacy (P > 0.05) while cold or frozen storage decreased bleaching efficacy (P < 0.05). Bleaching efficacy of 80% (w/w) protein liquid retentate was higher than liquid whey or 34% (w/w) protein liquid retentate (P < 0.05). Processing steps, particularly holding times and solids composition, influence bleaching efficacy of whey. Optimization of whey bleaching conditions is important to reduce the negative effects of bleaching on the flavor of dried whey ingredients. This study established that liquid storage and whey composition are critical processing points that influence bleaching efficacy. © 2012 Institute of Food Technologists®

CLEAN HYDROGEN TECHNOLOGY FOR 3-WHEEL TRANSPORTATION IN INDIA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Krishna Sapru

2005-11-15

Hydrogen is a clean burning, non-polluting transportation fuel. It is also a renewable energy carrier that can be produced from non-fossil fuel resources such as solar, wind and biomass. Utilizing hydrogen as an alternative fuel for vehicles will diversify the resources of energy, and reduce dependence on oil in the transportation sector. Additionally, clean burning hydrogen fuel will also alleviate air pollution that is a very severe problem in many parts of world, especially major metropolitan areas in developing countries, such as India and China. In our efforts to foster international collaborations in the research, development, and demonstration of hydrogenmore » technologies, through a USAID/DOE cost-shared project, Energy Conversion Devices, Inc.,(www.ovonic.com) a leading materials and alternative energy company, in collaboration with Bajaj Auto Limited, India's largest three-wheeler taxi manufacturer, has successfully developed and demonstrated prototype hydrogen ICE three-wheelers in the United States and India. ECD's proprietary Ovonic solid-state hydrogen storage technology is utilized on-board to provide a means of compact, low pressure, and safe hydrogen fuel. These prototype hydrogen three-wheelers have demonstrated comparable performance to the original CNG version of the vehicle, achieving a driving range of 130 km. The hydrogen storage system capable of storing 1 kg hydrogen can be refilled to 80% of its capacity in about 15 minutes at a pressure of 300 psi. The prototype vehicles developed under this project have been showcased and made available for test rides to the public at exhibits such as the 16th NHA annual meeting in April 2005, Washington, DC, and the SIAM (Society of Indian Automotive Manufacturers) annual conference in August 2005, New Delhi, India. Passengers have included members of the automotive industry, founders of both ECD and Bajaj, members of the World Bank, the Indian Union Minister for Finance, the President of the Asia Development Bank, members of USAID, USDOE and many other individuals, all of whom have had praise for the vehicle and the technology. The progress made through this phase I work and the importance of hydrogen three-wheelers has also resulted in extensive press coverage by the news media around the world.« less

Hydrogen Research for Spaceport and Space-Based Applications: Hydrogen Production, Storage, and Transport. Part 3

NASA Technical Reports Server (NTRS)

Anderson, Tim; Balaban, Canan

2008-01-01

The activities presented are a broad based approach to advancing key hydrogen related technologies in areas such as fuel cells, hydrogen production, and distributed sensors for hydrogen-leak detection, laser instrumentation for hydrogen-leak detection, and cryogenic transport and storage. Presented are the results from research projects, education and outreach activities, system and trade studies. The work will aid in advancing the state-of-the-art for several critical technologies related to the implementation of a hydrogen infrastructure. Activities conducted are relevant to a number of propulsion and power systems for terrestrial, aeronautics and aerospace applications. Hydrogen storage and in-space hydrogen transport research focused on developing and verifying design concepts for efficient, safe, lightweight liquid hydrogen cryogenic storage systems. Research into hydrogen production had a specific goal of further advancing proton conducting membrane technology in the laboratory at a larger scale. System and process trade studies evaluated the proton conducting membrane technology, specifically, scale-up issues.

Hydrogen Storage Materials for Mobile and Stationary Applications: Current State of the Art.

PubMed

Lai, Qiwen; Paskevicius, Mark; Sheppard, Drew A; Buckley, Craig E; Thornton, Aaron W; Hill, Matthew R; Gu, Qinfen; Mao, Jianfeng; Huang, Zhenguo; Liu, Hua Kun; Guo, Zaiping; Banerjee, Amitava; Chakraborty, Sudip; Ahuja, Rajeev; Aguey-Zinsou, Kondo-Francois

2015-09-07

One of the limitations to the widespread use of hydrogen as an energy carrier is its storage in a safe and compact form. Herein, recent developments in effective high-capacity hydrogen storage materials are reviewed, with a special emphasis on light compounds, including those based on organic porous structures, boron, nitrogen, and aluminum. These elements and their related compounds hold the promise of high, reversible, and practical hydrogen storage capacity for mobile applications, including vehicles and portable power equipment, but also for the large scale and distributed storage of energy for stationary applications. Current understanding of the fundamental principles that govern the interaction of hydrogen with these light compounds is summarized, as well as basic strategies to meet practical targets of hydrogen uptake and release. The limitation of these strategies and current understanding is also discussed and new directions proposed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quantum storage of a photonic polarization qubit in a solid.

PubMed

Gündoğan, Mustafa; Ledingham, Patrick M; Almasi, Attaallah; Cristiani, Matteo; de Riedmatten, Hugues

2012-05-11

We report on the quantum storage and retrieval of photonic polarization quantum bits onto and out of a solid state storage device. The qubits are implemented with weak coherent states at the single photon level, and are stored for a predetermined time of 500 ns in a praseodymium doped crystal with a storage and retrieval efficiency of 10%, using the atomic frequency comb scheme. We characterize the storage by using quantum state tomography, and find that the average conditional fidelity of the retrieved qubits exceeds 95% for a mean photon number μ=0.4. This is significantly higher than a classical benchmark, taking into account the poissonian statistics and finite memory efficiency, which proves that our crystal functions as a quantum storage device for polarization qubits. These results extend the storage capabilities of solid state quantum light matter interfaces to polarization encoding, which is widely used in quantum information science.

Creation of Novel Solid-Solution Alloy Nanoparticles on the Basis of Density-of-States Engineering by Interelement Fusion.

PubMed

Kobayashi, Hirokazu; Kusada, Kohei; Kitagawa, Hiroshi

2015-06-16

Currently 118 known elements are represented in the periodic table. Of these 118 elements, only about 80 elements are stable, nonradioactive, and widely available for our society. From the viewpoint of the "elements strategy", we need to make full use of the 80 elements to bring out their latent ability and create innovative materials. Furthermore, there is a strong demand that the use of rare or toxic elements be reduced or replaced while their important properties are retained. Advanced science and technology could create higher-performance materials even while replacing or reducing minor or harmful elements through the combination of more abundant elements. The properties of elements are correlated directly with their electronic states. In a solid, the magnitude of the density of states (DOS) at the Fermi level affects the physical and chemical properties. In the present age, more attention has been paid to improving the properties of materials by means of alloying elements. In particular, the solid-solution-type alloy is advantageous because the properties can be continuously controlled by tuning the compositions and/or combinations of the constituent elements. However, the majority of bulk alloys are of the phase-separated type under ambient conditions, where constituent elements are immiscible with each other. To overcome the challenge of the bulk-phase metallurgical aspects, we have focused on the nanosize effect and developed methods involving "nonequilibrium synthesis" or "a process of hydrogen absorption/desorption". We propose a new concept of "density-of-states engineering" for the design of materials having the most desirable and suitable properties by means of "interelement fusion". In this Account, we describe novel solid-solution alloys of Pd-Pt, Ag-Rh, and Pd-Ru systems in which the constituent elements are immiscible in the bulk state. The homogeneous solid-solution alloys of Pd and Pt were created from Pd core/Pt shell nanoparticles using a hydrogen absorption/desorption process as a trigger. Several atom percent replacements of Pd with Pt atoms resulted in a significantly enhanced hydrogen absorption capacity compared with Pd nanoparticles. AgxRh1-x and PdxRu1-x solid-solution alloy nanoparticles were also developed by nonequilibrium synthesis based on a polyol method. The AgxRh1-x nanoparticles demonstrated hydrogen storage properties, although pure metal nanoparticles of each constituent element do not adsorb hydrogen. AgxRh1-x is therefore considered to possess a similar electronic structure to Pd as a synthetic pseudo-palladium. The PdxRu1-x nanoparticles showed enhanced catalytic activity for CO oxidation, with the highest catalytic activity found using the equimolar Pd0.5Ru0.5 nanoparticles. The catalytic activity of the Pd0.5Ru0.5 nanoparticles exceeds that of the widely used and best-performing Ru catalysts for CO oxidation and is also higher than that of neighboring Rh on the periodic table. Our present work provides a guiding principle for the design of a suitable DOS shape according to the intended physical and/or chemical properties and a method for the development of novel solid-solution alloys.

Atmospheric Mining in the Outer Solar System: Resource Capturing, Storage, and Utilization

NASA Technical Reports Server (NTRS)

Palaszewski, Bryan

2014-01-01

Atmospheric mining in the outer solar system has been investigated as a means of fuel production for high energy propulsion and power. Fusion fuels such as helium 3 and hydrogen can be wrested from the atmospheres of Uranus and Neptune and either returned to Earth or used in-situ for energy production. Helium 3 and hydrogen (deuterium, etc.) were the primary gases of interest with hydrogen being the primary propellant for nuclear thermal solid core and gas core rocket-based atmospheric flight. A series of analyses were undertaken to investigate resource capturing aspects of atmospheric mining in the outer solar system. This included the gas capturing rate for hydrogen helium 4 and helium 3, storage options, and different methods of direct use of the captured gases. Additional supporting analyses were conducted to illuminate vehicle sizing and orbital transportation issues.

Hydrogen adsorption in metal-decorated silicon carbide nanotubes

NASA Astrophysics Data System (ADS)

Singh, Ram Sevak; Solanki, Ankit

2016-09-01

Hydrogen storage for fuel cell is an active area of research and appropriate materials with excellent hydrogen adsorption properties are highly demanded. Nanotubes, having high surface to volume ratio, are promising storage materials for hydrogen. Recently, silicon carbide nanotubes have been predicted as potential materials for future hydrogen storage application, and studies in this area are ongoing. Here, we report a systematic study on hydrogen adsorption properties in metal (Pt, Ni and Al) decorated silicon carbide nanotubes (SiCNTs) using first principles calculations based on density functional theory. The hydrogen adsorption properties are investigated by calculations of adsorption energy, electronic band structure, density of states (DOS) and Mulliken charge population analysis. Our findings show that hydrogen adsorptions on Pt, Ni and Al-decorated SiCNTs undergo spontaneous exothermic reactions with significant modulation of electronic structure of SiCNTs in all cases. Importantly, according to the Mulliken charge population analysis, dipole-dipole interaction causes chemisorptions of hydrogen in Pt, Ni and Al decorated SiCNTs with formation of chemical bonds. The study is a platform for the development of metal decorated SiCNTs for hydrogen adsorption or hydrogen storage application.

The TMI Regenerative Solid Oxide Fuel Cell

NASA Technical Reports Server (NTRS)

Cable, Thomas L.; Ruhl, Robert C.; Petrik, Michael

1996-01-01

Energy storage and production in space requires rugged, reliable hardware which minimizes weight, volume, and maintenance while maximizing power output and usable energy storage. Systems generally consist of photovoltaic solar arrays which operate (during sunlight cycles) to provide system power and regenerate fuel (hydrogen) via water electrolysis and (during dark cycles) fuel cells convert hydrogen into electricity. Common configurations use two separate systems (fuel cell and electrolyzer) in conjunction with photovoltaic cells. Reliability, power to weight and power to volume ratios could be greatly improved if both power production (fuel cells) and power storage (electrolysis) functions can be integrated into a single unit. The solid oxide fuel cell (SOFC) based design integrates fuel cell and electrolyzer functions and potentially simplifies system requirements. The integrated fuel cell/electrolyzer design also utilizes innovative gas storage concepts and operates like a rechargeable 'hydrogen-oxygen battery'. Preliminary research has been completed on improved H2/H20 electrode (SOFC anode/electrolyzer cathode) materials for regenerative fuel cells. Tests have shown improved cell performance in both fuel and electrolysis modes in reversible fuel cell tests. Regenerative fuel cell efficiencies, ratio of power out (fuel cell mode) to power in (electrolyzer mode), improved from 50 percent using conventional electrode materials to over 80 percent. The new materials will allow a single SOFC system to operate as both the electolyzer and fuel cell. Preliminary system designs have also been developed to show the technical feasibility of using the design for space applications requiring high energy storage efficiencies and high specific energy. Small space systems also have potential for dual-use, terrestrial applications.

A Joint Theory and Experimental Project in the Synthesis and Testing of Porous COFs for On-Board Vehicular Hydrogen Storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yaghi, Omar M.; Goddard, William A.

2013-06-29

Conventional storage of large amounts of hydrogen in its molecular form is difficult and expensive because it requires employing either extremely high pressure gas or very low temperature liquid. Because of the importance of hydrogen as a fuel, the DOE has set system targets for hydrogen storage of gravimetric (5.5 wt%) and volumetric (40 g/L) densities to be achieved by 2015. From our continuous efforts on hydrogen storage, it is believed that metalation of highly porous solids with high-valence metals is promising and provides a rational direction to realize high volumetric hydrogen density near room temperature. This grant was focusedmore » on the study of high surface area covalent organic frameworks (COFs) with these specific objectives (1) to introduce potential metal binding sites through the COF synthesis and (2) to implement metalation experiments and evaluate their respective hydrogen adsorption properties. To maximize our efforts, simulation calculations were also performed (prior to experiments) for the prediction of binding enthalpy of hydrogen for molecular building units containing transition metals and promising COF structures to increase volumetric hydrogen uptake at room temperature. In this effort, first molecular building units with optimal binding energy for hydrogen storage (20 kJ/mol) were designed by quantum mechanical (QM) methods. Employing these results, it was revealed that one of metalated COFs takes up 60 g/L (total) of H2 at 100 bar and 298 K. To realize proposed COF structures, chemistry of COF synthesis has been developed; for instance, new air stable COFs were synthesized via hydrazone (COF-41 to 43) and imine condensation (COF-301, 320, 340, and 366) and some of them were tested the effect on metalation. Finally, a new triazine COF with high volumetric hydrogen uptake capacity was presented as a proposed future direction.« less

A manganese-hydrogen battery with potential for grid-scale energy storage

NASA Astrophysics Data System (ADS)

Chen, Wei; Li, Guodong; Pei, Allen; Li, Yuzhang; Liao, Lei; Wang, Hongxia; Wan, Jiayu; Liang, Zheng; Chen, Guangxu; Zhang, Hao; Wang, Jiangyan; Cui, Yi

2018-05-01

Batteries including lithium-ion, lead-acid, redox-flow and liquid-metal batteries show promise for grid-scale storage, but they are still far from meeting the grid's storage needs such as low cost, long cycle life, reliable safety and reasonable energy density for cost and footprint reduction. Here, we report a rechargeable manganese-hydrogen battery, where the cathode is cycled between soluble Mn2+ and solid MnO2 with a two-electron reaction, and the anode is cycled between H2 gas and H2O through well-known catalytic reactions of hydrogen evolution and oxidation. This battery chemistry exhibits a discharge voltage of 1.3 V, a rate capability of 100 mA cm-2 (36 s of discharge) and a lifetime of more than 10,000 cycles without decay. We achieve a gravimetric energy density of 139 Wh kg-1 (volumetric energy density of 210 Wh l-1), with the theoretical gravimetric energy density of 174 Wh kg-1 (volumetric energy density of 263 Wh l-1) in a 4 M MnSO4 electrolyte. The manganese-hydrogen battery involves low-cost abundant materials and has the potential to be scaled up for large-scale energy storage.

Development of hydrogen gas getters for TRU waste

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaszuba, J. P.; Mroz, E. J.; Peterson, E.

2004-01-01

Alpha radiolysis of hydrogenous waste and packaging materials generates hydrogen gas in radioactive storage containers. For this reason, the flammable gas (hydrogen) concentration in waste shipment containers (Transuranic Package Transporter-II or TP-II containers) is limited to the lower explosion limit of hydrogen in air (5 vol%). The use of hydrogen getters is being investigated to prevent the build up of hydrogen during storage and transport of the TP-II containers (up to 60 days). Preferred hydrogen getters are solid materials that scavenge hydrogen from the gas phase and chemically and irreversibly bind it in the solid state. One proven getter, 1,4-bis(phenylethynyl)benzenemore » or DEB, belongs to a class of compounds called alkynes, which are characterized by the presence of carbon-carbon triple bonds. These carbon atoms will, in the presence of suitable catalysts such as palladium, irreversibly react with hydrogen to form the corresponding saturated alkane compounds. Because DEB contains two triple bonds, one mole of DEB reacts with 4 moles of hydrogen. The standard formulation for the 'DEB getter' is a mixture of 75% DEB and 25% carbon catalyst (5% palladium on carbon). Certain chemicals such as volatile organic compounds (VOCs) are known to 'poison' and reduce the activity of the catalyst. Therefore, in addition to the standard formulation, a semi-permeable barrier that encapsulates and protects the getter and its catalyst from poisons was also developed. The uncoated and polymer coated getter formulations were subjected to tests that determined the performance of the getters with regard to capacity, operating temperature range (with hydrogen in nitrogen and in air), hydrogen concentration, poisons, aging, pressure, reversibility, and radiation effects. This testing program was designed to address the following performance requirements: (1) Minimum rate for hydrogen removal of 1.2E-5 moles hydrogen per second for 60 days; (2) Sufficient getter material within the TP-II to ensure that no more than 50% of getter material is consumed during the 60 days; and (3) Adequate hydrogen removal rate from the getter reaction in the absence of the recombination reaction of hydrogen to produce water. This conservative approach provides a measure of safety for waste shipments by ensuring that sufficient getter material is present and by not taking credit for the recombination reaction. The rationale for measuring and reporting the hydrogen removal rate at 50% getter capacity is thus derived. All of the coated getters as well as the uncoated DEB performed well above the performance requirements. Coating the DEB with polymers did not significantly enhance getter performance in the presence of poisons relative to uncoated DEB. The next phase of the project is to evaluate a scaled-up getter package for performance under waste shipping conditions anticipated in the TP-II.« less

High temperature solid state storage cell

DOEpatents

Rea, Jesse R.; Kallianidis, Milton; Kelsey, G. Stephen

1983-01-01

A completely solid state high temperature storage cell comprised of a solid rechargeable cathode such as TiS.sub.2, a solid electrolyte which remains solid at the high temperature operating conditions of the cell and which exhibits high ionic conductivity at such elevated temperatures such as an electrolyte comprised of lithium iodide, and a solid lithium or other alkali metal alloy anode (such as a lithium-silicon alloy) with 5-50% by weight of said anode being comprised of said solid electrolyte.

Nuclear conversion theory: molecular hydrogen in non-magnetic insulators

NASA Astrophysics Data System (ADS)

Ilisca, Ernest; Ghiglieno, Filippo

2016-09-01

The hydrogen conversion patterns on non-magnetic solids sensitively depend upon the degree of singlet/triplet mixing in the intermediates of the catalytic reaction. Three main `symmetry-breaking' interactions are brought together. In a typical channel, the electron spin-orbit (SO) couplings introduce some magnetic excitations in the non-magnetic solid ground state. The electron spin is exchanged with a molecular one by the electric molecule-solid electron repulsion, mixing the bonding and antibonding states and affecting the molecule rotation. Finally, the magnetic hyperfine contact transfers the electron spin angular momentum to the nuclei. Two families of channels are considered and a simple criterion based on the SO coupling strength is proposed to select the most efficient one. The denoted `electronic' conversion path involves an emission of excitons that propagate and disintegrate in the bulk. In the other denoted `nuclear', the excited electron states are transients of a loop, and the electron system returns to its fundamental ground state. The described model enlarges previous studies by extending the electron basis to charge-transfer states and `continui' of band states, and focuses on the broadening of the antibonding molecular excited state by the solid conduction band that provides efficient tunnelling paths for the hydrogen conversion. After working out the general conversion algebra, the conversion rates of hydrogen on insulating and semiconductor solids are related to a few molecule-solid parameters (gap width, ionization and affinity potentials) and compared with experimental measures.

Nuclear conversion theory: molecular hydrogen in non-magnetic insulators

PubMed Central

Ghiglieno, Filippo

2016-01-01

The hydrogen conversion patterns on non-magnetic solids sensitively depend upon the degree of singlet/triplet mixing in the intermediates of the catalytic reaction. Three main ‘symmetry-breaking’ interactions are brought together. In a typical channel, the electron spin–orbit (SO) couplings introduce some magnetic excitations in the non-magnetic solid ground state. The electron spin is exchanged with a molecular one by the electric molecule–solid electron repulsion, mixing the bonding and antibonding states and affecting the molecule rotation. Finally, the magnetic hyperfine contact transfers the electron spin angular momentum to the nuclei. Two families of channels are considered and a simple criterion based on the SO coupling strength is proposed to select the most efficient one. The denoted ‘electronic’ conversion path involves an emission of excitons that propagate and disintegrate in the bulk. In the other denoted ‘nuclear’, the excited electron states are transients of a loop, and the electron system returns to its fundamental ground state. The described model enlarges previous studies by extending the electron basis to charge-transfer states and ‘continui’ of band states, and focuses on the broadening of the antibonding molecular excited state by the solid conduction band that provides efficient tunnelling paths for the hydrogen conversion. After working out the general conversion algebra, the conversion rates of hydrogen on insulating and semiconductor solids are related to a few molecule–solid parameters (gap width, ionization and affinity potentials) and compared with experimental measures. PMID:27703681

Porous Materials for Hydrolytic Dehydrogenation of Ammonia Borane

PubMed Central

Umegaki, Tetsuo; Xu, Qiang; Kojima, Yoshiyuki

2015-01-01

Hydrogen storage is still one of the most significant issues hindering the development of a “hydrogen energy economy”. Ammonia borane is notable for its high hydrogen densities. For the material, one of the main challenges is to release efficiently the maximum amount of the stored hydrogen. Hydrolysis reaction is a promising process by which hydrogen can be easily generated from this compound. High purity hydrogen from this compound can be evolved in the presence of solid acid or metal based catalyst. The reaction performance depends on the morphology and/or structure of these materials. In this review, we survey the research on nanostructured materials, especially porous materials for hydrogen generation from hydrolysis of ammonia borane. PMID:28793453

Structural and kinetic studies of metal hydride hydrogen storage materials using thin film deposition and characterization techniques

NASA Astrophysics Data System (ADS)

Kelly, Stephen Thomas

Hydrogen makes an attractive energy carrier for many reasons. It is an abundant chemical fuel that can be produced from a wide variety of sources and stored for very long periods of time. When used in a fuel cell, hydrogen emits only water at the point of use, making it very attractive for mobile applications such as in an automobile. Metal hydrides are promising candidates for on-board reversible hydrogen storage in mobile applications due to their very high volumetric storage capacities---in most cases exceeding even that of liquid hydrogen. The United States Department of Energy (DOE) has set fuel system targets for an automotive hydrogen storage system, but as of yet no single material meets all the requirements. In particular, slow reaction kinetics and/or inappropriate thermodynamics plague many metal hydride hydrogen storage materials. In order to engineer a practical material that meets the DOE targets, we need a detailed understanding of the kinetic and thermodynamic properties of these materials during the phase change. In this work I employed sputter deposited thin films as a platform to study materials with highly controlled chemistry, microstructure and catalyst placement using thin film characterization techniques such as in situ x-ray diffraction (XRD) and neutron reflectivity. I observed kinetic limitations in the destabilized Mg2Si system due to the slow diffusion of the host Mg and Si atoms while forming separate MgH2 and Si phases. Conversely, I observed that the presence of Al in the Mg/Al system inhibits hydrogen diffusion while the host Mg and Al atoms interdiffuse readily, allowing the material to fall into a kinetic and/or thermodynamic trap by forming intermetallic compounds such as Mg17Al 12. By using in situ XRD to analyze epitaxial Mg films grown on (001) oriented Al2O3 substrates I observed hydride growth consistent with a model of a planar hydride layer growing into an existing metal layer. Subsequent film cycling changes the hydrogen absorption and desorption kinetics and degrades the material texture. Cycling the films to greater hydrogen loading accelerates the changes to the kinetics and material texture. In addition to in situ XRD experiments, in situ neutron reflectivity experiments on epitaxial Mg films exposed to hydrogen gas reveal details about the microstructural development of the growing hydride layer as the film absorbs and releases hydrogen. Small (10 wt%) additions of Ti to epitaxial Mg films during growth result in metastable solid solution films of Ti in Mg that deposit epitaxially on (001) Al2O3 substrates with epitaxy similar to the pure Mg films. These metastable alloy films absorb hydrogen faster than pure Mg films under identical conditions. Subsequent film cycling results in altered reaction kinetics and a transition to a different kinetic mechanism during desorption than for pure Mg films.

Atmospheric Mining in the Outer Solar System: Resource Capturing, Storage, and Utilization

NASA Technical Reports Server (NTRS)

Palaszewski, Bryan

2012-01-01

Atmospheric mining in the outer solar system has been investigated as a means of fuel production for high energy propulsion and power. Fusion fuels such as Helium 3 (3He) and hydrogen can be wrested from the atmospheres of Uranus and Neptune and either returned to Earth or used in-situ for energy production. Helium 3 and hydrogen (deuterium, etc.) were the primary gases of interest with hydrogen being the primary propellant for nuclear thermal solid core and gas core rocket-based atmospheric flight. A series of analyses were undertaken to investigate resource capturing aspects of atmospheric mining in the outer solar system. This included the gas capturing rate for hydrogen helium 4 and helium 3, storage options, and different methods of direct use of the captured gases. Additional supporting analyses were conducted to illuminate vehicle sizing and orbital transportation issues.

Space Electrochemical Research and Technology

NASA Technical Reports Server (NTRS)

Wilson, Richard M. (Compiler)

1996-01-01

Individual papers presented at the conference address the following topics: development of a micro-fiber nickel electrode for nickel-hydrogen cell, high performance nickel electrodes for space power application, bending properties of nickel electrodes for nickel-hydrogen batteries, effect of KOH concentration and anions on the performance of a Ni-H2 battery positive plate, advanced dependent pressure vessel nickel hydrogen spacecraft cell and battery design, electrolyte management considerations in modern nickel hydrogen and nickel cadmium cell and battery design, a novel unitized regenerative proton exchange membrane fuel cell, fuel cell systems for first lunar outpost - reactant storage options, the TMI regenerable solid oxide fuel cell, engineering development program of a closed aluminum-oxygen semi-cell system for an unmanned underwater vehicle, SPE OBOGS on-board oxygen generating system, hermetically sealed aluminum electrolytic capacitor, sol-gel technology and advanced electrochemical energy storage materials, development of electrochemical supercapacitors for EMA applications, and high energy density electrolytic capacitor.

Storing energy in metal hydrides - A review of the physical metallurgy

NASA Astrophysics Data System (ADS)

Ivey, D. G.; Northwood, D. O.

1983-02-01

The properties of metal hydrides, which are significant in terms of their potential as a hydrogen storage medium, are discussed. Attention is given to bonding and electronic factors of metal hydrides, which, when combined with hydrogen, form saline, ionic, metallic, and covalent bonds, with the resultant materials being either solid, liquid, or gaseous. Metallic bonds are the most promising for hydrogen storage, and involve most of the elements of groups IIIA-VIIIA in the periodic table. An analysis of the thermodynamics and kinetics of metal hydrides is presented, noting the effects of alloy composition, crystal structure, and contaminants on the effectiveness of the materials as hydrides. Hysteresis has been found to occur when the transition pressure in a pressure-composition-temperature curve is higher for absorption than for desorption, although the actual causes for hysteresis are not understood. The AB group of intermetallics has been determined to store hydrogen at the lowest cost. Examples from tests using the AB compounds are outlined, and attempts to rectify storage requirement deficiencies by adjusting the alloy compositions are described.

Effects of hydrogen bonding between pyrrole-2-carboxaldehyde and nearest polar and nonpolar environment

NASA Astrophysics Data System (ADS)

Rana, Meenakshi; Chowdhury, Papia

2017-10-01

The present paper represents dominant effects of hydrogen bonding on the existence of different molecular aggregates in one of the heterocyclic pyrrole system: pyrrole-2-carboxaldehyde (PCL). Theoretical and experimental Raman spectral evidence verifies the existence of different molecular aggregates like dimeric, monomeric, hydrated complex states in PCL. Atoms in molecules (AIMs) analysis and fluorescence decay profile provide a strong signature of intermolecular hydrogen bonding (IerHB) as the possible reason for the existence of cis form of dimeric (X) molecular aggregates. The high remnant polarization of 3.13 μCcm- 2 and smaller dielectric loss in solid form of PCL arise due to in X by ordering of dipoles as a result of IerHB. A remarkable high ferroelectric response in solid phase makes PCL a desirable candidate to be used as raw material for energy storage devices. For solution phase, in presence of external hydroxylic environment, PCL reacts with external water molecules through weak IerHB and creates different hydrated PCL/(H2O)n complexes by creating water bridge with number of water molecules from 1 to n. An increasing number of water molecules helps to form stronger hydrated complex by separation of charges by lowering the transferring energy barrier.

Methods to Stabilize and Destabilize Ammonium Borohydride

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nielsen, Thomas K.; Karkamkar, Abhijeet J.; Bowden, Mark E.

2013-01-21

Ammonium borohydride, NH4BH4, has a high hydrogen content of ρm = 24.5 wt% H2 and releases 18 wt% H2 below T = 160 °C. However, the half-life of bulk NH4BH4 at ambient temperatures, ~6 h, is insufficient for practical applications. The decomposition of NH4BH4 (ABH2) was studied at variable hydrogen and argon back pressures to investigate possible pressure mediated stabilization effects. The hydrogen release rate from solid ABH2 at ambient temperatures is reduced by ~16 % upon increasing the hydrogen back pressure from 5 to 54 bar. Similar results were obtained using argon pressure and the observed stabilization may bemore » explained by a positive volume of activation in the transition state leading to hydrogen release. Nanoconfinement in mesoporous silica, MCM-41, was investigated as alternative means to stabilize NH4BH4. However, other factors appear to significantly destabilize NH4BH4 and it rapidly decomposes at ambient temperatures into [(NH3)2BH2][BH4] (DADB) in accordance with the bulk reaction scheme. The hydrogen desorption kinetics from nanoconfined [(NH3)2BH2][BH4] is moderately enhanced as evidenced by a reduction in the DSC decomposition peak temperature of ΔT = -13 °C as compared to the bulk material. Finally, we note a surprising result, storage of DADB at temperature < -30 °C transformed, reversibly, the [(NH3)2BH2][BH4] into a new low temperature polymorph as revealed by both XRD and solid state MAS 11B MAS NMR. TA & AK are thankful for support from the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. A portion of the research was performed using EMSL, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle.« less

An aqueous rechargeable formate-based hydrogen battery driven by heterogeneous Pd catalysis.

PubMed

Bi, Qing-Yuan; Lin, Jian-Dong; Liu, Yong-Mei; Du, Xian-Long; Wang, Jian-Qiang; He, He-Yong; Cao, Yong

2014-12-01

The formate-based rechargeable hydrogen battery (RHB) promises high reversible capacity to meet the need for safe, reliable, and sustainable H2 storage used in fuel cell applications. Described herein is an additive-free RHB which is based on repetitive cycles operated between aqueous formate dehydrogenation (discharging) and bicarbonate hydrogenation (charging). Key to this truly efficient and durable H2 handling system is the use of highly strained Pd nanoparticles anchored on graphite oxide nanosheets as a robust and efficient solid catalyst, which can facilitate both the discharging and charging processes in a reversible and highly facile manner. Up to six repeated discharging/charging cycles can be performed without noticeable degradation in the storage capacity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen bonding pattern in N-benzoyl(- DL-)- L-phenylalanines as revealed by solid-state NMR spectroscopy

NASA Astrophysics Data System (ADS)

Potrzebowski, M. J.; Schneider, C.; Tekely, P.

1999-11-01

The nature of the hydrogen bonding pattern has been investigated in N-benzoyl- DL-phenylalanine ( 1) and N-benzoyl- L-phenylalanine ( 2) polymorphes by solid-state NMR spectroscopy. It has been shown that the multiple resonances of carboxyl carbon in 2 are directly connected to different types of hydrogen bonding. The differences in intermolecular distances of carboxyl groups involved in different types of hydrogen bonding have been visualized by the 2D exchange and 1D ODESSA experiments. Potential applications of such a new approach include the exploration of intermolecular distances in hydrogen bonded compounds with singly labeled biomolecules.

Physical principles and current status of emerging non-volatile solid state memories

NASA Astrophysics Data System (ADS)

Wang, L.; Yang, C.-H.; Wen, J.

2015-07-01

Today the influence of non-volatile solid-state memories on persons' lives has become more prominent because of their non-volatility, low data latency, and high robustness. As a pioneering technology that is representative of non-volatile solidstate memories, flash memory has recently seen widespread application in many areas ranging from electronic appliances, such as cell phones and digital cameras, to external storage devices such as universal serial bus (USB) memory. Moreover, owing to its large storage capacity, it is expected that in the near future, flash memory will replace hard-disk drives as a dominant technology in the mass storage market, especially because of recently emerging solid-state drives. However, the rapid growth of the global digital data has led to the need for flash memories to have larger storage capacity, thus requiring a further downscaling of the cell size. Such a miniaturization is expected to be extremely difficult because of the well-known scaling limit of flash memories. It is therefore necessary to either explore innovative technologies that can extend the areal density of flash memories beyond the scaling limits, or to vigorously develop alternative non-volatile solid-state memories including ferroelectric random-access memory, magnetoresistive random-access memory, phase-change random-access memory, and resistive random-access memory. In this paper, we review the physical principles of flash memories and their technical challenges that affect our ability to enhance the storage capacity. We then present a detailed discussion of novel technologies that can extend the storage density of flash memories beyond the commonly accepted limits. In each case, we subsequently discuss the physical principles of these new types of non-volatile solid-state memories as well as their respective merits and weakness when utilized for data storage applications. Finally, we predict the future prospects for the aforementioned solid-state memories for the next generation of data-storage devices based on a comparison of their performance. [Figure not available: see fulltext.

Calorimetric Studies and Structural Aspects of Ionic Liquids in Designing Sorption Materials for Thermal Energy Storage.

PubMed

Brünig, Thorge; Krekić, Kristijan; Bruhn, Clemens; Pietschnig, Rudolf

2016-11-02

The thermal properties of a series of twenty-four ionic liquids (ILs) have been determined by isothermal titration calorimetry (ITC) with the aim of simulating processes involving water sorption. For eleven water-free ILs, the molecular structures have been determined by X-ray crystallography in the solid state, which have been used to derive the molecular volumes of the ionic components of the ILs. Moreover, the structures reveal a high prevalence of hydrogen bonding in these compounds. A relationship between the molecular volumes and the experimentally determined energies of dilution could be established. The highest energies of dilution observed in this series were obtained for the acetate-based ILs, which underlines their potential as working fluids in sorption-based thermal energy storage systems. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermodynamic and Kinetic Properties of Metal Hydrides from First-Principles Calculations

NASA Astrophysics Data System (ADS)

Michel, Kyle Jay

In an effort to minimize the worldwide dependence on fossil fuels, much research has focused on the development of hydrogen fuel cell vehicles. Among the many challenges currently facing the transition to such an alternative energy economy is the storage of hydrogen in an economical and practical way. One class of materials that has presented itself as a possible candidate is solid metal hydrides. These materials chemically bind hydrogen and on heating, release the gas which can then be used to generate power as needed for the vehicle. In order to meet guidelines that have been set for such a storage system, hydrogen must be released rapidly in a narrow temperature range of -40 to 80°C with all reactions being reversible. This sets both thermodynamic and kinetic requirements for the design of candidate metal hydrides. First-principles calculations are well-suited for the task of exploring reactions involving metal hydrides. Here, density-functional theory is used to calculate properties of these materials at the quantum mechanical level of accuracy. In particular, three systems have been investigated: 1. Li-Mg-N-H. Reactions between all known compounds in this system are systematically investigated in order to predict thermodynamically allowed reactions that release hydrogen. The properties of these reactions are compared to the requirements set for hydrogen storage systems. Additionally, ground-state structures are predicted for Li2Mg(NH)2 and Li 4Mg(NH)3. 2. Na-Al-H. The kinetics of mass transport during the (de)hydrogenation of the well-known metal hydride NaAlH4 are investigated. A model is developed to study the flux of native defects through phases involved in these reactions. Since it is also known that titanium is an effective catalyst for both dehydrogenation and rehydrogenation, the effect of Ti substitution in bulk lattices on the kinetics of mass transport is investigated. Results are compared to experiments in order to determine if mass transport represents the rate-limiting process during de- or rehydrogenation and what the effect of Ti may be. 3. Si-H. Properties of the recently synthesized compound SiH4(H 2)2 are investigated. Under high pressures, hydrogen binding to SiH4 exhibits characteristics of both physical and chemical bonds. A ground-state structure is predicted for this phase and the vibrational and bonding properties are investigated in order to determine the origin of the unusual binding between H2 and SiH4.

High-pressure melting curve of hydrogen.

PubMed

Davis, Sergio M; Belonoshko, Anatoly B; Johansson, Börje; Skorodumova, Natalia V; van Duin, Adri C T

2008-11-21

The melting curve of hydrogen was computed for pressures up to 200 GPa, using molecular dynamics. The inter- and intramolecular interactions were described by the reactive force field (ReaxFF) model. The model describes the pressure-volume equation of state solid hydrogen in good agreement with experiment up to pressures over 150 GPa, however the corresponding equation of state for liquid deviates considerably from density functional theory calculations. Due to this, the computed melting curve, although shares most of the known features, yields considerably lower melting temperatures compared to extrapolations of the available diamond anvil cell data. This failure of the ReaxFF model, which can reproduce many physical and chemical properties (including chemical reactions in hydrocarbons) of solid hydrogen, hints at an important change in the mechanism of interaction of hydrogen molecules in the liquid state.

Investigation for the amorphous state of ER-34122, a dual 5-lipoxygenase/cyclooxygenase inhibitor with poor aqueous solubility, in HPMC solid dispersion prepared by the solvent evaporation method.

PubMed

Kushida, Ikuo; Gotoda, Masaharu

2013-10-01

ER-34122, a poorly water-soluble dual 5-lipoxygenase/cyclooxygenase inhibitor, exists as a crystalline form. According to an Oak Ridge thermal ellipsoid plot drawing, carbonyl oxygen O (5) makes an intermolecular hydrogen bond with the hydrogen bonded to N (3) in the crystal structure. The FTIR and the solid-state ¹³C NMR spectra suggest that the network is spread out in the amorphous state and the hydrogen bonding gets weaker than that in the crystalline phase, because the carbonyl signals significantly shift in both spectra. When amorphous ER-34122 was heated, crystallization occurred at around 140°C. Similar crystallization happened in the solid dispersion; however, the degree of crystallization was much lower than that observed in the pure amorphous material. Also, the DSC thermogram of the solid dispersion did not show any exothermic peaks implying crystallization. The heat of fusion (ΔHf) determined in the pure amorphous material was nearly equal to that for the crystalline form, whereas the ΔHf value obtained in the solid dispersion was less than a third of them. These data prove that crystallization of the amorphous form is dramatically restrained in the solid dispersion system. The carbonyl wavenumber shifts in the FTIR spectra indicate that the average hydrogen bond in the solid dispersion is lower than that in the pure amorphous material. Therefore, HPMC will suppress formation of the intermolecular network observed in ER-34122 crystal and preserve the amorphous state, which is thermodynamically less stable, in the solid dispersed system.

Correlation between structural stability of LiBH4 and cation electronegativity in metal borides: an experimental insight for catalyst design.

PubMed

Cai, Weitong; Yang, Yuanzheng; Tao, Pingjun; Ouyang, Liuzhang; Wang, Hui

2018-04-03

Nanosized metal borides MBx (M = Mg, Ti, Fe, Si) are found to play an important role in enhancing the hydrogen storage performance of LiBH4 in this work. The hydrogen storage behavior and mechanism of these modified systems are investigated through TPD-MS, XRD, FTIR and SEM characterization methods. By introducing these metal borides into LiBH4 through ball milling, the systems display three dehydrogenation stages disclosing their similarity and distinction. The 1st stage starts at 190 °C, the 2nd stage ranges from 280 °C to 400 °C and the 3rd stage ends at 550 °C with a peak at round 440 °C similar to that of pristine LiBH4. Distinguishing features exist at the 2nd stage revealing the effectiveness of MBx in an order of MgB2 < TiB2 < FeB < SiB4. Significantly, reversibility up to 9.7 wt% is achieved from LiBH4 with assistance of SiB4. The catalytic effect of MBx is influenced by the Pauling electronegativity of M in MBx and the interfacial contact characteristic between LiBH4 and MBx. The larger electronegativity leads to an enhanced catalytic effect and consequently lower temperature at the major stage. In contrast to the components in the solid state, the molten LiBH4 promotes a catalytic effect due to a superior interfacial contact. These results provide an insight into designing high-performance catalysts applied to LiBH4 as a hydrogen storage material.

Hydrogen Research for Spaceport and Space-Based Applications: Fuel Cell Projects

NASA Technical Reports Server (NTRS)

Anderson, Tim; Balaban, Canan

2008-01-01

The activities presented are a broad based approach to advancing key hydrogen related technologies in areas such as fuel cells, hydrogen production, and distributed sensors for hydrogen-leak detection, laser instrumentation for hydrogen-leak detection, and cryogenic transport and storage. Presented are the results from research projects, education and outreach activities, system and trade studies. The work will aid in advancing the state-of-the-art for several critical technologies related to the implementation of a hydrogen infrastructure. Activities conducted are relevant to a number of propulsion and power systems for terrestrial, aeronautics and aerospace applications. Fuel cell research focused on proton exchange membranes (PEM), solid oxide fuel cells (SOFC). Specific technologies included aircraft fuel cell reformers, new and improved electrodes, electrolytes, interconnect, and seals, modeling of fuel cells including CFD coupled with impedance spectroscopy. Research was conducted on new materials and designs for fuel cells, along with using embedded sensors with power management electronics to improve the power density delivered by fuel cells. Fuel cell applications considered were in-space operations, aviation, and ground-based fuel cells such as; powering auxiliary power units (APUs) in aircraft; high power density, long duration power supplies for interplanetary missions (space science probes and planetary rovers); regenerative capabilities for high altitude aircraft; and power supplies for reusable launch vehicles.

Discovery of Novel Complex Metal Hydrides for Hydrogen Storage through Molecular Modeling and Combinatorial Methods

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lesch, David A; Adriaan Sachtler, J.W. J.; Low, John J

UOP LLC, a Honeywell Company, Ford Motor Company, and Striatus, Inc., collaborated with Professor Craig Jensen of the University of Hawaii and Professor Vidvuds Ozolins of University of California, Los Angeles on a multi-year cost-shared program to discover novel complex metal hydrides for hydrogen storage. This innovative program combined sophisticated molecular modeling with high throughput combinatorial experiments to maximize the probability of identifying commercially relevant, economical hydrogen storage materials with broad application. A set of tools was developed to pursue the medium throughput (MT) and high throughput (HT) combinatorial exploratory investigation of novel complex metal hydrides for hydrogen storage. Themore » assay programs consisted of monitoring hydrogen evolution as a function of temperature. This project also incorporated theoretical methods to help select candidate materials families for testing. The Virtual High Throughput Screening served as a virtual laboratory, calculating structures and their properties. First Principles calculations were applied to various systems to examine hydrogen storage reaction pathways and the associated thermodynamics. The experimental program began with the validation of the MT assay tool with NaAlH4/0.02 mole Ti, the state of the art hydrogen storage system given by decomposition of sodium alanate to sodium hydride, aluminum metal, and hydrogen. Once certified, a combinatorial 21-point study of the NaAlH4 LiAlH4Mg(AlH4)2 phase diagram was investigated with the MT assay. Stability proved to be a problem as many of the materials decomposed during synthesis, altering the expected assay results. This resulted in repeating the entire experiment with a mild milling approach, which only temporarily increased capacity. NaAlH4 was the best performer in both studies and no new mixed alanates were observed, a result consistent with the VHTS. Powder XRD suggested that the reverse reaction, the regeneration of the alanate from alkali hydride, Al and hydrogen, was hampering reversibility. The reverse reaction was then studied for the same phase diagram, starting with LiH, NaH, and MgH2, and Al. The study was extended to phase diagrams including KH and CaH2 as well. The observed hydrogen storage capacity in the Al hexahydrides was less than 4 wt. %, well short of DOE targets. The HT assay came on line and after certification with studies on NaAlH4, was first applied to the LiNH2 - LiBH4 - MgH2 phase diagram. The 60-point study elucidated trends within the system locating an optimum material of 0.6 LiNH2 0.3 MgH2 0.1 LiBH4 that stored about 4 wt. % H2 reversibly and operated below 220 °C. Also present was the phase Li4(NH2)3BH4, which had been discovered in the LiNH2 -LiBH4 system. This new ternary formulation performed much better than the well-known 2 LiNH2MgH2 system by 50 °C in the HT assay. The Li4(NH2)3BH4 is a low melting ionic liquid under our test conditions and facilitates the phase transformations required in the hydrogen storage reaction, which no longer relies on a higher energy solid state reaction pathway. Further study showed that the 0.6 LiNH2 0.3 MgH2 0.1 LiBH4 formulation was very stable with respect to ammonia and diborane desorption, the observed desorption was from hydrogen. This result could not have been anticipated and was made possible by the efficiency of HT combinatorial methods. Investigation of the analogous LiNH2 LiBH4 CaH2 phase diagram revealed new reversible hydrogen storage materials 0.625 LiBH4 + 0.375 CaH2 and 0.375 LiNH2 + 0.25 LiBH4 + 0.375 CaH2 operating at 1 wt. % reversible hydrogen below 175 °C. Powder x-ray diffraction revealed a new structure for the spent materials which had not been previously observed. While the storage capacity was not impressive, an important aspect is that it boron appears to participate in a low temperature reversible reaction. The last major area of study also focused on activating boron-based materials in order to exploit the tremendous gravimetric capacity of LiBH4. A number of LiNH2 LiBH4 transition metal (TM) systems were investigated for the following reasons. No additional leads were discovered in this system. Another major project activity was the assembly of a high throughput synthesis system. The automated synthesizer was set up in a glovebox and was capable of handling liquids and powders and carrying out sealed block syntheses up to 250 °C. Unfortunately, the synthesizer could not handle the delivery of the fine powders required fro hydrogen storage applications. Although the powder delivery system was overhauled and redesigned several times, this problem was never remedied.« less

Room temperature micro-hydrogen-generator

NASA Astrophysics Data System (ADS)

Gervasio, Don; Tasic, Sonja; Zenhausern, Frederic

A new compact and cost-effective hydrogen-gas generator has been made that is well suited for supplying hydrogen to a fuel-cell for providing base electrical power to hand-carried appliances. This hydrogen-generator operates at room temperature, ambient pressure and is orientation-independent. The hydrogen-gas is generated by the heterogeneous catalytic hydrolysis of aqueous alkaline borohydride solution as it flows into a micro-reactor. This reactor has a membrane as one wall. Using the membrane keeps the liquid in the reactor, but allows the hydrogen-gas to pass out of the reactor to a fuel-cell anode. Aqueous alkaline 30 wt% borohydride solution is safe and promotes long application life, because this solution is non-toxic, non-flammable, and is a high energy-density (≥2200 W-h per liter or per kilogram) hydrogen-storage solution. The hydrogen is released from this storage-solution only when it passes over the solid catalyst surface in the reactor, so controlling the flow of the solution over the catalyst controls the rate of hydrogen-gas generation. This allows hydrogen generation to be matched to hydrogen consumption in the fuel-cell, so there is virtually no free hydrogen-gas during power generation. A hydrogen-generator scaled for a system to provide about 10 W electrical power is described here. However, the technology is expected to be scalable for systems providing power spanning from 1 W to kW levels.

Hydrogen storage properties of nanosized MgH2-0.1TiH2 prepared by ultrahigh-energy-high-pressure milling.

PubMed

Lu, Jun; Choi, Young Joon; Fang, Zhigang Zak; Sohn, Hong Yong; Rönnebro, Ewa

2009-11-04

Magnesium hydride (MgH(2)) is an attractive candidate for solid-state hydrogen storage applications. To improve the kinetics and thermodynamic properties of MgH(2) during dehydrogenation-rehydrogenation cycles, a nanostructured MgH(2)-0.1TiH(2) material system prepared by ultrahigh-energy-high-pressure mechanical milling was investigated. High-resolution transmission electron microscope (TEM) and scanning TEM analysis showed that the grain size of the milled MgH(2)-0.1TiH(2) powder is approximately 5-10 nm with uniform distributions of TiH(2) among MgH(2) particles. Pressure-composition-temperature (PCT) analysis demonstrated that both the nanosize and the addition of TiH(2) contributed to the significant improvement of the kinetics of dehydrogenation and hydrogenation compared to commercial MgH(2). More importantly, PCT cycle analysis demonstrated that the MgH(2)-0.1TiH(2) material system showed excellent cycle stability. The results also showed that the DeltaH value for the dehydrogenation of nanostructured MgH(2)-0.1TiH(2) is significantly lower than that of commercial MgH(2). However, the DeltaS value of the reaction was also lower, which results in minimum net effects of the nanosize and the addition of TiH(2) on the equilibrium pressure of dehydrogenation reaction of MgH(2).

FLUSH: A tool for the design of slush hydrogen flow systems

NASA Technical Reports Server (NTRS)

Hardy, Terry L.

1990-01-01

As part of the National Aerospace Plane Project an analytical model was developed to perform calculations for in-line transfer of solid-liquid mixtures of hydrogen. This code, called FLUSH, calculates pressure drop and solid fraction loss for the flow of slush hydrogen through pipe systems. The model solves the steady-state, one-dimensional equation of energy to obtain slush loss estimates. A description of the code is provided as well as a guide for users of the program. Preliminary results are also presented showing the anticipated degradation of slush hydrogen solid content for various piping systems.

Metal Hydride Nanoparticles with Ultrahigh Structural Stability and Hydrogen Storage Activity Derived from Microencapsulated Nanoconfinement.

PubMed

Zhang, Jiguang; Zhu, Yunfeng; Lin, Huaijun; Liu, Yana; Zhang, Yao; Li, Shenyang; Ma, Zhongliang; Li, Liquan

2017-06-01

Metal hydrides (MHs) have recently been designed for hydrogen sensors, switchable mirrors, rechargeable batteries, and other energy-storage and conversion-related applications. The demands of MHs, particular fast hydrogen absorption/desorption kinetics, have brought their sizes to nanoscale. However, the nanostructured MHs generally suffer from surface passivation and low aggregation-resisting structural stability upon absorption/desorption. This study reports a novel strategy named microencapsulated nanoconfinement to realize local synthesis of nano-MHs, which possess ultrahigh structural stability and superior desorption kinetics. Monodispersed Mg 2 NiH 4 single crystal nanoparticles (NPs) are in situ encapsulated on the surface of graphene sheets (GS) through facile gas-solid reactions. This well-defined MgO coating layer with a thickness of ≈3 nm efficiently separates the NPs from each other to prevent aggregation during hydrogen absorption/desorption cycles, leading to excellent thermal and mechanical stability. More interestingly, the MgO layer shows superior gas-selective permeability to prevent further oxidation of Mg 2 NiH 4 meanwhile accessible for hydrogen absorption/desorption. As a result, an extremely low activation energy (31.2 kJ mol -1 ) for the dehydrogenation reaction is achieved. This study provides alternative insights into designing nanosized MHs with both excellent hydrogen storage activity and thermal/mechanical stability exempting surface modification by agents. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation, characterization and application of novel proton conducting ceramics

NASA Astrophysics Data System (ADS)

Wang, Siwei

Due to the immediate energy shortage and the requirement of environment protection nowadays, the efficient, effective and environmental friendly use of current energy sources is urgent. Energy conversion and storage is thus an important focus both for industry and academia. As one of the hydrogen energy related materials, proton conducting ceramics can be applied in solid oxide fuel cells and steam electrolysers, as well as high temperature hydrogen separation membranes and hydrogen sensors. For most of the practical applications, both high proton conductivity and chemical stability are desirable. However, the state-of-the-art proton conducting ceramics are facing great challenges in simultaneously fulfilling conductivity and stability requirements for practical applications. Consequently, understanding the properties for the proton conducting ceramics and developing novel materials that possess both high proton conductivity and enhanced chemical stability have both scientific and practical significances. The objective of this study is to develop novel proton conducting ceramics, either by evaluating the doping effects on the state-of-the-art simple perovskite structured barium cerates, or by investigating novel complex perovskite structured Ba3Ca1.18Nb1.82O 9-delta based proton conductors as potential proton conducting ceramics with improved proton conductivity and enhanced chemical stability. Different preparation methods were compared, and their influence on the structure, including the bulk and grain boundary environment has been investigated. In addition, the effects of microstructure on the electrical properties of the proton conducting ceramics have also been characterized. The solid oxide fuel cell application for the proton conducting ceramics performed as electrolyte membranes has been demonstrated.

Translational vibrations between chains of hydrogen-bonded molecules in solid-state aspirin form I

NASA Astrophysics Data System (ADS)

Takahashi, Masae; Ishikawa, Yoichi

2013-06-01

We perform dispersion-corrected first-principles calculations, and far-infrared (terahertz) spectroscopic experiments at 4 K, to examine translational vibrations between chains of hydrogen-bonded molecules in solid-state aspirin form I. The calculated frequencies and relative intensities reproduce the observed spectrum to accuracy of 11 cm-1 or less. The stronger one of the two peaks assigned to the translational mode includes the stretching vibration of the weak hydrogen bond between the acetyl groups of a neighboring one-dimensional chain. The calculation of aspirin form II performed for comparison gives the stretching vibration of the weak hydrogen bond in one-dimensional chain.

Integrated Refrigeration and Storage for Advanced Liquid Hydrogen Operations

NASA Technical Reports Server (NTRS)

Swanger, A. M.; Notardonato, W. U.; Johnson, W. L.; Tomsik, T. M.

2016-01-01

NASA has used liquefied hydrogen (LH2) on a large scale since the beginning of the space program as fuel for the Centaur and Apollo upper stages, and more recently to feed the three space shuttle main engines. The LH2 systems currently in place at the Kennedy Space Center (KSC) launch pads are aging and inefficient compared to the state-of-the-art. Therefore, the need exists to explore advanced technologies and operations that can drive commodity costs down, and provide increased capabilities. The Ground Operations Demonstration Unit for Liquid Hydrogen (GODU-LH2) was developed at KSC to pursue these goals by demonstrating active thermal control of the propellant state by direct removal of heat using a cryocooler. The project has multiple objectives including zero loss storage and transfer, liquefaction of gaseous hydrogen, and densification of liquid hydrogen. The key technology challenge was efficiently integrating the cryogenic refrigerator into the LH2 storage tank. A Linde LR1620 Brayton cycle refrigerator is used to produce up to 900W cooling at 20K, circulating approximately 22 g/s gaseous helium through the hydrogen via approximately 300 m of heat exchanger tubing. The GODU-LH2 system is fully operational, and is currently under test. This paper will discuss the design features of the refrigerator and storage system, as well as the current test results.

Melt extrusion vs. spray drying: The effect of processing methods on crystalline content of naproxen-povidone formulations.

PubMed

Haser, Abbe; Cao, Tu; Lubach, Joe; Listro, Tony; Acquarulo, Larry; Zhang, Feng

2017-05-01

Our hypothesis is that melt extrusion is a more suitable processing method than spray drying to prepare amorphous solid dispersions of drugs with a high crystallization tendency. Naproxen-povidone K25 was used as the model system in this study. Naproxen-povidone K25 solid dispersions at 30% and 60% drug loadings were characterized by modulated DSC, powder X-ray diffraction, FT-IR, and solid-state 13 C NMR to identify phase separation and drug recrystallization during processing and storage. At 30% drug loading, hydrogen bond (H-bond) sites of povidone K25 were not saturated and the glass transition (T g ) temperature of the formulation was higher. As a result, both melt-extruded and spray-dried materials were amorphous initially and remained so after storage at 40°C. At 60% drug loading, H-bond sites were saturated, and T g was low. We were not able to prepare amorphous materials. The initial crystallinity of the formulations was 0.4%±0.2% and 5.6%±0.6%, and increased to 2.7%±0.3% and 21.6%±1.0% for melt-extruded and spray-dried materials, respectively. Spray-dried material was more susceptible to re-crystallization during processing, due to the high diffusivity of naproxen molecules in the formulation matrix and lack of kinetic stabilization from polymer solution. A larger number of crystalline nucleation sites and high surface area made the spray-dried material more susceptible to recrystallization during storage. This study demonstrated the unique advantages of melt extrusion over spray drying for the preparation of amorphous solid dispersions of naproxen at high drug level. Copyright © 2017 Elsevier B.V. All rights reserved.

Solid state phase change materials for thermal energy storage in passive solar heated buildings

NASA Astrophysics Data System (ADS)

Benson, D. K.; Christensen, C.

1983-11-01

A set of solid state phase change materials was evaluated for possible use in passive solar thermal energy storage systems. The most promising materials are organic solid solutions of pentaerythritol, pentaglycerine and neopentyl glycol. Solid solution mixtures of these compounds can be tailored so that they exhibit solid-to-solid phase transformations at any desired temperature within the range from less than 25 deg to 188 deg. Thermophysical properties such as thermal conductivity, density and volumetric expansion were measured. Computer simulations were used to predict the performance of various Trombe wall designs incorporating solid state phase change materials. Optimum performance was found to be sensitive to the choice of phase change temperatures and to the thermal conductivity of the phase change material. A molecular mechanism of the solid state phase transition is proposed and supported by infrared spectroscopic evidence.

Can Csbnd H⋯Fsbnd C hydrogen bonds alter crystal packing features in the presence of Nsbnd H⋯Odbnd C hydrogen bond?

NASA Astrophysics Data System (ADS)

Yadav, Hare Ram; Choudhury, Angshuman Roy

2017-12-01

Intermolecular interactions involving organic fluorine have been the contemporary field of research in the area of organic solid state chemistry. While a group of researchers had refuted the importance of "organic fluorine" in guiding crystal structures, others have provided evidences for in favor of fluorine mediated interactions in the solid state. Many systematic studies have indicated that the "organic fluorine" is capable of offering weak hydrogen bonds through various supramolecular synthons, mostly in the absence of other stronger hydrogen bonds. Analysis of fluorine mediated interaction in the presence of strong hydrogen bonds has not been highlighted in detail. Hence a thorough structural investigation is needed to understand the role of "organic fluorine" in crystal engineering of small organic fluorinated molecules having the possibility of strong hydrogen bond formation in the solution and in the solid state. To fulfil this aim, we have synthesized a series of fluorinated amides using 3-methoxyphenylacetic acid and fluorinated anilines and studied their structural properties through single crystal and powder X-ray diffraction methods. Our results indicated that the "organic fluorine" plays a significant role in altering the packing characteristics of the molecule in building specific crystal lattices even in the presence of strong hydrogen bond.

Method and composition in which metal hydride particles are embedded in a silica network

DOEpatents

Heung, Leung K.

1999-01-01

A silica embedded metal hydride composition and a method for making such a composition. The composition is made via the following process: A quantity of fumed silica is blended with water to make a paste. After adding metal hydride particles, the paste is dried to form a solid. According to one embodiment of the invention, the solid is ground into granules for use of the product in hydrogen storage. Alternatively, the paste can be molded into plates or cylinders and then dried for use of the product as a hydrogen filter. Where mechanical strength is required, the paste can be impregnated in a porous substrate or wire network.

Amyloid Hydrogen Bonding Polymorphism Evaluated by (15)N{(17)O}REAPDOR Solid-State NMR and Ultra-High Resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry.

PubMed

Wei, Juan; Antzutkin, Oleg N; Filippov, Andrei V; Iuga, Dinu; Lam, Pui Yiu; Barrow, Mark P; Dupree, Ray; Brown, Steven P; O'Connor, Peter B

2016-04-12

A combined approach, using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) and solid-state NMR (Nuclear Magnetic Resonance), shows a high degree of polymorphism exhibited by Aβ species in forming hydrogen-bonded networks. Two Alzheimer's Aβ peptides, Ac-Aβ(16-22)-NH2 and Aβ(11-25), selectively labeled with (17)O and (15)N at specific amino acid residues were investigated. The total amount of peptides labeled with (17)O as measured by FTICR-MS enabled the interpretation of dephasing observed in (15)N{(17)O}REAPDOR solid-state NMR experiments. Specifically, about one-third of the Aβ peptides were found to be involved in the formation of a specific >C═(17)O···H-(15)N hydrogen bond with their neighbor peptide molecules, and we hypothesize that the rest of the molecules undergo ± n off-registry shifts in their hydrogen bonding networks.

A study of advanced magnesium-based hydride and development of a metal hydride thermal battery system

NASA Astrophysics Data System (ADS)

Zhou, Chengshang

Metal hydrides are a group of important materials known as energy carriers for renewable energy and thermal energy storage. A concept of thermal battery based on advanced metal hydrides is studied for heating and cooling of cabins in electric vehicles. The system utilizes a pair of thermodynamically matched metal hydrides as energy storage media. The hot hydride that is identified and developed is catalyzed MgH2 due to its high energy density and enhanced kinetics. TiV0.62Mn1.5, TiMn2, and LaNi5 alloys are selected as the matching cold hydride. A systematic experimental survey is carried out in this study to compare a wide range of additives including transitions metals, transition metal oxides, hydrides, intermetallic compounds, and carbon materials, with respect to their effects on dehydrogenation properties of MgH2. The results show that additives such as Ti and V-based metals, hydride, and certain intermetallic compounds have strong catalytic effects. Solid solution alloys of magnesium are exploited as a way to destabilize magnesium hydride thermodynamically. Various elements are alloyed with magnesium to form solid solutions, including indium and aluminum. Thermodynamic properties of the reactions between the magnesium solid solution alloys and hydrogen are investigated, showing that all the solid solution alloys that are investigated in this work have higher equilibrium hydrogen pressures than that of pure magnesium. Cyclic stability of catalyzed MgH2 is characterized and analyzed using a PCT Sievert-type apparatus. Three systems, including MgH2-TiH 2, MgH2-TiMn2, and MgH2-VTiCr, are examined. The hydrogenating and dehydrogenating kinetics at 300°C are stable after 100 cycles. However, the low temperature (25°C to 150°C) hydrogenation kinetics suffer a severe degradation during hydrogen cycling. Further experiments confirm that the low temperature kinetic degradation can be mainly related the extended hydrogenation-dehydrogenation reactions. Proof-of-concept prototypes are built and tested, demonstrating the potential of the system as HVAC for transportation vehicles. The performance of the concept-demonstration-unit show both high heating/cooling power and high energy densities. An extended cycling test shows degradation on the performance of the system. To solve this problem, a metal hydride hydrogen compressor is proposed for aiding the recharge process of the system.

Ceramic Electrolyte Membrane Technology: Enabling Revolutionary Electrochemical Energy Storage

DTIC Science & Technology

2015-10-05

ion batteries . Solid-state Li- ion batteries could significantly improve safety and eliminate the need for complex...advancing ceramic electrolyte technology for use in solid-state Li- ion batteries . Solid-state Li- ion batteries could significantly improve safety and...technology for use in solid-state Li- ion batteries and high specific energy Li-S and Li- air batteries . Solid-state Li- ion batteries could

Icosahedral quasicrystalline (Ti₁.₆V₀.₄Ni)₁₀₀₋xScx alloys: Synthesis, structure and their application in Ni-MH batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Wen; State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, CAS, Changchun 130022, Jilin; Yi, Jianhong

2013-06-01

Thanks to the revolutionary discovery of 5-fold symmetry contributed by Shechtman, quasicrystal is now recognized as another solid-state existing form. As the second largest class of quasicrystals, titanium-based icosahedral quasicrystals are very promising for hydrogen storage applications owing to their inherent abundant interstitial sites and favorable hydrogen-metal chemistry. In this context, (Ti₁.₆V₀.₄Ni)₁₀₀₋xScx (x=0.5–6) quaternary icosahedral quasicrystals have been successfully synthesized via arc-melting and subsequent melt-spinning techniques, and then their electrochemical performance toward hydrogen is explored. When the molar ratio of Sc addition is under 1%, a maximum discharge capacity of about 270 mA h g⁻¹ can be delivered. With furthermore » increasing Sc amount to 6%, good cycling stability as well as significantly retarded self-discharge rate (capacity retention 94% after 24 h relaxation) is observed. But meanwhile, the discharge capacities fall into 250-240 mA h g⁻¹, and the electrocatalytic activity improvement is highly demanded. - Graphical abstract: Quasicrystalline Ti–V–Ni–Sc hydrogen storage materials: Sc addition into Ti₁.₆V₀.₄Ni alloy forms the icosahedral phase (see picture). With optimal Sc dosage, the anodic cycling stability and self-discharge property are greatly enhanced. - Highlights: • Crystalline disallowed 5-fold symmetry is present in (Ti₁.₆V₀.₄Ni)₁₀₀₋xScx alloys. • Ti-based metastable quasicrystalline alloys can store hydrogen electrochemically. • A maximum discharge capacity of 270 mA h g⁻¹ can be delivered. • Advantageous cycle stability and self-discharge property benefit from Sc addition. • Ti and V dissolution is suppressed by an oxide layer resulting from Sc corrosion.« less

Solid-state pulse modulator using Marx generator for a medical linac electron-gun

NASA Astrophysics Data System (ADS)

Lim, Heuijin; Hyeok Jeong, Dong; Lee, Manwoo; Lee, Mujin; Yi, Jungyu; Yang, Kwangmo; Ro, Sung Chae

2016-04-01

A medical linac is used for the cancer treatment and consists of an accelerating column, waveguide components, a magnetron, an electron-gun, a pulse modulator, and an irradiation system. The pulse modulator based on hydrogen thyratron-switched pulse-forming network is commonly used in linac. As the improvement of the high power semiconductors in switching speed, voltage rating, and current rating, an insulated gate bipolar transistor has become the more popular device used for pulsed power systems. We propose a solid-state pulse modulator to generator high voltage by multi-stacked storage-switch stages based on the Marx generator. The advantage of our modulator comes from the use of two semiconductors to control charging and discharging of the storage capacitor at each stage and it allows to generate the pulse with various amplitudes, widths, and shapes. In addition, a gate driver for two semiconductors is designed to reduce the control channels and to protect the circuits. It is developed for providing the pulsed power to a medical linac electron-gun that requires 25 kV and 1 A as the first application. In order to improve the power efficiency and achieve the compactness modulator, a capacitor charging power supply, a Marx pulse generator, and an electron-gun heater isolated transformer are constructed and integrated. This technology is also being developed to extend the high power pulsed system with > 1 MW and also other applications such as a plasma immersed ion implantation and a micro pulse electrostatic precipitator which especially require variable pulse shape and high repetition rate > 1 kHz. The paper describes the design features and the construction of this solid-state pulse modulator. Also shown are the performance results into the linac electron-gun.

Solid-state supercapacitors with ionic liquid gel polymer electrolyte based on poly (3, 4-ethylenedioxythiophene), carbon nanotubes, and metal oxides nanocomposites for electrical energy storage

NASA Astrophysics Data System (ADS)

Obeidat, Amr M.

Clean and renewable energy systems have emerged as an important area of research having diverse and significant new applications. These systems utilize different energy storage methods such as the batteries and supercapacitors. Supercapacitors are electrochemical energy storage devices that are designed to bridge the gap between batteries and conventional capacitors. Supercapacitors which store electrical energy by electrical double layer capacitance are based on large surface area structured carbons. The materials systems in which the Faradaic reversible redox reactions store electrical energy are the transition metal oxides and electronically conducting polymers. Among the different types of conducting polymers, poly (3, 4- ethylenedioxythiophene) (PEDOT) is extensively investigated owing to its chemical and mechanical stability. Due to instability of aqueous electrolytes at high voltages and toxicity of organic electrolytes, potential of supercapacitors has not been fully exploited. A novel aspect of this work is in utilizing the ionic liquid gel polymer electrolyte to design solid-state supercapacitors for energy storage. Various electrochemical systems were investigated including graphene, PEDOT, PEDOT-carbon nanotubes, PEDOT-manganese oxide, and PEDOT-iron oxide nanocomposites. The electrochemical performance of solid-state supercapacitor devices was evaluated based on cyclic voltammetry (CV), charge-discharge (CD), prolonged cyclic tests, and electrochemical impedance spectroscopy (EIS) techniques. Raman spectroscopy technique was also utilized to analyze the bonding structure of the electrode materials. The graphene solid-state supercapacitor system displayed areal capacitance density of 141.83 mF cm-2 based on high potential window up to 4V. The PEDOT solid-state supercapacitor system was synthesized in acetonitrile and aqueous mediums achieving areal capacitance density of 219.17 mF cm-2. The hybrid structure of solid-state supercapacitors was also studied in solid-state design based on PEDOT and graphene electrodes that produced areal capacitance density of 198.26 mF cm-2. Symmetrical PEDOT-manganese oxide nanocomposites were synthesized by co-deposition and dip-coating techniques to fabricate solid-state supercapacitor systems achieving areal capacitance density of 122.08 mF cm-2 credited to the PEDOT-MnO2 supercapacitor that was synthesized by dipping the PEDOT electrode in pure KMnO4 solution. The electrochemical performance of PEDOT-carbon nanotube solid-state supercapacitors was also investigated in both acetonitrile and aqueous medium showing good dispersion characteristics with optimum CNT content of 1 mg. The PEDOT-CNT solid-state supercapacitor system synthesized in acetonitrile displayed areal capacitance density of 297.43 mF cm-2. PEDOT-Fe2O3 nanocomposites were synthesized by single-step co-deposition techniques, and these were used to fabricate solid-state supercapacitors achieving areal capacitance density of 96.89 mF cm-2. Furthermore, some of these thin flexible solid-state supercapacitors were integrated with solar cells for direct storage of solar electricity, which proved to be promising as autonomous power source for flexible and wearable electronics. This dissertation describes the electrode synthesis, design and properties of solid-state supercapacitors, and their electrochemical performance in the storage of electrical energy.

Design Concepts Studied for the Hydrogen On-Orbit Storage and Supply Experiment

NASA Technical Reports Server (NTRS)

Chato, David J.

1998-01-01

The NASA Lewis Research Center, in conjunction with the Utah State University Space Dynamics Laboratory, studied concepts for the Hydrogen On-Orbit Storage and Supply Experiment (HOSS). HOSS is a space flight experiment whose objectives are (1) to show stable gas supply for solar-thermal thruster designs by using both storage and direct-gain approaches and (2) to evaluate and compare the low-gravity performance of active and passive pressure control via a thermodynamic vent system (TVS) suitable for solar-thermal upper stages. This study showed that the necessary experimental equipment for HOSS can be accommodated in a small hydrogen Dewar (36 to 80 liter). Thermal designs can be achieved that meet the on-orbit storage requirements for these Dewars. Furthermore, ground hold insulation concepts are easily achieved that can store liquid hydrogen in these small Dewars for more than 144 hr without venting.

Bridging the gap between homogeneous and heterogeneous catalysis: ortho/para H(2) conversion, hydrogen isotope scrambling, and hydrogenation of olefins by Ir(CO)Cl(PPh(3))(2).

PubMed

Matthes, Jochen; Pery, Tal; Gründemann, Stephan; Buntkowsky, Gerd; Sabo-Etienne, Sylviane; Chaudret, Bruno; Limbach, Hans-Heinrich

2004-07-14

Some transition metal complexes are known to catalyze ortho/para hydrogen conversion, hydrogen isotope scrambling, and hydrogenation reactions in liquid solution. Using the example of Vaska's complex, we present here evidence by NMR that the solvent is not necessary for these reactions to occur. Thus, solid frozen solutions or polycrystalline powdered samples of homogeneous catalysts may become heterogeneous catalysts. Comparative liquid- and solid-state studies provide novel insight into the reaction mechanisms.

ERDA's Chemical Energy Storage Program

NASA Technical Reports Server (NTRS)

Swisher, J. H.; Kelley, J. H.

1977-01-01

The Chemical Energy Storage Program is described with emphasis on hydrogen storage. Storage techniques considered include pressurized hydrogen gas storage, cryogenic liquid hydrogen storage, storage in hydride compounds, and aromatic-alicyclic hydrogen storage. Some uses of energy storage are suggested. Information on hydrogen production and hydrogen use is also presented. Applications of hydrogen energy systems include storage of hydrogen for utilities load leveling, industrial marketing of hydrogen both as a chemical and as a fuel, natural gas supplementation, vehicular applications, and direct substitution for natural gas.

Hydrogen-fluorine exchange in NaBH4-NaBF4.

PubMed

Rude, L H; Filsø, U; D'Anna, V; Spyratou, A; Richter, B; Hino, S; Zavorotynska, O; Baricco, M; Sørby, M H; Hauback, B C; Hagemann, H; Besenbacher, F; Skibsted, J; Jensen, T R

2013-11-07

Hydrogen-fluorine exchange in the NaBH4-NaBF4 system is investigated using a range of experimental methods combined with DFT calculations and a possible mechanism for the reactions is proposed. Fluorine substitution is observed using in situ synchrotron radiation powder X-ray diffraction (SR-PXD) as a new Rock salt type compound with idealized composition NaBF2H2 in the temperature range T = 200 to 215 °C. Combined use of solid-state (19)F MAS NMR, FT-IR and DFT calculations supports the formation of a BF2H2(-) complex ion, reproducing the observation of a (19)F chemical shift at -144.2 ppm, which is different from that of NaBF4 at -159.2 ppm, along with the new absorption bands observed in the IR spectra. After further heating, the fluorine substituted compound becomes X-ray amorphous and decomposes to NaF at ~310 °C. This work shows that fluorine-substituted borohydrides tend to decompose to more stable compounds, e.g. NaF and BF3 or amorphous products such as closo-boranes, e.g. Na2B12H12. The NaBH4-NaBF4 composite decomposes at lower temperatures (300 °C) compared to NaBH4 (476 °C), as observed by thermogravimetric analysis. NaBH4-NaBF4 (1:0.5) preserves 30% of the hydrogen storage capacity after three hydrogen release and uptake cycles compared to 8% for NaBH4 as measured using Sievert's method under identical conditions, but more than 50% using prolonged hydrogen absorption time. The reversible hydrogen storage capacity tends to decrease possibly due to the formation of NaF and Na2B12H12. On the other hand, the additive sodium fluoride appears to facilitate hydrogen uptake, prevent foaming, phase segregation and loss of material from the sample container for samples of NaBH4-NaF.

Probing hydrogen bond networks in half-sandwich Ru(II) building blocks by a combined 1H DQ CRAMPS solid-state NMR, XRPD, and DFT approach.

PubMed

Chierotti, Michele R; Gobetto, Roberto; Nervi, Carlo; Bacchi, Alessia; Pelagatti, Paolo; Colombo, Valentina; Sironi, Angelo

2014-01-06

The hydrogen bond network of three polymorphs (1α, 1β, and 1γ) and one solvate form (1·H2O) arising from the hydration-dehydration process of the Ru(II) complex [(p-cymene)Ru(κN-INA)Cl2] (where INA is isonicotinic acid), has been ascertained by means of one-dimensional (1D) and two-dimensional (2D) double quantum (1)H CRAMPS (Combined Rotation and Multiple Pulses Sequences) and (13)C CPMAS solid-state NMR experiments. The resolution improvement provided by homonuclear decoupling pulse sequences, with respect to fast MAS experiments, has been highlighted. The solid-state structure of 1γ has been fully characterized by combining X-ray powder diffraction (XRPD), solid-state NMR, and periodic plane-wave first-principles calculations. None of the forms show the expected supramolecular cyclic dimerization of the carboxylic functions of INA, because of the presence of Cl atoms as strong hydrogen bond (HB) acceptors. The hydration-dehydration process of the complex has been discussed in terms of structure and HB rearrangements.

Icosahedral quasicrystalline (Ti1.6V0.4Ni)100-xScx alloys: Synthesis, structure and their application in Ni-MH batteries

NASA Astrophysics Data System (ADS)

Hu, Wen; Yi, Jianhong; Zheng, Biju; Wang, Limin

2013-06-01

Thanks to the revolutionary discovery of 5-fold symmetry contributed by Shechtman, quasicrystal is now recognized as another solid-state existing form. As the second largest class of quasicrystals, titanium-based icosahedral quasicrystals are very promising for hydrogen storage applications owing to their inherent abundant interstitial sites and favorable hydrogen-metal chemistry. In this context, (Ti1.6V0.4Ni)100-xScx (x=0.5-6) quaternary icosahedral quasicrystals have been successfully synthesized via arc-melting and subsequent melt-spinning techniques, and then their electrochemical performance toward hydrogen is explored. When the molar ratio of Sc addition is under 1%, a maximum discharge capacity of about 270 mA h g-1 can be delivered. With further increasing Sc amount to 6%, good cycling stability as well as significantly retarded self-discharge rate (capacity retention 94% after 24 h relaxation) is observed. But meanwhile, the discharge capacities fall into 250-240 mA h g-1, and the electrocatalytic activity improvement is highly demanded.

A Comprehensive Study on the Electronic State of Hydrogen in α-Phase PdH(D)x-Does a Chemical Bond Between Pd and H(D) Exist?

PubMed

Dekura, Shun; Kobayashi, Hirokazu; Ikeda, Ryuichi; Maesato, Mitsuhiko; Yoshino, Haruka; Ohba, Masaaki; Ishimoto, Takayoshi; Kawaguchi, Shogo; Kubota, Yoshiki; Yoshioka, Satoru; Matsumura, Syo; Sugiyama, Takeharu; Kitagawa, Hiroshi

2018-06-12

The palladium(Pd)-hydrogen(H) system is one of the most famous hydrogen storage systems. Although there has been much research on β-phase PdH(D)x, we comprehensively investigated the nature of the interaction between Pd and H(D) in α-phase PdH(D)x (x < 0.03 at 303 K), and revealed the existence of Pd-H(D) chemical bond for the first time, by various in situ experimental techniques and first-principles theoretical calculations. The lattice expansion by H(D) dissolution in the α-phase lattice suggests the existence of interaction between Pd and H(D). The decrease of magnetic susceptibility and the increase of electrical resistivity indicate that the electronic states are changed by the H(D) dissolution in the α phase. In situ solid-state 1H and 2H NMR results and first-principles theoretical calculations revealed that a Pd-H(D) chemical bond exists in the α phase, but the bonding character of the Pd-H(D) chemical bond in the α phase is quite different from that in the β phase; the nature of the Pd-H(D) chemical bond in the α phase is a localized covalent bond whereas that in the β phase is a metallic bond. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tailoring the properties of ammine metal borohydrides for solid-state hydrogen storage.

PubMed

Jepsen, Lars H; Ley, Morten B; Filinchuk, Yaroslav; Besenbacher, Flemming; Jensen, Torben R

2015-04-24

A series of halide-free ammine manganese borohydrides, Mn(BH4 )2 ⋅nNH3 , n=1, 2, 3, and 6, a new bimetallic compound Li2 Mn(BH4 )4 ⋅6NH3 , and the first ammine metal borohydride solid solution Mg1-x Mnx (BH4 )2 ⋅6NH3 are presented. Four new crystal structures have been determined by synchrotron radiation powder X-ray diffraction and the thermal decomposition is systematically investigated for all the new compounds. The solid-gas reaction between Mn(BH4 )2 and NH3 provides Mn(BH4 )2 ⋅6NH3 . The number of NH3 per Mn has been varied by mechanochemical treatment of Mn(BH4 )2 ⋅6NH3 -Mn(BH4 )2 mixtures giving rise to increased hydrogen purity for n/m≤1 for M(BH4 )m ⋅nNH3 . The structures of Mg(BH4 )2 ⋅3NH3 and Li2 Mg(BH4 )4 ⋅6NH3 have been revisited and new structural models are presented. Finally, we demonstrate that ammonia destabilizes metal borohydrides with low electronegativity of the metal (χp <∼1.6), while metal borohydrides with high electronegativity (χp >∼1.6) are generally stabilized. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

FLUSH - PREDICTION OF FLOW PARAMETERS OF SLUSH HYDROGEN

NASA Technical Reports Server (NTRS)

Hardy, T.

1994-01-01

Slush hydrogen, a mixture of the solid and liquid phases of hydrogen, is a possible source of fuel for the National Aerospace Plane (NASP) Project. Advantages of slush hydrogen over liquid hydrogen include greater heat capacity and greater density. However, practical use of slush hydrogen as a fuel requires systems of lines, valves, etc. which are designed to deliver the fuel in slush form with minimal solid loss as a result of pipe heating or flow friction. Engineers involved with the NASP Project developed FLUSH to calculate the pressure drop and slush hydrogen solid fraction loss for steady-state, one-dimensional flow. FLUSH solves the steady-state, one-dimensional energy equation and the Bernoulli equation for pipe flow. The program performs these calculations for each two-node element--straight pipe length, elbow, valve, fitting, or other part of the piping system--specified by the user. The user provides flow rate, upstream pressure, initial solid hydrogen fraction, element heat leak, and element parameters such as length and diameter. For each element, FLUSH first calculates the pressure drop, then figures the slush solid fraction exiting the element. The code employs GASPLUS routines to calculate thermodynamic properties for the slush hydrogen. FLUSH is written in FORTRAN IV for DEC VAX series computers running VMS. An executable is provided on the tape. The GASPLUS physical properties routines which are required for building the executable are included as one object library on the program media (full source code for GASPLUS is available separately as COSMIC Program Number LEW-15091). FLUSH is available in DEC VAX BACKUP format on a 9-track 1600 BPI magnetic tape (standard media) or on a TK50 tape cartridge. FLUSH was developed in 1989.

Redox-Active Hydrogel Polymer Electrolytes with Different pH Values for Enhancing the Energy Density of the Hybrid Solid-State Supercapacitor.

PubMed

Tang, Xiaohui; Lui, Yu Hui; Merhi, Abdul Rahman; Chen, Bolin; Ding, Shaowei; Zhang, Bowei; Hu, Shan

2017-12-27

To enhance the energy density of solid-state supercapacitors, a novel solid-state cell, made of redox-active poly(vinyl alcohol) (PVA) hydrogel electrolytes and functionalized carbon nanotube-coated cellulose paper electrodes, was investigated in this work. Briefly, acidic PVA-[BMIM]Cl-lactic acid-LiBr and neutral PVA-[BMIM]Cl-sodium acetate-LiBr hydrogel polymer electrolytes are used as catholyte and anolyte, respectively. The acidic condition of the catholyte contributes to suppression of the undesired irreversible reaction of Br - and extension of the oxygen evolution reaction potential to a higher value than that of the redox potential of Br - /Br 3 - reaction. The observed Br - /Br 3 - redox activity at the cathode contributes to enhance the cathode capacitance. The neutral condition of the anolyte helps extend the operating voltage window of the supercapacitor by introducing hydrogen evolution reaction overpotential to the anode. The electrosorption of nascent H on the negative electrode also increases the anode capacitance. As a result, the prepared solid-state hybrid supercapacitor shows a broad voltage window of 1.6 V, with a high Coulombic efficiency of 97.6% and the highest energy density of 16.3 Wh/kg with power density of 932.6 W/kg at 2 A/g obtained. After 10 000 cycles of galvanostatic charge and discharge tests at the current density of 10 A/g, it exhibits great cyclic stability with 93.4% retention of the initial capacitance. In addition, a robust capacitive performance can also be observed from the solid-state supercapacitor at different bending angles, indicating its great potential as a flexible energy storage device.

Putting Cocrystal Stoichiometry to Work: A Reactive Hydrogen-Bonded "Superassembly" Enables Nanoscale Enlargement of a Metal-Organic Rhomboid via a Solid-State Photocycloaddition.

PubMed

Chu, Qianli; Duncan, Andrew J E; Papaefstathiou, Giannis S; Hamilton, Tamara D; Atkinson, Manza B J; Mariappan, S V Santhana; MacGillivray, Leonard R

2018-04-11

Enlargement of a self-assembled metal-organic rhomboid is achieved via the organic solid state. The solid-state synthesis of an elongated organic ligand was achieved by a template directed [2 + 2] photodimerization in a cocrystal. Initial cocrystals obtained of resorcinol template and reactant alkene afforded a 1:2 cocrystal with the alkene in a stacked yet photostable geometry. Cocrystallization performed in the presence of excess template resulted in a 3:2 cocrystal composed of novel discrete 10-component hydrogen-bonded "superassemblies" wherein the alkenes undergo a head-to-head [2 + 2] photodimerization. Isolation and reaction of elongated photoproduct with Cu(II) ions afforded a metal-organic rhomboid of nanoscale dimensions that hosts small molecules in the solid state as guests.

Air Force Phillips Laboratory Battery Program overview

NASA Technical Reports Server (NTRS)

House, Shaun

1992-01-01

Battery development and testing efforts at Phillips Laboratory fall into three main categories: nickel hydrogen, sodium sulfur, and solid state batteries. Nickel hydrogen work is broken down into a Low Earth Orbit (LEO) Life Test Program, a LEO Pulse Test Program, and a Hydrogen Embrittlement Investigation. Sodium sulfur work is broken down into a Geosynchronous Earth Orbit (GEO) Battery Flight Test and a Hot Launch Evaluation. Solid state polymer battery work consists of a GEO Battery Development Program, a Pulse Power Battery Small Business Innovation Research (SBIR), and an in-house evaluation of current generation laboratory cells. An overview of the program is presented.

Effects of Drying Process on an IgG1 Monoclonal Antibody Using Solid-State Hydrogen Deuterium Exchange with Mass Spectrometric Analysis (ssHDX-MS).

PubMed

Moussa, Ehab M; Wilson, Nathan E; Zhou, Qi Tony; Singh, Satish K; Nema, Sandeep; Topp, Elizabeth M

2018-01-03

Lyophilization and spray drying are widely used to manufacture solid forms of therapeutic proteins. Lyophilization is used to stabilize proteins vulnerable to degradation in solution, whereas spray drying is mainly used to prepare inhalation powders or as an alternative to freezing for storing bulk drug substance. Both processes impose stresses that may adversely affect protein structure, stability and bioactivity. Here, we compared lyophilization with and without controlled ice nucleation, and spray drying for their effects on the solid-state conformation and matrix interactions of a model IgG1 monoclonal antibody (mAb). Solid-state conformation and matrix interactions of the mAb were probed using solid-state hydrogen-deuterium exchange with mass spectrometric analysis (ssHDX-MS), and solid-state Fourier transform infrared (ssFTIR) and solid-state fluorescence spectroscopies. mAb conformation and/or matrix interactions were most perturbed in mannitol-containing samples and the distribution of states was more heterogeneous in sucrose and trehalose samples that were spray dried. The findings demonstrate the sensitivity of ssHDX-MS to changes weakly indicated by spectroscopic methods, and support the broader use of ssHDX-MS to probe formulation and process effects on proteins in solid samples.

Measurement of backbone hydrogen-deuterium exchange in the type III secretion system needle protein PrgI by solid-state NMR

NASA Astrophysics Data System (ADS)

Chevelkov, Veniamin; Giller, Karin; Becker, Stefan; Lange, Adam

2017-10-01

In this report we present site-specific measurements of amide hydrogen-deuterium exchange rates in a protein in the solid state phase by MAS NMR. Employing perdeuteration, proton detection and a high external magnetic field we could adopt the highly efficient Relax-EXSY protocol previously developed for liquid state NMR. According to this method, we measured the contribution of hydrogen exchange on apparent 15N longitudinal relaxation rates in samples with differing D2O buffer content. Differences in the apparent T1 times allowed us to derive exchange rates for multiple residues in the type III secretion system needle protein.

Development of Automotive Liquid Hydrogen Storage Systems

NASA Astrophysics Data System (ADS)

Krainz, G.; Bartlok, G.; Bodner, P.; Casapicola, P.; Doeller, Ch.; Hofmeister, F.; Neubacher, E.; Zieger, A.

2004-06-01

Liquid hydrogen (LH2) takes up less storage volume than gas but requires cryogenic vessels. State-of-the-art applications for passenger vehicles consist of double-wall cylindrical tanks that hold a hydrogen storage mass of up to 10 kg. The preferred shell material of the tanks is stainless steel, since it is very resistant against hydrogen brittleness and shows negligible hydrogen permeation. Therefore, the weight of the whole tank system including valves and heat exchanger is more than 100 kg. The space between the inner and outer vessel is mainly used for thermal super-insulation purposes. Several layers of insulation foils and high vacuums of 10-3 Pa reduce the heat entry. The support structures, which keep the inner tank in position to the outer tank, are made of materials with low thermal conductivity, e.g. glass or carbon fiber reinforced plastics. The remaining heat in-leak leads to a boil-off rate of 1 to 3 percent per day. Active cooling systems to increase the stand-by time before evaporation losses occur are being studied. Currently, the production of several liquid hydrogen tanks that fulfill the draft of regulations of the European Integrated Hydrogen Project (EIHP) is being prepared. New concepts of lightweight liquid hydrogen storage tanks will be investigated.

High performance hydrogen storage from Be-BTB metal-organic framework at room temperature.

PubMed

Lim, Wei-Xian; Thornton, Aaron W; Hill, Anita J; Cox, Barry J; Hill, James M; Hill, Matthew R

2013-07-09

The metal-organic framework beryllium benzene tribenzoate (Be-BTB) has recently been reported to have one of the highest gravimetric hydrogen uptakes at room temperature. Storage at room temperature is one of the key requirements for the practical viability of hydrogen-powered vehicles. Be-BTB has an exceptional 298 K storage capacity of 2.3 wt % hydrogen. This result is surprising given that the low adsorption enthalpy of 5.5 kJ mol(-1). In this work, a combination of atomistic simulation and continuum modeling reveals that the beryllium rings contribute strongly to the hydrogen interaction with the framework. These simulations are extended with a thermodynamic energy optimization (TEO) model to compare the performance of Be-BTB to a compressed H2 tank and benchmark materials MOF-5 and MOF-177 in a MOF-based fuel cell. Our investigation shows that none of the MOF-filled tanks satisfy the United States Department of Energy (DOE) storage targets within the required operating temperatures and pressures. However, the Be-BTB tank delivers the most energy per volume and mass compared to the other material-based storage tanks. The pore size and the framework mass are shown to be contributing factors responsible for the superior room temperature hydrogen adsorption of Be-BTB.

Proton conducting membranes for high temperature fuel cells with solid state water free membranes

NASA Technical Reports Server (NTRS)

Narayanan, Sekharipuram R. (Inventor); Yen, Shiao-Pin S. (Inventor)

2006-01-01

A water free, proton conducting membrane for use in a fuel cell is fabricated as a highly conducting sheet of converted solid state organic amine salt, such as converted acid salt of triethylenediamine with two quaternized tertiary nitrogen atoms, combined with a nanoparticulate oxide and a stable binder combined with the converted solid state organic amine salt to form a polymeric electrolyte membrane. In one embodiment the membrane is derived from triethylenediamine sulfate, hydrogen phosphate or trifiate, an oxoanion with at least one ionizable hydrogen, organic tertiary amine bisulfate, polymeric quaternized amine bisulfate or phosphate, or polymeric organic compounds with quaternizable nitrogen combined with Nafion to form an intimate network with ionic interactions.

Hydrogen Atomic Positions of O-H···O Hydrogen Bonds in Solution and in the Solid State: The Synergy of Quantum Chemical Calculations with ¹H-NMR Chemical Shifts and X-ray Diffraction Methods.

PubMed

Siskos, Michael G; Choudhary, M Iqbal; Gerothanassis, Ioannis P

2017-03-07

The exact knowledge of hydrogen atomic positions of O-H···O hydrogen bonds in solution and in the solid state has been a major challenge in structural and physical organic chemistry. The objective of this review article is to summarize recent developments in the refinement of labile hydrogen positions with the use of: (i) density functional theory (DFT) calculations after a structure has been determined by X-ray from single crystals or from powders; (ii) ¹H-NMR chemical shifts as constraints in DFT calculations, and (iii) use of root-mean-square deviation between experimentally determined and DFT calculated ¹H-NMR chemical shifts considering the great sensitivity of ¹H-NMR shielding to hydrogen bonding properties.

NASA atomic hydrogen standards program - An update

NASA Technical Reports Server (NTRS)

Reinhardt, V. S.; Kaufmann, D. C.; Adams, W. A.; Deluca, J. J.; Soucy, J. L.

1976-01-01

Some of the design features of NASA hydrogen masers are discussed including the large hydrogen source bulb, the palladium purified, the state selector, the replaceable pumps, the small entrance stem, magnetic shields, the elongated storage bulb, the aluminum cavity, the electronics package, and the autotuner. Attention is also given to the reliability and operating life of these hydrogen atomic standards.

Effect of LEO cycling on 125 Ah advanced design IPV nickel-hydrogen flight cells. An update

NASA Technical Reports Server (NTRS)

Smithrick, John J.; Hall, Stephen W.

1991-01-01

Validation testing of the NASA Lewis 125 Ah advanced design individual pressure vessel (IPV) nickel-hydrogen flight cells was conducted. Work consisted of characterization, storage, and cycle life testing. There was no capacity degradation after 52 days of storage with the cells in the discharged state, an open circuit, 0 C, and a hydrogen pressure of 14.5 psia. The catalyzed wall wick cells were cycled for over 11,000 cycles with no cell failures in the continuing test. One of the noncatalyzed wall wick cells failed.

Nickel-hydrogen capacity loss on storage

NASA Technical Reports Server (NTRS)

Manzo, Michelle A.

1989-01-01

A controlled experiment evaluating the capacity loss experienced by nickel electrodes stored under various conditions of temperature, hydrogen pressure, and electrolyte concentration was conducted using nickel electrodes from four different manufacturers. It was found that capacity loss varied with respect to hydrogen pressure, and storage temperature as well as with respect to electrode manufacturing processes. Impedance characteristics were monitored and found to be indicative of electrode manufacturing processes and capacity loss. Cell testing to evaluate state-of-charge effects on capacity loss were inconclusive as no loss was sustained by the cells tested in this experiment.

Influence of Microstructure on the Fatigue Crack Growth of A516 in Hydrogen

NASA Technical Reports Server (NTRS)

Wachob, Harry F.; Nelson, Howard G.

1980-01-01

Some day hydrogen may be used as a viable energy storage and transport medium within the United States. Hydrogen gas may be used to dilute and extend our present methane supply as a blend or may even be used in its pure elemental form as a primary fuel. Independent of the methods of production, storage, and distribution, the interaction of hydrogen with its containment material will play an integral role in the success of a hydrogen energy program. Presently, the selection of hydrogen containment materials can be made such that the material will remain reasonably free from environmental degradation; however, costly alloying additions are required. Unfortunately, high alloy steels are economically prohibitive when large-scale hydrogen energy storage, transmission, and conversion systems are desired. Therefore, in order to implement such hydrogen energy systems in the future, existing low-cost materials must be improved via mechanical, thermal, or thermo-mechanical processing methods or new low-cost materials which are compatible with hydrogen must be developed. Originally, low strength, low alloy steels at room temperature were thought to be immune to hydrogen gas embrittlement, since no sustained load crack growth is observed. However, results of Clark in HY8O and Nelson in SAE 1020 have shown that the fatigue crack growth rate can be greatly accelerated in the presence of hydrogen gas. In recent results reported by Louthan and Mucci, the smooth bar fatigue life of an A1068 pipeline steel was reduced up to a factor of ten when the tests were performed in a 13.8 MPa hydrogen environment. These results suggest that the selection of material for structures designed to operate in hydrogen under cyclic loads must include consideration of hydrogen/metal fatigue interaction. Although the hydrogen/metal fatigue interaction can be severe in low strength low alloy steels, the degree of degradation may be altered by the underlying ferrous microstructure. At present, no correlation between microstructure and degree of hydrogen susceptibility exists for low strength steels. However, in high strength steels, susceptibility to hydrogen embrittlement has been shown to be strongly sensitive to the metallurgical microstructure. In addition, compositional effects and grain size can 703 Some day hydrogen may be used as a viable energy storage and transport medium within the United States. Hydrogen gas may be used to dilute and extend our present methane supply as a blend or may even be used in its pure elemental form as a primary fuel. Independent of the methods of production, storage, and distribution, the interaction of hydrogen with its containment material will play an integral role in the success of a hydrogen energy program. Presently, the selection of hydrogen containment materials can be made such that the material will remain reasonably free from environmental degradation; however, costly alloying additions are required. Unfortunately, high alloy steels are economically prohibitive when large-scale hydrogen energy storage, transmission, and conversion systems are desired. Therefore, in order to implement such hydrogen energy systems in the future, existing low-cost materials must be improved via mechanical, thermal, or thermo-mechanical processing methods or new low-cost materials which are compatible with hydrogen must be developed.

Large entropy derived from low-frequency vibrations and its implications for hydrogen storage

NASA Astrophysics Data System (ADS)

Wang, Xiaoxia; Chen, Hongshan

2018-02-01

Adsorption and desorption are driven by the energy and entropy competition, but the entropy effect is often ignored in hydrogen storage and the optimal adsorption strength for the ambient storage is controversial in the literature. This letter investigated the adsorption states of the H2 molecule on M-B12C6N6 (M = Li, Na, Mg, Ca, and Sc) and analyzed the correlation among the zero point energy (ZPE), the entropy change, and the adsorption energy and their effects on the delivery capacities. The ZPE has large correction to the adsorption energy due to the light mass of hydrogen. The computations show that the potential energies along the spherical surface centered at the alkali metals are very flat and it leads to large entropy (˜70 J/mol.K) of the adsorbed H2 molecules. The entropy change can compensate the enthalpy change effectively, and the ambient storage can be realized with relatively weak adsorption of ΔH = -12 kJ/mol. The results are encouraging and instructive for the design of hydrogen storage materials.

Comparison of solid-state and submerged-state fermentation for the bioprocessing of switchgrass to ethanol and acetate by Clostridium phytofermentans.

PubMed

Jain, Abhiney; Morlok, Charles K; Henson, J Michael

2013-01-01

The conversion of sustainable energy crops using microbiological fermentation to biofuels and bioproducts typically uses submerged-state processes. Alternatively, solid-state fermentation processes have several advantages when compared to the typical submerged-state processes. This study compares the use of solid-state versus submerged-state fermentation using the mesophilic anaerobic bacterium Clostridium phytofermentans in the conversion of switchgrass to the end products of ethanol, acetate, and hydrogen. A shift in the ratio of metabolic products towards more acetate and hydrogen production than ethanol production was observed when C. phytofermentans was grown under solid-state conditions as compared to submerged-state conditions. Results indicated that the end product concentrations (in millimolar) obtained using solid-state fermentation were higher than using submerged-state fermentation. In contrast, the total fermentation products (in weight of product per weight of carbohydrates consumed) and switchgrass conversion were higher for submerged-state fermentation. The conversion of xylan was greater than glucan conversion under both fermentation conditions. An initial pH of 7 and moisture content of 80 % resulted in maximum end products formation. Scanning electron microscopy study showed the presence of biofilm formed by C. phytofermentans growing on switchgrass under submerged-state fermentation whereas bacterial cells attached to surface and no apparent biofilm was observed when grown under solid-state fermentation. To our knowledge, this is the first study reporting consolidated bioprocessing of a lignocellulosic substrate by a mesophilic anaerobic bacterium under solid-state fermentation conditions.

Hydrolysis of ammonia borane as a hydrogen source: fundamental issues and potential solutions towards implementation.

PubMed

Sanyal, Udishnu; Demirci, Umit B; Jagirdar, Balaji R; Miele, Philippe

2011-12-16

In today's era of energy crisis and global warming, hydrogen has been projected as a sustainable alternative to depleting CO(2)-emitting fossil fuels. However, its deployment as an energy source is impeded by many issues, one of the most important being storage. Chemical hydrogen storage materials, in particular B-N compounds such as ammonia borane, with a potential storage capacity of 19.6 wt % H(2) and 0.145 kg(H2)L(-1), have been intensively studied from the standpoint of addressing the storage issues. Ammonia borane undergoes dehydrogenation through hydrolysis at room temperature in the presence of a catalyst, but its practical implementation is hindered by several problems affecting all of the chemical compounds in the reaction scheme, including ammonia borane, water, borate byproducts, and hydrogen. In this Minireview, we exhaustively survey the state of the art, discuss the fundamental problems, and, where applicable, propose solutions with the prospect of technological applications. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermal energy storage for solar power generation - State of the art

NASA Astrophysics Data System (ADS)

Shukla, K. N.

1981-12-01

High temperature storage for applications in solar-thermal electric systems is considered. Noting that thermal storage is in either the form of latent, sensible or chemically stored heat, sensible heat storage is stressed as the most developed of the thermal storage technologies, spanning direct heating of a storage medium from 120-1250 C. Current methods involve solids, packed beds, fluidized beds, liquids, hot water, organic liquids, and inorganic liquids and molten salts. Latent heat storage comprises phase-change materials that move from solid to liquid with addition of heat and liquid to solid with the removal of heat. Metals or inorganic salts are candidates, and the energy balances are outlined. Finally, chemical heat storage is examined, showing possible high energy densities through catalytic, thermal dissociation reactions.

Hydrogen generation using silicon nanoparticles and their mixtures with alkali metal hydrides

NASA Astrophysics Data System (ADS)

Patki, Gauri Dilip

Hydrogen is a promising energy carrier, for use in fuel cells, engines, and turbines for transportation or mobile applications. Hydrogen is desirable as an energy carrier, because its oxidation by air releases substantial energy (thermally or electrochemically) and produces only water as a product. In contrast, hydrocarbon energy carriers inevitably produce CO2, contributing to global warming. While CO2 capture may prove feasible in large stationary applications, implementing it in transportation and mobile applications is a daunting challenge. Thus a zero-emission energy carrier like hydrogen is especially needed in these cases. Use of H2 as an energy carrier also brings new challenges such as safe handling of compressed hydrogen and implementation of new transport, storage, and delivery processes and infrastructure. With current storage technologies, hydrogen's energy per volume is very low compared to other automobile fuels. High density storage of compressed hydrogen requires combinations of high pressure and/or low temperature that are not very practical. An alternative for storage is use of solid light weight hydrogenous material systems which have long durability, good adsorption properties and high activity. Substantial research has been conducted on carbon materials like activated carbon, carbon nanofibers, and carbon nanotubes due to their high theoretical hydrogen capacities. However, the theoretical values have not been achieved, and hydrogen uptake capacities in these materials are below 10 wt. %. In this thesis we investigated the use of silicon for hydrogen generation. Hydrogen generation via water oxidation of silicon had been ignored due to slow reaction kinetics. We hypothesized that the hydrogen generation rate could be improved by using high surface area silicon nanoparticles. Our laser-pyrolysis-produced nanoparticles showed surprisingly rapid hydrogen generation and high hydrogen yield, exceeding the theoretical maximum of two moles of H2 per mole of Si. We compare our silicon nanoparticles (˜10nm diameter) with commercial silicon nanopowder (<100nm diameter) and ball-milled silicon powder (325 mesh). The increase in rate upon decreasing the particle size to 10 nm was even greater than would be expected based upon the increase in surface area. While specific surface area increased by a factor of 6 in going from <100 nm to ˜10 nm particles, the hydrogen production rate increased by a factor of 150. However, in all cases, silicon requires a base (e.g. NaOH, KOH, hydrazine) to catalyze its reaction with water. Metal hydrides are also promising hydrogen storage materials. The optimum metal hydride would possess high hydrogen storage density at moderate temperature and pressure, release hydrogen safely and controllably, and be stable in air. Alkali metal hydrides have high hydrogen storage density, but exhibit high uncontrollable reactivity with water. In an attempt to control this explosive nature while maintaining high storage capacity, we mixed our silicon nanoparticles with the hydrides. This has dual benefits: (1) the hydride- water reaction produces the alkali hydroxide needed for base-catalyzed silicon oxidation, and (2) dilution with 10nm coating by, the silicon may temper the reactivity of the hydride, making the process more controllable. Initially, we analyzed hydrolysis of pure alkali metal hydrides and alkaline earth metal hydrides. Lithium hydride has particularly high hydrogen gravimetric density, along with faster reaction kinetics than sodium hydride or magnesium hydride. On analysis of hydrogen production we found higher hydrogen yield from the silicon nanoparticle—metal hydride mixture than from pure hydride hydrolysis. The silicon-hydride mixtures using our 10nm silicon nanoparticles produced high hydrogen yield, exceeding the theoretical yield. Some evidence of slowing of the hydride reaction rate upon addition of silicon nanoparticles was observed.

Early Market TRL/MRL Analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ronnebro, Ewa; Stetson, Ned

he focus of this report is TRL/MRL analysis of hydrogen storage; it documents the methodology and results of an effort to identify hydrogen storage technologies’ technical and manufacturing readiness for early market motive and non-motive applications and to provide a path forward toward commercialization. Motive applications include materials handling equipment (MHE) and ground support equipment (GSE), such as forklifts, tow tractors, and specialty vehicles such as golf carts, lawn mowers and wheel chairs. Non-motive applications are portable, stationary or auxiliary power units (APUs) and include portable laptops, backup power, remote sensor power, and auxiliary power for recreational vehicles, hotels, hospitals,more » etc. Hydrogen storage technologies assessed include metal hydrides, chemical hydrides, sorbents, gaseous storage, and liquid storage. The assessments are based on a combination of Technology Readiness Level (TRL) and Manufacturing Readiness Level (MRL) designations that enable evaluation of hydrogen storage technologies at varying levels of development. The manufacturing status could be established from eight risk elements: Technical Maturity, Design, Materials, Cost & Funding, Process Capability, Personnel, Facilities and Manufacturing Planning. This approach provides a logical methodology and roadmap to enable the identification of hydrogen storage technologies, their advantages/disadvantages, gaps and R&D needs on an unbiased and transparent scale that is easily communicated to interagency partners. This technology readiness assessment (TRA) report documents the process used to conduct the TRA/MRA (technology and manufacturing readiness assessment), reports the TRL and MRL for each assessed technology and provides recommendations based on the findings. To investigate the state of the art and needs to mature the technologies, PNNL prepared a questionnaire to assign TRL and MRL for each hydrogen storage technology. The questionnaire was sent to identified hydrogen storage technology developers and manufacturers who were asked to perform a self-assessment. We included both domestic and international organizations including U.S. national laboratories, U.S. companies, European companies and Japanese companies. PNNL collected the data and performed an analysis to deduce the level of maturity and to provide program recommendations.« less

Synthetic nanocomposite MgH2/5 wt. % TiMn2 powders for solid-hydrogen storage tank integrated with PEM fuel cell.

PubMed

El-Eskandarany, M Sherif; Shaban, Ehab; Aldakheel, Fahad; Alkandary, Abdullah; Behbehani, Montaha; Al-Saidi, M

2017-10-16

Storing hydrogen gas into cylinders under high pressure of 350 bar is not safe and still needs many intensive studies dedic ated for tank's manufacturing. Liquid hydrogen faces also severe practical difficulties due to its very low density, leading to larger fuel tanks three times larger than traditional gasoline tank. Moreover, converting hydrogen gas into liquid phase is not an economic process since it consumes high energy needed to cool down the gas temperature to -252.8 °C. One practical solution is storing hydrogen gas in metal lattice such as Mg powder and its nanocomposites in the form of MgH 2 . There are two major issues should be solved first. One related to MgH 2 in which its inherent poor hydrogenation/dehydrogenation kinetics and high thermal stability must be improved. Secondly, related to providing a safe tank. Here we have succeeded to prepare a new binary system of MgH 2 /5 wt. % TiMn 2 nanocomposite powder that show excellent hydrogenation/dehydrogenation behavior at relatively low temperature (250 °C) with long cycle-life-time (1400 h). Moreover, a simple hydrogen storage tank filled with our synthetic nanocomposite powders was designed and tested in electrical charging a battery of a cell phone device at 180 °C through a commercial fuel cell.

Evaluation of on-board hydrogen storage methods f or high-speed aircraft

NASA Technical Reports Server (NTRS)

Akyurtlu, Ates; Akyurtlu, Jale F.

1991-01-01

Hydrogen is the fuel of choice for hypersonic vehicles. Its main disadvantage is its low liquid and solid density. This increases the vehicle volume and hence the drag losses during atmospheric flight. In addition, the dry mass of the vehicle is larger due to larger vehicle structure and fuel tankage. Therefore it is very desirable to find a fuel system with smaller fuel storage requirements without deteriorating the vehicle performance substantially. To evaluate various candidate fuel systems, they were first screened thermodynamically with respect to their energy content and cooling capacities. To evaluate the vehicle performance with different fuel systems, a simple computer model is developed to compute the vehicle parameters such as the vehicle volume, dry mass, effective specific impulse, and payload capacity. The results indicate that if the payload capacity (or the gross lift-off mass) is the most important criterion, only slush hydrogen and liquid hydrogen - liquid methane gel shows better performance than the liquid hydrogen vehicle. If all the advantages of a smaller vehicle are considered and a more accurate mass analysis can be performed, other systems using endothermic fuels such as cyclohexane, and some boranes may prove to be worthy of further consideration.

A THEORETICAL INVESTIGATION OF RADIOLYTIC H2 GENERATION FROM SOLIDS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Westbrook, M.; Sindelar, R.; Fisher, D.

2012-02-01

Hydrogen generation from materials in nuclear materials storage is of critical interest due to the potential for pressurization and/or flammability issues. Studies have focused on aqueous systems or those with minor amounts of physisorbed water, since conventional knowledge identifies the radiolytic decomposition of water as the source of H{sub 2} gas. Furthermore, the approach to characterize gas generation is typically strictly empirical, relying on determination of G-values from which production in systems is estimated. Interestingly, exploratory work at SRNL1 on gamma exposure to fully-dried solids with chemically-bound water that are typical of those produced on aluminium-clad nuclear fuel in reactormore » and post-discharge storage has shown a profound production of hydrogen (as the sole gaseous species) from fully dried boehmite ({gamma}-AlOOH or Al{sub 2}O{sub 3} {center_dot} H{sub 2}O) powders and no observable hydrogen from gibbsite ({gamma}-Al(OH){sub 3} or Al{sub 2}O{sub 3} {center_dot} 3H{sub 2}O) under gamma irradiation from cobalt-60. This observation is significant in that gibbsite is known to thermally decompose at 80 C whereas boehmite is stable to 400 C. Radiation damage can have various effects on solids, including heating, bond breaking, and rearrangements in the bonding structure. For example, a molecule can be ionized resulting in the generation of free electrons which can, in turn, ionize another molecule. Alternately, reactive radical species such as {lg_bullet}OH or cation species may be formed, which can go on to change bonding structures.« less

Alternative Sources of Energy - An Introduction to Fuel Cells

USGS Publications Warehouse

Merewether, E.A.

2003-01-01

Fuel cells are important future sources of electrical power and could contribute to a reduction in the amount of petroleum imported by the United States. They are electrochemical devices similar to a battery and consist of a container, an anode, a cathode, catalysts, an intervening electrolyte, and an attached electrical circuit. In most fuel cell systems, hydrogen is supplied to the anode and oxygen to the cathode which results in the production of electricity, water, and heat. Fuel cells are comparatively efficient and reliable, have no moving parts, operate without combustion, and are modular and scale-able. Their size and shape are flexible and adaptable. In operation, they are nearly silent, are relatively safe, and generally do not pollute the environment. During recent years, scientists and engineers have developed and refined technologies relevant to a variety of fuel cells. Types of fuel cells are commonly identified by the composition of their electrolyte, which could be either phosphoric acid, an alkaline solution, a molten carbonate, a solid metal oxide, or a solid polymer membrane. The electrolyte in stationary power plants could be phosphoric acid, molten carbonates, or solid metal oxides. For vehicles and smaller devices, the electrolyte could be an alkaline solution or a solid polymer membrane. For most fuel cell systems, the fuel is hydrogen, which can be extracted by several procedures from many hydrogen-bearing substances, including alcohols, natural gas (mainly methane), gasoline, and water. There are important and perhaps unresolved technical problems associated with using fuel cells to power vehicles. The catalysts required in several systems are expensive metals of the platinum group. Moreover, fuel cells can freeze and not work in cold weather and can be damaged by impacts. Storage tanks for the fuels, particularly hydrogen, must be safe, inexpensive, of a reasonable size, and contain a supply sufficient for a trip of several hundred miles. Additional major problems will be the extensive and costly changes in the national infrastructure to obtain, store, and distribute large amounts of the fuels, and in related manufacturing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Blekhman, David

The College of Engineering, Computer Science, & Technology at California State University, Los Angeles as part of its alternative and renewable energy leadership efforts has built a sustainable hydrogen station to teach and demonstrate the production and application of hydrogen as the next generation of fully renewable fuel for transportation. The requested funding was applied toward the acquisition of the core hydrogen station equipment: electrolyzer, compressors and hydrogen storage.

Compositional, Atomic and Molecular Analysis in Support of Materials Needs of the U.S. Air Force.

DTIC Science & Technology

1982-09-01

internally hydrogen-bonded monomer in .which the keto group is involved in the hydrogen bond but the acid carbonyl is not. 3 ) 3 - Bromopyruvic Acid...The spectra and structure of 3 - bromopyruvic acid were investigated and compared to those of pyruvic acid. It has been found that the spectra of 3 ...phase, cyclic monomer in dilute solution). The solid state spectra are quite different, however. The solid states spectra of 3 - bromopyruvic acid show a

Determination of the heat of hydride formation/decomposition by high-pressure differential scanning calorimetry (HP-DSC).

PubMed

Rongeat, Carine; Llamas-Jansa, Isabel; Doppiu, Stefania; Deledda, Stefano; Borgschulte, Andreas; Schultz, Ludwig; Gutfleisch, Oliver

2007-11-22

Among the thermodynamic properties of novel materials for solid-state hydrogen storage, the heat of formation/decomposition of hydrides is the most important parameter to evaluate the stability of the compound and its temperature and pressure of operation. In this work, the desorption and absorption behaviors of three different classes of hydrides are investigated under different hydrogen pressures using high-pressure differential scanning calorimetry (HP-DSC). The HP-DSC technique is used to estimate the equilibrium pressures as a function of temperature, from which the heat of formation is derived. The relevance of this procedure is demonstrated for (i) magnesium-based compounds (Ni-doped MgH2), (ii) Mg-Co-based ternary hydrides (Mg-CoHx) and (iii) Alanate complex hydrides (Ti-doped NaAlH4). From these results, it can be concluded that HP-DSC is a powerful tool to obtain a good approximation of the thermodynamic properties of hydride compounds by a simple and fast study of desorption and absorption properties under different pressures.

Flexible, solid-state, ion-conducting membrane with 3D garnet nanofiber networks for lithium batteries

PubMed Central

Fu, Kun (Kelvin); Gong, Yunhui; Dai, Jiaqi; Gong, Amy; Han, Xiaogang; Yao, Yonggang; Wang, Chengwei; Wang, Yibo; Chen, Yanan; Yan, Chaoyi; Li, Yiju; Wachsman, Eric D.; Hu, Liangbing

2016-01-01

Beyond state-of-the-art lithium-ion battery (LIB) technology with metallic lithium anodes to replace conventional ion intercalation anode materials is highly desirable because of lithium’s highest specific capacity (3,860 mA/g) and lowest negative electrochemical potential (∼3.040 V vs. the standard hydrogen electrode). In this work, we report for the first time, to our knowledge, a 3D lithium-ion–conducting ceramic network based on garnet-type Li6.4La3Zr2Al0.2O12 (LLZO) lithium-ion conductor to provide continuous Li+ transfer channels in a polyethylene oxide (PEO)-based composite. This composite structure further provides structural reinforcement to enhance the mechanical properties of the polymer matrix. The flexible solid-state electrolyte composite membrane exhibited an ionic conductivity of 2.5 × 10−4 S/cm at room temperature. The membrane can effectively block dendrites in a symmetric Li | electrolyte | Li cell during repeated lithium stripping/plating at room temperature, with a current density of 0.2 mA/cm2 for around 500 h and a current density of 0.5 mA/cm2 for over 300 h. These results provide an all solid ion-conducting membrane that can be applied to flexible LIBs and other electrochemical energy storage systems, such as lithium–sulfur batteries. PMID:27307440

Flexible, solid-state, ion-conducting membrane with 3D garnet nanofiber networks for lithium batteries

NASA Astrophysics Data System (ADS)

Kun, Kelvin; Gong, Yunhui; Dai, Jiaqi; Gong, Amy; Han, Xiaogang; Yao, Yonggang; Wang, Chengwei; Wang, Yibo; Chen, Yanan; Yan, Chaoyi; Li, Yiju; Wachsman, Eric D.; Hu, Liangbing

2016-06-01

Beyond state-of-the-art lithium-ion battery (LIB) technology with metallic lithium anodes to replace conventional ion intercalation anode materials is highly desirable because of lithium's highest specific capacity (3,860 mA/g) and lowest negative electrochemical potential (˜3.040 V vs. the standard hydrogen electrode). In this work, we report for the first time, to our knowledge, a 3D lithium-ion-conducting ceramic network based on garnet-type Li6.4La3Zr2Al0.2O12 (LLZO) lithium-ion conductor to provide continuous Li+ transfer channels in a polyethylene oxide (PEO)-based composite. This composite structure further provides structural reinforcement to enhance the mechanical properties of the polymer matrix. The flexible solid-state electrolyte composite membrane exhibited an ionic conductivity of 2.5 × 10-4 S/cm at room temperature. The membrane can effectively block dendrites in a symmetric Li | electrolyte | Li cell during repeated lithium stripping/plating at room temperature, with a current density of 0.2 mA/cm2 for around 500 h and a current density of 0.5 mA/cm2 for over 300 h. These results provide an all solid ion-conducting membrane that can be applied to flexible LIBs and other electrochemical energy storage systems, such as lithium-sulfur batteries.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Huogen; Chen, Liang

Ti-Zr-Ni quasicrystals have been demonstrated to store a large number of hydrogen atoms, which implies strong potential application in hydrogen energy field for them. However, the desorption of hydrogen atoms in the quasicrystals is quite difficult, with the indication of high desorption temperature and slow desorption rate. The shortage limits their use in the field to a large extent. But this kind of quasicrystals might be used in nuclear fusion energy field, because tritium as a coral fuel for nuclear fusion needs tight storage. However, equilibrium pressure at room temperature of Ti-Zr-Ni quasicrystals, important for their application in fusion energymore » field, has not been clear yet. In this work, we designed a gas-solid reaction system with the pressure resolution of 10{sup −8}Pa and carried out hydrogen desorption investigation at different temperatures on Ti{sub 36}Zr{sub 40}Ni{sub 20}Pd{sub 4} icosahedral quasicrystal. Based on three Pressure-Composition-Temperature desorption curves, we speculate according to Van’t Hoff theory about hydrogen storage that its equilibrium pressure at room temperature could be at the magnitude of 10{sup −6}Pa, displaying good stability of hydrogen in the quasicrystal and also implying application prospects in fusion energy field for quasicrystals of this type.« less

Design Considerations of a Solid State Thermal Energy Storage

NASA Astrophysics Data System (ADS)

Janbozorgi, Mohammad; Houssainy, Sammy; Thacker, Ariana; Ip, Peggy; Ismail, Walid; Kavehpour, Pirouz

2016-11-01

With the growing governmental restrictions on carbon emission, renewable energies are becoming more prevalent. A reliable use of a renewable source however requires a built-in storage to overcome the inherent intermittent nature of the available energy. Thermal design of a solid state energy storage has been investigated for optimal performance. The impact of flow regime, laminar vs. turbulent, on the design and sizing of the system is also studied. The implications of low thermal conductivity of the storage material are discussed and a design that maximizes the round trip efficiency is presented. This study was supported by Award No. EPC-14-027 Granted by California Energy Commission (CEC).

Hydrogen-based electrochemical energy storage

DOEpatents

Simpson, Lin Jay

2013-08-06

An energy storage device (100) providing high storage densities via hydrogen storage. The device (100) includes a counter electrode (110), a storage electrode (130), and an ion conducting membrane (120) positioned between the counter electrode (110) and the storage electrode (130). The counter electrode (110) is formed of one or more materials with an affinity for hydrogen and includes an exchange matrix for elements/materials selected from the non-noble materials that have an affinity for hydrogen. The storage electrode (130) is loaded with hydrogen such as atomic or mono-hydrogen that is adsorbed by a hydrogen storage material such that the hydrogen (132, 134) may be stored with low chemical bonding. The hydrogen storage material is typically formed of a lightweight material such as carbon or boron with a network of passage-ways or intercalants for storing and conducting mono-hydrogen, protons, or the like. The hydrogen storage material may store at least ten percent by weight hydrogen (132, 134) at ambient temperature and pressure.

Theoretical study of hydrogen storage in metal hydrides.

PubMed

Oliveira, Alyson C M; Pavão, A C

2018-05-04

Adsorption, absorption and desorption energies and other properties of hydrogen storage in palladium and in the metal hydrides AlH 3 , MgH 2 , Mg(BH 4 ) 2 , Mg(BH 4 )(NH 2 ) and LiNH 2 were analyzed. The DFT calculations on cluster models show that, at a low concentration, the hydrogen atom remains adsorbed in a stable state near the palladium surface. By increasing the hydrogen concentration, the tetrahedral and the octahedral sites are sequentially occupied. In the α phase the tetrahedral site releases hydrogen more easily than at the octahedral sites, but the opposite occurs in the β phase. Among the hydrides, Mg(BH 4 ) 2 shows the highest values for both absorption and desorption energies. The absorption energy of LiNH 2 is higher than that of the palladium, but its desorption energy is too high, a recurrent problem of the materials that have been considered for hydrogen storage. The release of hydrogen, however, can be favored by using transition metals in the material structure, as demonstrated here by doping MgH 2 with 3d and 4d-transition metals to reduce the hydrogen atomic charge and the desorption energy.

From dense monomer salt crystals to CO2 selective microporous polyimides via solid-state polymerization.

PubMed

Unterlass, Miriam M; Emmerling, Franziska; Antonietti, Markus; Weber, Jens

2014-01-14

Fully aromatic polyimides are synthesized via solid-state polymerization of the corresponding monomer salts. The crystal structure of salts shows strong hydrogen bonding of the reactive groups and thereby paves the way for solid-state transformations. The polycondensation yields copies of the initial salt crystallite habits, accompanied by the development of a porosity especially suited for CO2.

Studies of the thermal and optical responses of H atoms in solid H2

NASA Technical Reports Server (NTRS)

Gaines, James R.; Vause, Chester A., III

1990-01-01

It was the goal of this reserch project to model both the storage of energy in solid hydrogen in the form of atoms and the conversion of this stored energy into other forms of useful energy. The basic ideas of rocket propulsion originate in classical physics and they remain unchanged. To escape a strong gravitational field, the 'burn time' must be minimized but in negligible force fields, the burn time is unimportant and only the relative masses of rocket to fuel determine a specific exhaust velocity. It is in this latter case that low mass fuels such as hydrogen become very important. The burning of hydrogen in oxygen is a 'benchmark' fuel today providing a specific impulse of 400 seconds or better. More exotic fuels will be needed for many of the interesting explorations of the future but they still must have large energy releases per unit mass. It is in this context that propulsion based on hydrogen atom recombination receives attention and these studies will serve as engineering guides.

Management of solid waste

NASA Astrophysics Data System (ADS)

Thompson, W. T.; Stinton, L. H.

1980-04-01

Compliance with the latest regulatory requirements addressing disposal of radioactive, hazardous, and sanitary solid waste criteria in the selection, design, and operation of solid waste management facilities. Due to the state of flux of these regulatory requirements from EPA and NRC, several waste management options were of solid waste. The current regulatory constraints and the design and operational requirements for construction of both storage and disposal facilities for use in management of DOE-ORO solid waste are highlighted. Capital operational costs are included for both disposal and storage options.

Analysis of H2 storage needs for early market non-motive fuel cell applications.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, Terry Alan; Moreno, Marcina; Arienti, Marco

Hydrogen fuel cells can potentially reduce greenhouse gas emissions and the United States dependence on foreign oil, but issues with hydrogen storage are impeding their widespread use. To help overcome these challenges, this study analyzes opportunities for their near-term deployment in five categories of non-motive equipment: portable power, construction equipment, airport ground support equipment, telecom backup power, and man-portable power and personal electronics. To this end, researchers engaged end users, equipment manufacturers, and technical experts via workshops, interviews, and electronic means, and then compiled these data into meaningful and realistic requirements for hydrogen storage in specific target applications. In additionmore » to developing these requirements, end-user benefits (e.g., low noise and emissions, high efficiency, potentially lower maintenance costs) and concerns (e.g., capital cost, hydrogen availability) of hydrogen fuel cells in these applications were identified. Market data show potential deployments vary with application from hundreds to hundreds of thousands of units.« less

Proceedings of the DOE Chemical Energy Storage and Hydrogen Energy Systems Contracts Review

NASA Technical Reports Server (NTRS)

Kelley, J. H.

1978-01-01

The background and objectives of thirty-nine hydrogen-related tasks were discussed, the status of the studies or technical effort is shown, and state projected solutions for resolving the identified problems are projected.

Proceedings of the DOE chemical energy storage and hydrogen energy systems contracts review

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

Sessions were held on electrolysis-based hydrogen storage systems, hydrogen production, hydrogen storage systems, hydrogen storage materials, end-use applications and system studies, chemical heat pump/chemical energy storage systems, systems studies and assessment, thermochemical hydrogen production cycles, advanced production concepts, and containment materials. (LHK)

Doped phosphorene for hydrogen capture: A DFT study

NASA Astrophysics Data System (ADS)

Zhang, Hong-ping; Hu, Wei; Du, Aijun; Lu, Xiong; Zhang, Ya-ping; Zhou, Jian; Lin, Xiaoyan; Tang, Youhong

2018-03-01

Hydrogen capture and storage is the core of hydrogen energy application. With its high specific surface area, direct bandgap, and variety of potential applications, phosphorene has attracted much research interest. In this study, density functional theory (DFT) is utilized to study the interactions between doped phosphorenes and hydrogen molecules. The effects of different dopants and metallic or nonmetallic atoms on phosphorene/hydrogen interactions is systematically studied by adsorption energy, electron density difference, partial density of states analysis, and Hirshfeld population. Our results indicate that the metallic dopants Pt, Co, and Ni can help to improve the hydrogen capture ability of phosphorene, whereas the nonmetallic dopants have no effect on it. Among the various metallic dopants, Pt performs very differently, such that it can help to dissociate H2 on phosphorene. Specified doped phosphorene could be a promising candidate for hydrogen storage, with behaviors superior to those of intrinsic graphene sheet.

Ground operations demonstration unit for liquid hydrogen initial test results

NASA Astrophysics Data System (ADS)

Notardonato, W. U.; Johnson, W. L.; Swanger, A. M.; Tomsik, T.

2015-12-01

NASA operations for handling cryogens in ground support equipment have not changed substantially in 50 years, despite major technology advances in the field of cryogenics. NASA loses approximately 50% of the hydrogen purchased because of a continuous heat leak into ground and flight vessels, transient chill down of warm cryogenic equipment, liquid bleeds, and vent losses. NASA Kennedy Space Center (KSC) needs to develop energy-efficient cryogenic ground systems to minimize propellant losses, simplify operations, and reduce cost associated with hydrogen usage. The GODU LH2 project has designed, assembled, and started testing of a prototype storage and distribution system for liquid hydrogen that represents an advanced end-to-end cryogenic propellant system for a ground launch complex. The project has multiple objectives including zero loss storage and transfer, liquefaction of gaseous hydrogen, and densification of liquid hydrogen. The system is unique because it uses an integrated refrigeration and storage system (IRAS) to control the state of the fluid. This paper will present and discuss the results of the initial phase of testing of the GODU LH2 system.

Ground Operations Demonstration Unit for Liquid Hydrogen Initial Test Results

NASA Technical Reports Server (NTRS)

Notardonato, W. U.; Johnson, W. L.; Swanger, A. M.; Tomsik, T.

2015-01-01

NASA operations for handling cryogens in ground support equipment have not changed substantially in 50 years, despite major technology advances in the field of cryogenics. NASA loses approximately 50% of the hydrogen purchased because of a continuous heat leak into ground and flight vessels, transient chill down of warm cryogenic equipment, liquid bleeds, and vent losses. NASA Kennedy Space Center (KSC) needs to develop energy-efficient cryogenic ground systems to minimize propellant losses, simplify operations, and reduce cost associated with hydrogen usage. The GODU LH2 project has designed, assembled, and started testing of a prototype storage and distribution system for liquid hydrogen that represents an advanced end-to-end cryogenic propellant system for a ground launch complex. The project has multiple objectives including zero loss storage and transfer, liquefaction of gaseous hydrogen, and densification of liquid hydrogen. The system is unique because it uses an integrated refrigeration and storage system (IRAS) to control the state of the fluid. This paper will present and discuss the results of the initial phase of testing of the GODU LH2 system.

Tautomeric and ionisation forms of dopamine and tyramine in the solid state

NASA Astrophysics Data System (ADS)

Cruickshank, Laura; Kennedy, Alan R.; Shankland, Norman

2013-11-01

Crystallisation of the phenylethylamine neurotransmitter dopamine from basic aqueous solution yielded the 3-phenoxide Zwitterionic tautomer, despite this being a minority form in the solution state. In the crystal structure, dopamine has a dimeric [OCCOH]2 hydrogen bonded catechol motif that expands through Nsbnd H⋯O interactions to give a 2-dimensional sheet of classical hydrogen bonds. These sheets are further interconnected by Nsbnd H⋯π interactions. The structurally related base tyramine crystallises under similar conditions as a hemihydrate with all four possible species of tyramine present (cationic, anionic, Zwitterionic and neutral) in the crystal structure. Single crystal X-ray diffraction studies at 121 and 293 K showed dynamic hydrogen atom disorder for the phenol/phenoxide group, suggesting that the tyramine speciation observed arises from a solid-state process.

Facile Uptake and Release of Ammonia by Nickel Halide Ammines.

PubMed

Breternitz, Joachim; Vilk, Yury E; Giraud, Elsa; Reardon, Hazel; Hoang, Tuan K A; Godula-Jopek, Agata; Gregory, Duncan H

2016-06-08

Although major difficulties are experienced for hydrogen- storage materials to meet performance requirements for mobile applications, alternative fuel cell feedstocks such as ammonia can be stored in the solid state safely at high capacity. We herein describe the NiX2 -NH3 (X=Cl, Br, I) systems and demonstrate their exceptional suitability for NH3 storage (up to 43 wt % NH3 with desorption that begins at 400 K). The structural effects that result from the uptake of NH3 were studied by powder X-ray diffraction (PXD), FTIR spectroscopy and SEM. NH3 release at elevated temperatures was followed by in situ PXD. The cycling capabilities and air stability of the systems were also explored. NH3 is released from the hexaammines in a three-step process to yield the diammine, monoammine and NiX2 dihalides respectively and (re)ammoniation occurs readily at room temperature. The hexaammines do not react with air after several hours of exposure. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wolverton, Christopher; Ozolins, Vidvuds; Kung, Harold H.

The objective of the proposed program is to discover novel mixed hydrides for hydrogen storage, which enable the DOE 2010 system-level goals. Our goal is to find a material that desorbs 8.5 wt.% H 2 or more at temperatures below 85°C. The research program will combine first-principles calculations of reaction thermodynamics and kinetics with material and catalyst synthesis, testing, and characterization. We will combine materials from distinct categories (e.g., chemical and complex hydrides) to form novel multicomponent reactions. Systems to be studied include mixtures of complex hydrides and chemical hydrides [e.g. LiNH 2+NH 3BH 3] and nitrogen-hydrogen based borohydrides [e.g.more » Al(BH 4) 3(NH 3) 3]. The 2010 and 2015 FreedomCAR/DOE targets for hydrogen storage systems are very challenging, and cannot be met with existing materials. The vast majority of the work to date has delineated materials into various classes, e.g., complex and metal hydrides, chemical hydrides, and sorbents. However, very recent studies indicate that mixtures of storage materials, particularly mixtures between various classes, hold promise to achieve technological attributes that materials within an individual class cannot reach. Our project involves a systematic, rational approach to designing novel multicomponent mixtures of materials with fast hydrogenation/dehydrogenation kinetics and favorable thermodynamics using a combination of state-of-the-art scientific computing and experimentation. We will use the accurate predictive power of first-principles modeling to understand the thermodynamic and microscopic kinetic processes involved in hydrogen release and uptake and to design new material/catalyst systems with improved properties. Detailed characterization and atomic-scale catalysis experiments will elucidate the effect of dopants and nanoscale catalysts in achieving fast kinetics and reversibility. And, state-of-the-art storage experiments will give key storage attributes of the investigated reactions, validate computational predictions, and help guide and improve computational methods. In sum, our approach involves a powerful blend of: 1) H2 Storage measurements and characterization, 2) State-of-the-art computational modeling, 3) Detailed catalysis experiments, 4) In-depth automotive perspective.« less

Dipolar induced para-hydrogen-induced polarization.

PubMed

Buntkowsky, Gerd; Gutmann, Torsten; Petrova, Marina V; Ivanov, Konstantin L; Bommerich, Ute; Plaumann, Markus; Bernarding, Johannes

2014-01-01

Analytical expressions for the signal enhancement in solid-state PHIP NMR spectroscopy mediated by homonuclear dipolar interactions and single pulse or spin-echo excitation are developed and simulated numerically. It is shown that an efficient enhancement of the proton NMR signal in solid-state NMR studies of chemisorbed hydrogen on surfaces is possible. Employing typical reaction efficacy, enhancement-factors of ca. 30-40 can be expected both under ALTADENA and under PASADENA conditions. This result has important consequences for the practical application of the method, since it potentially allows the design of an in-situ flow setup, where the para-hydrogen is adsorbed and desorbed from catalyst surfaces inside the NMR magnet. Copyright © 2014 Elsevier Inc. All rights reserved.

PNNL Development and Analysis of Material-Based Hydrogen Storage Systems for the Hydrogen Storage Engineering Center of Excellence

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brooks, Kriston P.; Alvine, Kyle J.; Johnson, Kenneth I.

The Hydrogen Storage Engineering Center of Excellence is a team of universities, industrial corporations, and federal laboratories with the mandate to develop lower-pressure, materials-based, hydrogen storage systems for hydrogen fuel cell light-duty vehicles. Although not engaged in the development of new hydrogen storage materials themselves, it is an engineering center that addresses engineering challenges associated with the currently available hydrogen storage materials. Three material-based approaches to hydrogen storage are being researched: 1) chemical hydrogen storage materials 2) cryo-adsorbents, and 3) metal hydrides. As a member of this Center, Pacific Northwest National Laboratory (PNNL) has been involved in the design andmore » evaluation of systems developed with each of these three hydrogen storage materials. This report is a compilation of the work performed by PNNL for this Center.« less

Association of 2-acylaminopyridines and benzoic acids. Steric and electronic substituent effect studied by XRD, solution and solid-state NMR and calculations

NASA Astrophysics Data System (ADS)

Ośmiałowski, Borys; Kolehmainen, Erkki; Ejsmont, Krzysztof; Ikonen, Satu; Valkonen, Arto; Rissanen, Kari; Nonappa

2013-12-01

Eight single crystal X-ray structures, solid-state NMR spectroscopic, and theoretical studies utilizing QTAIM methodology were used to characterize the 2-acyl (alkyl in acyl = methyl, ethyl, t-butyl, and 1-adamantyl) amino-6-R-pyridine/4-R‧-benzoic acid (R,R‧ = H or Me) cocrystals. As expected among alkyl groups 1-adamantyl due to its bulkiness has the most significant effect on the relative positions of molecules in cocrystals. In addition, the subtle electronic and steric effects by the methyl substituents were observed. The theoretical calculations with full geometry optimizations are in agreement with the experimental findings (geometry, energy of hydrogen bonds). Based on the crystal structures and calculations it is concluded that p-methyl substituent in benzoic acid increase the hydrogen bond accepting ability of the CO oxygen and decreases the hydrogen bond donating ability of OH proton. The 15N solid-state (CP MAS) NMR chemical shifts prove that molecules in cocrystal are held together by hydrogen bonding. The biggest variation in the 15N chemical shift of acylamino nitrogen can be related with the size of the alkyl group in acyl moiety.

Evaluation of on-board hydrogen storage methods for hypersonic vehicles

NASA Technical Reports Server (NTRS)

Akyurtlu, Ates; Akyurtlu, J. F.; Adeyiga, A. A.; Perdue, Samara; Northam, G. B.

1989-01-01

Hydrogen is the foremost candidate as a fuel for use in high speed transport. Since any aircraft moving at hypersonic speeds must have a very slender body, means of decreasing the storage volume requirements below that for liquid hydrogen are needed. The total performance of the hypersonic plane needs to be considered for the evaluation of candidate fuel and storage systems. To accomplish this, a simple model for the performance of a hypersonic plane is presented. To allow for the use of different engines and fuels during different phases of flight, the total trajectory is divided into three phases: subsonic-supersonic, hypersonic and rocket propulsion phase. The fuel fraction for the first phase is found be a simple energy balance using an average thrust to drag ratio for this phase. The hypersonic flight phase is investigated in more detail by taking small altitude increments. This approach allowed the use of flight profiles other than the constant dynamic pressure flight. The effect of fuel volume on drag, structural mass and tankage mass was introduced through simplified equations involving the characteristic dimension of the plane. The propellant requirement for the last phase is found by employing the basic rocket equations. The candidate fuel systems such as the cryogenic fuel combinations and solid and liquid endothermic hydrogen generators are first screened thermodynamically with respect to their energy densities and cooling capacities and then evaluated using the above model.

New chemical sources of energy: A theoretical study

NASA Astrophysics Data System (ADS)

Chaban, Galina

The research presented in this dissertation employs methods of quantum chemistry for the search of highly energetic chemical compounds that can have applications as possible energy sources. The areas of research include: (1) improvement of orbital optimization methods for different types of wavefunctions which leads to substantial savings of computer time and memory; (2) predicting new high energy isomers for singlet and triplet states of Nsb3F and their kinetic stability with respect to isomerisation and dissociation reactions; (3) estimation of minimum energy reaction paths for dissociation reactions of high energy isomers of Nsb2Osb2 including potential energy barriers and minimum energy crossing points between the closest singlet and triplet states; (4) investigation of thermodynamic and kinetic stability of Van der Waals complexes M-Hsb2 (M = Li, Be, B, C, Na, Mg, Al, Si) that can play an important role in improvement of energetic properties of hydrogen based rocket fuels; (5) mapping of the potential energy surface for AlHsb2 compound in the region of crossing between sp2Bsb2 and sp2Asb1 electronic states and predicting the kinetic stability of Al complex, which suggests that Al may be among the promising candidates for inclusion into solid hydrogen for the purpose of energy storage.

Scattering-layer-induced energy storage function in polymer-based quasi-solid-state dye-sensitized solar cells.

PubMed

Zhang, Xi; Jiang, Hongrui

2015-03-09

Photo-self-charging cells (PSCs) are compact devices with dual functions of photoelectric conversion and energy storage. By introducing a scattering layer in polymer-based quasi-solid-state dye-sensitized solar cells, two-electrode PSCs with highly compact structure were obtained. The charge storage function stems from the formed ion channel network in the scattering layer/polymer electrolyte system. Both the photoelectric conversion and the energy storage functions are integrated in only the photoelectrode of such PSCs. This design of PSC could continuously output power as a solar cell with considerable efficiency after being photo-charged. Such PSCs could be applied in highly-compact mini power devices.

On the purity assessment of solid sodium borohydride

NASA Astrophysics Data System (ADS)

Botasini, Santiago; Méndez, Eduardo

2012-01-01

Since sodium borohydride has become extensively used as chemical hydrogen storage material in fuel cells, many techniques have been proposed to assess the purity of this substance. However, all of them are developed in aqueous media, where the reagent is unstable. In addition, its hygroscopic nature was difficults in any attempt to make precise quantifications. The present work compares three different methods, namely, voltammetric, titrimetric, and Fourier transformed infrared spectroscopy (FTIR) in order to assess the purity of sodium borohydride, using an expired and a new sodium borohydride samples as references. Our results show that only the FTIR measurements provide a simple and semi-quantitative means to assess the purity of sodium borohydride due to the fact that it is the only one that measures the sample in the solid state. A comparison between the experimental data and theoretical calculation reveals the identification of the absorption bands at 1437 cm-1 of sodium metaborate and 2291 cm-1 of sodium borohydride which represent a good fingerprint for the qualitative assessment of the sample quality.

Crystallization of amorphous solid dispersions of resveratrol during preparation and storage-Impact of different polymers.

PubMed

Wegiel, Lindsay A; Mauer, Lisa J; Edgar, Kevin J; Taylor, Lynne S

2013-01-01

The objective of this study was to investigate intermolecular interactions between resveratrol and polymers in amorphous blends and to study the potential correlations between compound-polymer interactions, manufacturability, and stability of the amorphous system to crystallization during storage. Polymers included two grades of poly (vinylpyrrolidone) (PVP), Eudragit E100 (E100), hydroxypropyl methylcellulose (HPMC), hydroxypropyl methylcellulose acetate succinate (HPMCAS), carboxymethyl cellulose acetate butyrate, and poly (acrylic acid) (PAA). Amorphous blends ("solid dispersions") were prepared by dissolving both resveratrol and polymer in a solvent followed by rotary evaporation. Crystallinity was evaluated using X-ray powder diffraction and was studied as a function of time. Mid-infrared (IR) spectroscopy was used to investigate resveratrol-polymer interactions. Polymer influence on the crystallization behavior of resveratrol varied and could be correlated to the polymer structure, whereby polymers with good hydrogen bond acceptor groups performed better as crystallization inhibitors. Resveratrol-polymer hydrogen bonding interactions could be inferred from the IR spectra. Somewhat surprisingly, E100 and resveratrol showed evidence of an acid-base reaction, in addition to intermolecular hydrogen bonding interactions. PVP K29/32 appeared to form stronger hydrogen bond interactions with resveratrol relative to HPMC, HPMCAS, and PAA, consistent with acceptor group chemistry. Long-term stability of the systems against crystallization suggested that stability is linked to the type and strength of intermolecular interactions present. whereby resveratrol blended with E100 and PVP K29/32 showed the greatest stability to crystallization. In conclusion, amorphous resveratrol is unstable and difficult to form, requiring the assistance of a polymeric crystallization inhibitor to facilitate the formation of an amorphous solid dispersion. Polymers effective at inhibiting crystallization were identified, and it is rationalized that their effectiveness is based on the type and strength of their intermolecular interactions with resveratrol. Copyright © 2012 Wiley Periodicals, Inc.

Effect of Li Adsorption on the Electronic and Hydrogen Storage Properties of Acenes: A Dispersion-Corrected TAO-DFT Study

PubMed Central

Seenithurai, Sonai; Chai, Jeng-Da

2016-01-01

Due to the presence of strong static correlation effects and noncovalent interactions, accurate prediction of the electronic and hydrogen storage properties of Li-adsorbed acenes with n linearly fused benzene rings (n = 3–8) has been very challenging for conventional electronic structure methods. To meet the challenge, we study these properties using our recently developed thermally-assisted-occupation density functional theory (TAO-DFT) with dispersion corrections. In contrast to pure acenes, the binding energies of H2 molecules on Li-adsorbed acenes are in the ideal binding energy range (about 20 to 40 kJ/mol per H2). Besides, the H2 gravimetric storage capacities of Li-adsorbed acenes are in the range of 9.9 to 10.7 wt%, satisfying the United States Department of Energy (USDOE) ultimate target of 7.5 wt%. On the basis of our results, Li-adsorbed acenes can be high-capacity hydrogen storage materials for reversible hydrogen uptake and release at ambient conditions. PMID:27609626

Near-infrared analysis of hydrogen-bonding in glass- and rubber-state amorphous saccharide solids.

PubMed

Izutsu, Ken-ichi; Hiyama, Yukio; Yomota, Chikako; Kawanishi, Toru

2009-01-01

Near-infrared (NIR) spectroscopic analysis of noncrystalline polyols and saccharides (e.g., glycerol, sorbitol, maltitol, glucose, sucrose, maltose) was performed at different temperatures (30-80 degrees C) to elucidate the effect of glass transition on molecular interaction. Transmission NIR spectra (4,000-12,000 cm(-1)) of the liquids and cooled-melt amorphous solids showed broad absorption bands that indicate random configuration of molecules. Heating of the samples decreased an intermolecular hydrogen-bonding OH vibration band intensity (6,200-6,500 cm(-1)) with a concomitant increase in a free and intramolecular hydrogen-bonding OH group band (6,600-7,100 cm(-1)). Large reduction of the intermolecular hydrogen-bonding band intensity at temperatures above the glass transition (T(g)) of the individual solids should explain the higher molecular mobility and lower viscosity in the rubber state. Mixing of the polyols with a high T(g) saccharide (maltose) or an inorganic salt (sodium tetraborate) shifted both the glass transition and the inflection point of the hydrogen-bonding band intensity to higher temperatures. The implications of these results for pharmaceutical formulation design and process monitoring (PAT) are discussed.

Reversible hydrogen storage by NaAlH4 confined within a titanium-functionalized MOF-74(Mg) nanoreactor.

PubMed

Stavila, Vitalie; Bhakta, Raghunandan K; Alam, Todd M; Majzoub, Eric H; Allendorf, Mark D

2012-11-27

We demonstrate that NaAlH(4) confined within the nanopores of a titanium-functionalized metal-organic framework (MOF) template MOF-74(Mg) can reversibly store hydrogen with minimal loss of capacity. Hydride-infiltrated samples were synthesized by melt infiltration, achieving loadings up to 21 wt %. MOF-74(Mg) possesses one-dimensional, 12 Å channels lined with Mg atoms having open coordination sites, which can serve as sites for Ti catalyst stabilization. MOF-74(Mg) is stable under repeated hydrogen desorption and hydride regeneration cycles, allowing it to serve as a "nanoreactor". Confining NaAlH(4) within these pores alters the decomposition pathway by eliminating the stable intermediate Na(3)AlH(6) phase observed during bulk decomposition and proceeding directly to NaH, Al, and H(2), in agreement with theory. The onset of hydrogen desorption for both Ti-doped and undoped nano-NaAlH(4)@MOF-74(Mg) is ∼50 °C, nearly 100 °C lower than bulk NaAlH(4). However, the presence of titanium is not necessary for this increase in desorption kinetics but enables rehydriding to be almost fully reversible. Isothermal kinetic studies indicate that the activation energy for H(2) desorption is reduced from 79.5 kJ mol(-1) in bulk Ti-doped NaAlH(4) to 57.4 kJ mol(-1) for nanoconfined NaAlH(4). The structural properties of nano-NaAlH(4)@MOF-74(Mg) were probed using (23)Na and (27)Al solid-state MAS NMR, which indicates that the hydride is not decomposed during infiltration and that Al is present as tetrahedral AlH(4)(-) anions prior to desorption and as Al metal after desorption. Because of the highly ordered MOF structure and monodisperse pore dimensions, our results allow key template features to be identified to ensure reversible, low-temperature hydrogen storage.

Mixture including hydrogen and hydrocarbon having pressure-temperature stability

NASA Technical Reports Server (NTRS)

Mao, Wendy L. (Inventor); Mao, Ho-Kwang (Inventor)

2009-01-01

The invention relates to a method of storing hydrogen that employs a mixture of hydrogen and a hydrocarbon that can both be used as fuel. In one embodiment, the method involves maintaining a mixture including hydrogen and a hydrocarbon in the solid state at ambient pressure and a temperature in excess of about 10 K.

Mixture including hydrogen and hydrocarbon having pressure-temperature stability

DOEpatents

Mao, Wendy L [Washington, DC; Mao, Ho-Kwang [Washington, DC

2009-08-18

The invention relates to a method of storing hydrogen that employs a mixture of hydrogen and a hydrocarbon that can both be used as fuel. In one embodiment, the method involves maintaining a mixture including hydrogen and a hydrocarbon in the solid state at ambient pressure and a temperature in excess of about 10 K.

Exploration and exploitation of homologous series of bis(acrylamido)alkanes containing pyridyl and phenyl groups: β-sheet versus two-dimensional layers in solid-state photochemical [2 + 2] reactions.

PubMed

Garai, Mousumi; Biradha, Kumar

2015-09-01

The homologous series of phenyl and pyridyl substituted bis(acrylamido)alkanes have been synthesized with the aim of systematic analysis of their crystal structures and their solid-state [2 + 2] reactivities. The changes in the crystal structures with respect to a small change in the molecular structure, that is by varying alkyl spacers between acrylamides and/or by varying the end groups (phenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl) on the C-terminal of the amide, were analyzed in terms of hydrogen-bonding interference (N-H⋯Npy versus N-H⋯O=C) and network geometries. In this series, a greater tendency towards the formation of N-H⋯O hydrogen bonds (β-sheets and two-dimensional networks) over N-H⋯N hydrogen bonds was observed. Among all the structures seven structures were found to have the required alignments of double bonds for the [2 + 2] reaction such that the formations of single dimer, double dimer and polymer are facilitated. However, only four structures were found to exhibit such a solid-state [2 + 2] reaction to form a single dimer and polymers. The two-dimensional hydrogen-bonding layer via N-H⋯O hydrogen bonds was found to promote solid-state [2 + 2] photo-polymerization in a single-crystal-to-single-crystal manner. Such two-dimensional layers were encountered only when the spacer between acryl amide moieties is butyl. Only four out of the 16 derivatives were found to form hydrates, two each from 2-pyridyl and 4-pyridyl derivatives. The water molecules in these structures govern the hydrogen-bonding networks by the formation of an octameric water cluster and one-dimensional zigzag water chains. The trends in the melting points and densities were also analyzed.

Sizing and economic analysis of stand alone photovoltaic system with hydrogen storage

NASA Astrophysics Data System (ADS)

Nordin, N. D.; Rahman, H. A.

2017-11-01

This paper proposes a design steps in sizing of standalone photovoltaic system with hydrogen storage using intuitive method. The main advantage of this method is it uses a direct mathematical approach to find system’s size based on daily load consumption and average irradiation data. The keys of system design are to satisfy a pre-determined load requirement and maintain hydrogen storage’s state of charge during low solar irradiation period. To test the effectiveness of the proposed method, a case study is conducted using Kuala Lumpur’s generated meteorological data and rural area’s typical daily load profile of 2.215 kWh. In addition, an economic analysis is performed to appraise the proposed system feasibility. The finding shows that the levelized cost of energy for proposed system is RM 1.98 kWh. However, based on sizing results obtained using a published method with AGM battery as back-up supply, the system cost is lower and more economically viable. The feasibility of PV system with hydrogen storage can be improved if the efficiency of hydrogen storage technologies significantly increases in the future. Hence, a sensitivity analysis is performed to verify the effect of electrolyzer and fuel cell efficiencies towards levelized cost of energy. Efficiencies of electrolyzer and fuel cell available in current market are validated using laboratory’s experimental data. This finding is needed to envisage the applicability of photovoltaic system with hydrogen storage as a future power supply source in Malaysia.

Thin Film Photovoltaic Cells on Flexible Substrates Integrated with Energy Storage

DTIC Science & Technology

2012-07-01

selected mass-altered planes is varied, we have constructed a simple one-dimensional lattice that approximates the solids simulated previously with...to Sn atoms added to a silicon lattice). Development of Solid State Supercapacitors Integrated with Solar cells for Solar Electricity Storage This... supercapacitor for solar electricity storage. These areas and the major tasks therein are: (i) Supercapacitor Electrodes: We have investigated an approach to

Homogeneous Catalysis for Sustainable Hydrogen Storage in Formic Acid and Alcohols.

PubMed

Sordakis, Katerina; Tang, Conghui; Vogt, Lydia K; Junge, Henrik; Dyson, Paul J; Beller, Matthias; Laurenczy, Gábor

2018-01-24

Hydrogen gas is a storable form of chemical energy that could complement intermittent renewable energy conversion. One of the main disadvantages of hydrogen gas arises from its low density, and therefore, efficient handling and storage methods are key factors that need to be addressed to realize a hydrogen-based economy. Storage systems based on liquids, in particular, formic acid and alcohols, are highly attractive hydrogen carriers as they can be made from CO 2 or other renewable materials, they can be used in stationary power storage units such as hydrogen filling stations, and they can be used directly as transportation fuels. However, to bring about a paradigm change in our energy infrastructure, efficient catalytic processes that release the hydrogen from these molecules, as well as catalysts that regenerate these molecules from CO 2 and hydrogen, are required. In this review, we describe the considerable progress that has been made in homogeneous catalysis for these critical reactions, namely, the hydrogenation of CO 2 to formic acid and methanol and the reverse dehydrogenation reactions. The dehydrogenation of higher alcohols available from renewable feedstocks is also described. Key structural features of the catalysts are analyzed, as is the role of additives, which are required in many systems. Particular attention is paid to advances in sustainable catalytic processes, especially to additive-free processes and catalysts based on Earth-abundant metal ions. Mechanistic information is also presented, and it is hoped that this review not only provides an account of the state of the art in the field but also offers insights into how superior catalytic systems can be obtained in the future.

Liquid Organic Hydrogen Carriers (LOHCs): Toward a Hydrogen-free Hydrogen Economy.

PubMed

Preuster, Patrick; Papp, Christian; Wasserscheid, Peter

2017-01-17

The need to drastically reduce CO 2 emissions will lead to the transformation of our current, carbon-based energy system to a more sustainable, renewable-based one. In this process, hydrogen will gain increasing importance as secondary energy vector. Energy storage requirements on the TWh scale (to bridge extended times of low wind and sun harvest) and global logistics of renewable energy equivalents will create additional driving forces toward a future hydrogen economy. However, the nature of hydrogen requires dedicated infrastructures, and this has prevented so far the introduction of elemental hydrogen into the energy sector to a large extent. Recent scientific and technological progress in handling hydrogen in chemically bound form as liquid organic hydrogen carrier (LOHC) supports the technological vision that a future hydrogen economy may work without handling large amounts of elemental hydrogen. LOHC systems are composed of pairs of hydrogen-lean and hydrogen-rich organic compounds that store hydrogen by repeated catalytic hydrogenation and dehydrogenation cycles. While hydrogen handling in the form of LOHCs allows for using the existing infrastructure for fuels, it also builds on the existing public confidence in dealing with liquid energy carriers. In contrast to hydrogen storage by hydrogenation of gases, such as CO 2 or N 2 , hydrogen release from LOHC systems produces pure hydrogen after condensation of the high-boiling carrier compounds. This Account highlights the current state-of-the-art in hydrogen storage using LOHC systems. It first introduces fundamental aspects of a future hydrogen economy and derives therefrom requirements for suitable LOHC compounds. Molecular structures that have been successfully applied in the literature are presented, and their property profiles are discussed. Fundamental and applied aspects of the involved hydrogenation and dehydrogenation catalysis are discussed, characteristic differences for the catalytic conversion of pure hydrocarbon and nitrogen-containing LOHC compounds are derived from the literature, and attractive future research directions are highlighted. Finally, applications of the LOHC technology are presented. This part covers stationary energy storage (on-grid and off-grid), hydrogen logistics, and on-board hydrogen production for mobile applications. Technology readiness of these fields is very different. For stationary energy storage systems, the feasibility of the LOHC technology has been recently proven in commercial demonstrators, and cost aspects will decide on their further commercial success. For other highly attractive options, such as, hydrogen delivery to hydrogen filling stations or direct-LOHC-fuel cell applications, significant efforts in fundamental and applied research are still needed and, hopefully, encouraged by this Account.

Theoretical realization of cluster-assembled hydrogen storage materials based on terminated carbon atomic chains.

PubMed

Liu, Chun-Sheng; An, Hui; Guo, Ling-Ju; Zeng, Zhi; Ju, Xin

2011-01-14

The capacity of carbon atomic chains with different terminations for hydrogen storage is studied using first-principles density functional theory calculations. Unlike the physisorption of H(2) on the H-terminated chain, we show that two Li (Na) atoms each capping one end of the odd- or even-numbered carbon chain can hold ten H(2) molecules with optimal binding energies for room temperature storage. The hybridization of the Li 2p states with the H(2)σ orbitals contributes to the H(2) adsorption. However, the binding mechanism of the H(2) molecules on Na arises only from the polarization interaction between the charged Na atom and the H(2). Interestingly, additional H(2) molecules can be bound to the carbon atoms at the chain ends due to the charge transfer between Li 2s2p (Na 3s) and C 2p states. More importantly, dimerization of these isolated metal-capped chains does not affect the hydrogen binding energy significantly. In addition, a single chain can be stabilized effectively by the C(60) fullerenes termination. With a hydrogen uptake of ∼10 wt.% on Li-coated C(60)-C(n)-C(60) (n = 5, 8), the Li(12)C(60)-C(n)-Li(12)C(60) complex, keeping the number of adsorbed H(2) molecules per Li and stabilizing the dispersion of individual Li atoms, can serve as better building blocks of polymers than the (Li(12)C(60))(2) dimer. These findings suggest a new route to design cluster-assembled hydrogen storage materials based on terminated sp carbon chains.

Design and Development of a 30 Watt Solid Polymer Electrolyte Fuel Cell Power Source Fueled with Calcium Hydride.

DTIC Science & Technology

1978-12-12

hydri de and its integration with the fuel cell. I The combination of the SPE cel l with a hydride fuel offers -- comparedto batteries -- increased...demand changes without intermediate storage of hydrogen gas. In order to control the reacti on with water the hydri de is contained in a cartridge. The use

CP/MAS /sup 13/C NMR spectroscopic study of chlorophyll a in the solid state

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brown, C.E.; Spencer, R.B.; Burger, V.T.

1983-09-01

Solid-state cross-polarization, magic-angle sample spinning carbon-13 nuclear magnetic resonance spectra have been recorded on chlorophyll a- water aggregates, methyl pyrochlorophyllide a and methyl pyropheophorbide a (derivatives that lack a phytyl chain). Spectra have also been collected under a decoupling regime in which resonances of certain hydrogen-bearing carbon atoms are suppressed. These observations are used to assign the solid state spectra.

Cross-polarization/magic-angle sample-spinning /sup 13/C NMR spectroscopic study of chlorophyll a in the solid state

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brown, C.E.; Spencer, R.B.; Burger, V.T.

1984-01-01

Solid-state cross-polarization/magic-angle sample-spinning /sup 13/C NMR spectra have been recorded on chlorophyll a-water aggregates, methyl pyrochlorophyllide a, and methyl pyropheophorbide a. Spectra have also been collected under a decoupling regime in which resonances of certain hydrogen-bearing carbon atoms are suppressed. These observations are used to assign the solid-state spectra. 18 references, 2 figures, 1 table.

Storage rings for spin-polarized hydrogen

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thompson, D.; Lovelace, R.V.E.; Lee, D.

1989-11-01

A strong-focusing storage ring is proposed for the long-term magnetic confinement of a collisional gas of neutral spin-polarized hydrogen atoms in the Za{l arrow} and Zb{l arrow} hyperfine states. The trap uses the interaction of the magnetic moments of the gas atoms with a static magnetic field. Laser cooling and evaporative cooling can be utilized to enhance the confinement and to offset the influence of viscous heating. An important application of the trap is to the attainment of Bose--Einstein condensation.

Effects of rotational states on the c / a ratio in solid hydrogens

DOE PAGES

Strzhemechny, Mikhail A.; Hemley, Russell J.

2015-04-08

We propose an approach to the problem of lattice distortions at low temperatures and ambient pressure in the solid hydrogens in their rotational ground states that explicitly accounts for the molecular nature of the constituent particles. The model is based on the idea that the second-order rotation-related correction to the ground-state energy depends on the lattice parameters. The calculated ground-state rotation-related contributions, δ gs = c/a–(8/3) 1/2, are negative for all species, amounting to about –1.5×10 –5 for H 2 and D 2, whereas for HD this contribution is about –0.6×10 –3, which is roughly 50 times larger. This substantialmore » difference stems from the fact that the rotational dynamics in the homonuclear solids and in HD differ appreciably. Furthermore, the approach can be generalized to high pressures.« less

Hydrogen Storage Properties of New Hydrogen-Rich BH3NH3-Metal Hydride (TiH2, ZrH2, MgH2, and/or CaH2) Composite Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choi, Young Joon; Xu, Yimin; Shaw, Wendy J.

2012-04-19

Ammonia borane (AB = NH3BH3) is one of the most attractive materials for chemical hydrogen storage due to its high hydrogen contents of 19.6 wt.%, however, impurity levels of borazine, ammonia and diborane in conjunction with foaming and exothermic hydrogen release calls for finding ways to mitigate the decomposition reactions. In this paper we present a solution by mixing AB with metal hydrides (TiH2, ZrH2, MgH2 and CaH2) which have endothermic hydrogen release in order to control the heat release and impurity levels from AB upon decomposition. The composite materials were prepared by mechanical ball milling, and their H2 releasemore » properties were characterized by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The formation of volatile products from decomposition side reactions, such as borazine (N3B3H6) was determined by mass spectrometry (MS). Sieverts type pressure-composition-temperature (PCT) gas-solid reaction instrument was adopted to observe the kinetics of the H2 release reactions of the combined systems and neat AB. In situ 11B MAS-NMR revealed a destabilized decomposition pathway. We found that by adding specific metal hydrides to AB we can eliminate the impurities and mitigate the heat release.« less

3D Printed Graphene Based Energy Storage Devices

NASA Astrophysics Data System (ADS)

Foster, Christopher W.; Down, Michael P.; Zhang, Yan; Ji, Xiaobo; Rowley-Neale, Samuel J.; Smith, Graham C.; Kelly, Peter J.; Banks, Craig E.

2017-03-01

3D printing technology provides a unique platform for rapid prototyping of numerous applications due to its ability to produce low cost 3D printed platforms. Herein, a graphene-based polylactic acid filament (graphene/PLA) has been 3D printed to fabricate a range of 3D disc electrode (3DE) configurations using a conventional RepRap fused deposition moulding (FDM) 3D printer, which requires no further modification/ex-situ curing step. To provide proof-of-concept, these 3D printed electrode architectures are characterised both electrochemically and physicochemically and are advantageously applied as freestanding anodes within Li-ion batteries and as solid-state supercapacitors. These freestanding anodes neglect the requirement for a current collector, thus offering a simplistic and cheaper alternative to traditional Li-ion based setups. Additionally, the ability of these devices’ to electrochemically produce hydrogen via the hydrogen evolution reaction (HER) as an alternative to currently utilised platinum based electrodes (with in electrolysers) is also performed. The 3DE demonstrates an unexpectedly high catalytic activity towards the HER (-0.46 V vs. SCE) upon the 1000th cycle, such potential is the closest observed to the desired value of platinum at (-0.25 V vs. SCE). We subsequently suggest that 3D printing of graphene-based conductive filaments allows for the simple fabrication of energy storage devices with bespoke and conceptual designs to be realised.

3D Printed Graphene Based Energy Storage Devices

PubMed Central

Foster, Christopher W.; Down, Michael P.; Zhang, Yan; Ji, Xiaobo; Rowley-Neale, Samuel J.; Smith, Graham C.; Kelly, Peter J.; Banks, Craig E.

2017-01-01

3D printing technology provides a unique platform for rapid prototyping of numerous applications due to its ability to produce low cost 3D printed platforms. Herein, a graphene-based polylactic acid filament (graphene/PLA) has been 3D printed to fabricate a range of 3D disc electrode (3DE) configurations using a conventional RepRap fused deposition moulding (FDM) 3D printer, which requires no further modification/ex-situ curing step. To provide proof-of-concept, these 3D printed electrode architectures are characterised both electrochemically and physicochemically and are advantageously applied as freestanding anodes within Li-ion batteries and as solid-state supercapacitors. These freestanding anodes neglect the requirement for a current collector, thus offering a simplistic and cheaper alternative to traditional Li-ion based setups. Additionally, the ability of these devices’ to electrochemically produce hydrogen via the hydrogen evolution reaction (HER) as an alternative to currently utilised platinum based electrodes (with in electrolysers) is also performed. The 3DE demonstrates an unexpectedly high catalytic activity towards the HER (−0.46 V vs. SCE) upon the 1000th cycle, such potential is the closest observed to the desired value of platinum at (−0.25 V vs. SCE). We subsequently suggest that 3D printing of graphene-based conductive filaments allows for the simple fabrication of energy storage devices with bespoke and conceptual designs to be realised. PMID:28256602

Summary of workshop 'Theory Meets Industry'—the impact of ab initio solid state calculations on industrial materials research

NASA Astrophysics Data System (ADS)

Wimmer, E.

2008-02-01

A workshop, 'Theory Meets Industry', was held on 12-14 June 2007 in Vienna, Austria, attended by a well balanced number of academic and industrial scientists from America, Europe, and Japan. The focus was on advances in ab initio solid state calculations and their practical use in industry. The theoretical papers addressed three dominant themes, namely (i) more accurate total energies and electronic excitations, (ii) more complex systems, and (iii) more diverse and accurate materials properties. Hybrid functionals give some improvements in energies, but encounter difficulties for metallic systems. Quantum Monte Carlo methods are progressing, but no clear breakthrough is on the horizon. Progress in order-N methods is steady, as is the case for efficient methods for exploring complex energy hypersurfaces and large numbers of structural configurations. The industrial applications were dominated by materials issues in energy conversion systems, the quest for hydrogen storage materials, improvements of electronic and optical properties of microelectronic and display materials, and the simulation of reactions on heterogeneous catalysts. The workshop is a clear testimony that ab initio computations have become an industrial practice with increasingly recognized impact.

Study of Hydrogen Production Method using Latent Heat of Liquefied Natural Gas

NASA Astrophysics Data System (ADS)

Ogawa, Masaru; Seki, Tatsuyoshi; Honda, Hiroshi; Nakamura, Motomu; Takatani, Yoshiaki

In recent years, Fuel Cell Electrical Vehicle is expected to improve urban environment. Particularly a hydrogen fuel type FCEV expected for urban use, because its excellent characters such as short startup time, high responsibility and zero emission. On the other hand, as far as hydrogen production is concerned, large amount of CO2 is exhausted into the atmosphere by the process of LNG reforming. In our research, we studied the utilization of LNG latent heat for hydrogen gas production process as well as liquefied hydrogen process. Furthermore, CO2---Capturing as liquid state or solid state from hydrogen gas production process by LNG is also studied. Results of research shows that LNG latent heat is very effect to cool hydrogen gas for conventional hydrogen liquefied process. However, the LNG latent heat is not available for LNG reforming process. If we want to use LNG latent heat for this process, we have to develop new hydrogen gas produce process. In this new method, both hydrogen and CO2 is cooled by LNG directly, and CO2 is removed from the reforming gas. In order to make this method practical, we should develop a new type heat-exchanger to prevent solid CO2 from interfering the performance of it.

Effect of Storage on Performance of Super Nickel-Cadmium Cells

NASA Technical Reports Server (NTRS)

Vaidyanathan, Hari; Rao, Gopalakrishna M.

1997-01-01

A study was undertaken to examine the capacity maintenance features of SUPER nickel-cadmium cells when stored for extended periods to determine whether the features change when the same kinds of positive plates as that used in nickel-hydrogen cells are used, The cells maintained their capacity when stored at 0 C in the discharged state and at 0 C in the charged state by continuously trickle charging. There was a capacity loss when stored in the open-circuit condition at 28 C. A cycling test at 17% depth of discharge for 2400 cycles using cells stored at various conditions showed that cells maintained good end of discharge voltage regardless of their storage history. However, the EOD voltages of stored cells were lower by 10 mV compared to those of fresh cells. The capacity at the end of the cycling test decreased for the stored cells by 2-7 Ah. The storage related capacity loss is lower for SUPER Ni-Cd cells compared to that of Ni-H2 cells containing a hydrogen precharge. The results suggest the pivotal role of hydrogen pressure in the capacity loss phenomenon.

Evaluate the ability of PVP to inhibit crystallization of amorphous solid dispersions by density functional theory and experimental verify.

PubMed

Wang, Bing; Wang, Dandan; Zhao, Shan; Huang, Xiaobin; Zhang, Jianbin; Lv, Yan; Liu, Xiaocen; Lv, Guojun; Ma, Xiaojun

2017-01-01

In this study, we used density functional theory (DFT) to predict polymer-drug interactions, and then evaluated the ability of poly (vinyl pyrrolidone) (PVP) to inhibit crystallization of amorphous solid dispersions by experimental-verification. Solid dispersions of PVP/resveratrol (Res) and PVP/griseofulvin (Gri) were adopted for evaluating the ability of PVP to inhibit crystallization. The density functional theory (DFT) with the B3LYP was used to calculate polymer-drug and drug-drug interactions. Fourier transform infrared spectroscopy (FTIR) was used to confirm hydrogen bonding interactions. Polymer-drug miscibility and drug crystallinity were characterized by the modulated differential scanning calorimetry (MDSC) and X-ray powder diffraction (XRD). The release profiles were studied to investigate the dissolution advantage. DFT results indicated that E PVP-Res >E Res-Res (E: represents hydrogen bonding energy). A strong interaction was formed between PVP and Res. In addition, Fourier transform infrared spectroscopy (FTIR) analysis showed hydrogen bonding formed between PVP and Res, but not between PVP and Gri. MDSC and XRD results suggested that 70-90wt% PVP/Res and PVP/Gri solid dispersions formed amorphous solid dispersions (ASDs). Under the accelerated testing condition, PVP/Res dispersions with higher miscibility quantified as 90/10wt% were more stable than PVP/Gri dispersions. The cumulative dissolution rate of 90wt% PVP/Res dispersions still kept high after 90days storage due to the strong interaction. However, the cumulative dissolution rate of PVP/Gri solid dispersions significantly dropped because of the recrystallization of Gri. Copyright © 2016 Elsevier B.V. All rights reserved.

High-pressure/low-temperature neutron scattering of gas inclusion compounds: Progress and prospects

PubMed Central

Zhao, Yusheng; Xu, Hongwu; Daemen, Luke L.; Lokshin, Konstantin; Tait, Kimberly T.; Mao, Wendy L.; Luo, Junhua; Currier, Robert P.; Hickmott, Donald D.

2007-01-01

Alternative energy resources such as hydrogen and methane gases are becoming increasingly important for the future economy. A major challenge for using hydrogen is to develop suitable materials to store it under a variety of conditions, which requires systematic studies of the structures, stability, and kinetics of various hydrogen-storing compounds. Neutron scattering is particularly useful for these studies. We have developed high-pressure/low-temperature gas/fluid cells in conjunction with neutron diffraction and inelastic neutron scattering instruments allowing in situ and real-time examination of gas uptake/release processes. We studied the formation of methane and hydrogen clathrates, a group of inclusion compounds consisting of frameworks of hydrogen-bonded H2O molecules with gas molecules trapped inside the cages. Our results reveal that clathrate can store up to four hydrogen molecules in each of its large cages with an intermolecular H2–H2 distance of only 2.93 Å. This distance is much shorter than that in the solid/metallic hydrogen (3.78 Å), suggesting a strong densification effect of the clathrate framework on the enclosed hydrogen molecules. The framework-pressurizing effect is striking and may exist in other inclusion compounds such as metal-organic frameworks (MOFs). Owing to the enormous variety and flexibility of their frameworks, inclusion compounds may offer superior properties for storage of hydrogen and/or hydrogen-rich molecules, relative to other types of compounds. We have investigated the hydrogen storage properties of two MOFs, Cu3[Co(CN)6]2 and Cu3(BTC)2 (BTC = benzenetricarboxylate), and our preliminary results demonstrate that the developed neutron-scattering techniques are equally well suited for studying MOFs and other inclusion compounds. PMID:17389387

C sbnd H…F hydrogen bonds as the organising force in F-substituted α-phenyl cinnamic acid aggregates studied by the combination of FTIR spectroscopy and computations

NASA Astrophysics Data System (ADS)

Tolnai, B.; Kiss, J. T.; Felföldi, K.; Pálinkó, I.

2009-04-01

Various F-substituted E-2,3-diphenyl propenoic acid molecules were synthesised and their aggregation behaviour was studied by experimental (FT-IR spectroscopy) and computational (semiempirical and DFT) methods. Experimental approach embraced the identification of potential hydrogen bonding sites through finding the relevant IR bands and monitoring their shifts upon increasing the acid concentration and on going to the solid state. It was found that fluorine engaged in C sbnd H…F hydrogen bonding easily, where the carbon atom could be of any kind available in the molecule (aromatic, aliphatic or olefinic). Shifts were found even in moderately concentrated solutions and in the solid state too. Hydrogen bonding sites could be assigned and relevant aggregate models could be built. Molecular modelling allowed obtaining good estimates for hydrogen bond lengths and angles and visualisation of the geometric arrangements even of extended networks also became feasible.

Improving the photovoltaic performance of the all-solid-state TiO2 NR/CuInS2 solar cell by hydrogen plasma treatment.

PubMed

Chen, Bingfeng; Niu, Wenzhe; Lou, Zirui; Ye, Zhizhen; Zhu, Liping

2018-07-06

The interfacial properties of the heterojunction between p-type and n-type materials play an important role in the performance of the solar cell. In this paper, a p-type CuInS 2 film was deposited on TiO 2 nanorod arrays by spin coating to fabricate an all-solid-state solar cell and the TiO 2 nanorod arrays were treated with hydrogen plasma(H:TiO 2 ) to ameliorate the interfacial properties. The influence of the hydrogen plasma treatment on the performance of the solar cell was investigated. The short-circuit current density was obviously raised and the power conversion efficiency of the solar cell improved to 0.30%, which is three times that of solar cells without hydrogen plasma treatment. The enhancement of the performance is attributed to not only the enhancement of carrier separation and transport, but the reduction of the recombination of electrons and holes, which is caused by hydrogen plasma treatment.

Improving the photovoltaic performance of the all-solid-state TiO2 NR/CuInS2 solar cell by hydrogen plasma treatment

NASA Astrophysics Data System (ADS)

Chen, Bingfeng; Niu, Wenzhe; Lou, Zirui; Ye, Zhizhen; Zhu, Liping

2018-07-01

The interfacial properties of the heterojunction between p-type and n-type materials play an important role in the performance of the solar cell. In this paper, a p-type CuInS2 film was deposited on TiO2 nanorod arrays by spin coating to fabricate an all-solid-state solar cell and the TiO2 nanorod arrays were treated with hydrogen plasma(H:TiO2) to ameliorate the interfacial properties. The influence of the hydrogen plasma treatment on the performance of the solar cell was investigated. The short-circuit current density was obviously raised and the power conversion efficiency of the solar cell improved to 0.30%, which is three times that of solar cells without hydrogen plasma treatment. The enhancement of the performance is attributed to not only the enhancement of carrier separation and transport, but the reduction of the recombination of electrons and holes, which is caused by hydrogen plasma treatment.

NASICON-Structured Materials for Energy Storage.

PubMed

Jian, Zelang; Hu, Yong-Sheng; Ji, Xiulei; Chen, Wen

2017-05-01

The demand for electrical energy storage (EES) is ever increasing, which calls for better batteries. NASICON-structured materials represent a family of important electrodes due to its superior ionic conductivity and stable structures. A wide range of materials have been considered, where both vanadium-based and titanium-based materials are recommended as being of great interest. NASICON-structured materials are suitable for both the cathode and the anode, where the operation potential can be easily tuned by the choice of transition metal and/or polyanion group in the structure. NASICON-structured materials also represent a class of solid electrolytes, which are widely employed in all-solid-state ion batteries, all-solid-state air batteries, and hybrid batteries. NASICON-structured materials are reviewed with a focus on both electrode materials and solid-state electrolytes. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A novel accelerated oxidative stability screening method for pharmaceutical solids.

PubMed

Zhu, Donghua Alan; Zhang, Geoff G Z; George, Karen L S T; Zhou, Deliang

2011-08-01

Despite the fact that oxidation is the second most frequent degradation pathway for pharmaceuticals, means of evaluating the oxidative stability of pharmaceutical solids, especially effective stress testing, are still lacking. This paper describes a novel experimental method for peroxide-mediated oxidative stress testing on pharmaceutical solids. The method utilizes urea-hydrogen peroxide, a molecular complex that undergoes solid-state decomposition and releases hydrogen peroxide vapor at elevated temperatures (e.g., 30°C), as a source of peroxide. The experimental setting for this method is simple, convenient, and can be operated routinely in most laboratories. The fundamental parameter of the system, that is, hydrogen peroxide vapor pressure, was determined using a modified spectrophotometric method. The feasibility and utility of the proposed method in solid form selection have been demonstrated using various solid forms of ephedrine. No degradation was detected for ephedrine hydrochloride after exposure to the hydrogen peroxide vapor for 2 weeks, whereas both anhydrate and hemihydrate free base forms degraded rapidly under the test conditions. In addition, both the anhydrate and the hemihydrate free base degraded faster when exposed to hydrogen peroxide vapor at 30°C under dry condition than at 30°C/75% relative humidity (RH). A new degradation product was also observed under the drier condition. The proposed method provides more relevant screening conditions for solid dosage forms, and is useful in selecting optimal solid form(s), determining potential degradation products, and formulation screening during development. Copyright © 2011 Wiley-Liss, Inc.

Ultrafine hydrogen storage powders

DOEpatents

Anderson, Iver E.; Ellis, Timothy W.; Pecharsky, Vitalij K.; Ting, Jason; Terpstra, Robert; Bowman, Robert C.; Witham, Charles K.; Fultz, Brent T.; Bugga, Ratnakumar V.

2000-06-13

A method of making hydrogen storage powder resistant to fracture in service involves forming a melt having the appropriate composition for the hydrogen storage material, such, for example, LaNi.sub.5 and other AB.sub.5 type materials and AB.sub.5+x materials, where x is from about -2.5 to about +2.5, including x=0, and the melt is gas atomized under conditions of melt temperature and atomizing gas pressure to form generally spherical powder particles. The hydrogen storage powder exhibits improved chemcial homogeneity as a result of rapid solidfication from the melt and small particle size that is more resistant to microcracking during hydrogen absorption/desorption cycling. A hydrogen storage component, such as an electrode for a battery or electrochemical fuel cell, made from the gas atomized hydrogen storage material is resistant to hydrogen degradation upon hydrogen absorption/desorption that occurs for example, during charging/discharging of a battery. Such hydrogen storage components can be made by consolidating and optionally sintering the gas atomized hydrogen storage powder or alternately by shaping the gas atomized powder and a suitable binder to a desired configuration in a mold or die.

Solid-state acid-base interactions in complexes of heterocyclic bases with dicarboxylic acids: crystallography, hydrogen bond analysis, and 15N NMR spectroscopy.

PubMed

Li, Z Jane; Abramov, Yuriy; Bordner, Jon; Leonard, Jason; Medek, Ales; Trask, Andrew V

2006-06-28

A cancer candidate, compound 1, is a weak base with two heterocyclic basic nitrogens and five hydrogen-bonding functional groups, and is sparingly soluble in water rendering it unsuitable for pharmaceutical development. The crystalline acid-base pairs of 1, collectively termed solid acid-base complexes, provide significant increases in the solubility and bioavailability compared to the free base, 1. Three dicarboxylic acid-base complexes, sesquisuccinate 2, dimalonate 3, and dimaleate 4, show the most favorable physicochemical profiles and are studied in greater detail. The structural analyses of the three complexes using crystal structure and solid-state NMR reveal that the proton-transfer behavior in these organic acid-base complexes vary successively correlating with Delta pKa. As a result, 2 is a neutral complex, 3 is a mixed ionic and zwitterionic complex and 4 is an ionic salt. The addition of the acidic components leads to maximized hydrogen bond interactions forming extended three-dimensional networks. Although structurally similar, the packing arrangements of the three complexes are considerably different due to the presence of multiple functional groups and the flexible backbone of 1. The findings in this study provide insight into the structural characteristics of complexes involving heterocyclic bases and carboxylic acids, and demonstrate that X-ray crystallography and 15N solid-state NMR are truly complementary in elucidating hydrogen bonding interactions and the degree of proton transfer of these complexes.

Hydrogen-Enhanced Lunar Oxygen Extraction and Storage Using Only Solar Power

NASA Technical Reports Server (NTRS)

Burton, rodney; King, Darren

2013-01-01

The innovation consists of a thermodynamic system for extracting in situ oxygen vapor from lunar regolith using a solar photovoltaic power source in a reactor, a method for thermally insulating the reactor, a method for protecting the reactor internal components from oxidation by the extracted oxygen, a method for removing unwanted chemical species produced in the reactor from the oxygen vapor, a method for passively storing the oxygen, and a method for releasing high-purity oxygen from storage for lunar use. Lunar oxygen exists in various types of minerals, mostly silicates. The energy required to extract the oxygen from the minerals is 30 to 60 MJ/kg O. Using simple heating, the extraction rate depends on temperature. The minimum temperature is approximately 2,500 K, which is at the upper end of available oven temperatures. The oxygen is released from storage in a purified state, as needed, especially if for human consumption. This method extracts oxygen from regolith by treating the problem as a closed batch cycle system. The innovation works equally well in Earth or Lunar gravity fields, at low partial pressure of oxygen, and makes use of in situ regolith for system insulation. The innovation extracts oxygen from lunar regolith using a method similar to vacuum pyrolysis, but with hydrogen cover gas added stoichiometrically to react with the oxygen as it is produced by radiatively heating regolith to 2,500 K. The hydrogen flows over and through the heating element (HE), protecting it from released oxygen. The H2 O2 heat of reaction is regeneratively recovered to assist the heating process. Lunar regolith is loaded into a large-diameter, low-height pancake reactor powered by photovoltaic cells. The reactor lid contains a 2,500 K HE that radiates downward onto the regolith to heat it and extract oxygen, and is shielded above by a multi-layer tungsten radiation shield. Hydrogen cover gas percolates through the perforated tungsten shielding and HE, preventing oxidation of the shielding and HE, and reacting with the oxygen to form water vapor. The water vapor is filtered through solid regolith to remove unwanted extraction byproducts, and then condensed to a liquid state and stored at 300 to 325 K. Conversion to usable oxygen is achieved by pumping liquid water into a high-pressure electrolyzer, storing the gaseous oxygen at high pressure for use, and diverting the hydrogen back to the reactor or to storage. The results from this design effort show that this oxygen-generating concept can be developed in an efficient system with low specific mass. Advantages include use of regolith as an oxygen source, filter, and thermal insulator. The system can be tested in Earth gravity and can be expected to operate similarly in lunar gravity. The system is scalable, either by increasing the power level and output of a standard module, or by employing multiple modules.

Polymeric hydrogen diffusion barrier, high-pressure storage tank so equipped, method of fabricating a storage tank and method of preventing hydrogen diffusion

DOEpatents

Lessing, Paul A [Idaho Falls, ID

2008-07-22

An electrochemically active hydrogen diffusion barrier which comprises an anode layer, a cathode layer, and an intermediate electrolyte layer, which is conductive to protons and substantially impermeable to hydrogen. A catalytic metal present in or adjacent to the anode layer catalyzes an electrochemical reaction that converts any hydrogen that diffuses through the electrolyte layer to protons and electrons. The protons and electrons are transported to the cathode layer and reacted to form hydrogen. The hydrogen diffusion barrier is applied to a polymeric substrate used in a storage tank to store hydrogen under high pressure. A storage tank equipped with the electrochemically active hydrogen diffusion barrier, a method of fabricating the storage tank, and a method of preventing hydrogen from diffusing out of a storage tank are also disclosed.

Polymeric hydrogen diffusion barrier, high-pressure storage tank so equipped, method of fabricating a storage tank and method of preventing hydrogen diffusion

DOEpatents

Lessing, Paul A.

2004-09-07

An electrochemically active hydrogen diffusion barrier which comprises an anode layer, a cathode layer, and an intermediate electrolyte layer, which is conductive to protons and substantially impermeable to hydrogen. A catalytic metal present in or adjacent to the anode layer catalyzes an electrochemical reaction that converts any hydrogen that diffuses through the electrolyte layer to protons and electrons. The protons and electrons are transported to the cathode layer and reacted to form hydrogen. The hydrogen diffusion barrier is applied to a polymeric substrate used in a storage tank to store hydrogen under high pressure. A storage tank equipped with the electrochemically active hydrogen diffusion barrier, a method of fabricating the storage tank, and a method of preventing hydrogen from diffusing out of a storage tank are also disclosed.

Investigation of the stability of Co-doped apatite ionic conductors in NH 3

NASA Astrophysics Data System (ADS)

Headspith, D. A.; Orera, A.; Slater, P. R.; Young, N. A.; Francesconi, M. G.

2010-12-01

Hydrogen powered solid oxide fuel cells (SOFCs) are of enormous interest as devices for the efficient and clean production of electrical energy. However, a number of problems linked to hydrogen production, storage and transportation are slowing down the larger scale use of SOFCs. Identifying alternative fuel sources to act as intermediate during the transition to the full use of hydrogen is, therefore, of importance. One excellent alternative is ammonia, which is produced on a large scale, is relatively cheap and has the infrastructure for storage and transportation already in place. However, considering that SOFCs operate at temperatures higher than 500 °C, a potential problem is the interaction of gaseous ammonia with the materials in the cathode, anode and solid electrolyte. In this paper, we extend earlier work on high temperature reactions of apatite electrolytes with NH 3 to the transition metal (Co) doped systems, La 9.67Si 5CoO 26 and La 10(Si/Ge) 5CoO 26.5. A combination of PXRD, TGA and XAFS spectroscopy data showed a better structural stability for the silicate systems. Apatite silicates and germanates not containing transition metals tend to substitute nitride anions for their interstitial oxide anions, when reacted with NH 3 at high temperature and, consequentially, lower the interstitial oxide content. In La 9.67Si 5CoO 26 and La 10(Si/Ge) 5CoO 26.5 reduction of Co occurs as a competing process, favouring lower levels of nitride-oxide substitution.

Progress and prospect on failure mechanisms of solid-state lithium batteries

NASA Astrophysics Data System (ADS)

Ma, Jun; Chen, Bingbing; Wang, Longlong; Cui, Guanglei

2018-07-01

By replacing traditional liquid organic electrolyte with solid-state electrolyte, the solid-state lithium batteries powerfully come back to the energy storage field due to their eminent safety and energy density. In recent years, a variety of solid-state lithium batteries based on excellent solid-state electrolytes are developed. However, the performance degradation of solid-state lithium batteries during cycling and storing is still a serious challenge for practical application. Therefore, this review summarizes the research progress of solid-state lithium batteries from the perspectives of failure phenomena and failure mechanisms. Additionally, the development of methodologies on studying the failure mechanisms of solid-state lithium batteries is also reviewed. Moreover, some perspectives on the remaining questions for understanding the failure behaviors and achieving long cycle life, high safety and high energy density solid-state lithium batteries are presented. This review will help researchers to recognize the status of solid-state lithium batteries objectively and attract much more research interest in conquering the failure issues of solid-state lithium batteries.

Liquid-solid phase transition of hydrogen and deuterium in silica aerogel

NASA Astrophysics Data System (ADS)

Van Cleve, E.; Worsley, M. A.; Kucheyev, S. O.

2014-10-01

Behavior of hydrogen isotopes confined in disordered low-density nanoporous solids remains essentially unknown. Here, we use relaxation calorimetry to study freezing and melting of H2 and D2 in an ˜85%-porous base-catalyzed silica aerogel. We find that liquid-solid transition temperatures of both isotopes inside the aerogel are depressed. The phase transition takes place over a wide temperature range of ˜4 K and non-trivially depends on the liquid filling fraction, reflecting the broad pore size distribution in the aerogel. Undercooling is observed for both H2 and D2 confined inside the aerogel monolith. Results for H2 and D2 are extrapolated to tritium-containing hydrogens with the quantum law of corresponding states.

New perspectives on potential hydrogen storage materials using high pressure.

PubMed

Song, Yang

2013-09-21

In addressing the global demand for clean and renewable energy, hydrogen stands out as the most suitable candidate for many fuel applications that require practical and efficient storage of hydrogen. Supplementary to the traditional hydrogen storage methods and materials, the high-pressure technique has emerged as a novel and unique approach to developing new potential hydrogen storage materials. Static compression of materials may result in significant changes in the structures, properties and performance that are important for hydrogen storage applications, and often lead to the formation of unprecedented phases or complexes that have profound implications for hydrogen storage. In this perspective article, 22 types of representative potential hydrogen storage materials that belong to four major classes--simple hydride, complex hydride, chemical hydride and hydrogen containing materials--were reviewed. In particular, their structures, stabilities, and pressure-induced transformations, which were reported in recent experimental works together with supporting theoretical studies, were provided. The important contextual aspects pertinent to hydrogen storage associated with novel structures and transitions were discussed. Finally, the summary of the recent advances reviewed and the insight into the future research in this direction were given.

Hydrogen storage and integrated fuel cell assembly

DOEpatents

Gross, Karl J.

2010-08-24

Hydrogen is stored in materials that absorb and desorb hydrogen with temperature dependent rates. A housing is provided that allows for the storage of one or more types of hydrogen-storage materials in close thermal proximity to a fuel cell stack. This arrangement, which includes alternating fuel cell stack and hydrogen-storage units, allows for close thermal matching of the hydrogen storage material and the fuel cell stack. Also, the present invention allows for tailoring of the hydrogen delivery by mixing different materials in one unit. Thermal insulation alternatively allows for a highly efficient unit. Individual power modules including one fuel cell stack surrounded by a pair of hydrogen-storage units allows for distribution of power throughout a vehicle or other electric power consuming devices.

Ford/BASF/UM Activities in Support of the Hydrogen Storage Engineering Center of Excellence

DOE Office of Scientific and Technical Information (OSTI.GOV)

Veenstra, Mike; Purewal, Justin; Xu, Chunchuan

Widespread adoption of hydrogen as a vehicular fuel depends critically on the development of low-cost, on-board hydrogen storage technologies capable of achieving high energy densities and fast kinetics for hydrogen uptake and release. As present-day technologies -- which rely on physical storage methods such as compressed hydrogen -- are incapable of attaining established Department of Energy (DOE) targets, development of materials-based approaches for storing hydrogen have garnered increasing attention. Material-based storage technologies have potential to store hydrogen beyond twice the density of liquid hydrogen. To hasten development of these ‘hydride’ materials, the DOE previously established three centers of excellence formore » materials storage R&D associated with the key classes of materials: metal hydrides, chemical hydrogen, and adsorbents. While these centers made progress in identifying new storage materials, the challenges associated with the engineering of the system around a candidate storage material are in need of further advancement. In 2009 the DOE established the Hydrogen Storage Engineering Center of Excellence with the objective of developing innovative engineering concepts for materials-based hydrogen storage systems. As a partner in the Hydrogen Storage Engineering Center of Excellence, the Ford-UM-BASF team conducted a multi-faceted research program that addresses key engineering challenges associated with the development of materials-based hydrogen storage systems. First, we developed a novel framework that allowed for a material-based hydrogen storage system to be modeled and operated within a virtual fuel cell vehicle. This effort resulted in the ability to assess dynamic operating parameters and interactions between the storage system and fuel cell power plant, including the evaluation of performance throughout various drive cycles. Second, we engaged in cost modeling of various incarnations of the storage systems. This analysis revealed cost gaps and opportunities that identified a storage system that was lower cost than a 700 bar compressed system. Finally, we led the HSECoE efforts devoted to characterizing and enhancing metal organic framework (MOF) storage materials. This report serves as a final documentation of the Ford-UM-BASF project contributions to the HSECoE during the 6-year timeframe of the Center. The activities of the HSECoE have impacted the broader goals of the DOE-EERE and USDRIVE, leading to improved understanding in the engineering of materials-based hydrogen storage systems. This knowledge is a prerequisite to the development of a commercially-viable hydrogen storage system.« less

Use of triphenyl phosphate as risk mitigant for metal amide hydrogen storage materials

DOEpatents

Cortes-Concepcion, Jose A.; Anton, Donald L.

2016-04-26

A process in a resulting product of the process in which a hydrogen storage metal amide is modified by a ball milling process using an additive of TPP. The resulting product provides for a hydrogen storage metal amide having a coating that renders the hydrogen storage metal amide resistant to air, ambient moisture, and liquid water while improving useful hydrogen storage and release kinetics.

Florida Hydrogen Initiative

DOE Office of Scientific and Technical Information (OSTI.GOV)

Block, David L

2013-06-30

The Florida Hydrogen Initiative (FHI) was a research, development and demonstration hydrogen and fuel cell program. The FHI program objectives were to develop Florida?s hydrogen and fuel cell infrastructure and to assist DOE in its hydrogen and fuel cell activities The FHI program funded 12 RD&D projects as follows: Hydrogen Refueling Infrastructure and Rental Car Strategies -- L. Lines, Rollins College This project analyzes strategies for Florida's early stage adaptation of hydrogen-powered public transportation. In particular, the report investigates urban and statewide network of refueling stations and the feasibility of establishing a hydrogen rental-car fleet based in Orlando. Methanol Fuelmore » Cell Vehicle Charging Station at Florida Atlantic University ? M. Fuchs, EnerFuel, Inc. The project objectives were to design, and demonstrate a 10 kWnet proton exchange membrane fuel cell stationary power plant operating on methanol, to achieve an electrical energy efficiency of 32% and to demonstrate transient response time of less than 3 milliseconds. Assessment of Public Understanding of the Hydrogen Economy Through Science Center Exhibits, J. Newman, Orlando Science Center The project objective was to design and build an interactive Science Center exhibit called: ?H2Now: the Great Hydrogen Xchange?. On-site Reformation of Diesel Fuel for Hydrogen Fueling Station Applications ? A. Raissi, Florida Solar Energy Center This project developed an on-demand forecourt hydrogen production technology by catalytically converting high-sulfur hydrocarbon fuels to an essentially sulfur-free gas. The removal of sulfur from reformate is critical since most catalysts used for the steam reformation have limited sulfur tolerance. Chemochromic Hydrogen Leak Detectors for Safety Monitoring ? N. Mohajeri and N. Muradov, Florida Solar Energy Center This project developed and demonstrated a cost-effective and highly selective chemochromic (visual) hydrogen leak detector for safety monitoring at any facility engaged in transport, handling and use of hydrogen. Development of High Efficiency Low Cost Electrocatalysts for Hydrogen Production and PEM Fuel Cell Applications ? M. Rodgers, Florida Solar Energy Center The objective of this project was to decrease platinum usage in fuel cells by conducting experiments to improve catalyst activity while lowering platinum loading through pulse electrodeposition. Optimum values of several variables during electrodeposition were selected to achieve the highest electrode performance, which was related to catalyst morphology. Understanding Mechanical and Chemical Durability of Fuel Cell Membrane Electrode Assemblies ? D. Slattery, Florida Solar Energy Center The objective of this project was to increase the knowledge base of the degradation mechanisms for membranes used in proton exchange membrane fuel cells. The results show the addition of ceria (cerium oxide) has given durability improvements by reducing fluoride emissions by an order of magnitude during an accelerated durability test. Production of Low-Cost Hydrogen from Biowaste (HyBrTec?) ? R. Parker, SRT Group, Inc., Miami, FL This project developed a hydrogen bromide (HyBrTec?) process which produces hydrogen bromide from wet-cellulosic waste and co-produces carbon dioxide. Eelectrolysis dissociates hydrogen bromide producing recyclable bromine and hydrogen. A demonstration reactor and electrolysis vessel was designed, built and operated. Development of a Low-Cost and High-Efficiency 500 W Portable PEMFC System ? J. Zheng, Florida State University, H. Chen, Bing Energy, Inc. The objectives of this project were to develop a new catalyst structures comprised of highly conductive buckypaper and Pt catalyst nanoparticles coated on its surface and to demonstrate fuel cell efficiency improvement and durability and cell cost reductions in the buckypaper based electrodes. Development of an Interdisciplinary Hydrogen and Fuel Cell Technology Academic Program ? J. Politano, Florida Institute of Technology, Melbourne, FL This project developed a hydrogen and fuel cell technology academic program at Florida Institute of Technology in Melbourne, Florida. Design and Development of an Advanced Hydrogen Storage System using Novel Materials ? E. Stefanakos, University of South Florida The goal of this project was to design and develop novel conducting polymeric nanomaterials for on-board hydrogen storage. The project approach was to examine synthesis of polyaniline solid state hydrogen storage materials. Advanced HiFoil ? Bipolar Plates ? J. Braun, M. Fuchs, EnerFuel, Inc. The goal of this project was to provide a durable, low cost bipolar plate for high temperature proton exchange membrane fuel cells. The project results produced a durable, low cost bipolar plate with very high in-plane thermal conductivity.« less

Review of Current State of the Art and Key Design Issues With Potential Solutions for Liquid Hydrogen Cryogenic Storage Tank Structures for Aircraft Applications

NASA Technical Reports Server (NTRS)

Mital, Subodh K.; Gyekenyesi, John Z.; Arnold, Steven M.; Sullivan, Roy M.; Manderscheid, Jane M.; Murthy, Pappu L. N.

2006-01-01

Due to its high specific energy content, liquid hydrogen (LH2) is emerging as an alternative fuel for future aircraft. As a result, there is a need for hydrogen tank storage systems, for these aircraft applications, that are expected to provide sufficient capacity for flight durations ranging from a few minutes to several days. It is understood that the development of a large, lightweight, reusable cryogenic liquid storage tank is crucial to meet the goals of and supply power to hydrogen-fueled aircraft, especially for long flight durations. This report provides an annotated review (including the results of an extensive literature review) of the current state of the art of cryogenic tank materials, structural designs, and insulation systems along with the identification of key challenges with the intent of developing a lightweight and long-term storage system for LH2. The broad classes of insulation systems reviewed include foams (including advanced aerogels) and multilayer insulation (MLI) systems with vacuum. The MLI systems show promise for long-term applications. Structural configurations evaluated include single- and double-wall constructions, including sandwich construction. Potential wall material candidates are monolithic metals as well as polymer matrix composites and discontinuously reinforced metal matrix composites. For short-duration flight applications, simple tank designs may suffice. Alternatively, for longer duration flight applications, a double-wall construction with a vacuum-based insulation system appears to be the most optimum design. The current trends in liner material development are reviewed in the case that a liner is required to minimize or eliminate the loss of hydrogen fuel through permeation.

All-solid-state reduced graphene oxide supercapacitor with large volumetric capacitance and ultralong stability prepared by electrophoretic deposition method.

PubMed

Wang, Mei; Duong, Le Dai; Mai, Nguyen Thi; Kim, Sanghoon; Kim, Youngjun; Seo, Heewon; Kim, Ye Chan; Jang, Woojin; Lee, Youngkwan; Suhr, Jonghwan; Nam, Jae-Do

2015-01-21

Portable energy storage devices have gained special attention due to the growing demand for portable electronics. Herein, an all-solid-state supercapacitor is successfully fabricated based on a poly(vinyl alcohol)-H3PO4 (PVA-H3PO4) polymer electrolyte and a reduced graphene oxide (RGO) membrane electrode prepared by electrophoretic deposition (EPD). The RGO electrode fabricated by EPD contains an in-plane layer-by-layer alignment and a moderate porosity that accommodate the electrolyte ions. The all-solid-state RGO supercapacitor is thoroughly tested to give high specific volumetric capacitance (108 F cm(-3)) and excellent energy and power densities (7.5 Wh cm(-3) and 2.9 W cm(-3), respectively). In addition, the all-solid-state RGO supercapacitor exhibits an ultralong lifetime for as long as 180 days (335 000 cycles), which is an ultrahigh cycling capability for a solid-state supercapacitor. The RGO is also tested for being used as a transparent supercapacitor electrode demonstrating its possible use in various transparent optoelectronic devices. Due to the facile scale-up capability of the EPD process and RGO dispersion, the developed all-solid-state supercapacitor is highly applicable to large-area portable energy storage devices.

Chemical-clathrate hybrid hydrogen storage: storage in both guest and host.

PubMed

Strobel, Timothy A; Kim, Yongkwan; Andrews, Gary S; Ferrell, Jack R; Koh, Carolyn A; Herring, Andrew M; Sloan, E Dendy

2008-11-12

Hydrogen storage from two independent sources of the same material represents a novel approach to the hydrogen storage problem, yielding storage capacities greater than either of the individual constituents. Here we report a novel hydrogen storage scheme in which recoverable hydrogen is stored molecularly within clathrate cavities as well as chemically in the clathrate host material. X-ray diffraction and Raman spectroscopic measurements confirm the formation of beta-hydroquinone (beta-HQ) clathrate with molecular hydrogen. Hydrogen within the beta-HQ clathrate vibrates at considerably lower frequency than hydrogen in the free gaseous phase and rotates nondegenerately with splitting comparable to the rotational constant. Compared with water-based clathrate hydrate phases, the beta-HQ+H2 clathrate shows remarkable stability over a range of p-T conditions. Subsequent to clathrate decomposition, the host HQ was used to directly power a PEM fuel cell. With one H2 molecule per cavity, 0.61 wt % hydrogen may be stored in the beta-HQ clathrate cavities. When this amount is combined with complete dehydrogenation of the host hydroxyl hydrogens, the maximum hydrogen storage capacity increases nearly 300% to 2.43 wt %.

An Approach to Understanding Cohesive Slurry Settling, Mobilization, and Hydrogen Gas Retention in Pulsed Jet Mixed Vessels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gauglitz, Phillip A.; Wells, Beric E.; Fort, James A.

2009-05-22

The Hanford Waste Treatment and Immobilization Plant (WTP) is being designed and built to pretreat and vitrify a large portion of the waste in Hanford’s 177 underground waste storage tanks. Numerous process vessels will hold waste at various stages in the WTP. Some of these vessels have mixing-system requirements to maintain conditions where the accumulation of hydrogen gas stays below acceptable limits, and the mixing within the vessels is sufficient to release hydrogen gas under normal conditions and during off-normal events. Some of the WTP process streams are slurries of solid particles suspended in Newtonian fluids that behave as non-Newtonianmore » slurries, such as Bingham yield-stress fluids. When these slurries are contained in the process vessels, the particles can settle and become progressively more concentrated toward the bottom of the vessels, depending on the effectiveness of the mixing system. One limiting behavior is a settled layer beneath a particle-free liquid layer. The settled layer, or any region with sufficiently high solids concentration, will exhibit non-Newtonian rheology where it is possible for the settled slurry to behave as a soft solid with a yield stress. In this report, these slurries are described as settling cohesive slurries.« less

Solid-state energy storage module employing integrated interconnect board

DOEpatents

Rouillard, Jean; Comte, Christophe; Daigle, Dominik; Hagen, Ronald A.; Knudson, Orlin B.; Morin, Andre; Ranger, Michel; Ross, Guy; Rouillard, Roger; St-Germain, Philippe; Sudano, Anthony; Turgeon, Thomas A.

2003-11-04

The present invention is directed to an improved electrochemical energy storage device. The electrochemical energy storage device includes a number of solid-state, thin-film electrochemical cells which are selectively interconnected in series or parallel through use of an integrated interconnect board. The interconnect board is typically disposed within a sealed housing which also houses the electrochemical cells, and includes a first contact and a second contact respectively coupled to first and second power terminals of the energy storage device. The interconnect board advantageously provides for selective series or parallel connectivity with the electrochemical cells, irrespective of electrochemical cell position within the housing. Fuses and various electrical and electromechanical devices, such as bypass, equalization, and communication devices for example, may also be mounted to the interconnect board and selectively connected to the electrochemical cells.

Polarization insensitive frequency conversion for an atom-photon entanglement distribution via a telecom network.

PubMed

Ikuta, Rikizo; Kobayashi, Toshiki; Kawakami, Tetsuo; Miki, Shigehito; Yabuno, Masahiro; Yamashita, Taro; Terai, Hirotaka; Koashi, Masato; Mukai, Tetsuya; Yamamoto, Takashi; Imoto, Nobuyuki

2018-05-21

Long-lifetime quantum storages accessible to the telecom photonic infrastructure are essential to long-distance quantum communication. Atomic quantum storages have achieved subsecond storage time corresponding to 1000 km transmission time for a telecom photon through a quantum repeater algorithm. However, the telecom photon cannot be directly interfaced to typical atomic storages. Solid-state quantum frequency conversions fill this wavelength gap. Here we report on the experimental demonstration of a polarization-insensitive solid-state quantum frequency conversion to a telecom photon from a short-wavelength photon entangled with an atomic ensemble. Atom-photon entanglement has been generated with a Rb atomic ensemble and the photon has been translated to telecom range while retaining the entanglement by our nonlinear-crystal-based frequency converter in a Sagnac interferometer.

Nanostructured materials for hydrogen storage

DOEpatents

Williamson, Andrew J.; Reboredo, Fernando A.

2007-12-04

A system for hydrogen storage comprising a porous nano-structured material with hydrogen absorbed on the surfaces of the porous nano-structured material. The system of hydrogen storage comprises absorbing hydrogen on the surfaces of a porous nano-structured semiconductor material.

Reactive Desorption of CO Hydrogenation Products under Cold Pre-stellar Core Conditions

NASA Astrophysics Data System (ADS)

Chuang, K.-J.; Fedoseev, G.; Qasim, D.; Ioppolo, S.; van Dishoeck, E. F.; Linnartz, H.

2018-02-01

The astronomical gas-phase detection of simple species and small organic molecules in cold pre-stellar cores, with abundances as high as ∼10‑8–10‑9 n H, contradicts the generally accepted idea that at 10 K, such species should be fully frozen out on grain surfaces. A physical or chemical mechanism that results in a net transfer from solid-state species into the gas phase offers a possible explanation. Reactive desorption, i.e., desorption following the exothermic formation of a species, is one of the options that has been proposed. In astronomical models, the fraction of molecules desorbed through this process is handled as a free parameter, as experimental studies quantifying the impact of exothermicity on desorption efficiencies are largely lacking. In this work, we present a detailed laboratory study with the goal of deriving an upper limit for the reactive desorption efficiency of species involved in the CO–H2CO–CH3OH solid-state hydrogenation reaction chain. The limit for the overall reactive desorption fraction is derived by precisely investigating the solid-state elemental carbon budget, using reflection absorption infrared spectroscopy and the calibrated solid-state band-strength values for CO, H2CO and CH3OH. We find that for temperatures in the range of 10 to 14 K, an upper limit of 0.24 ± 0.02 for the overall elemental carbon loss upon CO conversion into CH3OH. This corresponds with an effective reaction desorption fraction of ≤0.07 per hydrogenation step, or ≤0.02 per H-atom induced reaction, assuming that H-atom addition and abstraction reactions equally contribute to the overall reactive desorption fraction along the hydrogenation sequence. The astronomical relevance of this finding is discussed.

Solid-state modeling of the terahertz spectrum of the high explosive HMX.

PubMed

Allis, Damian G; Prokhorova, Darya A; Korter, Timothy M

2006-02-09

The experimental solid-state terahertz (THz) spectrum (3-120 cm(-1)) of the beta-crystal form of the high explosive octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) has been analyzed using solid-state density functional theory calculations. Various density functionals (both generalized gradient approximation and local density approximation) are compared in terms of their abilities to reproduce the experimentally observed solid-state structure and low-frequency vibrational motions. Good-to-excellent agreement between solid-state theory and experiment can be achieved in the THz region where isolated-molecule calculations fail to reproduce the observed spectral features, demonstrating a clear limitation of using isolated-molecule calculations for the assignment of THz frequency motions in molecular solids. The deficiency of isolated-molecule calculations is traced to modification of the molecular structure in the solid state through crystal packing effects and the formation of weak C-H...O hydrogen bonds.

Aryl C—H···Cl– Hydrogen Bonding in a Fluorescent Anion Sensor

PubMed Central

Tresca, Blakely W.; Zakharov, Lev N.; Carroll, Calden N.; Johnson, Darren W.; Haley, Michael M.

2014-01-01

A new phenyl-acetylene receptor containing a carbonaceous hydrogen bond donor activates anion binding in conjunction with two stabilizing ureas. The unusual CH···Cl– hydrogen bond is apparent in solution by large 1H NMR chemical shifts and by a short, linear contact in the solid state. PMID:23843050

A study of hydriding kinetics of metal hydrides using a physically based model

NASA Astrophysics Data System (ADS)

Voskuilen, Tyler G.

The reaction of hydrogen with metals to form metal hydrides has numerous potential energy storage and management applications. The metal hydrogen system has a high volumetric energy density and is often reversible with a high cycle life. The stored hydrogen can be used to produce energy through combustion, reaction in a fuel cell, or electrochemically in metal hydride batteries. The high enthalpy of the metal-hydrogen reaction can also be used for rapid heat removal or delivery. However, improving the often poor gravimetric performance of such systems through the use of lightweight metals usually comes at the cost of reduced reaction rates or the requirement of pressure and temperature conditions far from the desired operating conditions. In this work, a 700 bar Sievert system was developed at the Purdue Hydrogen Systems Laboratory to study the kinetic and thermodynamic behavior of high pressure hydrogen absorption under near-ambient temperatures. This system was used to determine the kinetic and thermodynamic properties of TiCrMn, an intermetallic metal hydride of interest due to its ambient temperature performance for vehicular applications. A commonly studied intermetallic hydride, LaNi5, was also characterized as a base case for the phase field model. The analysis of the data obtained from such a system necessitate the use of specialized techniques to decouple the measured reaction rates from experimental conditions. These techniques were also developed as a part of this work. Finally, a phase field model of metal hydride formation in mass-transport limited interstitial solute reactions based on the regular solution model was developed and compared with measured kinetics of LaNi5 and TiCrMn. This model aided in the identification of key reaction features and was used to verify the proposed technique for the analysis of gas-solid reaction rates determined volumetrically. Additionally, the phase field model provided detailed quantitative predictions of the effects of multidimensional phase growth and transitions between rate-limiting processes on the experimentally determined reaction rates. Unlike conventional solid state reaction analysis methods, this model relies fully on rate parameters based on the physical mechanisms occurring in the hydride reaction and can be extended to reactions in any dimension.

Enhanced electrocaloric analysis and energy-storage performance of lanthanum modified lead titanate ceramics for potential solid-state refrigeration applications.

PubMed

Zhang, Tian-Fu; Huang, Xian-Xiong; Tang, Xin-Gui; Jiang, Yan-Ping; Liu, Qiu-Xiang; Lu, Biao; Lu, Sheng-Guo

2018-01-10

The unique properties and great variety of relaxer ferroelectrics make them highly attractive in energy-storage and solid-state refrigeration technologies. In this work, lanthanum modified lead titanate ceramics are prepared and studied. The giant electrocaloric effect in lanthanum modified lead titanate ceramics is revealed for the first time. Large refrigeration efficiency (27.4) and high adiabatic temperature change (1.67 K) are achieved by indirect analysis. Direct measurements of electrocaloric effect show that reversible adiabatic temperature change is also about 1.67 K, which exceeds many electrocaloric effect values in current direct measured electrocaloric studies. Both theoretical calculated and direct measured electrocaloric effects are in good agreements in high temperatures. Temperature and electric field related energy storage properties are also analyzed, maximum energy-storage density and energy-storage efficiency are about 0.31 J/cm 3 and 91.2%, respectively.

Graphene Based Ultra-Capacitors for Safer, More Efficient Energy Storage

NASA Technical Reports Server (NTRS)

Roberson, Luke B.; Mackey, Paul J.; Zide, Carson J.

2016-01-01

Current power storage methods must be continuously improved in order to keep up with the increasingly competitive electronics industry. This technological advancement is also essential for the continuation of deep space exploration. Today's energy storage industry relies heavily on the use of dangerous and corrosive chemicals such as lithium and phosphoric acid. These chemicals can prove hazardous to the user if the device is ruptured. Similarly they can damage the environment if they are disposed of improperly. A safer, more efficient alternative is needed across a wide range of NASA missions. One solution would a solid-state carbon based energy storage device. Carbon is a safer, less environmentally hazardous alternative to current energy storage materials. Using the amorphous carbon nanostructure, graphene, this idea of a safer portable energy is possible. Graphene was electrochemically produced in the lab and several coin cell devices were built this summer to create a working prototype of a solid-state graphene battery.

Spacecraft cryogenic gas storage systems

NASA Technical Reports Server (NTRS)

Rysavy, G.

1971-01-01

Cryogenic gas storage systems were developed for the liquid storage of oxygen, hydrogen, nitrogen, and helium. Cryogenic storage is attractive because of the high liquid density and low storage pressure of cryogens. This situation results in smaller container sizes, reduced container-strength levels, and lower tankage weights. The Gemini and Apollo spacecraft used cryogenic gas storage systems as standard spacecraft equipment. In addition to the Gemini and Apollo cryogenic gas storage systems, other systems were developed and tested in the course of advancing the state of the art. All of the cryogenic storage systems used, developed, and tested to date for manned-spacecraft applications are described.

First Principles Based Simulation of Reaction-Induced Phase Transition in Hydrogen Storage and Other Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ge, Qingfeng

2014-08-31

This major part of this proposal is simulating hydrogen interactions in the complex metal hydrides. Over the period of DOE BES support, key achievements include (i) Predicted TiAl 3Hx as a precursor state for forming TiAl 3 through analyzing the Ti-doped NaAlH 4 and demonstrated its catalytic role for hydrogen release; (ii) Explored the possibility of forming similar complex structures with other 3d transition metals in NaAlH 4 as well as the impact of such complex structures on hydrogen release/uptake; (iii) Demonstrated the role of TiAl 3 in hydriding process; (iv) Predicted a new phase of NaAlH 4 that linksmore » to Na3AlH6 using first-principles metadynamics; (v) Examined support effect on hydrogen release from supported/encapsulated NaAlH 4; and (vi) Expanded research scope beyond hydrogen storage. The success of our research is documented by the peer-reviewed publications.« less

A new family of metal borohydride guanidinate complexes: Synthesis, structures and hydrogen-storage properties

NASA Astrophysics Data System (ADS)

Wu, Hui; Zhou, Xiuquan; Rodriguez, Efrain E.; Zhou, Wei; Udovic, Terrence J.; Yildirim, Taner; Rush, John J.

2016-10-01

We report on a new class of complex hydrides: borohydride guanidinate complexes (MBH4·nCN3H5, M=Li, Mg, and Ca). They can be prepared via facile solid-state synthesis routes. Their crystal structures were successfully determined using a combination of X-ray diffraction, first-principles calculations and neutron vibrational spectroscopy. Among these compounds, Mg(BH4)2·6CN3H5 is composed of large complex Mg[CN3H5]62+ cations and surrounding BH4- ions, while Ca(BH4)2·2CN3H5 possesses layers of corner-sharing Ca[BH4]4(CN3H5)2 octahedra. Our dehydrogenation results show that ≈10 wt% hydrogen can be released from MBH4·nCN3H5 (M=Li, Mg, and Ca) at moderate temperatures with minimal ammonia and diborane contamination thanks to the synergistic effect of C-N bonds from guanidine and hydridic H from borohydrides leading to a weakening of the N-H bonds, thus impeding ammonia gas liberation. Further tuning the dehydrogenation with different cation species indicates that Mg(BH4)2·nCN3H5 can exhibit the optimum properties with nearly thermally neutral dehydrogenation and very high purity hydrogen release.

From Fundamental Understanding To Predicting New Nanomaterials For High Capacity Hydrogen/Methane Storage and Carbon Capture

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yildirim, Taner

2015-03-03

On-board hydrogen/methane storage in fuel cell-powered vehicles is a major component of the national need to achieve energy independence and protect the environment. The main obstacles in hydrogen storage are slow kinetics, poor reversibility and high dehydrogenation temperatures for the chemical hydrides; and very low desorption temperatures/energies for the physisorption materials (MOF’s, porous carbons). Similarly, the current methane storage technologies are mainly based on physisorption in porous materials but the gravimetric and volumetric storage capacities are below the target values. Finally, carbon capture, a critical component of the mitigation of CO2 emissions from industrial plants, also suffers from similar problems.more » The solid-absorbers such as MOFs are either not stable against real flue-gas conditions and/or do not have large enough CO2 capture capacity to be practical and cost effective. In this project, we addressed these challenges using a unique combination of computational, synthetic and experimental methods. The main scope of our research was to achieve fundamental understanding of the chemical and structural interactions governing the storage and release of hydrogen/methane and carbon capture in a wide spectrum of candidate materials. We studied the effect of scaffolding and doping of the candidate materials on their storage and dynamics properties. We reviewed current progress, challenges and prospect in closely related fields of hydrogen/methane storage and carbon capture.[1-5] For example, for physisorption based storage materials, we show that tap-densities or simply pressing MOFs into pellet forms reduce the uptake capacities by half and therefore packing MOFs is one of the most important challenges going forward. For room temperature hydrogen storage application of MOFs, we argue that MOFs are the most promising scaffold materials for Ammonia-Borane (AB) because of their unique interior active metal-centers for AB binding and well defined and ordered pores. Here the main challenge is to find a chemically stable MOF required for regeneration of the AB-spent fuel. Finally, for carbon capture application of MOFs, we investigate the performance of a number of metal–organic frameworks with particular focus on their behavior at the low pressures commonly used in swing adsorption. This comparison clearly shows that it is the process that determines which MOF is optimal rather than there being one best MOF, though MOFs that possess enhanced binding at open metal sites generally perform better than those with high surface area. References: 1. Y. Peng, V. Krungleviciute, J. T. Hupp, O. K. Farha, and T. Yildirim, J. Am. Chem. Soc. 135, 11887 (2013). 2. G. Srinivas, V. Krungleviciute, Z. Guo, and T. Yildirim, Ener. Environ. Sci. 7, 335 (2014). 3. G. Burres, and T. Yildirim, Ener. Environ. Sci. 5, 6453 (2012). 4. G. Srinivas, W. Travis, J. Ford, H. Wu, Z. X. Guo, and T. Yildirim, J. Mat. Chem.1, 4167 (2013). 5. For details, please see http://www.ncnr.nist.gov/staff/taner« less

Nickel-based anode with water storage capability to mitigate carbon deposition for direct ethanol solid oxide fuel cells.

PubMed

Wang, Wei; Su, Chao; Ran, Ran; Zhao, Bote; Shao, Zongping; Tade, Moses O; Liu, Shaomin

2014-06-01

The potential to use ethanol as a fuel places solid oxide fuel cells (SOFCs) as a sustainable technology for clean energy delivery because of the renewable features of ethanol versus hydrogen. In this work, we developed a new class of anode catalyst exemplified by Ni+BaZr0.4Ce0.4Y0.2O3 (Ni+BZCY) with a water storage capability to overcome the persistent problem of carbon deposition. Ni+BZCY performed very well in catalytic efficiency, water storage capability and coking resistance tests. A stable and high power output was well maintained with a peak power density of 750 mW cm(-2) at 750 °C. The SOFC with the new robust anode performed for seven days without any sign of performance decay, whereas SOFCs with conventional anodes failed in less than 2 h because of significant carbon deposition. Our findings indicate the potential applications of these water storage cermets as catalysts in hydrocarbon reforming and as anodes for SOFCs that operate directly on hydrocarbons. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Methyllithium-Doped Naphthyl-Containing Conjugated Microporous Polymer with Enhanced Hydrogen Storage Performance.

PubMed

Xu, Dan; Sun, Lei; Li, Gang; Shang, Jin; Yang, Rui-Xia; Deng, Wei-Qiao

2016-06-01

Hydrogen storage is a primary challenge for using hydrogen as a fuel. With ideal hydrogen storage kinetics, the weak binding strength of hydrogen to sorbents is the key barrier to obtain decent hydrogen storage performance. Here, we reported the rational synthesis of a methyllithium-doped naphthyl-containing conjugated microporous polymer with exceptional binding strength of hydrogen to the polymer guided by theoretical simulations. Meanwhile, the experimental results showed that isosteric heat can reach up to 8.4 kJ mol(-1) and the methyllithium-doped naphthyl-containing conjugated microporous polymer exhibited an enhanced hydrogen storage performance with 150 % enhancement compared with its counterpart naphthyl-containing conjugated microporous polymer. These results indicate that this strategy provides a direction for design and synthesis of new materials that meet the US Department of Energy (DOE) hydrogen storage target. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of characteristics of compounds on maintenance of an amorphous state in solid dispersion with crospovidone.

PubMed

Shibata, Yusuke; Fujii, Makiko; Kokudai, Makiko; Noda, Shinobu; Okada, Hideko; Kondoh, Masuo; Watanabe, Yoshiteru

2007-06-01

Solid dispersion (SD) of indomethacin with crospovidone (CrosPVP) shows useful characteristics for preparation of dosage forms. This study aimed to determine the types of drugs that could adopt a stable amorphous form in SD. Twenty compounds with various melting points (70-218 degrees C), molecular weights (135-504) and functional groups (amide, amino, carbonyl, hydroxyl, ketone etc.) were prepared in SD with CrosPVP. The CrosPVP SDs were prepared using a mechanical mixing and heating method. Melting point and molecular weight were found to have no influence on the ability of a compound to maintain an amorphous state in SD. All compounds containing hydrogen-bond-donor functional groups existed in an amorphous state in SD for at least 6 months. Infrared spectra suggested an interaction between the functional groups of these compounds and amide carbonyl group of CrosPVP. Compounds without hydrogen-bond-donor groups could not maintain an amorphous state and underwent recrystallization within 1 month. It was suggested that the presence of a hydrogen-bond-donor functional group in a compound is an important factor affecting the stable formation of SD with CrosPVP, which contains a hydrogen-bond acceptor.

DFT investigations of hydrogen storage materials

NASA Astrophysics Data System (ADS)

Wang, Gang

Hydrogen serves as a promising new energy source having no pollution and abundant on earth. However the most difficult problem of applying hydrogen is to store it effectively and safely, which is smartly resolved by attempting to keep hydrogen in some metal hydrides to reach a high hydrogen density in a safe way. There are several promising metal hydrides, the thermodynamic and chemical properties of which are to be investigated in this dissertation. Sodium alanate (NaAlH4) is one of the promising metal hydrides with high hydrogen storage capacity around 7.4 wt. % and relatively low decomposition temperature of around 100 °C with proper catalyst. Sodium hydride is a product of the decomposition of NaAlH4 that may affect the dynamics of NaAlH4. The two materials with oxygen contamination such as OH- may influence the kinetics of the dehydriding/rehydriding processes. Thus the solid solubility of OH - groups (NaOH) in NaAlH4 and NaH is studied theoretically by DFT calculations. Magnesium boride [Mg(BH4)2] is has higher hydrogen capacity about 14.9 wt. % and the decomposition temparture of around 250 °C. However one flaw restraining its application is that some polyboron compounds like MgB12H12 preventing from further release of hydrogen. Adding some transition metals that form magnesium transition metal ternary borohydride [MgaTMb(BH4)c] may simply the decomposition process to release hydrogen with ternary borides (MgaTMbBc). The search for the probable ternary borides and the corresponding pseudo phase diagrams as well as the decomposition thermodynamics are performed using DFT calculations and GCLP method to present some possible candidates.

Biredox ionic liquids with solid-like redox density in the liquid state for high-energy supercapacitors.

PubMed

Mourad, Eléonore; Coustan, Laura; Lannelongue, Pierre; Zigah, Dodzi; Mehdi, Ahmad; Vioux, André; Freunberger, Stefan A; Favier, Frédéric; Fontaine, Olivier

2017-04-01

Kinetics of electrochemical reactions are several orders of magnitude slower in solids than in liquids as a result of the much lower ion diffusivity. Yet, the solid state maximizes the density of redox species, which is at least two orders of magnitude lower in liquids because of solubility limitations. With regard to electrochemical energy storage devices, this leads to high-energy batteries with limited power and high-power supercapacitors with a well-known energy deficiency. For such devices the ideal system should endow the liquid state with a density of redox species close to the solid state. Here we report an approach based on biredox ionic liquids to achieve bulk-like redox density at liquid-like fast kinetics. The cation and anion of these biredox ionic liquids bear moieties that undergo very fast reversible redox reactions. As a first demonstration of their potential for high-capacity/high-rate charge storage, we used them in redox supercapacitors. These ionic liquids are able to decouple charge storage from an ion-accessible electrode surface, by storing significant charge in the pores of the electrodes, to minimize self-discharge and leakage current as a result of retaining the redox species in the pores, and to raise working voltage due to their wide electrochemical window.

Characterization of Pharmaceutical Cocrystals and Salts by Dynamic Nuclear Polarization-Enhanced Solid-State NMR Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Li; Hanrahan, Michael P.; Chakravarty, Paroma

Multicomponent solids such as cocrystals have emerged as a way to control and engineer the stability, solubility and manufacturability of solid active pharmaceutical ingredients (APIs). Cocrystals are typically formed by solution- or solid-phase reactions of APIs with suitable cocrystal coformers, which are often weak acids. One key structural question about a given multicomponent solid is whether it should be classified as a salt, where the basic API is protonated by the acid, or as a cocrystal, where the API and coformer remain neutral and engage in hydrogen bonding interactions. It has previously been demonstrated that solid-state NMR spectroscopy is amore » powerful probe of structure in cocrystals and salts of APIs, however, the poor sensitivity of solid-state NMR spectroscopy usually restricts the types of experiments that can be performed. Here relayed dynamic nuclear polarization (DNP) was applied to reduce solid-state NMR experiments by one to two orders of magnitude for salts and cocrystals of a complex API. The large sensitivity gains from DNP facilitates rapid acquisition of natural isotopic abundance 13C and 15N solid-state NMR spectra. Critically, DNP enables double resonance 1H-15N solid-state NMR experiments such as 2D 1H-15N HETCOR, 1H-15N CP-build up, 15N{1H} J-resolved/attached proton tests, 1H-15N DIPSHIFT and 1H-15N PRESTO. The latter two experiments allow 1H-15N dipolar coupling constants and H-N bond lengths to be accurately measured, providing an unambiguous assignment of nitrogen protonation state and definitive classification of the multi-component solids as cocrystals or salts. In conclusion, these types of measurements should also be extremely useful in the context of polymorph discrimination, NMR crystallography structure determination and for probing hydrogen bonding in a variety of organic materials.« less

Characterization of Pharmaceutical Cocrystals and Salts by Dynamic Nuclear Polarization-Enhanced Solid-State NMR Spectroscopy

DOE PAGES

Zhao, Li; Hanrahan, Michael P.; Chakravarty, Paroma; ...

2018-02-15

Multicomponent solids such as cocrystals have emerged as a way to control and engineer the stability, solubility and manufacturability of solid active pharmaceutical ingredients (APIs). Cocrystals are typically formed by solution- or solid-phase reactions of APIs with suitable cocrystal coformers, which are often weak acids. One key structural question about a given multicomponent solid is whether it should be classified as a salt, where the basic API is protonated by the acid, or as a cocrystal, where the API and coformer remain neutral and engage in hydrogen bonding interactions. It has previously been demonstrated that solid-state NMR spectroscopy is amore » powerful probe of structure in cocrystals and salts of APIs, however, the poor sensitivity of solid-state NMR spectroscopy usually restricts the types of experiments that can be performed. Here relayed dynamic nuclear polarization (DNP) was applied to reduce solid-state NMR experiments by one to two orders of magnitude for salts and cocrystals of a complex API. The large sensitivity gains from DNP facilitates rapid acquisition of natural isotopic abundance 13C and 15N solid-state NMR spectra. Critically, DNP enables double resonance 1H-15N solid-state NMR experiments such as 2D 1H-15N HETCOR, 1H-15N CP-build up, 15N{1H} J-resolved/attached proton tests, 1H-15N DIPSHIFT and 1H-15N PRESTO. The latter two experiments allow 1H-15N dipolar coupling constants and H-N bond lengths to be accurately measured, providing an unambiguous assignment of nitrogen protonation state and definitive classification of the multi-component solids as cocrystals or salts. In conclusion, these types of measurements should also be extremely useful in the context of polymorph discrimination, NMR crystallography structure determination and for probing hydrogen bonding in a variety of organic materials.« less

NASA Hydrogen Research for Spaceport and Space Based Applications

NASA Technical Reports Server (NTRS)

Anderson, Tim

2006-01-01

The activities presented are a broad based approach to advancing key hydrogen related technologies in areas such as hydrogen production, distributed sensors for hydrogen-leak detection, laser instrumentation for hydrogen-leak detection, and cryogenic transport and storage. Presented are the results form 15 research projects, education, and outreach activities, system and trade studies, and project management. The work will aid in advancing the state-of-the-art for several critical technologies related to the implementation of a hydrogen infrastructure. Activities conducted are relevant to a number of propulsion and power systems for terrestrial, aeronautics, and aerospace applications.

Fabrication of ultrathin solid electrolyte membranes of β-Li 3PS 4 nanoflakes by evaporation-induced self-assembly for all-solid-state batteries

DOE PAGES

Wang, Hui; Hood, Zachary D.; Xia, Younan; ...

2016-04-25

All-solid-state lithium batteries are attractive candidates for next-generation energy storage devices because of their anticipated high energy density and intrinsic safety. Owing to their excellent ionic conductivity and stability with metallic lithium anodes, nanostructured lithium thiophosphate solid electrolytes such as β-Li 3PS 4 have found use in the fabrication of all-solid lithium batteries for large-scale energy storage systems. However, current methods for preparing air-sensitive solid electrolyte membranes of lithium thiophosphates can only generate thick membranes that compromise the battery's gravimetric/volumetric energy density and thus its rate performance. To overcome this limitation, the solid electrolyte's thickness needs to be effectively decreasedmore » to achieve ideal energy density and enhanced rate performance. In this paper, we show that the evaporation-induced self-assembly (EISA) technique produces ultrathin membranes of a lithium thiophosphate solid electrolyte with controllable thicknesses between 8 and 50 μm while maintaining the high ionic conductivity of β-Li 3PS 4 and stability with metallic lithium anodes up to 5 V. Finally, it is clearly demonstrated that this facile EISA approach allows for the preparation of ultrathin lithium thiophosphate solid electrolyte membranes for all-solid-state batteries.« less

Storing Renewable Energy in the Hydrogen Cycle.

PubMed

Züttel, Andreas; Callini, Elsa; Kato, Shunsuke; Atakli, Züleyha Özlem Kocabas

2015-01-01

An energy economy based on renewable energy requires massive energy storage, approx. half of the annual energy consumption. Therefore, the production of a synthetic energy carrier, e.g. hydrogen, is necessary. The hydrogen cycle, i.e. production of hydrogen from water by renewable energy, storage and use of hydrogen in fuel cells, combustion engines or turbines is a closed cycle. Electrolysis splits water into hydrogen and oxygen and represents a mature technology in the power range up to 100 kW. However, the major technological challenge is to build electrolyzers in the power range of several MW producing high purity hydrogen with a high efficiency. After the production of hydrogen, large scale and safe hydrogen storage is required. Hydrogen is stored either as a molecule or as an atom in the case of hydrides. The maximum volumetric hydrogen density of a molecular hydrogen storage is limited to the density of liquid hydrogen. In a complex hydride the hydrogen density is limited to 20 mass% and 150 kg/m(3) which corresponds to twice the density of liquid hydrogen. Current research focuses on the investigation of new storage materials based on combinations of complex hydrides with amides and the understanding of the hydrogen sorption mechanism in order to better control the reaction for the hydrogen storage applications.

Hydrogenation-controlled phase transition on two-dimensional transition metal dichalcogenides and their unique physical and catalytic properties.

PubMed

Qu, Yuanju; Pan, Hui; Kwok, Chi Tat

2016-09-30

Two-dimensional (2D) transition metal dichalcogenides (TMDs) have been widely used from nanodevices to energy harvesting/storage because of their tunable physical and chemical properties. In this work, we systematically investigate the effects of hydrogenation on the structural, electronic, magnetic, and catalytic properties of 33 TMDs based on first-principles calculations. We find that the stable phases of TMD monolayers can transit from 1T to 2H phase or vice versa upon the hydrogenation. We show that the hydrogenation can switch their magnetic and electronic states accompanying with the phase transition. The hydrogenation can tune the magnetic states of TMDs among non-, ferro, para-, and antiferro-magnetism and their electronic states among semiconductor, metal, and half-metal. We further show that, out of 33 TMD monolayers, 2H-TiS 2 has impressive catalytic ability comparable to Pt in hydrogen evolution reaction in a wide range of hydrogen coverages. Our findings would shed the light on the multi-functional applications of TMDs.

A new family of metal borohydride guanidinate complexes: Synthesis, structures and hydrogen-storage properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Hui, E-mail: huiwu@nist.gov; Zhou, Xiuquan; Rodriguez, Efrain E.

We report on a new class of complex hydrides: borohydride guanidinate complexes (MBH{sub 4}·nCN{sub 3}H{sub 5}, M=Li, Mg, and Ca). They can be prepared via facile solid-state synthesis routes. Their crystal structures were successfully determined using a combination of X-ray diffraction, first-principles calculations and neutron vibrational spectroscopy. Among these compounds, Mg(BH{sub 4}){sub 2}·6CN{sub 3}H{sub 5} is composed of large complex Mg[CN{sub 3}H{sub 5}]{sub 6}{sup 2+} cations and surrounding BH{sub 4}{sup -} ions, while Ca(BH{sub 4}){sub 2}·2CN{sub 3}H{sub 5} possesses layers of corner-sharing Ca[BH{sub 4}]{sub 4}(CN{sub 3}H{sub 5}){sub 2} octahedra. Our dehydrogenation results show that ≈10 wt% hydrogen can be releasedmore » from MBH{sub 4}·nCN{sub 3}H{sub 5} (M=Li, Mg, and Ca) at moderate temperatures with minimal ammonia and diborane contamination thanks to the synergistic effect of C-N bonds from guanidine and hydridic H from borohydrides leading to a weakening of the N-H bonds, thus impeding ammonia gas liberation. Further tuning the dehydrogenation with different cation species indicates that Mg(BH{sub 4}){sub 2}·nCN{sub 3}H{sub 5} can exhibit the optimum properties with nearly thermally neutral dehydrogenation and very high purity hydrogen release. - Graphical abstract: A new family of complex hydrides: borohydride guanidinates, was developed with diverse crystal structures and remarkable hydrogen storage properties. - Highlights: • A new family of complex hydrides, borohydride guanidinate complexes, are synthesized. • Their diverse crystal structures are determined using combined characterizations. • These compounds can release ~10 wt% pure H{sub 2} at moderate temperatures. • Dehydrogenation thermodynamics and H{sub 2} purity can be tuned by varying cation species.« less

Liquid–solid phase transition of hydrogen and deuterium in silica aerogel

DOE PAGES

Van Cleve, E.; Worsley, M. A.; Kucheyev, S. O.

2014-10-30

Behavior of hydrogen isotopes confined in disordered low-density nanoporous solids remains essentially unknown. Here, we use relaxation calorimetry to study freezing and melting of H 2 and D 2 in an ~85%-porous base-catalyzed silica aerogel. In this work, we find that liquid–solid transition temperatures of both isotopes inside the aerogel are depressed. The phase transition takes place over a wide temperature range of ~4 K and non-trivially depends on the liquid filling fraction, reflecting the broad pore size distribution in the aerogel. Undercooling is observed for both H 2 and D 2 confined inside the aerogel monolith. Lastly, results formore » H 2 and D 2 are extrapolated to tritium-containing hydrogens with the quantum law of corresponding states.« less

Microscale Enhancement of Heat and Mass Transfer for Hydrogen Energy Storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Drost, Kevin; Jovanovic, Goran; Paul, Brian

2015-09-30

The document summarized the technical progress associated with OSU’s involvement in the Hydrogen Storage Engineering Center of Excellence. OSU focused on the development of microscale enhancement technologies for improving heat and mass transfer in automotive hydrogen storage systems. OSU’s key contributions included the development of an extremely compact microchannel combustion system for discharging hydrogen storage systems and a thermal management system for adsorption based hydrogen storage using microchannel cooling (the Modular Adsorption Tank Insert or MATI).

Hydrogen Storage Performance in Pd/Graphene Nanocomposites.

PubMed

Zhou, Chunyu; Szpunar, Jerzy A

2016-10-05

We have developed a Pd-graphene nanocomposite for hydrogen storage. The spherically shaped Pd nanoparticles of 5-45 nm in size are homogeneously distributed over the graphene matrix. This new hydrogen storage system has favorable features like desirable hydrogen storage capacity, ambient conditions of hydrogen uptake, and low temperature of hydrogen release. At a hydrogen charging pressure of 50 bar, the material could yield a gravimetric density of 6.7 wt % in the 1% Pd/graphene nanocomposite. As we increased the applied pressure to 60 bar, the hydrogen uptake capacity reached 8.67 wt % in the 1% Pd/graphene nanocomposite and 7.16 wt % in the 5% Pd/graphene nanocomposite. This system allows storage of hydrogen in amounts that exceed the capacity of the gravimetric target announced by the U.S. Department of Energy (DOE).

Ground state energy of solid molecular hydrogen at high pressure

NASA Technical Reports Server (NTRS)

Ebner, C.; Sung, C. C.

1972-01-01

The present status of the theoretical equation of state of solid molecular hydrogen is reviewed. Different quantum mechanical calculations by several groups lead to results which generally agree with each other but which disagree systematically with the measured pressure-volume curve at pressures larger than about 3000 atm. A new calculation of this curve is presented including the effect of the anisotropic interaction between H2 molecules within a completely quantum-mechanical formalism. The results show that inclusion of this interaction removes the discrepancy between theory and experiment at high pressures and that a quantum-mechanical treatment is necessary to realize its full effect.

A Facile Method for the Preparation of Colored Bi4Ti3O12−x Nanosheets with Enhanced Visible-Light Photocatalytic Hydrogen Evolution Activity

PubMed Central

Zhang, Yizeng; Chen, Zhiwu; Lu, Zhenya

2018-01-01

Bi4Ti3O12−x nanosheet photocatalysts with abundant oxygen vacancies are fabricated by a facile solid-state chemical reduction method for the first time. This method is simple in operation, has short reaction time, and can be conducted at mild temperatures (300~400 °C). The electron paramagnetic resonance, thermogravimetric analysis, X-ray photoelectron spectrometer, and positron annihilation lifetime spectra results indicate that oxygen vacancies are produced in Bi4Ti3O12−x, and they can be adjusted by tuning the reduction reaction conditions. Control experiments show that the reduction time and temperature have great influences on the photocatalytic activities of Bi4Ti3O12−x. The optimal Bi4Ti3O12−x is the sample undergoing the reduction treatment at 350 °C for 60 min and it affords a hydrogen evolution rate of 129 μmol·g−1·h−1 under visible-light irradiation, which is about 3.4 times that of the pristine Bi4Ti3O12. The Bi4Ti3O12−x photocatalysts have good reusability and storage stability and can be used to decompose formaldehyde and formic acid for hydrogen production. The surface oxygen vacancies states result in the broadening of the valence band and the narrowing of the band gap. Such energy level structure variation helps promote the separation of photo-generated electron-hole pairs thus leading to enhancement in the visible-light photocatalytic hydrogen evolution. Meanwhile, the narrowing of the band gap leads to a broader visible light absorption of Bi4Ti3O12−x. PMID:29690518

Fabrication, testing and simulation of all solid state three dimensional Li-ion batteries

DOE PAGES

Talin, Albert Alec; Ruzmetov, Dmitry; Kolmakov, Andrei; ...

2016-11-10

Realization of safe, long cycle life and simple to package solid-state rechargeable batteries with high energy and power density has been a long-standing goal of the energy storage community. [1,2] Much of the research activity has been focused on developing new solid electrolytes with high Li ionic conductivity. In addition, LiPON, the only solid electrolyte currently used in commercial thin film solid state Li-ion batteris (SSLIBs), has a conductivity of ~10 -6 S/cm, compared to ~0.01 S/cm typically observed for liquid organic electrolytes [3].

A first-principles study of hydrogen storage capacity based on Li-Na-decorated silicene.

PubMed

Sheng, Zhe; Wu, Shujing; Dai, Xianying; Zhao, Tianlong; Hao, Yue

2018-05-23

Surface decoration with alkali metal adatoms has been predicted to be promising for silicene to obtain high hydrogen storage capacity. Herein, we performed a detailed study of the hydrogen storage properties of Li and Na co-decorated silicene (Li-Na-decorated silicene) based on first-principles calculations using van der Waals correction. The hydrogen adsorption behaviors, including the adsorption order, the maximum capacity, and the corresponding mechanism were analyzed in detail. Our calculations show that up to three hydrogen molecules can firmly bind to each Li atom and six for each Na atom, respectively. The hydrogen storage capacity is estimated to be as high as 6.65 wt% with a desirable average adsorption energy of 0.29 eV/H2. It is confirmed that both the charge-induced electrostatic interaction and the orbital hybridizations play a great role in hydrogen storage. Our results may enhance our fundamental understanding of the hydrogen storage mechanism, which is of great importance for the practical application of Li-Na-decorated silicene in hydrogen storage.

Fuel Cell Propulsion Systems for an All-electric Personal Air Vehicle

NASA Technical Reports Server (NTRS)

Kohout, Lisa L.; Schmitz, Paul C.

2003-01-01

There is a growing interest in the use of fuel cells as a power source for all-electric aircraft propulsion as a means to substantially reduce or eliminate environmentally harmful emissions. Among the technologies under consideration for these concepts are advanced proton exchange membrane and solid oxide fuel cells, alternative fuels and fuel processing, and fuel storage. This paper summarizes the results of a first-order feasibility study for an all-electric personal air vehicle utilizing a fuel cell-powered propulsion system. A representative aircraft with an internal combustion engine was chosen as a baseline to provide key parameters to the study, including engine power and subsystem mass, fuel storage volume and mass, and aircraft range. The engine, fuel tank, and associated ancillaries were then replaced with a fuel cell subsystem. Various configurations were considered including: a proton exchange membrane (PEM) fuel cell with liquid hydrogen storage; a direct methanol PEM fuel cell; and a direct internal reforming solid oxide fuel cell (SOFC)/turbine hybrid system using liquid methane fuel. Each configuration was compared to the baseline case on a mass and range basis.

Fuel Cell Propulsion Systems for an All-Electric Personal Air Vehicle

NASA Technical Reports Server (NTRS)

Kohout, Lisa L.

2003-01-01

There is a growing interest in the use of fuel cells as a power source for all-electric aircraft propulsion as a means to substantially reduce or eliminate environmentally harmful emissions. Among the technologies under consideration for these concepts are advanced proton exchange membrane and solid oxide fuel cells, alternative fuels and fuel processing, and fuel storage. This paper summarizes the results of a first-order feasibility study for an all-electric personal air vehicle utilizing a fuel cell-powered propulsion system. A representative aircraft with an internal combustion engine was chosen as a baseline to provide key parameters to the study, including engine power and subsystem mass, fuel storage volume and mass, and aircraft range. The engine, fuel tank, and associated ancillaries were then replaced with a fuel cell subsystem. Various configurations were considered including: a proton exchange membrane (PEM) fuel cell with liquid hydrogen storage; a direct methanol PEM fuel cell; and a direct internal reforming solid oxide fuel cell (SOFC)/turbine hybrid system using liquid methane fuel. Each configuration was compared to the baseline case on a mass and range basis.

Magnesium Nanoparticles for Hydrogen Storage: Structure, Kinetics and Thermodynamics

NASA Astrophysics Data System (ADS)

Pasquini, L.; Brighi, M.; Montone, A.; Vittori Antisari, M.; Dam, B.; Palmisano, V.; Bonetti, E.

2012-08-01

Magnesium nanoparticles coated by a native oxide shell and decorated by palladium clusters were synthesized by the inert gas condensation technique. The kinetics and thermodynamics of hydrogen sorption were investigated by Sieverts measurements at high temperature and by optical hydrogenography close to ambient temperature. The structure and morphology of the nanoparticles were studied by electron microscopy and X-ray diffraction both in the as-prepared state and after hydrogen sorption cycles.

Nonpolluting automobiles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hoolboom, G.J.; Szabados, B.

The advantages/disadvantages of energy storage devices, which can provide nonpolluting automobile systems are discussed. Four types of storage devices are identified: electrochemical (batteries); hydrogen; electromechanical (flywheels); and molten salt heat storage. A high-speed flywheel with a small permanent magnet motor/generator has more advantages than any of the other systems and might become a real competitor to the internal combustion engine. A flywheel/motor/generator system for automobiles now becomes practical, because of the technological advances in materials, bearings and solid state control circuits. The motor of choice is the squirrel cage induction motor, specially designed for automobile applications. The preferred controller formore » the induction motor is a forced commutated cycloconverter, which transforms a variable voltage/variable frequency source into a controlled variable-voltage/variable-frequency supply. A modulation strategy of the cycloconverter elements is selected to maintain a unity input displacement factor (power factor) under all conditions of loads voltages and frequencies. The system is similar to that of the existing automobile, if only one motor is used: master controller-controller-motor-gears (fixed)-differential-wheels. In the case of two motors, the mechanical differential is replaced by an electric one: master controller-controller-motor-gears (fixed)-wheel. A four-wheel drive vehicle is obtained when four motors with their own controllers are used. 24 refs.« less

Chemical shift and electric field gradient tensors for the amide and carboxyl hydrogens in the model peptide N-acetyl-D,L-valine. Single-crystal deuterium NMR study.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gerald, R. E., II; Bernhard, T.; Haeberlen, U.

1993-01-01

Solid-state NMR spectroscopy is well established as a method for describing molecular structure with resolution on the atomic scale. Many of the NMR observables result from anisotropic interactions between the nuclear spin and its environment. These observables can be described by second-rank tensors. For example, the eigenvalues of the traceless symmetric part of the hydrogen chemical shift (CS) tensor provide information about the strength of inter- or intramolecular hydrogen bonding. On the other hand, the eigenvectors of the deuterium electric field gradient (EFG) tensor give deuteron/proton bond directions with an accuracy rivalled only by neutron diffraction. In this paper themore » authors report structural information of this type for the amide and carboxyl hydrogen sites in a single crystal of the model peptide N-acetyl-D,L-valine (NAV). They use deuterium NMR to infer both the EFG and CS tensors at the amide and carboxyl hydrogen sites in NAV. Advantages of this technique over multiple-pulse proton NMR are that it works in the presence of {sup 14}N spins which are very hard to decouple from protons and that additional information in form of the EFG tensors can be derived. The change in the CS and EFG tensors upon exchange of a deuteron for a proton (the isotope effect) is anticipated to be very small; the effect on the CS tensors is certainly smaller than the experimental errors. NAV has served as a model peptide before in a variety of NMR studies, including those concerned with developing solid-state NMR spectroscopy as a method for determining the structure of proteins. NMR experiments on peptide or protein samples which are oriented in at least one dimension can provide important information about the three-dimensional structure of the peptide or the protein. In order to interpret the NMR data in terms of the structure of the polypeptide, the relationship of the CS and EFG tensors to the local symmetry elements of an amino acide, e.g., the peptide plane, is essential. The main purpose of this work is to investigate this relationship for the amide hydrogen CS tensor. The amide hydrogen CS tensor will also provide orientational information for peptide bonds in proteins complementary to that from the nitrogen CS and EFG tensors and the nitrogen-hydrogen heteronuclear dipole-dipole coupling which have been used previously to determine protein structures by solid-state NMR spectroscopy. This information will be particularly valuable because the amide hydrogen CS tensor is not axially symmetric. In addition, the use of the amide hydrogen CS interaction in high-field solid-state NMR experiments will increase the available resolution among peptide sites.« less

Dehydrogenation of liquid fuel in microchannel catalytic reactor

DOEpatents

Toseland, Bernard Allen; Pez, Guido Peter; Puri, Pushpinder Singh

2010-08-03

The present invention is an improved process for the storage and delivery of hydrogen by the reversible hydrogenation/dehydrogenation of an organic compound wherein the organic compound is initially in its hydrogenated state. The improvement in the route to generating hydrogen is in the dehydrogenation step and recovery of the dehydrogenated organic compound resides in the following steps: introducing a hydrogenated organic compound to a microchannel reactor incorporating a dehydrogenation catalyst; effecting dehydrogenation of said hydrogenated organic compound under conditions whereby said hydrogenated organic compound is present as a liquid phase; generating a reaction product comprised of a liquid phase dehydrogenated organic compound and gaseous hydrogen; separating the liquid phase dehydrogenated organic compound from gaseous hydrogen; and, recovering the hydrogen and liquid phase dehydrogenated organic compound.

Dehydrogenation of liquid fuel in microchannel catalytic reactor

DOEpatents

Toseland, Bernard Allen [Allentown, PA; Pez, Guido Peter [Allentown, PA; Puri, Pushpinder Singh [Emmaus, PA

2009-02-03

The present invention is an improved process for the storage and delivery of hydrogen by the reversible hydrogenation/dehydrogenation of an organic compound wherein the organic compound is initially in its hydrogenated state. The improvement in the route to generating hydrogen is in the dehydrogenation step and recovery of the dehydrogenated organic compound resides in the following steps: introducing a hydrogenated organic compound to a microchannel reactor incorporating a dehydrogenation catalyst; effecting dehydrogenation of said hydrogenated organic compound under conditions whereby said hydrogenated organic compound is present as a liquid phase; generating a reaction product comprised of a liquid phase dehydrogenated organic compound and gaseous hydrogen; separating the liquid phase dehydrogenated organic compound from gaseous hydrogen; and, recovering the hydrogen and liquid phase dehydrogenated organic compound.

Electrochemical Hydrogen Storage in Facile Synthesized Co@N-Doped Carbon Nanoparticle Composites.

PubMed

Zhou, Lina; Qu, Xiaosheng; Zheng, Dong; Tang, Haolin; Liu, Dan; Qu, Deyang; Xie, ZhiZhong; Li, Junsheng; Qu, Deyu

2017-11-29

A Co@nitrogen-doped carbon nanoparticle composite was synthesized via a facile molecular self-assembling procedure. The material was used as the host for the electrochemical storage of hydrogen. The hydrogen storage capacity of the material was over 300 mAh g -1 at a rate of 100 mAg -1 . It also exhibited superior stability for storage of hydrogen, high rate capability, and good cyclic life. Hybridizing metallic cobalt nanoparticle with nitrogen-doped mesoporous carbon is found to be a good approach for the electrochemical storage of hydrogen.

Systems and methods for facilitating hydrogen storage using naturally occurring nanostructure assemblies

DOEpatents

Fliermans,; Carl, B [Augusta, GA

2012-08-07

Some or all of the needs above can be addressed by embodiments of the invention. According to embodiments of the invention, systems and methods for facilitating hydrogen storage using naturally occurring nanostructure assemblies can be implemented. In one embodiment, a method for storing hydrogen can be provided. The method can include providing diatoms comprising diatomaceous earth or diatoms from a predefined culture. In addition, the method can include heating the diatoms in a sealed environment in the presence of at least one of titanium, a transition metal, or a noble metal to provide a porous hydrogen storage medium. Furthermore, the method can include exposing the porous hydrogen storage medium to hydrogen. In addition, the method can include storing at least a portion of the hydrogen in the porous hydrogen storage medium.

Liquid-phase chemical hydrogen storage: catalytic hydrogen generation under ambient conditions.

PubMed

Jiang, Hai-Long; Singh, Sanjay Kumar; Yan, Jun-Min; Zhang, Xin-Bo; Xu, Qiang

2010-05-25

There is a demand for a sufficient and sustainable energy supply. Hence, the search for applicable hydrogen storage materials is extremely important owing to the diversified merits of hydrogen energy. Lithium and sodium borohydride, ammonia borane, hydrazine, and formic acid have been extensively investigated as promising hydrogen storage materials based on their relatively high hydrogen content. Significant advances, such as hydrogen generation temperatures and reaction kinetics, have been made in the catalytic hydrolysis of aqueous lithium and sodium borohydride and ammonia borane as well as in the catalytic decomposition of hydrous hydrazine and formic acid. In this Minireview we briefly survey the research progresses in catalytic hydrogen generation from these liquid-phase chemical hydrogen storage materials.

Changing scene highlights III. [Iowa State University

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fassel, V. A.; Harl, Neil E.; Legvold, Sam

1979-01-01

The research programs in progress at Ames Laboratory, Iowa State University, are reviewed: hydrogen (storage), materials, catalysts, TRISTAN (their laboratory isotope separator), coal preparation, coal classification, land reclamation (after surface mining, nitinol, neutron radiography, grain dust explosions, biomass conversion, etc). (LTC)

Thermal energy storage material

DOEpatents

Leifer, Leslie

1976-01-01

A thermal energy storage material which is stable at atmospheric temperature and pressure and has a melting point higher than 32.degree.F. is prepared by dissolving a specific class of clathrate forming compounds, such as tetra n-propyl or tetra n-butyl ammonium fluoride, in water to form a substantially solid clathrate. The resultant thermal energy storage material is capable of absorbing heat from or releasing heat to a given region as it transforms between solid and liquid states in response to temperature changes in the region above and below its melting point.

Solid-state energy storage module employing integrated interconnect board

DOEpatents

Rouillard, Jean; Comte, Christophe; Daigle, Dominik; Hagen, Ronald A.; Knudson, Orlin B.; Morin, Andre; Ranger, Michel; Ross, Guy; Rouillard, Roger; St-Germain, Philippe; Sudano, Anthony; Turgeon, Thomas A.

2004-09-28

An electrochemical energy storage device includes a number of solid-state thin-film electrochemical cells which are selectively interconnected in series or parallel through use of an integrated interconnect board. The interconnect board is typically disposed within a sealed housing which also houses the electrochemical cells, and includes a first contact and a second contact respectively coupled to first and second power terminals of the energy storage device. The interconnect board advantageously provides for selective series or parallel connectivity with the electrochemical cells, irrespective of electrochemical cell position within the housing. Fuses and various electrical and electro-mechanical devices, such as bypass, equalization, and communication devices for example, may also be mounted to the interconnect board and selectively connected to the electrochemical cells.

Detection of hydrogen dissolved in acrylonitrile butadiene rubber by 1H nuclear magnetic resonance

NASA Astrophysics Data System (ADS)

Nishimura, Shin; Fujiwara, Hirotada

2012-01-01

Rubber materials, which are used for hydrogen gas seal, can dissolve hydrogen during exposure in high-pressure hydrogen gas. Dissolved hydrogen molecules were detected by solid state 1H NMR of the unfilled vulcanized acrylonitrile butadiene rubber. Two signals were observed at 4.5 ppm and 4.8 ppm, which were assignable to dissolved hydrogen, in the 1H NMR spectrum of NBR after being exposed 100 MPa hydrogen gas for 24 h at room temperature. These signals were shifted from that of gaseous hydrogen molecules. Assignment of the signals was confirmed by quantitative estimation of dissolved hydrogen and peak area of the signals.

Molecular dynamics simulations of hydrogen diffusion in aluminum

DOE PAGES

Zhou, X. W.; El Gabaly, F.; Stavila, V.; ...

2016-03-23

In this study, hydrogen diffusion impacts the performance of solid-state hydrogen storage materials and contributes to the embrittlement of structural materials under hydrogen-containing environments. In atomistic simulations, the diffusion energy barriers are usually calculated using molecular statics simulations where a nudged elastic band method is used to constrain a path connecting the two end points of an atomic jump. This approach requires prior knowledge of the “end points”. For alloy and defective systems, the number of possible atomic jumps with respect to local atomic configurations is tremendous. Even when these jumps can be exhaustively studied, it is still unclear howmore » they can be combined to give an overall diffusion behavior seen in experiments. Here we describe the use of molecular dynamics simulations to determine the overall diffusion energy barrier from the Arrhenius equation. This method does not require information about atomic jumps, and it has additional advantages, such as the ability to incorporate finite temperature effects and to determine the pre-exponential factor. As a test case for a generic method, we focus on hydrogen diffusion in bulk aluminum. We find that the challenge of this method is the statistical variation of the results. However, highly converged energy barriers can be achieved by an appropriate set of temperatures, output time intervals (for tracking hydrogen positions), and a long total simulation time. Our results help elucidate the inconsistencies of the experimental diffusion data published in the literature. The robust approach developed here may also open up future molecular dynamics simulations to rapidly study diffusion properties of complex material systems in multidimensional spaces involving composition and defects.« less

Impact of pH on hydrogen oxidizing redox processes in aquifers due to gas intrusions

NASA Astrophysics Data System (ADS)

Metzgen, Adrian; Berta, Marton; Dethlefsen, Frank; Ebert, Markus; Dahmke, Andreas

2017-04-01

Hydrogen production from excess energy and its storage can help increasing the efficiency of solar and wind in the energy mix. Therefore, hydrogen needs large-scale intermediate storage independent of the intended later use as hydrogen gas or as reactant to produce methane in the Sabatier process. A possible storage solution is using the geological subsurface such as caverns built in salt deposits or aquifers that are not used for drinking water production. However, underground storage of hydrogen gas potentially leads to accidental gas leakages into near-surface potable aquifers triggering subsequent geochemical processes. These leakages pose potential risks that are currently not sufficiently understood. To close this gap in knowledge, a high-pressure laboratory column system was used to simulate a hydrogen gas intrusion into a shallow aquifer. Water and sediment were gained from a sandy Pleistocene aquifer near Neumünster, Germany. In the first stage of the experiment, 100% hydrogen gas was used to simulate dissolved hydrogen concentrations between 800 and 4000 µM by varying pH2 between 2 and 15 bars. pH values rose to between 7.9 and 10.4, partly due to stripping CO2 from the groundwater used during H2 gas addition. In a second stage, the pH was regulated in a range of 6.7 to 7.9 by using a gas mixture of 99% H2 and 1% CO2 at 5 bars of total gas pressure. Observed processes included hydrogen oxidation, sulfate reduction, acetogenesis, formate production, and methanogenesis, which were independent of the hydrogen concentration. Hydrogen oxidation and sulfate reduction showed zeroth order reaction rates and rate constants (106 to 412 µM/h and 12 to 33 µM/h, respectively) in the pH range between 8 and 10. At pH levels between 7 and 8, both reactions started out faster near the column's inflow but then seemed limited towards the columns outflow, suggesting the dependence of sulfate reduction on the pH-value. Acetogenesis dominated the pH range between 8 and 10 (first order rate constants between 0.029 and 0.036 1/h). Between pH 7 and 8, acetogenesis showed a linear trend (zeroth order rates between 3 and 5 µM/h) whereas formate production became the main process (zeroth order rates between 38 to 197 µM/h) together with methanogenesis as a minor process. The results indicated a strong dependency of the biogeochemical hydrogenotrophic redox reactions on the pH milieu. Thus, pH buffers such as dissolved or solid phase carbonates should be taken into account when predicting effects a hydrogen leakage may have on shallow aquifers. Additionally, parameters derived from the observed processes and their rates allow the design of a process based numerical model simulating a hydrogen intrusion into a shallow aquifer. Consequently the presented outcomes allow an exemplary quantification of the resulting geochemical effects. This study was carried out within the ANGUS+ project and was funded by the German Federal Ministry of Education and Research (BMBF) energy storage funding initiative.

Facile solid-state synthesis of Ni@C nanosheet-assembled hierarchical network for high-performance lithium storage

NASA Astrophysics Data System (ADS)

Gu, Jinghe; Li, Qiyun; Zeng, Pan; Meng, Yulin; Zhang, Xiukui; Wu, Ping; Zhou, Yiming

2017-08-01

Micro/nano-architectured transition-metal@C hybrids possess unique structural and compositional features toward lithium storage, and are thus expected to manifest ideal anodic performances in advanced lithium-ion batteries (LIBs). Herein, we propose a facile and scalable solid-state coordination and subsequent pyrolysis route for the formation of a novel type of micro/nano-architectured transition-metal@C hybrid (i.e., Ni@C nanosheet-assembled hierarchical network, Ni@C network). Moreover, this coordination-pyrolysis route has also been applied for the construction of bare carbon network using zinc salts instead of nickel salts as precursors. When applied as potential anodic materials in LIBs, the Ni@C network exhibits Ni-content-dependent electrochemical performances, and the partially-etched Ni@C network manifests markedly enhanced Li-storage performances in terms of specific capacities, cycle life, and rate capability than the pristine Ni@C network and carbon network. The proposed solid-state coordination and pyrolysis strategy would open up new opportunities for constructing micro/nano-architectured transition-metal@C hybrids as advanced anode materials for LIBs.

IEA agreement on the production and utilization of hydrogen: 2000 annual report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elam, Carolyn C.

2001-12-01

The 2000 annual report of the IEA Hydrogen Agreement contains an overview of the agreement, including its guiding principles, latest strategic plan, and a report from the Chairman, Mr. Neil P. Rossmeissl, U.S. Department of Energy. Overviews of the National Hydrogen Programs of nine member countries are given: Canada, Japan, Lithuania, the Netherlands, Norway, Spain, Sweden, Switzerland, and the United States. Task updates are provided on the following annexes: Annex 12 - Metal Hydrides and Carbon for Hydrogen Storage, Annex 13 - Design and Optimization of Integrated Systems, Annex 14 - Photoelectrolytic Production of Hydrogen, and, Annex 15 - Photobiologicalmore » Production of Hydrogen.« less

Liquid–solid phase transition of hydrogen and deuterium in silica aerogel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Van Cleve, E.; Worsley, M. A.; Kucheyev, S. O., E-mail: kucheyev@llnl.gov

2014-10-28

Behavior of hydrogen isotopes confined in disordered low-density nanoporous solids remains essentially unknown. Here, we use relaxation calorimetry to study freezing and melting of H{sub 2} and D{sub 2} in an ∼85%-porous base-catalyzed silica aerogel. We find that liquid–solid transition temperatures of both isotopes inside the aerogel are depressed. The phase transition takes place over a wide temperature range of ∼4 K and non-trivially depends on the liquid filling fraction, reflecting the broad pore size distribution in the aerogel. Undercooling is observed for both H{sub 2} and D{sub 2} confined inside the aerogel monolith. Results for H{sub 2} and D{sub 2}more » are extrapolated to tritium-containing hydrogens with the quantum law of corresponding states.« less

Activated aluminum hydride hydrogen storage compositions and uses thereof

DOEpatents

Sandrock, Gary; Reilly, James; Graetz, Jason; Wegrzyn, James E.

2010-11-23

In one aspect, the invention relates to activated aluminum hydride hydrogen storage compositions containing aluminum hydride in the presence of, or absence of, hydrogen desorption stimulants. The invention particularly relates to such compositions having one or more hydrogen desorption stimulants selected from metal hydrides and metal aluminum hydrides. In another aspect, the invention relates to methods for generating hydrogen from such hydrogen storage compositions.

Experimental and theoretical studies of novel hydrogen diffuson in fullerite C_60

NASA Astrophysics Data System (ADS)

Fitzgerald, Stephen; Hannachi, Rym; Sholl, David; Sieber, Kurt; Gerogiorgis, Dimitrios

2004-03-01

Given the present interest in hydrogen storage within novel forms of carbon we have investigated the behavior of molecular H2 within solid fullerite C_60. Although C_60 will never be a practical storage medium, it does offer an ideal system to study the interaction of hydrogen within a well-characterized curved graphitic matrix. Our results based on infrared spectroscopy and loading isotherms indicate that isolated interstitial H2 bind preferentially in the lattice octahedral sites and diffuse by hopping between octahedral and tetrahedral sites^1. Parallel replica dynamics and minimum energy path calculations reveal an unexpected diffusion mechanism involving H2 molecules hopping into an already occupied octahedral site^2. This creates a short-lived H2 dimer, with a lower activation barrier for hopping that greatly enhances the diffusion rates. These calculations have been confirmed by experimental isotherm measurements and simulations using a rigorously derived lattice model that show a greatly reduced outgassing life-time with increasing H2 concentrations. ^1 S. A. FitzGerald, S. Forth and M. Rinkoski, Phys. Rev. B, 65, 140302 (2002). ^2 B. P. Uberuaga, A. F. Voter, K. K. Sieber, and D. S. Sholl, Phys. Rev. Lett., 91, 105901 (2003).

Pressure-induced orientational glass phase in molecular para-hydrogen.

PubMed

Schelkacheva, T I; Tareyeva, E E; Chtchelkatchev, N M

2009-02-01

We propose a theoretical description of a possible orientational glass transition in solid molecular para-hydrogen and ortho-deuterium under pressure supposing that they are mixtures of J=0 and J=2 states of molecules. The theory uses the basic concepts and methods of standard spin-glass theory. We expect our orientational glass to correspond to the II' phase of the high-pressure hydrogen phase diagram.

New insights into designing metallacarborane based room temperature hydrogen storage media.

PubMed

Bora, Pankaj Lochan; Singh, Abhishek K

2013-10-28

Metallacarboranes are promising towards realizing room temperature hydrogen storage media because of the presence of both transition metal and carbon atoms. In metallacarborane clusters, the transition metal adsorbs hydrogen molecules and carbon can link these clusters to form metal organic framework, which can serve as a complete storage medium. Using first principles density functional calculations, we chalk out the underlying principles of designing an efficient metallacarborane based hydrogen storage media. The storage capacity of hydrogen depends upon the number of available transition metal d-orbitals, number of carbons, and dopant atoms in the cluster. These factors control the amount of charge transfer from metal to the cluster, thereby affecting the number of adsorbed hydrogen molecules. This correlation between the charge transfer and storage capacity is general in nature, and can be applied to designing efficient hydrogen storage systems. Following this strategy, a search for the best metallacarborane was carried out in which Sc based monocarborane was found to be the most promising H2 sorbent material with a 9 wt.% of reversible storage at ambient pressure and temperature.

New insights into designing metallacarborane based room temperature hydrogen storage media

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bora, Pankaj Lochan; Singh, Abhishek K.

Metallacarboranes are promising towards realizing room temperature hydrogen storage media because of the presence of both transition metal and carbon atoms. In metallacarborane clusters, the transition metal adsorbs hydrogen molecules and carbon can link these clusters to form metal organic framework, which can serve as a complete storage medium. Using first principles density functional calculations, we chalk out the underlying principles of designing an efficient metallacarborane based hydrogen storage media. The storage capacity of hydrogen depends upon the number of available transition metal d-orbitals, number of carbons, and dopant atoms in the cluster. These factors control the amount of chargemore » transfer from metal to the cluster, thereby affecting the number of adsorbed hydrogen molecules. This correlation between the charge transfer and storage capacity is general in nature, and can be applied to designing efficient hydrogen storage systems. Following this strategy, a search for the best metallacarborane was carried out in which Sc based monocarborane was found to be the most promising H{sub 2} sorbent material with a 9 wt.% of reversible storage at ambient pressure and temperature.« less

Assessment of feasible strategies for seasonal underground hydrogen storage in a saline aquifer

NASA Astrophysics Data System (ADS)

Sáinz-García, Alvaro; Abarca, Elena; Rubí, Violeta; Grandia, Fidel

2017-04-01

Renewable energies are unsteady, which results in temporary mismatches between demand and supply. The conversion of surplus energy to hydrogen and its storage in geological formations is one option to balance this energy gap. This study evaluates the feasibility of seasonal storage of hydrogen produced from wind power in Castilla-León region (northern Spain). A 3D multiphase numerical model is used to test different extraction well configurations during three annual injection-production cycles in a saline aquifer. Results demonstrate that underground hydrogen storage in saline aquifers can be operated with reasonable recovery ratios. A maximum hydrogen recovery ratio of 78%, which represents a global energy efficiency of 30%, has been estimated. Hydrogen upconing emerges as the major risk on saline aquifer storage. However, shallow extraction wells can minimize its effects. Steeply dipping geological structures are key for an efficient hydrogen storage.

Solid state recorders for airborne reconnaissance

NASA Astrophysics Data System (ADS)

Klang, Mark R.

2003-08-01

Solid state recorders have become the recorder of choice for meeting airborne ruggedized requirements for reconnaissance and flight test. The cost of solid state recorders have decreased over the past few years that they are now less expense than the traditional high speed tape recorders. CALCULEX, Inc manufactures solid state recorders called MONSSTR (Modular Non-volatile Solid State Recorder). MONSSTR is being used on many different platforms such as F/A-22, Global Hawk, F-14, F-15, F-16, U-2, RF-4, and Tornado. This paper will discuss the advantages of using solid state recorders to meet the airborne reconnaissance requirement and the ability to record instrumentation data. The CALCULEX recorder has the ability to record sensor data and flight test data in the same chassis. This is an important feature because it eliminates additional boxes on the aircraft. The major advantages to using a solid state recorder include; reliability, small size, light weight, and power. Solid state recorders also have a larger storage capacity and higher bandwidth capability than other recording devices.

Pillared Graphene: A New 3-D Innovative Network Nanostructure Augments Hydrogen Storage

NASA Astrophysics Data System (ADS)

Georgios, Dimitrakakis K.; Emmanuel, Tylianakis; George, Froudakis E.

2009-08-01

Nowadays, people have turned into finding an alternative power source for everyday applications. One of the most promising energy fuels is hydrogen. It can be used as an energy carrier at small portable devices (e.g. laptops and/or cell phones) up to larger, like cars. Hydrogen is considered as the perfect fuel. It can be burnt in combustion engines and the only by-product is water. For hydrogen-powered vehicles a big liming factor is the gas tank and is the reason for not using widely hydrogen in automobile applications. According to United States' Department of Energy (D.O.E.) the target for reversible hydrogen storage in mobile applications is 6% wt. and 45 gr. H2/L and these should be met by 2010. After their synthesis Carbon Nanotubes (CNTs) were considered as ideal candidates for hydrogen storage especially after some initially incorrect but invitingly results. As it was proven later, pristine carbon nanotubes cannot achieve D.O.E.'s targets in ambient conditions of pressure and temperature. Therefore, a way to increase their hydrogen storage capacity should be found. An attempt was done by doping CNTs with alkali metal atoms. Although the results were promising, even that increment was not enough. Consequently, new architectures were suggested as materials that could potentially enhance hydrogen storage. In this work a novel three dimensional (3-D) nanoporous carbon structure called Pillared Graphene (Figure 1) is proposed for augmented hydrogen storage in ambient conditions. Pillared Graphene consists of parallel graphene sheets and CNTs that act like pillars and support the graphene sheets. The entire structure (Figure 1) can be resembled like a building in its early stages of construction, where the floors are represented by graphene sheets and the pillars are the CNTs. As shown in Figure 1, CNTs do not penetrate the structure from top to bottom. Instead, they alternately go up and down, so that on the same plane do not exist two neighboring CNTs with the same orientation. In addition, the structure has no expanding limits and this is shown by the unfinished CNTs on the top and bottom of the structure (Figure 1). Obviously, the length and the intertube distance of the CNTs can be changed at will in order to have a material with tunable pores. This tailored porosity is a key aspect of our material and thus its usage can be extended to other applications besides hydrogen storage. The stability of the structure was determined by DFT calculations using the Turbomole ab-initio package. As it was shown by these calculations, our material is stable and in principle it can be formed. Its hydrogen storage capacity was then evaluated by Grand Canonical Monte Carlo (GCMC) calculations and the results showed a spectacular increase when Pillared Graphene was doped with lithium atoms. The increment on the loading when lithium atoms were present was so high that our material was able to store 6.1% wt. and 41 gr./L of hydrogen under ambient conditions.

Hydrogen underground storage in siliciclastic reservoirs - intention and topics of the H2STORE project

NASA Astrophysics Data System (ADS)

Pudlo, Dieter; Ganzer, Leonhard; Henkel, Steven; Liebscher, Axel; Kühn, Michael; De Lucia, Marco; Panfilov, Michel; Pilz, Peter; Reitenbach, Viktor; Albrecht, Daniel; Würdemann, Hilke; Gaupp, Reinhard

2013-04-01

The transfer of energy supply from nuclear and CO2-emitting power generation to renewable energy production sources is strongly reliant to the potential of storing high capacities of energy in a safe and reliable way in time spans of several months. One conceivable option can be the storage of hydrogen and (related) synthetic natural gas (SNG) production in appropriate underground structures, like salt caverns and pore space reservoirs. Successful storage of hydrogen in the form of town gas in salt caverns has been proven in several demonstration projects and can be considered as state of the art technology. However, salt structures have only limited importance for hydrogen storage due to only small cavern volumes and the limited occurrence of salt deposits suitable for flushing of cavern constructions. Thus, regarding potential high-volume storage sites, siliciclastic deposits like saline aquifers and depleted gas reservoirs are of increasing interest. Motivated by a project call and sponsored by the German government the H2STORE ("Hydrogen to Store") collaborative project will investigate the feasibility and the requirements for pore space storage of hydrogen. Thereby depleted gas reservoirs are a major concern of this study. This type of geological structure is chosen because of their well investigated geological settings and proved sealing capacities, which already enable a present (and future) use as natural (and synthetic) reservoir gas storages. Nonetheless hydrogen and hydrocarbon in porous media exhibit major differences in physico-chemical behaviour, essentially due to the high diffusivity and reactivity of hydrogen. The biotic and abiotic reactions of hydrogen with rocks and fluids will be necessary observed in siliciclastic sediments which consist of numerous inorganic and organic compounds and comprise original formation fluids. These features strongly control petrophysical behaviour (e.g. porosity, permeability) and therefore fluid (hydrogen) migration. To reveal the relevance of these interactions and their impact on petrophysics and fluid mechanics in H2STORE six subprojects are included, which are devoted to various aspects of hydrogen storage in pore space reservoirs. The analytical and (laboratory) experimental studies will be based on rock and fluid samples issued from different reservoir sandstone and cap rock mudstone types originated from different depths all over Germany. Thereby data on sedimentological, geochemical, mineralogical, hydrochemical, petrophysical and microbiological rock composition will be gained. These studies will be completed with conceptual mathematical and numerical modelling of dynamic reservoir processes, including basin/facies burial evolution, mineralogical alteration, hydro-/geochemical reactions and gas mixing processes coupled with population dynamics of methanogenic microorganisms and dynamic displacement instability effects. The estimation of the hydrogen impact on reservoir behaviour of different rock types at depths will enable an evaluation of the feasibility of "Eco-/Green" methane and synthetic natural gas (SNG) generation by hydrogen reaction with CO2. The verification/falsification of specific processes will also enhance predictions on the operational reliability, the ecological tolerance, and the economic efficiency of future energy storing plants. These aspects are main motivations for any industrial investors and the public acceptance of such new technologies within the framework of an overall power supply by renewable energy production.

Lifecycle Verification of Tank Liner Polymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anovitz, Lawrence; Smith, Barton

2014-03-01

This report describes a method that was developed for the purpose of assessing the durability of thermoplastic liners used in a Type IV hydrogen storage tank during the tank s expected service life. In the method, a thermoplastic liner specimen is cycled between the maximum and minimum expected working temperatures while it is differentially pressurized with high-pressure hydrogen gas. The number of thermal cycling intervals corresponds to those expected within the tank s design lifetime. At prescribed intervals, hydrogen permeation measurements are done in situ to assess the ability of the liner specimen to maintain its hydrogen barrier properties andmore » to model its permeability over the tank lifetime. Finally, the model is used to assess whether the steady-state leakage rate in the tank could potentially exceed the leakage specification for hydrogen fuel cell passenger vehicles. A durability assessment was performed on a specimen of high-density polyethylene (HDPE) that is in current use as a tank liner. Hydrogen permeation measurements were performed on several additional tank liner polymers as well as novel polymers proposed for use as storage tank liners and hydrogen barrier materials. The following technical barriers from the Fuel Cell Technologies Program MYRDD were addressed by the project: D. Durability of on-board storage systems lifetime of at least 1500 cycles G. Materials of construction vessel containment that is resistant to hydrogen permeation M. Lack of Tank Performance Data and Understanding of Failure Mechanisms And the following technical targets1 for on-board hydrogen storage systems R&D were likewise addressed: Operational cycle life (1/4 tank to full) FY 2017: 1500 cycles; Ultimate: 1500 cycles Environmental health & safety Permeation and leakage: Meets or exceeds applicable standards Loss of useable H2: FY 2017: 0.05 g/h/kg H2; Ultimate: 0.05 g/h/kg H2« less

Costs of Storing and Transporting Hydrogen

DOE Office of Scientific and Technical Information (OSTI.GOV)

Amos, W. A.

An analysis was performed to estimate the costs associated with storing and transporting hydrogen. These costs can be added to a hydrogen production cost to determine the total delivered cost of hydrogen. Storage methods analyzed included compressed gas, liquid hydrogen, metal hydride, and underground storage. Major capital and operating costs were considered over a range of production rates and storage times.

Preparation and characterization of mechanically alloyed AB3-type based material LaMg2Ni5Al4 and its solid-gaz hydrogen storage reaction

NASA Astrophysics Data System (ADS)

Jaafar, Hassen; Aymard, Luc; Dachraoui, Walid; Demortière, Arnaud; Abdellaoui, Mohieddine

2018-04-01

We developed in the present paper the synthesis of a new AB3-type compound LaMg2Ni5Al4 by mechanical alloying (MA) process. ​​X-ray diffraction analysis (XRD) was used to determine the structural properties and the phase evolution of the powder mixtures. Two different synthesis pathways have been investigated. The first starting from elemental metals and the second from a mixture of two binary compounds LaNi5 (CaCu5-type structure, P6/mmm space group) and Al(Mg) solid solution (cubic Fm-3 m space group). The results show multiphase alloys which contain LaMg2Ni5Al4 main phase with hexagonal PuNi3-type structure (R-3 m space group). Rietveld analysis shows that using a planetary ball mill, we obtain a good yield of LaMg2Ni5Al4 compound after 5 h of mechanical alloying for both synthesis pathways. TEM analysis confirmed XRD results. SEM-EDX analysis of the final product was in agreement with the nominal chemical formula. A setup of possible solid-gaz hydrogenation reaction will be described so far at the end of this work. Electrochemical results demonstrate evidence on hydrogen absorption in the AB3 material and the discharge capacity was equal to 5.9 H/f.u.

Using Solid State Disk Array as a Cache for LHC ATLAS Data Analysis

NASA Astrophysics Data System (ADS)

Yang, W.; Hanushevsky, A. B.; Mount, R. P.; Atlas Collaboration

2014-06-01

User data analysis in high energy physics presents a challenge to spinning-disk based storage systems. The analysis is data intense, yet reads are small, sparse and cover a large volume of data files. It is also unpredictable due to users' response to storage performance. We describe here a system with an array of Solid State Disk as a non-conventional, standalone file level cache in front of the spinning disk storage to help improve the performance of LHC ATLAS user analysis at SLAC. The system uses several days of data access records to make caching decisions. It can also use information from other sources such as a work-flow management system. We evaluate the performance of the system both in terms of caching and its impact on user analysis jobs. The system currently uses Xrootd technology, but the technique can be applied to any storage system.

Solid-state supercapacitors with rationally designed heterogeneous electrodes fabricated by large area spray processing for wearable energy storage applications.

PubMed

Huang, Chun; Zhang, Jin; Young, Neil P; Snaith, Henry J; Grant, Patrick S

2016-05-10

Supercapacitors are in demand for short-term electrical charge and discharge applications. Unlike conventional supercapacitors, solid-state versions have no liquid electrolyte and do not require robust, rigid packaging for containment. Consequently they can be thinner, lighter and more flexible. However, solid-state supercapacitors suffer from lower power density and where new materials have been developed to improve performance, there remains a gap between promising laboratory results that usually require nano-structured materials and fine-scale processing approaches, and current manufacturing technology that operates at large scale. We demonstrate a new, scalable capability to produce discrete, multi-layered electrodes with a different material and/or morphology in each layer, and where each layer plays a different, critical role in enhancing the dynamics of charge/discharge. This layered structure allows efficient utilisation of each material and enables conservative use of hard-to-obtain materials. The layered electrode shows amongst the highest combinations of energy and power densities for solid-state supercapacitors. Our functional design and spray manufacturing approach to heterogeneous electrodes provide a new way forward for improved energy storage devices.

Storage of multiple single-photon pulses emitted from a quantum dot in a solid-state quantum memory.

PubMed

Tang, Jian-Shun; Zhou, Zong-Quan; Wang, Yi-Tao; Li, Yu-Long; Liu, Xiao; Hua, Yi-Lin; Zou, Yang; Wang, Shuang; He, De-Yong; Chen, Geng; Sun, Yong-Nan; Yu, Ying; Li, Mi-Feng; Zha, Guo-Wei; Ni, Hai-Qiao; Niu, Zhi-Chuan; Li, Chuan-Feng; Guo, Guang-Can

2015-10-15

Quantum repeaters are critical components for distributing entanglement over long distances in presence of unavoidable optical losses during transmission. Stimulated by the Duan-Lukin-Cirac-Zoller protocol, many improved quantum repeater protocols based on quantum memories have been proposed, which commonly focus on the entanglement-distribution rate. Among these protocols, the elimination of multiple photons (or multiple photon-pairs) and the use of multimode quantum memory are demonstrated to have the ability to greatly improve the entanglement-distribution rate. Here, we demonstrate the storage of deterministic single photons emitted from a quantum dot in a polarization-maintaining solid-state quantum memory; in addition, multi-temporal-mode memory with 1, 20 and 100 narrow single-photon pulses is also demonstrated. Multi-photons are eliminated, and only one photon at most is contained in each pulse. Moreover, the solid-state properties of both sub-systems make this configuration more stable and easier to be scalable. Our work will be helpful in the construction of efficient quantum repeaters based on all-solid-state devices.

Storage of multiple single-photon pulses emitted from a quantum dot in a solid-state quantum memory

PubMed Central

Tang, Jian-Shun; Zhou, Zong-Quan; Wang, Yi-Tao; Li, Yu-Long; Liu, Xiao; Hua, Yi-Lin; Zou, Yang; Wang, Shuang; He, De-Yong; Chen, Geng; Sun, Yong-Nan; Yu, Ying; Li, Mi-Feng; Zha, Guo-Wei; Ni, Hai-Qiao; Niu, Zhi-Chuan; Li, Chuan-Feng; Guo, Guang-Can

2015-01-01

Quantum repeaters are critical components for distributing entanglement over long distances in presence of unavoidable optical losses during transmission. Stimulated by the Duan–Lukin–Cirac–Zoller protocol, many improved quantum repeater protocols based on quantum memories have been proposed, which commonly focus on the entanglement-distribution rate. Among these protocols, the elimination of multiple photons (or multiple photon-pairs) and the use of multimode quantum memory are demonstrated to have the ability to greatly improve the entanglement-distribution rate. Here, we demonstrate the storage of deterministic single photons emitted from a quantum dot in a polarization-maintaining solid-state quantum memory; in addition, multi-temporal-mode memory with 1, 20 and 100 narrow single-photon pulses is also demonstrated. Multi-photons are eliminated, and only one photon at most is contained in each pulse. Moreover, the solid-state properties of both sub-systems make this configuration more stable and easier to be scalable. Our work will be helpful in the construction of efficient quantum repeaters based on all-solid-state devices. PMID:26468996

Reversible Interconversion between 2,5-Dimethylpyrazine and 2,5-Dimethylpiperazine by Iridium-Catalyzed Hydrogenation/Dehydrogenation for Efficient Hydrogen Storage.

PubMed

Fujita, Ken-Ichi; Wada, Tomokatsu; Shiraishi, Takumi

2017-08-28

A new hydrogen storage system based on the hydrogenation and dehydrogenation of nitrogen heterocyclic compounds, employing a single iridium catalyst, has been developed. Efficient hydrogen storage using relatively small amounts of solvent compared with previous systems was achieved by this new system. Reversible transformations between 2,5-dimethylpyrazine and 2,5-dimethylpiperazine, accompanied by the uptake and release of three equivalents of hydrogen, could be repeated almost quantitatively at least four times without any loss of efficiency. Furthermore, hydrogen storage under solvent-free conditions was also accomplished. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-pressure torsion for new hydrogen storage materials.

PubMed

Edalati, Kaveh; Akiba, Etsuo; Horita, Zenji

2018-01-01

High-pressure torsion (HPT) is widely used as a severe plastic deformation technique to create ultrafine-grained structures with promising mechanical and functional properties. Since 2007, the method has been employed to enhance the hydrogenation kinetics in different Mg-based hydrogen storage materials. Recent studies showed that the method is effective not only for increasing the hydrogenation kinetics but also for improving the hydrogenation activity, for enhancing the air resistivity and more importantly for synthesizing new nanostructured hydrogen storage materials with high densities of lattice defects. This manuscript reviews some major findings on the impact of HPT process on the hydrogen storage performance of different titanium-based and magnesium-based materials.

Hydrogen storage in a combined M.sub.xAlH.sub.6/M'.sub.y(NH.sub.2).sub.z system and methods of making and using the same

DOEpatents

Lu, Jun [Salt Lake City, UT; Fang, Zhigang Zak [Salt Lake City, UT; Sohn, Hong Yong [Salt Lake City, UT

2012-04-03

As a promising clean fuel for vehicles, hydrogen can be used for propulsion, either directly or in fuel cells. Hydrogen storage compositions having high storage capacity, good dehydrogenation kinetics, and hydrogen release and uptake reactions which are reversible are disclosed and described. Generally a hydrogen storage composition of a metal aluminum hexahydride and a metal amide can be used. A combined system (Li.sub.3AIH.sub.6/3LiNH.sub.2) with a very high inherent hydrogen capacity (7.3 wt %) can be carried out at moderate temperatures, and with approximately 95% of that inherent hydrogen storage capacity (7.0%) is reversible over repeated cycling of release and uptake.

Theoretical and Experimental Flow Cell Studies of a Hydrogen-Bromine Fuel Cell, Part 1. M.S. Thesis. Final Report

NASA Technical Reports Server (NTRS)

Savinell, R. F.; Fritts, S. D.

1986-01-01

There is increasing interest in hydrogen-bromine fuel cells as both primary and regenerative energy storage systems. One promising design for a hydrogen-bromine fuel cell is a negative half cell having only a gas phase, which is separated by a cationic exchange membrane from a positive half cell having an aqueous electrolyte. The hydrogen gas and the aqueous bromide solution are stored external to the cell. In order to calculate the energy storage capacity and to predict and assess the performance of a single cell, the open circuit potential (OCV) must be estimated for different states of change, under various conditions. Theoretical expressions were derived to estimate the OCV of a hydrogen-bromine fuel cell. In these expressions temperature, hydrogen pressure, and bromine and hydrobromic acid concentrations were taken into consideration. Also included are the effects of the Nafion membrance separator and the various bromide complex species. Activity coefficients were taken into account in one of the expressions. The sensitivity of these parameters on the calculated OCV was studied.

Two-tier tube-trailer pressure consolidation operation method for hydrogen refueling station cost reduction

DOE PAGES

Reddi, Krishna; Elgowainy, Amgad; Rustagi, Neha; ...

2018-01-10

An operation strategy known as two-tier “pressure consolidation” of delivered tube-trailers (or equivalent supply storage) has been developed to maximize the throughput at gaseous hydrogen refueling stations (HRSs) for fuel cell electric vehicles (FCEVs). The high capital costs of HRSs and the consequent high investment risk are deterring growth of the infrastructure needed to promote the deployment of FCEVs. Stations supplied by gaseous hydrogen will be necessary for FCEV deployment in both the near and long term. Here, the two-tier pressure consolidation method enhances gaseous HRSs in the following ways: (1) reduces the capital cost compared with conventional stations, asmore » well as those operating according to the original pressure consolidation approach described by Elgowainy et al. (2014) [1], (2) minimizes pressure cycling of HRS supply storage relative to the original pressure consolidation approach; and (3) increases use of the station’s supply storage (or delivered tube-trailers) while maintaining higher state-of-charge vehicle fills.« less

Two-tier tube-trailer pressure consolidation operation method for hydrogen refueling station cost reduction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reddi, Krishna; Elgowainy, Amgad; Rustagi, Neha

An operation strategy known as two-tier “pressure consolidation” of delivered tube-trailers (or equivalent supply storage) has been developed to maximize the throughput at gaseous hydrogen refueling stations (HRSs) for fuel cell electric vehicles (FCEVs). The high capital costs of HRSs and the consequent high investment risk are deterring growth of the infrastructure needed to promote the deployment of FCEVs. Stations supplied by gaseous hydrogen will be necessary for FCEV deployment in both the near and long term. Here, the two-tier pressure consolidation method enhances gaseous HRSs in the following ways: (1) reduces the capital cost compared with conventional stations, asmore » well as those operating according to the original pressure consolidation approach described by Elgowainy et al. (2014) [1], (2) minimizes pressure cycling of HRS supply storage relative to the original pressure consolidation approach; and (3) increases use of the station’s supply storage (or delivered tube-trailers) while maintaining higher state-of-charge vehicle fills.« less

In Pursuit of Sustainable Hydrogen Storage with Boron-Nitride Fullerene as the Storage Medium.

PubMed

Ganguly, Gaurab; Malakar, Tanmay; Paul, Ankan

2016-06-22

Using well calibrated DFT studies we predict that experimentally synthesized B24 N24 fullerene can serve as a potential reversible chemical hydrogen storage material with hydrogen-gas storage capacity up to 5.13 wt %. Our theoretical studies show that hydrogenation and dehydrogenation of the fullerene framework can be achieved at reasonable rates using existing metal-free hydrogenating agents and base metal-containing dehydrogenation catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quasi-Solid-State Rechargeable Li-O2 Batteries with High Safety and Long Cycle Life at Room Temperature.

PubMed

Cho, Sung Man; Shim, Jimin; Cho, Sung Ho; Kim, Jiwoong; Son, Byung Dae; Lee, Jong-Chan; Yoon, Woo Young

2018-05-09

As interest in electric vehicles and mass energy storage systems continues to grow, Li-O 2 batteries are attracting much attention as a candidate for next-generation energy storage systems owing to their high energy density. However, safety problems related to the use of lithium metal anodes have hampered the commercialization of Li-O 2 batteries. Herein, we introduced a quasi-solid polymer electrolyte with excellent electrochemical, chemical, and thermal stabilities into Li-O 2 batteries. The ion-conducting QSPE was prepared by gelling a polymer network matrix consisting of poly(ethylene glycol) methyl ether methacrylate, methacrylated tannic acid, lithium trifluoromethanesulfonate, and nanofumed silica with a small amount of liquid electrolyte. The quasi-solid-state Li-O 2 cell consisted of a lithium powder anode, a quasi-solid polymer electrolyte, and a Pd 3 Co/multiwalled carbon nanotube cathode, which enhanced the electrochemical performance of the cell. This cell, which exhibited improved safety owing to the suppression of lithium dendrite growth, achieved a lifetime of 125 cycles at room temperature. These results show that the introduction of a quasi-solid electrolyte is a potentially new alternative for the commercialization of solid-state Li-O 2 batteries.

Computational study of sodium magnesium hydride for hydrogen storage applications

NASA Astrophysics Data System (ADS)

Soto Valle, Fernando Antonio

Hydrogen offers considerable potential benefits as an energy carrier. However, safe and convenient storage of hydrogen is one of the biggest challenges to be resolved in the near future. Sodium magnesium hydride (NaMgH 3) has attracted attention as a hydrogen storage material due to its light weight and high volumetric hydrogen density of 88 kg/m3. Despite the advantages, hydrogen release in this material occurs at approximately 670 K, which is well above the operable range for on-board hydrogen storage applications. In this regard, hydrogen release may be facilitated by substitution doping of transition-metals. This dissertation describes first-principles computational methods that enable an examination of the hydrogen storage properties of NaMgH3. The novel contribution of this dissertation includes a combination of crystal, supercell, and surface slab calculations that provides new and relevant insights about the thermodynamic and kinetic properties of NaMgH3. First-principles calculations on the pristine crystal structure provide a starting reference point for the study of this material as a hydrogen storage material. To the best of our knowledge, it is reported for the first time that a 25% mol doping concentration of Ti, V, Cu, and Zn dopants reduce the reaction enthalpy of hydrogen release for NaMgH3. The largest decrease in the DeltaH(298 K) value corresponds to the Zn-doped model (67.97 kJ/(mol H2)). Based on cohesive energy calculations, it is reported that at the 6.25% mol doping concentration, Ti and Zn dopants are the only transition metals that destabilize the NaMgH3 hydride. In terms of hydrogen removal energy, it is quantified that the energy cost to remove a single H from the Ti-doped supercell model is 0.76 eV, which is lower with respect to the pristine model and other prototypical hydrogen storage materials. From the calculation of electronic properties such as density of states, electron density difference, and charge population analysis schemes it is shown that the effectiveness of these two dopants is due to the modified chemical bonding induce by the overlap of d orbitals. For the surface slab calculations, a key finding is that the preferred layer for the simultaneous substitution of Ti and Zn dopants at two different Na sites is the outermost layer with substitution energy values of -5.27 eV and -5.24 eV, respectively. The kinetic barrier for hydrogen desorption from the (001) surface is studied using DFT calculations, LST/QST, and NEB methods. We find that for the pristine model, the direct recombination of a H 2 molecule has a kinetic barrier of 1.16 eV. More importantly, we find that the calculated kinetic barrier of H2 desorption when the (001) surface is co-doped with Ti and Zn is 0.42 eV. These results show that the combined use of a Ti dopant and a Zn dopant is the best mix for reducing the energy barrier to release hydrogen from the (001) NaMgH3 surface.

Hydrogen storage in the form of metal hydrides

NASA Technical Reports Server (NTRS)

Zwanziger, M. G.; Santana, C. C.; Santos, S. C.

1984-01-01

Reversible reactions between hydrogen and such materials as iron/titanium and magnesium/ nickel alloy may provide a means for storing hydrogen fuel. A demonstration model of an iron/titanium hydride storage bed is described. Hydrogen from the hydride storage bed powers a converted gasoline electric generator.

Influence of drying restraint on physical and mechanical properties of nanofibrillated cellulose films

Treesearch

Carlos Baez; John Considine; Robert Rowlands

2014-01-01

Nanofibrillated cellulose (NFC) is a renewable and biodegradable fibril that possesses high strength and stiffness resulting from high level hydrogen bonding. Films made from NFC shrink and distort as they transition from a wet state (20 wt% solids) to a state of moisture equilibrium (90 wt% solids at 50 % RH, 23 °C). Material distortions are driven by development of...

Hydrogen Storage Technologies for Future Energy Systems.

PubMed

Preuster, Patrick; Alekseev, Alexander; Wasserscheid, Peter

2017-06-07

Future energy systems will be determined by the increasing relevance of solar and wind energy. Crude oil and gas prices are expected to increase in the long run, and penalties for CO 2 emissions will become a relevant economic factor. Solar- and wind-powered electricity will become significantly cheaper, such that hydrogen produced from electrolysis will be competitively priced against hydrogen manufactured from natural gas. However, to handle the unsteadiness of system input from fluctuating energy sources, energy storage technologies that cover the full scale of power (in megawatts) and energy storage amounts (in megawatt hours) are required. Hydrogen, in particular, is a promising secondary energy vector for storing, transporting, and distributing large and very large amounts of energy at the gigawatt-hour and terawatt-hour scales. However, we also discuss energy storage at the 120-200-kWh scale, for example, for onboard hydrogen storage in fuel cell vehicles using compressed hydrogen storage. This article focuses on the characteristics and development potential of hydrogen storage technologies in light of such a changing energy system and its related challenges. Technological factors that influence the dynamics, flexibility, and operating costs of unsteady operation are therefore highlighted in particular. Moreover, the potential for using renewable hydrogen in the mobility sector, industrial production, and the heat market is discussed, as this potential may determine to a significant extent the future economic value of hydrogen storage technology as it applies to other industries. This evaluation elucidates known and well-established options for hydrogen storage and may guide the development and direction of newer, less developed technologies.

Hydrogen-bromine fuel cell advance component development

NASA Technical Reports Server (NTRS)

Charleston, Joann; Reed, James

1988-01-01

Advanced cell component development is performed by NASA Lewis to achieve improved performance and longer life for the hydrogen-bromine fuel cells system. The state-of-the-art hydrogen-bromine system utilizes the solid polymer electrolyte (SPE) technology, similar to the SPE technology developed for the hydrogen-oxygen fuel cell system. These studies are directed at exploring the potential for this system by assessing and evaluating various types of materials for cell parts and electrode materials for Bromine-hydrogen bromine environment and fabricating experimental membrane/electrode-catalysts by chemical deposition.

Hydrogen: A Promising Fuel and Energy Storage Solution - Continuum

Science.gov Websites

Magazine | NREL Hydrogen: A Promising Fuel and Energy Storage Solution Fuel cell electric Ainscough, NREL Hydrogen: A Promising Fuel and Energy Storage Solution Electrolysis-generated hydrogen may provide a solution to fluctuations in renewable-sourced energy. As electricity from renewable resources

Enhanced catalytic hydrogenation activity of Ni/reduced graphene oxide nanocomposite prepared by a solid-state method

NASA Astrophysics Data System (ADS)

Li, Yizhao; Cao, Yali; Jia, Dianzeng

2018-01-01

A simple solid-state method has been applied to synthesize Ni/reduced graphene oxide (Ni/rGO) nanocomposite under ambient condition. Ni nanoparticles with size of 10-30 nm supported on reduced graphene oxide (rGO) nanosheets are obtained through one-pot solid-state co-reduction among nickel chloride, graphene oxide, and sodium borohydride. The Ni/rGO nanohybrid shows enhanced catalytic activity toward the reduction of p-nitrophenol (PNP) into p-aminophenol compared with Ni nanoparticles. The results of kinetic research display that the pseudo-first-order rate constant for hydrogenation reaction of PNP with Ni/rGO nanocomposite is 7.66 × 10-3 s-1, which is higher than that of Ni nanoparticles (4.48 × 10-3 s-1). It also presents superior turnover frequency (TOF, 5.36 h-1) and lower activation energy ( E a, 29.65 kJ mol-1) in the hydrogenation of PNP with Ni/rGO nanocomposite. Furthermore, composite catalyst can be magnetically separated and reused for five cycles. The large surface area and high electron transfer property of rGO support are beneficial for good catalytic performance of Ni/rGO nanocomposite. Our study demonstrates a simple approach to fabricate metal-rGO heterogeneous nanostructures with advanced functions.

Hydrogen Energy Storage (HES) and Power-to-Gas Economic Analysis; NREL (National Renewable Energy Laboratory)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eichman, Joshua

This presentation summarizes opportunities for hydrogen energy storage and power-to-gas and presents the results of a market analysis performed by the National Renewable Energy Laboratory to quantify the value of energy storage. Hydrogen energy storage and power-to-gas systems have the ability to integrate multiple energy sectors including electricity, transportation, and industrial. On account of the flexibility of hydrogen systems, there are a variety of potential system configurations. Each configuration will provide different value to the owner, customers and grid system operator. This presentation provides an economic comparison of hydrogen storage, power-to-gas and conventional storage systems. The total cost is comparedmore » to the revenue with participation in a variety of markets to assess the economic competitiveness. It is found that the sale of hydrogen for transportation or industrial use greatly increases competitiveness. Electrolyzers operating as demand response devices (i.e., selling hydrogen and grid services) are economically competitive, while hydrogen storage that inputs electricity and outputs only electricity have an unfavorable business case. Additionally, tighter integration with the grid provides greater revenue (e.g., energy, ancillary service and capacity markets are explored). Lastly, additional hours of storage capacity is not necessarily more competitive in current energy and ancillary service markets and electricity markets will require new mechanisms to appropriately compensate long duration storage devices.« less

Storage, transmission and distribution of hydrogen

NASA Technical Reports Server (NTRS)

Kelley, J. H.; Hagler, R., Jr.

1979-01-01

Current practices and future requirements for the storage, transmission and distribution of hydrogen are reviewed in order to identify inadequacies to be corrected before hydrogen can achieve its full potential as a substitute for fossil fuels. Consideration is given to the storage of hydrogen in underground solution-mined salt caverns, portable high-pressure containers and dewars, pressure vessels and aquifers and as metal hydrides, hydrogen transmission in evacuated double-walled insulated containers and by pipeline, and distribution by truck and internal distribution networks. Areas for the improvement of these techniques are indicated, and these technological deficiencies, including materials development, low-cost storage and transmission methods, low-cost, long-life metal hydrides and novel methods for hydrogen storage, are presented as challenges for research and development.

Highly efficient hydrogen storage system based on ammonium bicarbonate/formate redox equilibrium over palladium nanocatalysts.

PubMed

Su, Ji; Yang, Lisha; Lu, Mi; Lin, Hongfei

2015-03-01

A highly efficient, reversible hydrogen storage-evolution process has been developed based on the ammonium bicarbonate/formate redox equilibrium over the same carbon-supported palladium nanocatalyst. This heterogeneously catalyzed hydrogen storage system is comparable to the counterpart homogeneous systems and has shown fast reaction kinetics of both the hydrogenation of ammonium bicarbonate and the dehydrogenation of ammonium formate under mild operating conditions. By adjusting temperature and pressure, the extent of hydrogen storage and evolution can be well controlled in the same catalytic system. Moreover, the hydrogen storage system based on aqueous-phase ammonium formate is advantageous owing to its high volumetric energy density. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen Storage for Aircraft Applications Overview

NASA Technical Reports Server (NTRS)

Colozza, Anthony J.; Kohout, Lisa (Technical Monitor)

2002-01-01

Advances in fuel cell technology have brought about their consideration as sources of power for aircraft. This power can be utilized to run aircraft systems or even provide propulsion power. One of the key obstacles to utilizing fuel cells on aircraft is the storage of hydrogen. An overview of the potential methods of hydrogen storage was compiled. This overview identifies various methods of hydrogen storage and points out their advantages and disadvantages relative to aircraft applications. Minimizing weight and volume are the key aspects to storing hydrogen within an aircraft. An analysis was performed to show how changes in certain parameters of a given storage system affect its mass and volume.

Mechanism of drug release from polymethacrylate-based extrudates and milled strands prepared by hot-melt extrusion.

PubMed

Albers, Jessica; Alles, Rainer; Matthée, Karin; Knop, Klaus; Nahrup, Julia Schulze; Kleinebudde, Peter

2009-02-01

The aim of the study was the formulation of solid dispersions of the poorly water-soluble drug celecoxib and a polymethacrylate carrier by hot-melt extrusion. The objectives were to elucidate the mechanism of drug release from obtained extrudates and milled strands addicted to the solid-state properties of the solid dispersions and to examine and eliminate stability problems occurring under storage, exposure of mechanical stress, and in vitro dissolution. Transparent extrudates containing up to 60% drug could be prepared with a temperature setting below the melting point of celecoxib. XRPD and DSC measurements indicated the formation of a glassy solid solution, where the drug is molecularly dispersed in the carrier. The amorphous state of the glassy solid solution could be maintained during the exposure of mechanical stress in a milling process, and was stable under storage for at least 6 months. Solid-state properties and SEM images of extrudates after dissolution indicated a carrier-controlled dissolution, whereby the drug is molecularly dispersed within the concentrated carrier layer. The glassy solid solution showed a 58-fold supersaturation in 0.1 N HCl within the first 10 min, which was followed by a recrystallization process. Recrystallization could be inhibited by an external addition of HPMC.

Multi-scale theoretical investigation of hydrogen storage in covalent organic frameworks.

PubMed

Tylianakis, Emmanuel; Klontzas, Emmanouel; Froudakis, George E

2011-03-01

The quest for efficient hydrogen storage materials has been the limiting step towards the commercialization of hydrogen as an energy carrier and has attracted a lot of attention from the scientific community. Sophisticated multi-scale theoretical techniques have been considered as a valuable tool for the prediction of materials storage properties. Such techniques have also been used for the investigation of hydrogen storage in a novel category of porous materials known as Covalent Organic Frameworks (COFs). These framework materials are consisted of light elements and are characterized by exceptional physicochemical properties such as large surface areas and pore volumes. Combinations of ab initio, Molecular Dynamics (MD) and Grand Canonical Monte-Carlo (GCMC) calculations have been performed to investigate the hydrogen adsorption in these ultra-light materials. The purpose of the present review is to summarize the theoretical hydrogen storage studies that have been published after the discovery of COFs. Experimental and theoretical studies have proven that COFs have comparable or better hydrogen storage abilities than other competitive materials such as MOF. The key factors that can lead to the improvement of the hydrogen storage properties of COFs are highlighted, accompanied with some recently presented theoretical multi-scale studies concerning these factors.

Composition and method for hydrogen storage

NASA Technical Reports Server (NTRS)

Mao, Wendy L. (Inventor); Mao, Ho-Kwang (Inventor)

2004-01-01

A method for hydrogen storage includes providing water and hydrogen gas to a containment volume, reducing the temperature of the water and hydrogen gas to form a hydrogen clathrate at a first cryogenic temperature and a first pressure and maintaining the hydrogen clathrate at second cryogenic temperature within a temperature range of up to 250 K to effect hydrogen storage. The low-pressure hydrogen hydrate includes H.sub.2 O molecules, H.sub.2 molecules and a unit cell including polyhedron cages of hydrogen-bonded frameworks of the H.sub.2 O molecules built around the H.sub.2 molecules.

Solid state electrolyte composites based on complex hydrides and metal doped fullerenes/fulleranes for batteries and electrochemical applications

DOEpatents

Zidan, Ragaiy; Teprovich, Jr., Joseph A.; Colon-Mercado, Hector R.; Greenway, Scott D.

2018-05-01

A LiBH₄--C₆₀ nanocomposite that displays fast lithium ionic conduction in the solid state is provided. The material is a homogenous nanocomposite that contains both LiBH₄ and a hydrogenated fullerene species. In the presence of C₆₀, the lithium ion mobility of LiBH₄ is significantly enhanced in the as prepared state when compared to pure LiBH₄. After the material is annealed the lithium ion mobility is further enhanced. Constant current cycling demonstrated that the material is stable in the presence of metallic lithium electrodes. The material can serve as a solid state electrolyte in a solid-state lithium ion battery.

High-pressure torsion for new hydrogen storage materials

PubMed Central

Edalati, Kaveh; Akiba, Etsuo; Horita, Zenji

2018-01-01

Abstract High-pressure torsion (HPT) is widely used as a severe plastic deformation technique to create ultrafine-grained structures with promising mechanical and functional properties. Since 2007, the method has been employed to enhance the hydrogenation kinetics in different Mg-based hydrogen storage materials. Recent studies showed that the method is effective not only for increasing the hydrogenation kinetics but also for improving the hydrogenation activity, for enhancing the air resistivity and more importantly for synthesizing new nanostructured hydrogen storage materials with high densities of lattice defects. This manuscript reviews some major findings on the impact of HPT process on the hydrogen storage performance of different titanium-based and magnesium-based materials. PMID:29511396

Design of a Hydrogen Community for Santa Monica

DTIC Science & Technology

2011-01-01

transportation of hydrogen fuel have been discussed. Cascade simulations were conducted for different compressor capacities and storage bank configurations...been discussed. Cascade simulations were conducted for different compressor capacities and storage bank configurations. Hydrogen dispensing using...tanks (Storage capacity of 198 kg of H2 at 350 and 700 bar), four compressors which assist in dispensing 400 kg of hydrogen in 14 hours, two hydrogen

1H, 13C, 15N NMR analysis of sildenafil base and citrate (Viagra) in solution, solid state and pharmaceutical dosage forms.

PubMed

Wawer, Iwona; Pisklak, Maciej; Chilmonczyk, Zdzisław

2005-08-10

Sildenafil citrate (SC) (Viagra) and sildenafil base in pure form are easily and unequivocally characterized by multinuclear NMR spectroscopy. Analysis of chemical shifts indicates that: (i) N6-H forms intramolecular hydrogen bonds, (ii) N25 is protonated in the salt and (iii) intermolecular OH...N hydrogen bonds involving N2 and N4 are present in the solid sildenafil citrate. 13C CPMAS NMR method has been proposed for the identification and quantitation of Viagra in its pharmaceutical formulations.

Facilitated ion transport in all-solid-state flexible supercapacitors.

PubMed

Choi, Bong Gill; Hong, Jinkee; Hong, Won Hi; Hammond, Paula T; Park, HoSeok

2011-09-27

The realization of highly flexible and all-solid-state energy-storage devices strongly depends on both the electrical properties and mechanical integrity of the constitutive materials and the controlled assembly of electrode and solid electrolyte. Herein we report the preparation of all-solid-state flexible supercapacitors (SCs) through the easy assembly of functionalized reduced graphene oxide (f-RGO) thin films (as electrode) and solvent-cast Nafion electrolyte membranes (as electrolyte and separator). In particular, the f-RGO-based SCs (f-RGO-SCs) showed a 2-fold higher specific capacitance (118.5 F/g at 1 A/g) and rate capability (90% retention at 30 A/g) compared to those of all-solid-state graphene SCs (62.3 F/g at 1A/g and 48% retention at 30 A/g). As proven by the 4-fold faster relaxation of the f-RGO-SCs than that of the RGO-SCs and more capacitive behavior of the former at the low-frequency region, these results were attributed to the facilitated ionic transport at the electrical double layer by means of the interfacial engineering of RGO by Nafion. Moreover, the superiority of all-solid-state flexible f-RGO-SCs was demonstrated by the good performance durability under the 1000 cycles of charging and discharging due to the mechanical integrity as a consequence of the interconnected networking structures. Therefore, this research provides new insight into the rational design and fabrication of all-solid-state flexible energy-storage devices as well as the fundamental understanding of ion and charge transport at the interface. © 2011 American Chemical Society

NO ICE HYDROGENATION: A SOLID PATHWAY TO NH{sub 2}OH FORMATION IN SPACE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Congiu, Emanuele; Dulieu, Francois; Chaabouni, Henda

2012-05-01

Icy dust grains in space act as catalytic surfaces onto which complex molecules form. These molecules are synthesized through exothermic reactions from precursor radicals and, mostly, hydrogen atom additions. Among the resulting products are species of biological relevance, such as hydroxylamine-NH{sub 2}OH-a precursor molecule in the formation of amino acids. In this Letter, laboratory experiments are described that demonstrate NH{sub 2}OH formation in interstellar ice analogs for astronomically relevant temperatures via successive hydrogenation reactions of solid nitric oxide (NO). Inclusion of the experimental results in an astrochemical gas-grain model proves the importance of a solid-state NO+H reaction channel as amore » starting point for prebiotic species in dark interstellar clouds and adds a new perspective to the way molecules of biological importance may form in space.« less

Hydrogen storage in graphite nanofibers: effect of synthesis catalyst and pretreatment conditions.

PubMed

Lueking, Angela D; Yang, Ralph T; Rodriguez, Nelly M; Baker, R Terry K

2004-02-03

A series of graphite nanofibers (GNFs) that were subjected to various pretreatments were used to determine how modifications in the carbon structure formed during either synthesis or pretreatment steps results in active or inactive materials for hydrogen storage. The nanofibers possessing a herringbone structure and a high degree of defects were found to exhibit the best performance for hydrogen storage. These materials were exposed to several pretreatment procedures, including oxidative, reductive, and inert environments. Significant hydrogen storage levels were found for several in situ pretreatments. Examination of the nanofibers by high-resolution transmission electron microscopy (TEM) after pretreatment and subsequent hydrogen storage revealed the existence of edge attack and an enhancement in the generation of structural defects. These findings suggest that pretreatment in certain environments results in the creation of catalytic sites that are favorable toward hydrogen storage. The best pretreatment resulted in a 3.8% hydrogen release after exposure at 69 bar and room temperature.

Integrated lunar materials manufacturing process

NASA Technical Reports Server (NTRS)

Gibson, Michael A. (Inventor); Knudsen, Christian W. (Inventor)

1990-01-01

A manufacturing plant and process for production of oxygen on the moon uses lunar minerals as feed and a minimum of earth-imported, process materials. Lunar feed stocks are hydrogen-reducible minerals, ilmenite and lunar agglutinates occurring in numerous, explored locations mixed with other minerals in the pulverized surface layer of lunar soil known as regolith. Ilmenite (FeTiO.sub.3) and agglutinates contain ferrous (Fe.sup.+2) iron reducible by hydrogen to yield H.sub.2 O and metallic Fe at about 700.degree.-1,200.degree. C. The H.sub.2 O is electrolyzed in gas phase to yield H.sub.2 for recycle and O.sub.2 for storage and use. Hydrogen losses to lunar vacuum are minimized, with no net hydrogen (or any other earth-derived reagent) consumption except for small leaks. Feed minerals are surface-mined by front shovels and transported in trucks to the processing area. The machines are manned or robotic. Ilmenite and agglutinates occur mixed with silicate minerals which are not hydrogen-reducible at 700.degree.-1,200.degree. C. and consequently are separated and concentrated before feeding to the oxygen generation process. Solids rejected from the separation step and reduced solids from the oxygen process are returned to the mine area. The plant is powered by nuclear or solar power generators. Vapor-phase water electrolysis, a staged, countercurrent, fluidized bed reduction reactor and a radio-frequency-driven ceramic gas heater are used to improve thermal efficiency.

Li-Decorated β12-Borophene as Potential Candidates for Hydrogen Storage: A First-Principle Study.

PubMed

Liu, Tingting; Chen, Yuhong; Wang, Haifeng; Zhang, Meiling; Yuan, Lihua; Zhang, Cairong

2017-12-07

The hydrogen storage properties of pristine β 12 -borophene and Li-decorated β 12 -borophene are systemically investigated by means of first-principles calculations based on density functional theory. The adsorption sites, adsorption energies, electronic structures, and hydrogen storage performance of pristine β 12 -borophene/H₂ and Li- β 12 -borophene/H₂ systems are discussed in detail. The results show that H₂ is dissociated into Two H atoms that are then chemisorbed on β 12 -borophene via strong covalent bonds. Then, we use Li atom to improve the hydrogen storage performance and modify the hydrogen storage capacity of β 12 -borophene. Our numerical calculation shows that Li- β 12 -borophene system can adsorb up to 7 H₂ molecules; while 2Li- β 12 -borophene system can adsorb up to 14 H₂ molecules and the hydrogen storage capacity up to 10.85 wt %.

Single-catalyst high-weight% hydrogen storage in an N-heterocycle synthesized from lignin hydrogenolysis products and ammonia

PubMed Central

Forberg, Daniel; Schwob, Tobias; Zaheer, Muhammad; Friedrich, Martin; Miyajima, Nobuyoshi; Kempe, Rhett

2016-01-01

Large-scale energy storage and the utilization of biomass as a sustainable carbon source are global challenges of this century. The reversible storage of hydrogen covalently bound in chemical compounds is a particularly promising energy storage technology. For this, compounds that can be sustainably synthesized and that permit high-weight% hydrogen storage would be highly desirable. Herein, we report that catalytically modified lignin, an indigestible, abundantly available and hitherto barely used biomass, can be harnessed to reversibly store hydrogen. A novel reusable bimetallic catalyst has been developed, which is able to hydrogenate and dehydrogenate N-heterocycles most efficiently. Furthermore, a particular N-heterocycle has been identified that can be synthesized catalytically in one step from the main lignin hydrogenolysis product and ammonia, and in which the new bimetallic catalyst allows multiple cycles of high-weight% hydrogen storage. PMID:27762267

Single-catalyst high-weight% hydrogen storage in an N-heterocycle synthesized from lignin hydrogenolysis products and ammonia.

PubMed

Forberg, Daniel; Schwob, Tobias; Zaheer, Muhammad; Friedrich, Martin; Miyajima, Nobuyoshi; Kempe, Rhett

2016-10-20

Large-scale energy storage and the utilization of biomass as a sustainable carbon source are global challenges of this century. The reversible storage of hydrogen covalently bound in chemical compounds is a particularly promising energy storage technology. For this, compounds that can be sustainably synthesized and that permit high-weight% hydrogen storage would be highly desirable. Herein, we report that catalytically modified lignin, an indigestible, abundantly available and hitherto barely used biomass, can be harnessed to reversibly store hydrogen. A novel reusable bimetallic catalyst has been developed, which is able to hydrogenate and dehydrogenate N-heterocycles most efficiently. Furthermore, a particular N-heterocycle has been identified that can be synthesized catalytically in one step from the main lignin hydrogenolysis product and ammonia, and in which the new bimetallic catalyst allows multiple cycles of high-weight% hydrogen storage.

Hydrogen generation by electrolysis of aqueous organic solutions

NASA Technical Reports Server (NTRS)

Jeffries-Nakamura, Barbara (Inventor); Narayanan, Sekharipuram R. (Inventor); Chun, William (Inventor); Valdez, Thomas I. (Inventor)

2006-01-01

A device for electrolysis of an aqueous solution of an organic fuel. The electrolyte is a solid-state polymer membrane with anode and cathode catalysts on both surfaces for electro-oxidization and electro-reduction. A low-cost and portable hydrogen generator can be made based on the device with organic fuels such as methanol.

Hydrogen generation by electrolysis of aqueous organic solutions

NASA Technical Reports Server (NTRS)

Narayanan, Sekharipuram R. (Inventor); Chun, William (Inventor); Jeffries-Nakamura, Barbara (Inventor); Valdez, Thomas I. (Inventor)

2002-01-01

A device for electrolysis of an aqueous solution of an organic fuel. The electrolyte is a solid-state polymer membrane with anode and cathode catalysts on both surfaces for electro-oxidization and electro-reduction. A low-cost and portable hydrogen generator can be made based on the device with organic fuels such as methanol.

Physico-Geometrical Kinetics of Solid-State Reactions in an Undergraduate Thermal Analysis Laboratory

ERIC Educational Resources Information Center

Koga, Nobuyoshi; Goshi, Yuri; Yoshikawa, Masahiro; Tatsuoka, Tomoyuki

2014-01-01

An undergraduate kinetic experiment of the thermal decomposition of solids by microscopic observation and thermal analysis was developed by investigating a suitable reaction, applicable techniques of thermal analysis and microscopic observation, and a reliable kinetic calculation method. The thermal decomposition of sodium hydrogen carbonate is…

Solid dispersions of Myricetin with enhanced solubility: Formulation, characterization and crystal structure of stability-impeding Myricetin monohydrate crystals

NASA Astrophysics Data System (ADS)

Mureşan-Pop, M.; Pop, M. M.; Borodi, G.; Todea, M.; Nagy-Simon, T.; Simon, S.

2017-08-01

Three solid dispersion forms of Myricetin combined with the Polyvinylpyrrolidone were successfully prepared by spray drying method, and characterized by X-ray powder diffraction, thermal analysis, infrared spectroscopy and optical microscopy. Zeta potential measurements provided indications on solid dispersions stability in aqueous suspension related to their storage at elevated temperature and relative humidity, which depends on the Myricetin load. By increase of Myricetin load, the stability of the solid dispersion is impeded due to growth of Myricetin monohydrate crystals. The amorphous dispersions with 10% and 50% Myricetin load are stable and, compared to pure Myricetin, their aqueous solubility is enhanced by a factor of 47 and 13, respectively. The dispersion with 80% Myricetin load is unstable on storage, and this behavior acts in conjunction with the development of Myricetin monohydrate crystals. Single-crystal X-ray diffraction results obtained for Myricetin monohydrate reveal a structure of an infinite 2D network of hydrogen-bonded molecules involving all six hydroxyl groups of Myricetin. The water molecules are positioned in between the infinite chains, and contribute via H-bonds to robust crystal packing. The calculated needle-like morphology of monohydrate form is in agreement with the optical microscopy results. The study shows that the solid amorphous dispersions with up to 50% Myricetin load are a viable option for achieving substantial solubility improvement of Myricetin, and supports their potential use in pharmaceutical applications.

Prediction of a new graphenelike Si2BN solid

NASA Astrophysics Data System (ADS)

Andriotis, Antonis N.; Richter, Ernst; Menon, Madhu

2016-02-01

While the possibility to create a single-atom-thick two-dimensional layer from any material remains, only a few such structures have been obtained other than graphene and a monolayer of boron nitride. Here, based upon ab initio theoretical simulations, we propose a new stable graphenelike single-atomic-layer Si2BN structure that has all of its atoms with s p2 bonding with no out-of-plane buckling. The structure is found to be metallic with a finite density of states at the Fermi level. This structure can be rolled into nanotubes in a manner similar to graphene. Combining first- and second-row elements in the Periodic Table to form a one-atom-thick material that is also flat opens up the possibility for studying new physics beyond graphene. The presence of Si will make the surface more reactive and therefore a promising candidate for hydrogen storage.

Simultaneous manipulation and observation of multiple ro-vibrational eigenstates in solid para-hydrogen.

PubMed

Katsuki, Hiroyuki; Ohmori, Kenji

2016-09-28

We have experimentally performed the coherent control of delocalized ro-vibrational wave packets (RVWs) of solid para-hydrogen (p-H 2 ) by the wave packet interferometry (WPI) combined with coherent anti-Stokes Raman scattering (CARS). RVWs of solid p-H 2 are delocalized in the crystal, and the wave function with wave vector k ∼ 0 is selectively excited via the stimulated Raman process. We have excited the RVW twice by a pair of femtosecond laser pulses with delay controlled by a stabilized Michelson interferometer. Using a broad-band laser pulse, multiple ro-vibrational states can be excited simultaneously. We have observed the time-dependent Ramsey fringe spectra as a function of the inter-pulse delay by a spectrally resolved CARS technique using a narrow-band probe pulse, resolving the different intermediate states. Due to the different fringe oscillation periods among those intermediate states, we can manipulate their amplitude ratio by tuning the inter-pulse delay on the sub-femtosecond time scale. The state-selective manipulation and detection of the CARS signal combined with the WPI is a general and efficient protocol for the control of the interference of multiple quantum states in various quantum systems.

Hexagonal boron nitride nanoparticles decorated halloysite clay nanotubes as a potential hydrogen storage medium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Muthu, R. Naresh, E-mail: rnaresh7708@gmail.com; Rajashabala, S.; Kannan, R.

2016-05-23

The light weight and compact hydrogen storage materials is still prerequisite for the carbon free hydrogen fuel cell technology. In this work, the hydrogen storage performance of acid treated halloysite clay nanotubes (A-HNTs) and hexagonal boron nitride (h-BN) nanoparticles decorated acid treated halloysite nanoclay composite (A-HNT-h-BN) are demonstrated, where facile ultrasonic technique is adopted for the synthesis of A-HNT-h-BN nanoclay composite. Hydrogen storage studies were carried out using Sieverts-like hydrogenation setup. The A-HNTs and A-HNT-h-BN nanoclay composite were analyzed by XRD, FTIR, HRTEM, EDX, CHNS-elemental analysis and TGA. The A-HNT-h-BN nanoclay composite shows superior storage capacity of 2.19 wt% atmore » 50 °C compared to the A-HNTs (0.58 wt%). A 100% desorption of stored hydrogen is noted in the temperature range of 138–175 °C. The average binding energy of hydrogen was found to be 0.34 eV for the prepared A-HNT-h-BN nanoclay composite. The excellent storage capability of A-HNT-h-BN nanoclay composite towards hydrogen at ambient temperature may find bright perspective in hydrogen fuel cell technology in near future.« less

Hydrogen storage materials and method of making by dry homogenation

DOEpatents

Jensen, Craig M.; Zidan, Ragaiy A.

2002-01-01

Dry homogenized metal hydrides, in particular aluminum hydride compounds, as a material for reversible hydrogen storage is provided. The reversible hydrogen storage material comprises a dry homogenized material having transition metal catalytic sites on a metal aluminum hydride compound, or mixtures of metal aluminum hydride compounds. A method of making such reversible hydrogen storage materials by dry doping is also provided and comprises the steps of dry homogenizing metal hydrides by mechanical mixing, such as be crushing or ball milling a powder, of a metal aluminum hydride with a transition metal catalyst. In another aspect of the invention, a method of powering a vehicle apparatus with the reversible hydrogen storage material is provided.

Hydrogen storage compositions

DOEpatents

Li, Wen; Vajo, John J.; Cumberland, Robert W.; Liu, Ping

2011-04-19

Compositions for hydrogen storage and methods of making such compositions employ an alloy that exhibits reversible formation/deformation of BH.sub.4.sup.- anions. The composition includes a ternary alloy including magnesium, boron and a metal and a metal hydride. The ternary alloy and the metal hydride are present in an amount sufficient to render the composition capable of hydrogen storage. The molar ratio of the metal to magnesium and boron in the alloy is such that the alloy exhibits reversible formation/deformation of BH.sub.4.sup.- anions. The hydrogen storage composition is prepared by combining magnesium, boron and a metal to prepare a ternary alloy and combining the ternary alloy with a metal hydride to form the hydrogen storage composition.

Wax: A benign hydrogen-storage material that rapidly releases H2-rich gases through microwave-assisted catalytic decomposition

PubMed Central

Gonzalez-Cortes, S.; Slocombe, D. R.; Xiao, T.; Aldawsari, A.; Yao, B.; Kuznetsov, V. L.; Liberti, E.; Kirkland, A. I.; Alkinani, M. S.; Al-Megren, H. A.; Thomas, J. M.; Edwards, P. P.

2016-01-01

Hydrogen is often described as the fuel of the future, especially for application in hydrogen powered fuel-cell vehicles (HFCV’s). However, its widespread implementation in this role has been thwarted by the lack of a lightweight, safe, on-board hydrogen storage material. Here we show that benign, readily-available hydrocarbon wax is capable of rapidly releasing large amounts of hydrogen through microwave-assisted catalytic decomposition. This discovery offers a new material and system for safe and efficient hydrogen storage and could facilitate its application in a HFCV. Importantly, hydrogen storage materials made of wax can be manufactured through completely sustainable processes utilizing biomass or other renewable feedstocks. PMID:27759014

New solid state forms of antineoplastic 5-fluorouracil with anthelmintic piperazine

NASA Astrophysics Data System (ADS)

Moisescu-Goia, C.; Muresan-Pop, M.; Simon, V.

2017-12-01

The aim of the present study was to asses the formation of solid forms between the 5-fluorouracil chemotherapy drug and the anthelmintic piperazine. Two new solid forms of antineoplastic agent 5-fluorouracil with anthelmintic piperazine were obtained by liquid assisted ball milling and slurry crystallization methods. The Nsbnd H hydrogen bonding donors and C = O hydrogen bonding acceptors of 5-fluorouracil allow to form co-crystals with other drugs delivering improved properties for medical applications, as proved for other compounds of pharmaceutical interest. Both new solid forms were investigated using X-ray powder diffraction (XRD), differential thermal analysis (DTA) and Fourier transform infrared (FTIR) spectroscopy. The XRD results show that by both methods were successfully synthesized new solid forms of 5-fluorouracil with piperazine. According to FTIR results the form prepared by lichid assisted grinding process was obtained as co-crystal and the other one, prepared by slurry method, resulted as a salt.

Hydrogen Storage Characteristics of Nanocrystalline and Amorphous Nd-Mg-Ni-Based NdMg12-Type Alloys Synthesized via Mechanical Milling

NASA Astrophysics Data System (ADS)

Zhang, Yanghuan; Shang, Hongwei; Hou, Zhonghui; Yuan, Zeming; Yang, Tai; Qi, Yan

2016-12-01

In this study, Mg was partially substituted by Ni with the intent of improving the hydrogen storage kinetics performance of NdMg12-type alloy. Mechanical milling technology was adopted to fabricate the nanocrystalline and amorphous NdMg11Ni + x wt pct Ni ( x = 100, 200) alloys. The effects of Ni content and milling duration on the microstructures and hydrogen storage kinetics of as-milled alloys have been systematically investigated. The structures were characterized by XRD and HRTEM. The electrochemical hydrogen storage properties were tested by an automatic galvanostatic system. Moreover, the gaseous hydrogen storage properties were investigated by Sievert apparatus and a differential scanning calorimeter connected with a H2 detector. Hydrogen desorption activation energy of alloy hydrides was estimated by using Arrhenius and Kissinger methods. The results reveal that the increase of Ni content dramatically ameliorates the gaseous and electrochemical hydrogen storage kinetics performance of the as-milled alloys. Furthermore, high rate discharge ability (HRD) reach the maximum value with the variation of milling time. The maximum HRDs of the NdMg11Ni + x wt pct Ni ( x = 100, 200) alloys are 80.24 and 85.17 pct. The improved gaseous hydrogen storage kinetics of alloys via increasing Ni content and milling time can be attributed to a decrease in the hydrogen desorption activation energy.

Thermo-physical performance prediction of the KSC Ground Operation Demonstration Unit for liquid hydrogen

NASA Astrophysics Data System (ADS)

Baik, J. H.; Notardonato, W. U.; Karng, S. W.; Oh, I.

2015-12-01

NASA Kennedy Space Center (KSC) researchers have been working on enhanced and modernized cryogenic liquid propellant handling techniques to reduce life cycle costs of propellant management system for the unique KSC application. The KSC Ground Operation Demonstration Unit (GODU) for liquid hydrogen (LH2) plans to demonstrate integrated refrigeration, zero-loss flexible term storage of LH2, and densified hydrogen handling techniques. The Florida Solar Energy Center (FSEC) has partnered with the KSC researchers to develop thermal performance prediction model of the GODU for LH2. The model includes integrated refrigeration cooling performance, thermal losses in the tank and distribution lines, transient system characteristics during chilling and loading, and long term steady-state propellant storage. This paper will discuss recent experimental data of the GODU for LH2 system and modeling results.

Methane Post-Processing for Oxygen Loop Closure

NASA Technical Reports Server (NTRS)

Greenwood, Zachary W.; Abney, Morgan B.; Miller, Lee

2016-01-01

State-of-the-art United States Atmospheric Revitalization carbon dioxide (CO2) reduction is based on the Sabatier reaction process, which recovers approximately 50% of the oxygen (O2) from crew metabolic CO2. Oxygen recovery from carbon dioxide is constrained by the limited availability of reactant hydrogen. Post-processing of methane to recover hydrogen with the Umpqua Research Company Plasma Pyrolysis Assembly (PPA) has the potential to further close the Atmospheric Revitalization oxygen loop. The PPA decomposes methane into hydrogen and hydrocarbons, predominantly acetylene, and a small amount of solid carbon. The hydrogen must then be purified before it can be recycled for additional oxygen recovery. Long duration testing and evaluation of a four crew-member sized PPA and a discussion of hydrogen recycling system architectures are presented.

40 CFR 280.22 - Notification requirements.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Section 280.22 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES... STORAGE TANKS (UST) UST Systems: Design, Construction, Installation and Notification § 280.22 Notification... to notify the designated state or local agency in accordance with the Hazardous and Solid Waste...

40 CFR 280.22 - Notification requirements.

Code of Federal Regulations, 2011 CFR

2011-07-01

... Section 280.22 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES... STORAGE TANKS (UST) UST Systems: Design, Construction, Installation and Notification § 280.22 Notification... to notify the designated state or local agency in accordance with the Hazardous and Solid Waste...

40 CFR 280.22 - Notification requirements.

Code of Federal Regulations, 2012 CFR

2012-07-01

... Section 280.22 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES... STORAGE TANKS (UST) UST Systems: Design, Construction, Installation and Notification § 280.22 Notification... to notify the designated state or local agency in accordance with the Hazardous and Solid Waste...

40 CFR 280.22 - Notification requirements.

Code of Federal Regulations, 2013 CFR

2013-07-01

... Section 280.22 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES... STORAGE TANKS (UST) UST Systems: Design, Construction, Installation and Notification § 280.22 Notification... to notify the designated state or local agency in accordance with the Hazardous and Solid Waste...

40 CFR 280.22 - Notification requirements.

Code of Federal Regulations, 2014 CFR

2014-07-01

... Section 280.22 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES... STORAGE TANKS (UST) UST Systems: Design, Construction, Installation and Notification § 280.22 Notification... to notify the designated state or local agency in accordance with the Hazardous and Solid Waste...

Realization of reliable solid-state quantum memory for photonic polarization qubit.

PubMed

Zhou, Zong-Quan; Lin, Wei-Bin; Yang, Ming; Li, Chuan-Feng; Guo, Guang-Can

2012-05-11

Faithfully storing an unknown quantum light state is essential to advanced quantum communication and distributed quantum computation applications. The required quantum memory must have high fidelity to improve the performance of a quantum network. Here we report the reversible transfer of photonic polarization states into collective atomic excitation in a compact solid-state device. The quantum memory is based on an atomic frequency comb (AFC) in rare-earth ion-doped crystals. We obtain up to 0.999 process fidelity for the storage and retrieval process of single-photon-level coherent pulse. This reliable quantum memory is a crucial step toward quantum networks based on solid-state devices.

Preparation of platinum-decorated porous graphite nanofibers, and their hydrogen storage behaviors.

PubMed

Kim, Byung-Joo; Lee, Young-Seak; Park, Soo-Jin

2008-02-15

In this work, the hydrogen storage behaviors of porous graphite nanofibers (GNFs) decorated by Pt nanoparticles were investigated. The Pt nanoparticles were introduced onto the GNF surfaces using a well-known chemical reduction method. We investigated the hydrogen storage capacity of the Pt-doped GNFs for the platinum content range of 1.3-7.5 mass%. The microstructure of the Pt/porous GNFs was characterized by X-ray diffraction and transmission electron microscopy. The hydrogen storage behaviors of the Pt/GNFs were studied using a PCT apparatus at 298 K and 10 MPa. It was found that amount of hydrogen stored increased with increasing Pt content to 3.4 mass%, and then decreased. This result indicates that the hydrogen storage capacity of porous carbons is based on both their metal content and dispersion rate.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brammer, L.; Mareque Rivas, J.C.; Zhao, D.

Low-temperature crystal structures of QuinH{sup +}Co(CO){sub 4}{sup {minus}}, 1 (QuinH{sup +} = quinuclidinium), (DABCO)H{sup +}Co(CO){sub 3}P-(p-tolyl){sub 3}{sup {minus}}, 2, and (DABCO)H{sup +}Co(CO){sub 3}PPh{sub 2}(p-tolyl){sup {minus}}, 3 (DABCO = 1,4-diazabicyclooctane), 2 and 3 as their acetonitrile solvates, demonstrate that these salts exhibit intermolecular N--H{hor_ellipsis}Co hydrogen bonding between the cation and anion components. NMR and IR data demonstrate the persistence of these interactions in toluene solution. Such solution-state data, which examine solvated ion pairs, suggest little difference between these salts and the corresponding previously reported salts (DABCO)H{sup +}Co(CO){sub 3}L{sup {minus}} (4, L = CO; 5, L = PPh{sub 3}). However, in themore » solid state, the N--H{hor_ellipsis}Co hydrogen bonds in 1--3 are some 0.1--0.15 {angstrom} longer than would be predicted from consideration of the structures of 4 and 5 and the aforementioned similarity to 4 and 5 in solution. In previous reports the authors have shown that major steric or electronic changes to the anion or cation have resulted in substantial changes (0.15--0.3 {angstrom}) in the N{hor_ellipsis}Co [H{hor_ellipsis}] separation for N--H{hor_ellipsis}Co hydrogen bonds in related R{sub 3}NH{sup +}Co(CO){sub 3}L{sup {minus}} (L = CO, PR{sub 3}) salts. In this report, the authors present examples in which small changes are made to the anion or cation remote from the N--H{hor_ellipsis}Co hydrogen bond. In the solid state, the effect of these small changes on this hydrogen bond is subsumed by the effect of changes in the supramolecular structure. This clearly indicates the sensitivity of the geometry of these hydrogen bonds to the overall balance of intermolecular interactions in the solid state and as such is pertinent to current interest in weak (intermolecular) interactions for which characterization by X-ray crystallography is important.« less

Control method for high-pressure hydrogen vehicle fueling station dispensers

DOEpatents

Kountz, Kenneth John; Kriha, Kenneth Robert; Liss, William E.

2006-06-13

A method for quick filling a vehicle hydrogen storage vessel with hydrogen, the key component of which is an algorithm used to control the fill process, which interacts with the hydrogen dispensing apparatus to determine the vehicle hydrogen storage vessel capacity.

Solid-state supercapacitors with rationally designed heterogeneous electrodes fabricated by large area spray processing for wearable energy storage applications

PubMed Central

Huang, Chun; Zhang, Jin; Young, Neil P.; Snaith, Henry J.; Grant, Patrick S.

2016-01-01

Supercapacitors are in demand for short-term electrical charge and discharge applications. Unlike conventional supercapacitors, solid-state versions have no liquid electrolyte and do not require robust, rigid packaging for containment. Consequently they can be thinner, lighter and more flexible. However, solid-state supercapacitors suffer from lower power density and where new materials have been developed to improve performance, there remains a gap between promising laboratory results that usually require nano-structured materials and fine-scale processing approaches, and current manufacturing technology that operates at large scale. We demonstrate a new, scalable capability to produce discrete, multi-layered electrodes with a different material and/or morphology in each layer, and where each layer plays a different, critical role in enhancing the dynamics of charge/discharge. This layered structure allows efficient utilisation of each material and enables conservative use of hard-to-obtain materials. The layered electrode shows amongst the highest combinations of energy and power densities for solid-state supercapacitors. Our functional design and spray manufacturing approach to heterogeneous electrodes provide a new way forward for improved energy storage devices. PMID:27161379

Final test results for the ground operations demonstration unit for liquid hydrogen

NASA Astrophysics Data System (ADS)

Notardonato, W. U.; Swanger, A. M.; Fesmire, J. E.; Jumper, K. M.; Johnson, W. L.; Tomsik, T. M.

2017-12-01

Described herein is a comprehensive project-a large-scale test of an integrated refrigeration and storage system called the Ground Operations and Demonstration Unit for Liquid Hydrogen (GODU LH2), sponsored by the Advanced Exploration Systems Program and constructed at Kennedy Space Center. A commercial cryogenic refrigerator interfaced with a 125,000 l liquid hydrogen tank and auxiliary systems in a manner that enabled control of the propellant state by extracting heat via a closed loop Brayton cycle refrigerator coupled to a novel internal heat exchanger. Three primary objectives were demonstrating zero-loss storage and transfer, gaseous liquefaction, and propellant densification. Testing was performed at three different liquid hydrogen fill-levels. Data were collected on tank pressure, internal tank temperature profiles, mass flow in and out of the system, and refrigeration system performance. All test objectives were successfully achieved during approximately two years of testing. A summary of the final results is presented in this paper.

The 100 kW space station. [regenerative fuel cells and nickel hydrogen and nickel cadmium batteries for solar arrays

NASA Technical Reports Server (NTRS)

Mckhann, G.

1977-01-01

Solar array power systems for the space construction base are discussed. Nickel cadmium and nickel hydrogen batteries are equally attractive relative to regenerative fuel cell systems at 5 years life. Further evaluation of energy storage system life (low orbit conditions) is required. Shuttle and solid polymer electrolyte fuel cell technology appears adequate; large units (approximately four times shuttle) are most appropriate and should be studied for a 100 KWe SCB system. A conservative NiH2 battery DOD (18.6%) was elected due to lack of test data and offers considerable improvement potential. Multiorbit load averaging and reserve capacity requirements limit nominal DOD to 30% to 50% maximum, independent of life considerations.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brady, Michael P.; Ievlev, Anton V.; Fayek, Mostafa

Hydrogen gas is formed when Mg corrodes in water; however, the manner and extent to which the hydrogen may also enter the Mg metal is poorly understood. Such knowledge is critical as stress corrosion cracking (SCC)/embrittlement phenomena limit many otherwise promising structural and functional uses of Mg. Here, we report via D 2O/D isotopic tracer and H 2O exposures with characterization by secondary ion mass spectrometry, inelastic neutron scattering vibrational spectrometry, electron microscopy, and atom probe tomography techniques direct evidence that hydrogen rapidly penetrated tens of micrometers into Mg metal after only 4 h of exposure to water at roommore » temperature. Further, technologically important microalloying additions of <1 wt % Zr and Nd used to improve the manufacturability and mechanical properties of Mg significantly increased the extent of hydrogen ingress, whereas Al additions in the 2–3 wt % range did not. Segregation of hydrogen species was observed at regions of high Mg/Zr/Nd nanoprecipitate density and at Mg(Zr) metastable solid solution microstructural features. We also report evidence that this ingressed hydrogen was unexpectedly present in the alloy as nanoconfined, molecular H 2. These new insights provide a basis for strategies to design Mg alloys to resist SCC in aqueous environments as well as potentially impact functional uses such as hydrogen storage where increased hydrogen uptake is desired.« less

Hydrogenation of carbonyl compounds of relevance to hydrogen storage in alcohols

NASA Astrophysics Data System (ADS)

Suárez, Andrés

2018-02-01

Alcohols are a promising source for the sustainable production of hydrogen that may also serve as rechargeable liquid organic hydrogen carriers (LOHCs). Metal-catalyzed acceptorless dehydrogenation of alcohols produces carbonyl derivatives as H2-depleted by-products, which by means of a hydrogenation reaction can be reconverted to the initial alcohols. Hence, reversible H2-storage systems based on pairs of secondary alcohols/ketones and primary alcohols/carboxylic acid derivatives may be envisaged. In this contribution, the hydrogenation of carbonyl derivatives, including ketones, esters, amides and carboxylic acids, is reviewed from the perspective of the hydrogen storage in alcohols.

Application of sorption heat pumps for increasing of new power sources efficiency

NASA Astrophysics Data System (ADS)

Vasiliev, L.; Filatova, O.; Tsitovich, A.

2010-07-01

In the 21st century the way to increase the efficiency of new sources of energy is directly related with extended exploration of renewable energy. This modern tendency ensures the fuel economy needs to be realized with nature protection. The increasing of new power sources efficiency (cogeneration, trigeneration systems, fuel cells, photovoltaic systems) can be performed by application of solid sorption heat pumps, regrigerators, heat and cold accumulators, heat transformers, natural gas and hydrogen storage systems and efficient heat exchangers.

Recent Developments of All-Solid-State Lithium Secondary Batteries with Sulfide Inorganic Electrolytes.

PubMed

Xu, Ruochen; Zhang, Shengzhao; Wang, Xiuli; Xia, Yan; Xia, Xinhui; Wu, Jianbo; Gu, Changdong; Tu, Jiangping

2018-04-20

Due to the increasing demand of security and energy density, all-solid-state lithium ion batteries have become the promising next-generation energy storage devices to replace the traditional liquid batteries with flammable organic electrolytes. In this Minireview, we focus on the recent developments of sulfide inorganic electrolytes for all-solid-state batteries. The challenges of assembling bulk-type all-solid-state batteries for industrialization are discussed, including low ionic conductivity of the present sulfide electrolytes, high interfacial resistance and poor compatibility between electrolytes and electrodes. Many efforts have been focused on the solutions for these issues. Although some progresses have been achieved, it is still far away from practical application. The perspectives for future research on all-solid-state lithium ion batteries are presented. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analysis and Design of Cryogenic Pressure Vessels for Automotive Hydrogen Storage

NASA Astrophysics Data System (ADS)

Espinosa-Loza, Francisco Javier

Cryogenic pressure vessels maximize hydrogen storage density by combining the high pressure (350-700 bar) typical of today's composite pressure vessels with the cryogenic temperature (as low as 25 K) typical of low pressure liquid hydrogen vessels. Cryogenic pressure vessels comprise a high-pressure inner vessel made of carbon fiber-coated metal (similar to those used for storage of compressed gas), a vacuum space filled with numerous sheets of highly reflective metalized plastic (for high performance thermal insulation), and a metallic outer jacket. High density of hydrogen storage is key to practical hydrogen-fueled transportation by enabling (1) long-range (500+ km) transportation with high capacity vessels that fit within available spaces in the vehicle, and (2) reduced cost per kilogram of hydrogen stored through reduced need for expensive structural material (carbon fiber composite) necessary to make the vessel. Low temperature of storage also leads to reduced expansion energy (by an order of magnitude or more vs. ambient temperature compressed gas storage), potentially providing important safety advantages. All this is accomplished while simultaneously avoiding fuel venting typical of cryogenic vessels for all practical use scenarios. This dissertation describes the work necessary for developing and demonstrating successive generations of cryogenic pressure vessels demonstrated at Lawrence Livermore National Laboratory. The work included (1) conceptual design, (2) detailed system design (3) structural analysis of cryogenic pressure vessels, (4) thermal analysis of heat transfer through cryogenic supports and vacuum multilayer insulation, and (5) experimental demonstration. Aside from succeeding in demonstrating a hydrogen storage approach that has established all the world records for hydrogen storage on vehicles (longest driving range, maximum hydrogen storage density, and maximum containment of cryogenic hydrogen without venting), the work also demonstrated a methodology for computationally efficient detailed modeling of cryogenic pressure vessels. The work continues with support of the US Department of Energy to demonstrate a new generation of cryogenic vessels anticipated to improve on the hydrogen storage performance figures previously imposed in this project. The author looks forward to further contributing to a future of long-range, inexpensive, and safe zero emissions transportation.

Enhancing hydrogen spillover and storage

DOEpatents

Yang, Ralph T [Ann Arbor, MI; Li, Yingwel [Ann Arbor, MI; Lachawiec, Jr., Anthony J.

2011-05-31

Methods for enhancing hydrogen spillover and storage are disclosed. One embodiment of the method includes doping a hydrogen receptor with metal particles, and exposing the hydrogen receptor to ultrasonification as doping occurs. Another embodiment of the method includes doping a hydrogen receptor with metal particles, and exposing the doped hydrogen receptor to a plasma treatment.

Enhancing hydrogen spillover and storage

DOEpatents

Yang, Ralph T; Li, Yingwei; Lachawiec, Jr., Anthony J

2013-02-12

Methods for enhancing hydrogen spillover and storage are disclosed. One embodiment of the method includes doping a hydrogen receptor with metal particles, and exposing the hydrogen receptor to ultrasonication as doping occurs. Another embodiment of the method includes doping a hydrogen receptor with metal particles, and exposing the doped hydrogen receptor to a plasma treatment.

Container and method for absorbing and reducing hydrogen concentration

DOEpatents

Wicks, George G.; Lee, Myung W.; Heung, Leung K.

2001-01-01

A method for absorbing hydrogen from an enclosed environment comprising providing a vessel; providing a hydrogen storage composition in communication with a vessel, the hydrogen storage composition further comprising a matrix defining a pore size which permits the passage of hydrogen gas while blocking the passage of gaseous poisons; placing a material within the vessel, the material evolving hydrogen gas; sealing the vessel; and absorbing the hydrogen gas released into the vessel by the hydrogen storage composition. A container for absorbing evolved hydrogen gas comprising: a vessel having an interior and adapted for receiving materials which release hydrogen gas; a hydrogen absorbing composition in communication with the interior, the composition defining a matrix surrounding a hydrogen absorber, the matrix permitting the passage of hydrogen gas while excluding gaseous poisons; wherein, when the vessel is sealed, hydrogen gas, which is released into the vessel interior, is absorbed by the hydrogen absorbing composition.

Probing the oxygen environment in UO(2)(2+) by solid-state 17O nuclear magnetic resonance spectroscopy and relativistic density functional calculations.

PubMed

Cho, Herman; de Jong, Wibe A; Soderquist, Chuck Z

2010-02-28

A combined theoretical and solid-state (17)O nuclear magnetic resonance (NMR) study of the electronic structure of the uranyl ion UO(2)(2+) in (NH(4))(4)UO(2)(CO(3))(3) and rutherfordine (UO(2)CO(3)) is presented, the former representing a system with a hydrogen-bonding environment around the uranyl oxygens and the latter exemplifying a uranyl environment without hydrogens. Relativistic density functional calculations reveal unique features of the U-O covalent bond, including the finding of (17)O chemical shift anisotropies that are among the largest for oxygen ever reported (>1200 ppm). Computational results for the oxygen electric field gradient tensor are found to be consistently larger in magnitude than experimental solid-state (17)O NMR measurements in a 7.05 T magnetic field indicate. A modified version of the Solomon theory of the two-spin echo amplitude for a spin-5/2 nucleus is developed and applied to the analysis of the (17)O echo signal of U (17)O(2)(2+).

Three-dimensional analysis for liquid hydrogen in a cryogenic storage tank with heat pipe pump system

NASA Astrophysics Data System (ADS)

Ho, Son H.; Rahman, Muhammad M.

2008-01-01

This paper presents a study on fluid flow and heat transfer of liquid hydrogen in a zero boil-off cryogenic storage tank in a microgravity environment. The storage tank is equipped with an active cooling system consisting of a heat pipe and a pump-nozzle unit. The pump collects cryogen at its inlet and discharges it through its nozzle onto the evaporator section of the heat pipe in order to prevent the cryogen from boiling off due to the heat leaking through the tank wall from the surroundings. A three-dimensional (3-D) finite element model is employed in a set of numerical simulations to solve for velocity and temperature fields of liquid hydrogen in steady state. Complex structures of 3-D velocity and temperature distributions determined from the model are presented. Simulations with an axisymmetric model were also performed for comparison. Parametric study results from both models predict that as the speed of the cryogenic fluid discharged from the nozzle increases, the mean or bulk cryogenic fluid speed increases linearly and the maximum temperature within the cryogenic fluid decreases.

Review of hydrogen storage in inorganic fullerene-like nanotubes

NASA Astrophysics Data System (ADS)

Chen, J.; Wu, F.

Following the discovery of carbon nanotubes, inorganic fullerene-like nanotubes such as WS2-MoS2, NbS2, TiS2, and BN were reported. Inorganic (non-carbon) nanotubes constitute an important class of nanomaterials with interesting properties and potential applications. As known, efficient hydrogen storage is one key problem in the development of a hydrogen energy system. Hydrogen storage using carbon nanostructures is scientifically interesting and challenging. It thus would be worthwhile to look into hydrogen storage in inorganic nanotubes because the van der Waals gaps between the nanotube layers are potential candidates for hydrogen uptake. Furthermore, the inorganic nanotubes combine two elements, which is different from the pure carbon nanotubes. These may show a novel hydrogen adsorption-desorption mechanism. The present review provides a brief study of hydrogen adsorption on MoS2, TiS2, and BN nanotubes.

Mechanical ball-milling preparation of fullerene/cobalt core/shell nanocomposites with high electrochemical hydrogen storage ability.

PubMed

Bao, Di; Gao, Peng; Shen, Xiande; Chang, Cheng; Wang, Longqiang; Wang, Ying; Chen, Yujin; Zhou, Xiaoming; Sun, Shuchao; Li, Guobao; Yang, Piaoping

2014-02-26

The design and synthesis of new hydrogen storage nanomaterials with high capacity at low cost is extremely desirable but remains challenging for today's development of hydrogen economy. Because of the special honeycomb structures and excellent physical and chemical characters, fullerenes have been extensively considered as ideal materials for hydrogen storage materials. To take the most advantage of its distinctive symmetrical carbon cage structure, we have uniformly coated C60's surface with metal cobalt in nanoscale to form a core/shell structure through a simple ball-milling process in this work. The X-ray diffraction (XRD), scanning electron microscope (SEM), Raman spectra, high-solution transmission electron microscopy (HRTEM), energy-dispersive X-ray spectrometry (EDX) elemental mappings, and X-ray photoelectron spectroscopy (XPS) measurements have been conducted to evaluate the size and the composition of the composites. In addition, the blue shift of C60 pentagonal pinch mode demonstrates the formation of Co-C chemical bond, and which enhances the stability of the as-obtained nanocomposites. And their electrochemical experimental results demonstrate that the as-obtained C60/Co composites have excellent electrochemical hydrogen storage cycle reversibility and considerably high hydrogen storage capacities of 907 mAh/g (3.32 wt % hydrogen) under room temperature and ambient pressure, which is very close to the theoretical hydrogen storage capacities of individual metal Co (3.33 wt % hydrogen). Furthermore, their hydrogen storage processes and the mechanism have also been investigated, in which the quasi-reversible C60/Co↔C60/Co-Hx reaction is the dominant cycle process.

Development of the ReaxFFCBN reactive force field for the improved design of liquid CBN hydrogen storage materials.

PubMed

Pai, Sung Jin; Yeo, Byung Chul; Han, Sang Soo

2016-01-21

Liquid CBN (carbon-boron-nitrogen) hydrogen-storage materials such as 3-methyl-1,2-BN-cyclopentane have the advantage of being easily accessible for use in current liquid-fuel infrastructure. To develop practical liquid CBN hydrogen-storage materials, it is of great importance to understand the reaction pathways of hydrogenation/dehydrogenation in the liquid phase, which are difficult to discover by experimental methods. Herein, we developed a reactive force field (ReaxFFCBN) from quantum mechanical (QM) calculations based on density functional theory for the storage of hydrogen in BN-substituted cyclic hydrocarbon materials. The developed ReaxFFCBN provides similar dehydrogenation pathways and energetics to those predicted by QM calculations. Moreover, molecular dynamics (MD) simulations with the developed ReaxFFCBN can predict the stability and dehydrogenation behavior of various liquid CBN hydrogen-storage materials. Our simulations reveal that a unimolecular dehydrogenation mechanism is preferred in liquid CBN hydrogen-storage materials. However, as the temperature in the simulation increases, the contribution of a bimolecular dehydrogenation mechanism also increases. Moreover, our ReaxFF MD simulations show that in terms of thermal stability and dehydrogenation kinetics, liquid CBN materials with a hexagonal structure are more suitable materials than those with a pentagonal structure. We expect that the developed ReaxFFCBN could be a useful protocol in developing novel liquid CBN hydrogen-storage materials.

Calcium-Iron Oxide as Energy Storage Medium in Rechargeable Oxide Batteries

DOE PAGES

Berger, Cornelius M.; Mahmoud, Abdelfattah; Hermann, Raphaël P.; ...

2016-08-08

Rechargeable oxide batteries (ROB) comprise a regenerative solid oxide cell (rSOC) and a storage medium for oxygen ions. A sealed ROB avoids pumping loss, heat loss, and gas purity expenses in comparison with conventional rSOC. However, the iron oxide base storage medium degrades during charging–discharging cycles. In comparison, CaFe 3O 5 has improved cyclability and a high reversible oxygen storage capacity of 22.3 mol%. In this paper, we analyzed the redox mechanism of this compound. After a solid-state synthesis of CaFe 3O 5, we verified the phase composition and studied the redox reaction by means of X-ray diffraction, Mössbauer spectrometry,more » and scanning electron microscopy. Finally, results show a great potential to operate the battery with this storage material during multiple charging–discharging cycles.« less

Catalyzed borohydrides for hydrogen storage

DOEpatents

Au, Ming [Augusta, GA

2012-02-28

A hydrogen storage material and process is provided in which alkali borohydride materials are created which contain effective amounts of catalyst(s) which include transition metal oxides, halides, and chlorides of titanium, zirconium, tin, and combinations of the various catalysts. When the catalysts are added to an alkali borodydride such as a lithium borohydride, the initial hydrogen release point of the resulting mixture is substantially lowered. Additionally, the hydrogen storage material may be rehydrided with weight percent values of hydrogen at least about 9 percent.

Analytical Modeling of Variable Density Multilayer Insulation for Cryogenic Storage

NASA Technical Reports Server (NTRS)

Hedayat, A.; Hastings, L. J.; Brown, T.; Cruit, Wendy (Technical Monitor)

2001-01-01

A unique foam/Multilayer Insulation (MLI) combination concept for orbital cryogenic storage was experimentally evaluated at NASA Marshall Space Flight Center (MSFC) using the Multipurpose Hydrogen Test Bed (MHTB). The MLI was designed for an on-orbit storage period of 45 days and included several unique features such as: a variable layer density and larger but fewer perforations for venting during ascent to orbit. Test results with liquid hydrogen indicated that the MLI weight or heat leak is reduced by about half in comparison with standard MLI. The focus of this paper is on analytical modeling of the Variable Density MLI (VD-MLI) on-orbit performance (i.e. vacuum/low pressure environment). The foam/VD-MLI combination model is considered to have five segments. The first segment represents the optional foam layer. The second, third, and fourth segments represent three MLI segments with different layer densities. The last segment is considered to be a shroud that surrounds the last MLI layer. Two approaches are considered. In the first approach, the variable density MLI is modeled layer by layer while in the second approach, a semi-empirical model is applied. Both models account for thermal radiation between shields, gas conduction, and solid conduction through the layer separator materials.

Structural, vibrational and thermodynamic properties of Mg2 FeH6 complex hydride

NASA Astrophysics Data System (ADS)

Zhou, H. L.; Yu, Y.; Zhang, H. F.; Gao, T.

2011-02-01

Mg2FeH6, which has one of the highest hydrogen storage capacities among Mg based 3d-transitional metal hydrides, is considered as an attractive material for hydrogen storage. Within density-functional perturbation theory (DFPT), we have investigated the structural, vibrational and thermodynamic properties of Mg2FeH6. The band structure calculation shows that this compound is a semiconductor with a direct X-X energy gap of 1.96 eV. The calculated phonon frequencies for the Raman-active and the infrared-active modes are assigned. The phonon dispersion curves together with the corresponding phonon density of states and longitudinal-transverse optical (LO-TO) splitting are also calculated. Findings are also presented for the temperature-dependent behaviors of some thermodynamic properties such as free energy, internal energy, entropy and heat capacity within the quasi-harmonic approximation based on the calculated phonon density of states.

Porous substrates filled with nanomaterials

DOEpatents

Worsley, Marcus A.; Baumann, Theodore F.; Satcher, Jr., Joe H.; Stadermann, Michael

2018-04-03

A composition comprising: at least one porous carbon monolith, such as a carbon aerogel, comprising internal pores, and at least one nanomaterial, such as carbon nanotubes, disposed uniformly throughout the internal pores. The nanomaterial can be disposed in the middle of the monolith. In addition, a method for making a monolithic solid with both high surface area and good bulk electrical conductivity is provided. A porous substrate having a thickness of 100 microns or more and comprising macropores throughout its thickness is prepared. At least one catalyst is deposited inside the porous substrate. Subsequently, chemical vapor deposition is used to uniformly deposit a nanomaterial in the macropores throughout the thickness of the porous substrate. Applications include electrical energy storage, such as batteries and capacitors, and hydrogen storage.

Porous substrates filled with nanomaterials

DOEpatents

Worsley, Marcus A.; Baumann, Theodore F.; Satcher, Jr., Joe H.; Stadermann, Michael

2014-08-19

A composition comprising: at least one porous carbon monolith, such as a carbon aerogel, comprising internal pores, and at least one nanomaterial, such as carbon nanotubes, disposed uniformly throughout the internal pores. The nanomaterial can be disposed in the middle of the monolith. In addition, a method for making a monolithic solid with both high surface area and good bulk electrical conductivity is provided. A porous substrate having a thickness of 100 microns or more and comprising macropores throughout its thickness is prepared. At least one catalyst is deposited inside the porous substrate. Subsequently, chemical vapor deposition is used to uniformly deposit a nanomaterial in the macropores throughout the thickness of the porous substrate. Applications include electrical energy storage, such as batteries and capacitors, and hydrogen storage.

Carbon material for hydrogen storage

DOEpatents

Bourlinos, Athanasios; Steriotis, Theodore; Stubos, Athanasios; Miller, Michael A

2016-09-13

The present invention relates to carbon based materials that are employed for hydrogen storage applications. The material may be described as the pyrolysis product of a molecular precursor such as a cyclic quinone compound. The pyrolysis product may then be combined with selected transition metal atoms which may be in nanoparticulate form, where the metals may be dispersed on the material surface. Such product may then provide for the reversible storage of hydrogen. The metallic nanoparticles may also be combined with a second metal as an alloy to further improve hydrogen storage performance.

Pad B Liquid Hydrogen Storage Tank

NASA Technical Reports Server (NTRS)

Hall, Felicia

2007-01-01

Kennedy Space Center is home to two liquid hydrogen storage tanks, one at each launch pad of Launch Complex 39. The liquid hydrogen storage tank at Launch Pad B has a significantly higher boil off rate that the liquid hydrogen storage tank at Launch Pad A. This research looks at various calculations concerning the at Launch Pad B in an attempt to develop a solution to the excess boil off rate. We will look at Perlite levels inside the tank, Boil off rates, conductive heat transfer, and radiant heat transfer through the tank. As a conclusion to the research, we will model the effects of placing an external insulation to the tank in order to reduce the boil off rate and increase the economic efficiency of the liquid hydrogen storage tanks.

High capacity hydrogen storage nanocomposite materials

DOEpatents

Zidan, Ragaiy; Wellons, Matthew S.

2017-12-12

A novel hydrogen absorption material is provided comprising a mixture of a lithium hydride with a fullerene. The subsequent reaction product provides for a hydrogen storage material which reversibly stores and releases hydrogen at temperatures of about 270.degree. C.

High capacity hydrogen storage nanocomposite materials

DOEpatents

Zidan, Ragaiy; Wellons, Matthew S

2015-02-03

A novel hydrogen absorption material is provided comprising a mixture of a lithium hydride with a fullerene. The subsequent reaction product provides for a hydrogen storage material which reversibly stores and releases hydrogen at temperatures of about 270.degree. C.

The Quest for Greater Chemical Energy Storage: A Deceiving Game of Nanometer Manipulation

NASA Astrophysics Data System (ADS)

Lindsay, C. Michael

2015-06-01

It is well known that modern energetic materials based on organic chemistry have nearly reached a plateau in performance with only ~ 40% improvement realized over the past half century. This fact has stimulated research on alternative chemical energy storage schema in various US government funded ``High Energy Density Materials'' (HEDM) programs since the 1950's. These efforts have examined a wide range of phenomena such as free radical stabilization, metallic hydrogen, metastable helium, polynitrogens, extended molecular solids, nanothermites, and others. In spite of the substantial research investments, significant improvements in energetic material performance have not been forthcoming. In this talk we will survey various fundamental modes of chemical energy storage, lesson's learned in the various HEDM programs, and areas that are being explored currently. A recurring theme in all of this work is the challenge to successfully manipulate and stabilize matter at the ~ 1 nm scale.

Development of a Ground Operations Demonstration Unit for Liquid Hydrogen at Kennedy Space Center

NASA Astrophysics Data System (ADS)

Notardonato, W. U.

NASA operations for handling cryogens in ground support equipment have not changed substantially in 50 years, despite major technology advances in the field of cryogenics. NASA loses approximately 50% of the hydrogen purchased because of a continuous heat leak into ground and flight vessels, transient chill down of warm cryogenic equipment, liquid bleeds, and vent losses. NASA Kennedy Space Center (KSC) needs to develop energy-efficient cryogenic ground systems to minimize propellant losses, simplify operations, and reduce cost associated with hydrogen usage. The GODU LH2 project will design, assemble, and test a prototype storage and distribution system for liquid hydrogen that represents an advanced end-to-end cryogenic propellant system for a ground launch complex. The project has multiple objectives and will culminate with an operational demonstration of the loading of a simulated flight tank with densified propellants. The system will be unique because it uses an integrated refrigeration and storage system (IRAS) to control the state of the fluid. The integrated refrigerator is the critical feature enabling the testing of the following three functions: zero-loss storage and transfer, propellant densification/conditioning, and on-site liquefaction. This paper will discuss the test objectives, the design of the system, and the current status of the installation.

Relationship between crystal structure and solid-state properties of pharmaceuticals

NASA Astrophysics Data System (ADS)

Sheth, Agam R.

This thesis strives to understand the structure-property relationships of some pharmaceutical crystals at the molecular level with emphasis on the effect of secondary processing on the solid phase. Using single crystal X-ray diffractometry (SCXRD), the structure of warfarin sodium 2-propanol adduct (W) was established to be a true solvate, contrary to previous reports. Using dynamic water vapor sorption, optical and environmental scanning electron microscopy, SCXRD, powder X-ray diffractometry (PXRD), volume computations and molecular modeling, the effect of relative humidity and temperature on the crystal structure of W was investigated. Ab initio calculations on piroxicam showed that the difference in energy between the two polymorphs, I and II, arises predominantly from the difference between their lattice energies. The detailed hydrogen bonding networks of the two polymorphs are described and compared using graph sets. Despite stabilization of the polymorphs by hydrogen bonds, pair-wise distribution function transforms show a loss of polymorphic memory upon cryogrinding the two polymorphs, leading to a difference in recrystallization behavior between amorphous piroxicam prepared from polymorphs I and II. Structural and solid-state changes of piroxicam polymorphs under mechanical stress were investigated using cryogenic grinding, PXRD, diffuse-reflectance solid-state ultraviolet-visible spectroscopy, 13C solid-state nuclear magnetic resonance spectroscopy, and diffuse-reflectance solid-state Fourier-transform infrared spectroscopy. Intermolecular proton transfer was found to accompany changes in phase and color observed upon cryogrinding the two polymorphs. Model-free and model-fitting studies of the dehydration kinetics of piroxicam monohydrate (PM) showed the dependence of activation energy ( Ea) on both isothermal and non-isothermal heating conditions, and on the fraction of conversion. In the constant-E a region, isothermal dehydration follows the two-dimensional phase boundary model, while non-isothermal dehydration follows a mechanism intermediate between two- and three-dimensional diffusion that cannot be described by any of the common models. Structural studies suggest that the complex hydrogen bond pattern in PM is responsible for the observed dehydration behavior. Ab initio calculations provide an explanation for the changes in the molecular and crystal structures accompanying the reversible change in hydration state between anhydrous piroxicam Form I and PM. The thesis further demonstrates the utility of model-free analysis in describing complex dehydration kinetics.

Vehicular hydrogen storage using lightweight tanks (regenerative fuel cell systems)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mitlitsky, F; Myers, B; Weisberg, A H

1999-06-01

Energy storage systems with extremely high specific energy (>400 Wh/kg) have been designed that use lightweight tankage to contain the gases generated by reversible (unitized) regenerative fuel cells (URFCs). Lawrence Livermore National Laboratory (LLNL) will leverage work for aerospace applications supported by other sponsors (including BMDO, NASA, and USAF) to develop URFC systems for transportation and utility applications. Lightweight tankage is important for primary fuel cell powered vehicles that use on-board storage of hydrogen. Lightweight pressure vessels with state-of-the-art performance factors were designed, and prototypes are being fabricated to meet the DOE 2000 goals (4000 Wh/kg, 12% hydrogen by weight,more » 700 Wh/liter, and $20/kWh in high volume production). These pressure vessels use technologies that are easily adopted by industrial partners. Advanced liners provide permeation barriers for gas storage and are mandrels for composite overwrap. URFCs are important to the efficient use of hydrogen as a transportation fuel and enabler of renewable energy. H{sub 2}/halogen URFCs may be advantageous for stationary applications whereas H{sub 2}/O{sub 2} or H{sub 2}/air URFCs are advantageous for vehicular applications. URFC research and development is required to improve performance (efficiency), reduce catalyst loading, understand engineering operation, and integrate systems. LLNL has the experimental equipment and advanced URFC membrane electrode assemblies (some with reduced catalyst loading) for evaluating commercial hardware (not funded by DOE in FY1999).« less

Design tool for estimating chemical hydrogen storage system characteristics for light-duty fuel cell vehicles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brooks, Kriston P.; Sprik, Samuel J.; Tamburello, David A.

The U.S. Department of Energy (DOE) has developed a vehicle framework model to simulate fuel cell-based light-duty vehicle operation for various hydrogen storage systems. This transient model simulates the performance of the storage system, fuel cell, and vehicle for comparison to DOE’s Technical Targets using four drive cycles/profiles. Chemical hydrogen storage models have been developed for the Framework model for both exothermic and endothermic materials. Despite the utility of such models, they require that material researchers input system design specifications that cannot be easily estimated. To address this challenge, a design tool has been developed that allows researchers to directlymore » enter kinetic and thermodynamic chemical hydrogen storage material properties into a simple sizing module that then estimates the systems parameters required to run the storage system model. Additionally, this design tool can be used as a standalone executable file to estimate the storage system mass and volume outside of the framework model and compare it to the DOE Technical Targets. These models will be explained and exercised with existing hydrogen storage materials.« less

All-solid-state supercapacitors on silicon using graphene from silicon carbide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Bei; Ahmed, Mohsin; Iacopi, Francesca, E-mail: f.iacopi@griffith.edu.au

2016-05-02

Carbon-based supercapacitors are lightweight devices with high energy storage performance, allowing for faster charge-discharge rates than batteries. Here, we present an example of all-solid-state supercapacitors on silicon for on-chip applications, paving the way towards energy supply systems embedded in miniaturized electronics with fast access and high safety of operation. We present a nickel-assisted graphitization method from epitaxial silicon carbide on a silicon substrate to demonstrate graphene as a binder-free electrode material for all-solid-state supercapacitors. We obtain graphene electrodes with a strongly enhanced surface area, assisted by the irregular intrusion of nickel into the carbide layer, delivering a typical double-layer capacitancemore » behavior with a specific area capacitance of up to 174 μF cm{sup −2} with about 88% capacitance retention over 10 000 cycles. The fabrication technique illustrated in this work provides a strategic approach to fabricate micro-scale energy storage devices compatible with silicon electronics and offering ultimate miniaturization capabilities.« less

Ab Initio Simulation Beryllium in Solid Molecular Hydrogen: Elastic Constant

NASA Astrophysics Data System (ADS)

Guerrero, Carlo L.; Perlado, Jose M.

2016-03-01

In systems of inertial confinement fusion targets Deuterium-Tritium are manufactured with a solid layer, it must have specific properties to increase the efficiency of ignition. Currently there have been some proposals to model the phases of hydrogen isotopes and hence their high pressure, but these works do not allow explaining some of the structures present at the solid phase change effect of increased pressure. By means of simulation with first principles methods and Quantum Molecular Dynamics, we compare the structural difference of solid molecular hydrogen pure and solid molecular hydrogen with beryllium, watching beryllium inclusion in solid hydrogen matrix, we obtain several differences in mechanical properties, in particular elastic constants. For C11 the difference between hydrogen and hydrogen with beryllium is 37.56%. This may produce a non-uniform initial compression and decreased efficiency of ignition.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Valery, N.

The calorific values of the fuels being studied were compared. Petrol is the most efficient, followed by methane in the form of LGN, then methanol and liquid hydrogen. Hydrogen is attractive only on a weight basis, but the storage problems are serious for its liquefied state. Liquid methane requires the same costly storage equipment as hydrogen, making it prohibitive for road vehicles. Methanol is a clean burning fuel and manufacturing processes are being developed. Tests are being sponsored by the Office of Coal Research and the American Gas Association and large-scale commercial plants could be capable of being onstream bymore » 1978. Synthetic crude oil has been manufactured in Sasol, South Africa since 1955. The technique is based on the Fischer-Tropsch process for synthesizing oil from coal, not only making synthetic petrol from coal but also the full range of products normally derived from crude oil. (MCW)« less

Liquid Hydrogen Zero-Boiloff Testing and Analysis for Long-Term Orbital Storage

NASA Astrophysics Data System (ADS)

Hastings, L. J.; Hedayat, A.; Bryant, C. B.; Flachbart, R. H.

2004-06-01

Advancement of cryocooler and passive insulation technologies in recent years has improved the prospects for zero-boiloff (ZBO) storage of cryogenic fluids. The ZBO concept involves the use of a cryocooler/radiator system to balance storage system incoming and extracted energy such that zero boiloff (no venting) occurs. A large-scale demonstration of the ZBO concept was conducted using the Marshall Space Flight Center (MSFC) multipurpose hydrogen test bed (MHTB) along with a commercial cryocooler unit. The liquid hydrogen (LH2) was withdrawn from the tank, passed through the cryocooler heat exchanger, and then the chilled liquid was sprayed back into the tank through a spray bar. The spray bar recirculation system was designed to provide destratification independent of ullage and liquid positions in a zero-gravity environment. The insulated MHTB tank, combined with the vacuum chamber conditions, enabled orbital storage simulation. ZBO was demonstrated for fill levels of 95%, 50%, and 25%. At each fill level, a steady-state boiloff test was performed prior to operating the cryocooler to establish the baseline heat leak. Control system logic based on real-time thermal data and ullage pressure response was implemented to automatically provide a constant tank pressure. A comparison of test data and analytical results is presented in this paper.

Impact of metal and anion substitutions on the hydrogen storage properties of M-BTT metal-organic frameworks.

PubMed

Sumida, Kenji; Stück, David; Mino, Lorenzo; Chai, Jeng-Da; Bloch, Eric D; Zavorotynska, Olena; Murray, Leslie J; Dincă, Mircea; Chavan, Sachin; Bordiga, Silvia; Head-Gordon, Martin; Long, Jeffrey R

2013-01-23

Microporous metal-organic frameworks are a class of materials being vigorously investigated for mobile hydrogen storage applications. For high-pressure storage at ambient temperatures, the M(3)[(M(4)Cl)(3)(BTT)(8)](2) (M-BTT; BTT(3-) = 1,3,5-benzenetristetrazolate) series of frameworks are of particular interest due to the high density of exposed metal cation sites on the pore surface. These sites give enhanced zero-coverage isosteric heats of adsorption (Q(st)) approaching the optimal value for ambient storage applications. However, the Q(st) parameter provides only a limited insight into the thermodynamics of the individual adsorption sites, the tuning of which is paramount for optimizing the storage performance. Here, we begin by performing variable-temperature infrared spectroscopy studies of Mn-, Fe-, and Cu-BTT, allowing the thermodynamics of H(2) adsorption to be probed experimentally. This is complemented by a detailed DFT study, in which molecular fragments representing the metal clusters within the extended solid are simulated to obtain a more thorough description of the structural and thermodynamic aspects of H(2) adsorption at the strongest binding sites. Then, the effect of substitutions at the metal cluster (metal ion and anion within the tetranuclear cluster) is discussed, showing that the configuration of this unit indeed plays an important role in determining the affinity of the framework toward H(2). Interestingly, the theoretical study has identified that the Zn-based analogs would be expected to facilitate enhanced adsorption profiles over the compounds synthesized experimentally, highlighting the importance of a combined experimental and theoretical approach to the design and synthesis of new frameworks for H(2) storage applications.

First-principles studies of hydrogen interaction with ultrathin Mg and Mg-based alloy films

NASA Astrophysics Data System (ADS)

Yoon, Mina; Weitering, Hanno H.; Zhang, Zhenyu

2011-01-01

The search for technologically and economically viable storage solutions for hydrogen fuel would benefit greatly from research strategies that involve systematic property tuning of potential storage materials via atomic-level modification. Here, we use first-principles density-functional theory to investigate theoretically the structural and electronic properties of ultrathin Mg films and Mg-based alloy films and their interaction with atomic hydrogen. Additional delocalized charges are distributed over the Mg films upon alloying them with 11.1% of Al or Na atoms. These extra charges contribute to enhance the hydrogen binding strength to the films. We calculated the chemical potential of hydrogen in Mg films for different dopant species and film thickness, and we included the vibrational degrees of freedom. By comparing the chemical potential with that of free hydrogen gas at finite temperature (T) and pressure (P), we construct a hydrogenation phase diagram and identify the conditions for hydrogen absorption or desorption. The formation enthalpies of metal hydrides are greatly increased in thin films, and in stark contrast to its bulk phase, the hydride state can only be stabilized at high P and T (where the chemical potential of free H2 is very high). Metal doping increases the thermodynamic stabilities of the hydride films and thus significantly helps to reduce the required pressure condition for hydrogen absorption from H2 gas. In particular, with Na alloying, hydrogen can be absorbed and/or desorbed at experimentally accessible T and P conditions.

Metallic glassy Zr70Ni20Pd10 powders for improving the hydrogenation/dehydrogenation behavior of MgH2

PubMed Central

El-Eskandarany, M. Sherif

2016-01-01

Because of its low density, storage of hydrogen in the gaseous and liquids states possess technical and economic challenges. One practical solution for utilizing hydrogen in vehicles with proton-exchange fuel cells membranes is storing hydrogen in metal hydrides. Magnesium hydride (MgH2) remains the best hydrogen storage material due to its high hydrogen capacity and low cost of production. Due to its high activation energy and poor hydrogen sorption/desorption kinetics at moderate temperatures, the pure form of MgH2 is usually mechanically treated by high-energy ball mills and catalyzed with different types of catalysts. These steps are necessary for destabilizing MgH2 to enhance its kinetics behaviors. In the present work, we used a small mole fractions (5 wt.%) of metallic glassy of Zr70Ni20Pd10 powders as a new enhancement agent to improve its hydrogenation/dehydrogenation behaviors of MgH2. This short-range ordered material led to lower the decomposition temperature of MgH2 and its activation energy by about 121 °C and 51 kJ/mol, respectively. Complete hydrogenation/dehydrogenation processes were successfully achieved to charge/discharge about 6 wt.%H2 at 100 °C/200 °C within 1.18 min/3.8 min, respectively. In addition, this new nanocomposite system shows high performance of achieving continuous 100 hydrogen charging/discharging cycles without degradation. PMID:27220994

rac-4-(2-Meth-oxy-phen-yl)-2,6-dimethyl-cyclo-hex-3-ene-carb-oxy-lic acid.

PubMed

Xie, Songwen; Fowler, Brian P; Deyo, Sara M; Pink, Maren

2010-05-29

The title compound, C(16)H(20)O(3), was synthesized to study the hydrogen-bonding inter-actions of the two enanti-omers in the solid state. Inter-molecular O-H⋯O hydrogen bonds produce centrosymmetric R(2) (2)(8) rings which dimerize the two chiral enanti-omers together through their carboxyl groups.

Highly flexible and all-solid-state paperlike polymer supercapacitors.

PubMed

Meng, Chuizhou; Liu, Changhong; Chen, Luzhuo; Hu, Chunhua; Fan, Shoushan

2010-10-13

In recent years, much effort have been dedicated to achieve thin, lightweight and even flexible energy-storage devices for wearable electronics. Here we demonstrate a novel kind of ultrathin all-solid-state supercapacitor configuration with an extremely simple process using two slightly separated polyaniline-based electrodes well solidified in the H(2)SO(4)-polyvinyl alcohol gel electrolyte. The thickness of the entire device is much comparable to that of a piece of commercial standard A4 print paper. Under its highly flexible (twisting) state, the integrate device shows a high specific capacitance of 350 F/g for the electrode materials, well cycle stability after 1000 cycles and a leakage current of as small as 17.2 μA. Furthermore, due to its polymer-based component structure, it has a specific capacitance of as high as 31.4 F/g for the entire device, which is more than 6 times that of current high-level commercial supercapacitor products. These highly flexible and all-solid-state paperlike polymer supercapacitors may bring new design opportunities of device configuration for energy-storage devices in the future wearable electronic area.

Rapid Diffusion and Nanosegregation of Hydrogen in Magnesium Alloys from Exposure to Water.

PubMed

Brady, Michael P; Ievlev, Anton V; Fayek, Mostafa; Leonard, Donovan N; Frith, Matthew G; Meyer, Harry M; Ramirez-Cuesta, Anibal J; Daemen, Luke L; Cheng, Yongqiang; Guo, Wei; Poplawsky, Jonathan D; Ovchinnikova, Olga S; Thomson, Jeffrey; Anovitz, Lawrence M; Rother, Gernot; Shin, Dongwon; Song, Guang-Ling; Davis, Bruce

2017-11-01

Hydrogen gas is formed when Mg corrodes in water; however, the manner and extent to which the hydrogen may also enter the Mg metal is poorly understood. Such knowledge is critical as stress corrosion cracking (SCC)/embrittlement phenomena limit many otherwise promising structural and functional uses of Mg. Here, we report via D 2 O/D isotopic tracer and H 2 O exposures with characterization by secondary ion mass spectrometry, inelastic neutron scattering vibrational spectrometry, electron microscopy, and atom probe tomography techniques direct evidence that hydrogen rapidly penetrated tens of micrometers into Mg metal after only 4 h of exposure to water at room temperature. Further, technologically important microalloying additions of <1 wt % Zr and Nd used to improve the manufacturability and mechanical properties of Mg significantly increased the extent of hydrogen ingress, whereas Al additions in the 2-3 wt % range did not. Segregation of hydrogen species was observed at regions of high Mg/Zr/Nd nanoprecipitate density and at Mg(Zr) metastable solid solution microstructural features. We also report evidence that this ingressed hydrogen was unexpectedly present in the alloy as nanoconfined, molecular H 2 . These new insights provide a basis for strategies to design Mg alloys to resist SCC in aqueous environments as well as potentially impact functional uses such as hydrogen storage where increased hydrogen uptake is desired.

Rapid Diffusion and Nanosegregation of Hydrogen in Magnesium Alloys from Exposure to Water

DOE PAGES

Brady, Michael P.; Ievlev, Anton V.; Fayek, Mostafa; ...

2017-10-10

Hydrogen gas is formed when Mg corrodes in water; however, the manner and extent to which the hydrogen may also enter the Mg metal is poorly understood. Such knowledge is critical as stress corrosion cracking (SCC)/embrittlement phenomena limit many otherwise promising structural and functional uses of Mg. Here, we report via D 2O/D isotopic tracer and H 2O exposures with characterization by secondary ion mass spectrometry, inelastic neutron scattering vibrational spectrometry, electron microscopy, and atom probe tomography techniques direct evidence that hydrogen rapidly penetrated tens of micrometers into Mg metal after only 4 h of exposure to water at roommore » temperature. Further, technologically important microalloying additions of <1 wt % Zr and Nd used to improve the manufacturability and mechanical properties of Mg significantly increased the extent of hydrogen ingress, whereas Al additions in the 2–3 wt % range did not. Segregation of hydrogen species was observed at regions of high Mg/Zr/Nd nanoprecipitate density and at Mg(Zr) metastable solid solution microstructural features. We also report evidence that this ingressed hydrogen was unexpectedly present in the alloy as nanoconfined, molecular H 2. These new insights provide a basis for strategies to design Mg alloys to resist SCC in aqueous environments as well as potentially impact functional uses such as hydrogen storage where increased hydrogen uptake is desired.« less

Environment-dependent conformation investigation of 3-amino-1,2,4-triazole (3-AT): Raman Spectroscopy and density functional theory

NASA Astrophysics Data System (ADS)

Meng, Shuang; Zhao, Yanying; Xue, Jiadan; Zheng, Xuming

2018-02-01

In the paper, diverse tautomers of 3-amino-1,2,4-triazole (3AT) in solid and polar solvent have been explored by FT-IR, FT-Raman and 488 nm Raman experiments combing with quantum chemical theoretical calculation using PCM solvent model and normal mode analysis. The vibrational spectra prefer the 3-amino-1,2,4-2H-triazole (2H-3AT) dimer in solid, while in a polar solvent 3AT is apt to the 3-amino-1,2,4-2H-triazole (2H-3AT) monomer. The significant wavenumber difference and Raman intensity patterns in solid and different solvents are induced by hydrogen bond perturbation along > NH ⋯ N ≤ hydrogen bonds on five-membered N-heterocyclic ring. The ground state proton transfer reaction mechanism along the five-membered N-heterocyclic ring is supported by intermolecular hydrogen bonding between 3AT and protonic solvent molecules.

Process for hydrocracking carbonaceous material in liquid carrier

DOEpatents

Duncan, Dennis A.

1980-01-01

Solid carbonaceous material is hydrocracked to provide aliphatic and aromatic hydrocarbons for use as gaseous and liquid fuels or chemical feed stock. Particulate carbonaceous material such as coal in slurry with recycled product oil is preheated in liquid state to a temperature of 600.degree.-1200.degree. F. in the presence of hydrogen gas. The product oil acts as a sorbing agent for the agglomerating bitumins to minimize caking within the process. In the hydrocracking reactor, the slurry of oil and carbonaceous particles is heated within a tubular passageway to vaporize the oil and form a gas-solid mixture which is further heated to a hydropyrolysis temperature in excess of 1200.degree. F. The gas-solid mixture is quenched by contact with additional oil to condense normally liquid hydrocarbons for separation from the gases. A fraction of the hydrocarbon liquid product is recycled for quenching and slurrying with the carbonaceous feed. Hydrogen is recovered from the gas for recycle and additional hydrogen is produced by gasification of residual char.

Metal-functionalized silicene for efficient hydrogen storage.

PubMed

Hussain, Tanveer; Chakraborty, Sudip; Ahuja, Rajeev

2013-10-21

First-principles calculations based on density functional theory are used to investigate the electronic structure along with the stability, bonding mechanism, band gap, and charge transfer of metal-functionalized silicene to envisage its hydrogen-storage capacity. Various metal atoms including Li, Na, K, Be, Mg, and Ca are doped into the most stable configuration of silicene. The corresponding binding energies and charge-transfer mechanisms are discussed from the perspective of hydrogen-storage compatibility. The Li and Na metal dopants are found to be ideally suitable, not only for strong metal-to-substrate binding and uniform distribution over the substrate, but also for the high-capacity storage of hydrogen. The stabilities of both Li- and Na-functionalized silicene are also confirmed through molecular dynamics simulations. It is found that both of the alkali metals, Li(+) and Na(+), can adsorb five hydrogen molecules, attaining reasonably high storage capacities of 7.75 and 6.9 wt %, respectively, with average adsorption energies within the range suitable for practical hydrogen-storage applications. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Toward highly stable solid-state unconventional thin-film battery-supercapacitor hybrid devices: Interfacing vertical core-shell array electrodes with a gel polymer electrolyte

NASA Astrophysics Data System (ADS)

Pandey, Gaind P.; Klankowski, Steven A.; Liu, Tao; Wu, Judy; Li, Jun

2017-02-01

A novel solid-state battery-supercapacitor hybrid device is fabricated for high-performance electrical energy storage using a Si anode and a TiO2 cathode in conjunction with a flexible, solid-like gel polymer electrolyte film as the electrolyte and separator. The electrodes were fabricated as three-dimensional nanostructured vertical arrays by sputtering active materials as conformal shells on vertically aligned carbon nanofibers (VACNFs) which serve as the current collector and structural template. Such nanostructured vertical core-shell array-electrodes enable short Li-ion diffusion path and large pseudocapacitive contribution by fast surface reactions, leading to the hybrid features of batteries and supercapacitors that can provide high specific energy over a wide range of power rates. Due to the improved mechanical stability of the infiltrated composite structure, the hybrid cell shows excellent cycling stability and is able to retain more than 95% of the original capacity after 3500 cycles. More importantly, this solid-state device can stably operate in a temperature range from -20 to 60 °C with a very low self-discharge rate and an excellent shelf life. This solid-state architecture is promising for the development of highly stable thin-film hybrid energy storage devices for unconventional applications requiring largely varied power, wider operation temperature, long shelf-life and higher safety standards.

Engineering Solid-State Materials. Strategies for Modeling and Packing Control of Molecular Assemblies into 3-D Networks

DTIC Science & Technology

1993-04-22

cocrystal /materials design/hydrogen bonding 19 ABSTRACT (Continue on reverse if necessary and identify by block number) The crystal structure and...proterties of a number of urea cocrystals are studied with regard to symmetry of the hydrogen-bonded molecular assemblies. The logical consequences of...symmetry element A or M. ¶/or 2 Results: Our specific goals are to design and synthesize urea based cocrystals in which the twofold symmetry and hydrogen

Hydrogen Infrastructure Testing and Research Facility Animation | Hydrogen

Science.gov Websites

at full pressure. This system provides hydrogen to fill fuel cell forklifts and feeds the high pressure compressor. View Photos High Pressure Storage The high pressure hydrogen storage system consists full pressure. This system provides hydrogen to high pressure research projects and for fuel cell

Hydrogen Infrastructure Testing and Research Facility | Energy Systems

Science.gov Websites

hydrogen production through renewable electrolysis, fuel cell manufacturing and testing, high-pressure system provides hydrogen to fill fuel cell forklifts and feeds the high pressure compressor. View Photos High Pressure Storage The high pressure hydrogen storage system consists of four Type II hydrogen tanks

Polyaniline-polypyrrole composites with enhanced hydrogen storage capacities.

PubMed

Attia, Nour F; Geckeler, Kurt E

2013-06-13

A facile method for the synthesis of polyaniline-polypyrrole composite materials with network morphology is developed based on polyaniline nanofibers covered by a thin layer of polypyrrole via vapor phase polymerization. The hydrogen storage capacity of the composites is evaluated at room temperature exhibits a twofold increase in hydrogen storage capacity. The HCl-doped polyaniline nanofibers exhibit a storage capacity of 0.46 wt%, whereas the polyaniline-polypyrrole composites could store 0.91 wt% of hydrogen gas. In addition, the effect of the dopant type, counteranion size, and the doping with palladium nanoparticles on the storage properties are also investigated. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen transmission/storage with a metal hydride/organic slurry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Breault, R.W.; Rolfe, J.; McClaine, A.

1998-08-01

Thermo Power Corporation has developed a new approach for the production, transmission, and storage of hydrogen. In this approach, a chemical hydride slurry is used as the hydrogen carrier and storage media. The slurry protects the hydride from unanticipated contact with moisture in the air and makes the hydride pumpable. At the point of storage and use, a chemical hydride/water reaction is used to produce high-purity hydrogen. An essential feature of this approach is the recovery and recycle of the spent hydride at centralized processing plants, resulting in an overall low cost for hydrogen. This approach has two clear benefits:more » it greatly improves energy transmission and storage characteristics of hydrogen as a fuel, and it produces the hydrogen carrier efficiently and economically from a low cost carbon source. The preliminary economic analysis of the process indicates that hydrogen can be produced for $3.85 per million Btu based on a carbon cost of $1.42 per million Btu and a plant sized to serve a million cars per day. This compares to current costs of approximately $9.00 per million Btu to produce hydrogen from $3.00 per million Btu natural gas, and $25 per million Btu to produce hydrogen by electrolysis from $0.05 per Kwh electricity. The present standard for production of hydrogen from renewable energy is photovoltaic-electrolysis at $100 to $150 per million Btu.« less

Polyaniline as a material for hydrogen storage applications.

PubMed

Attia, Nour F; Geckeler, Kurt E

2013-07-12

The main challenge of commercialization of the hydrogen economy is the lack of convenient and safe hydrogen storage materials, which can adsorb and release a significant amount of hydrogen at ambient conditions. Finding and designing suitable cost-effective materials are vital requirements to overcome the drawbacks of investigated materials. Because of its outstanding electronic, thermal, and chemical properties, the electrically conducting polyaniline (PANI) has a high potential in hydrogen storage applications. In this review, the progress in the use of different structures of conducting PANI, its nanocomposites as well as activated porous materials based on PANI as hydrogen storage materials is presented and discussed. The effect of the unique electronic properties based on the π-electron system in the backbone of these materials in view of the hydrogen uptake and the relevant mechanisms are highlighted. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berger, Cornelius M.; Mahmoud, Abdelfattah; Hermann, Raphaël P.

Rechargeable oxide batteries (ROB) comprise a regenerative solid oxide cell (rSOC) and a storage medium for oxygen ions. A sealed ROB avoids pumping loss, heat loss, and gas purity expenses in comparison with conventional rSOC. However, the iron oxide base storage medium degrades during charging–discharging cycles. In comparison, CaFe 3O 5 has improved cyclability and a high reversible oxygen storage capacity of 22.3 mol%. In this paper, we analyzed the redox mechanism of this compound. After a solid-state synthesis of CaFe 3O 5, we verified the phase composition and studied the redox reaction by means of X-ray diffraction, Mössbauer spectrometry,more » and scanning electron microscopy. Finally, results show a great potential to operate the battery with this storage material during multiple charging–discharging cycles.« less

High Density Hydrogen Storage System Demonstration Using NaAlH4 Based Complex Compound Hydrides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Daniel A. Mosher; Xia Tang; Ronald J. Brown

2007-07-27

This final report describes the motivations, activities and results of the hydrogen storage independent project "High Density Hydrogen Storage System Demonstration Using NaAlH4 Based Complex Compound Hydrides" performed by the United Technologies Research Center under the Department of Energy Hydrogen Program, contract # DE-FC36-02AL67610. The objectives of the project were to identify and address the key systems technologies associated with applying complex hydride materials, particularly ones which differ from those for conventional metal hydride based storage. This involved the design, fabrication and testing of two prototype systems based on the hydrogen storage material NaAlH4. Safety testing, catalysis studies, heat exchangermore » optimization, reaction kinetics modeling, thermochemical finite element analysis, powder densification development and material neutralization were elements included in the effort.« less

Multi-fuel reformers for fuel cells used in transportation: Assessment of hydrogen storage technologies

NASA Astrophysics Data System (ADS)

1994-03-01

This report documents a portion of the work performed on Multi-fuel Reformers for Fuel Cells Used in Transportation. One objective of this program is to develop advanced fuel processing systems to reform methanol, ethanol, natural gas, and other hydrocarbons into hydrogen for use in transportation fuel cell systems, while a second objective is to develop better systems for on-board hydrogen storage. This report examines techniques and technology available for storage of pure hydrogen on board a vehicle as pure hydrogen of hydrides. The report focuses separately on near and far-term technologies, with particular emphasis on the former. Development of lighter, more compact near-term storage systems is recommended to enhance competitiveness and simplify fuel cell design. The far-term storage technologies require substantial applied research in order to become serious contenders.

Analysis of Pressure Variations in a Low-Pressure Nickel-Hydrogen Battery – Part 1

PubMed Central

Purushothaman, B. K.; Wainright, J. S.

2012-01-01

A low pressure nickel-hydrogen battery using either a metal hydride or gaseous hydrogen for H2 storage has been developed for use in implantable neuroprosthetic devices. In this paper, pressure variations inside the cell for the gaseous hydrogen version are analyzed and correlated with oxygen evolution side reaction at the end of charging, the recombination of oxygen with hydrogen during charging and a subsequent rest period, and the self-discharge of the nickel electrode. About 70% of the recombination occurred simultaneously with oxygen evolution during charging and the remaining oxygen recombined with hydrogen during the 1st hour after charging. Self-discharge of the cell varies linearly with hydrogen pressure at a given state of charge and increased with increasing battery charge levels. The coulometric efficiency calculated based on analysis of the pressure-time data agreed well with the efficiency calculated based on the current-time data. Pressure variations in the battery are simulated accurately to predict coulometric efficiency and the state of charge of the cell, factors of extreme importance for a battery intended for implantation within the human body. PMID:22423175

Analysis of Pressure Variations in a Low-Pressure Nickel-Hydrogen Battery - Part 1.

PubMed

Purushothaman, B K; Wainright, J S

2012-05-15

A low pressure nickel-hydrogen battery using either a metal hydride or gaseous hydrogen for H(2) storage has been developed for use in implantable neuroprosthetic devices. In this paper, pressure variations inside the cell for the gaseous hydrogen version are analyzed and correlated with oxygen evolution side reaction at the end of charging, the recombination of oxygen with hydrogen during charging and a subsequent rest period, and the self-discharge of the nickel electrode. About 70% of the recombination occurred simultaneously with oxygen evolution during charging and the remaining oxygen recombined with hydrogen during the 1(st) hour after charging. Self-discharge of the cell varies linearly with hydrogen pressure at a given state of charge and increased with increasing battery charge levels. The coulometric efficiency calculated based on analysis of the pressure-time data agreed well with the efficiency calculated based on the current-time data. Pressure variations in the battery are simulated accurately to predict coulometric efficiency and the state of charge of the cell, factors of extreme importance for a battery intended for implantation within the human body.

Technical and economic aspects of hydrogen storage in metal hydrides

NASA Technical Reports Server (NTRS)

Schmitt, R.

1981-01-01

The recovery of hydrogen from such metal hydrides as LiH, MgH2, TiH2, CaH2 and FeTiH compounds is studied, with the aim of evaluating the viability of the technique for the storage of hydrogen fuel. The pressure-temperature dependence of the reactions, enthalpies of formation, the kinetics of the hydrogen absorption and desorption, and the mechanical and chemical stability of the metal hydrides are taken into account in the evaluation. Economic aspects are considered. Development of portable metal hydride hydrogen storage reservoirs is also mentioned.

Room-temperature storage of quantum entanglement using decoherence-free subspace in a solid-state spin system

NASA Astrophysics Data System (ADS)

Wang, F.; Huang, Y.-Y.; Zhang, Z.-Y.; Zu, C.; Hou, P.-Y.; Yuan, X.-X.; Wang, W.-B.; Zhang, W.-G.; He, L.; Chang, X.-Y.; Duan, L.-M.

2017-10-01

We experimentally demonstrate room-temperature storage of quantum entanglement using two nuclear spins weakly coupled to the electronic spin carried by a single nitrogen-vacancy center in diamond. We realize universal quantum gate control over the three-qubit spin system and produce entangled states in the decoherence-free subspace of the two nuclear spins. By injecting arbitrary collective noise, we demonstrate that the decoherence-free entangled state has coherence time longer than that of other entangled states by an order of magnitude in our experiment.

Study of storage capacity in various carbon/graphene-based solid-state supercapacitors

NASA Astrophysics Data System (ADS)

Subramaniam, C. K.; Boopalan, G.

2014-09-01

Solid-state electrochemical double-layer capacitor (SEDLC) forms excellent energy storage device for high-power applications. They are highly reliable, with no electrolyte leaks, and can be packaged to suit various applications. The electrode material can be activated carbon to graphene. These can have a range of particle size, surface area, pore size and pore distribution for charge storage. The emphasis will be to optimize the graphene to carbon blend in the electrodes which would provide appreciable storage density of the SEDLC. We can use perfluorosulfonic acid polymer as the solid electrolyte in the SEDLC assembly. They have high ionic conductivity, good thermal stability, and mechanical strength. They also have excellent long-term chemical stability. Carbon is widely used for many practical applications, especially for the adsorption of ions and molecules, as it is possible to synthesize one-, two- or three-dimensional (1-, 2-, or 3-D) carbons. Some of the problems in activated carbon like varying micro or mesopores, poor ion mobility due to varying pore distribution, low electrical conductivity, can be overcome using graphene and blends of graphene with carbon of the right pore dimension and distribution. Graphene in various structural nomenclatures have been used by various groups for charge storage. Graphene nanoplates (GNP), with narrow mesopore distributions have been effectively used for SEDLCs. SEDLCs assembled with GNP and blends of GNP with Vulcan XC and solid polymer electrolyte like Nafion show exceptional performance. The cyclic voltammetric studies show that they support high scan rates with substantial smaller capacitance drop as we increase scan rates. Optimization of the electrode structure in terms of blend percentage, binder content and interface character in the frequency and time domain provides excellent insight into the double-layer interface.

The Behavior of Hydrogen Under Extreme Conditions on Ultrafast Timescales (A "Life at the Frontiers of Energy Research" contest entry from the 2011 Energy Frontier Research Centers (EFRCs) Summit and Forum)

ScienceCinema

Mao, Ho-kwang (Director, Center for Energy Frontier Research in Extreme Environments); EFree Staff

2017-12-09

'The Behavior of Hydrogen Under Extreme Conditions on Ultrafast Timescales ' was submitted by the Center for Energy Frontier Research in Extreme Environments (EFree) to the 'Life at the Frontiers of Energy Research' video contest at the 2011 Science for Our Nation's Energy Future: Energy Frontier Research Centers (EFRCs) Summit and Forum. Twenty-six EFRCs created short videos to highlight their mission and their work. EFree is directed by Ho-kwang Mao at the Carnegie Institute of Washington and is a partnership of scientists from thirteen institutions.The Office of Basic Energy Sciences in the U.S. Department of Energy's Office of Science established the 46 Energy Frontier Research Centers (EFRCs) in 2009. These collaboratively-organized centers conduct fundamental research focused on 'grand challenges' and use-inspired 'basic research needs' recently identified in major strategic planning efforts by the scientific community. The overall purpose is to accelerate scientific progress toward meeting the nation's critical energy challenges. The mission of Energy Frontier Research in Extreme Environments is 'to accelerate the discovery and creation of energy-relevant materials using extreme pressures and temperatures.' Research topics are: catalysis (CO{sub 2}, water), photocatalysis, solid state lighting, optics, thermelectric, phonons, thermal conductivity, solar electrodes, fuel cells, superconductivity, extreme environment, radiation effects, defects, spin dynamics, CO{sub 2} (capture, convert, store), greenhouse gas, hydrogen (fuel, storage), ultrafast physics, novel materials synthesis, and defect tolerant materials.

Borazine-boron nitride hybrid hydrogen storage system

DOEpatents

Narula, Chaitanya K [Knoxville, TN; Simonson, J Michael [Knoxville, TN; Maya, Leon [Knoxville, TN; Paine, Robert T [Albuquerque, NM

2008-04-22

A hybrid hydrogen storage composition includes a first phase and a second phase adsorbed on the first phase, the first phase including BN for storing hydrogen by physisorption and the second phase including a borazane-borazine system for storing hydrogen in combined form as a hydride.

Hydrogen as a fuel for today and tomorrow: expectations for advanced hydrogen storage materials/systems research.

PubMed

Hirose, Katsuhiko

2011-01-01

History shows that the evolution of vehicles is promoted by several environmental restraints very similar to the evolution of life. The latest environmental strain is sustainability. Transport vehicles are now facing again the need to advance to use sustainable fuels such as hydrogen. Hydrogen fuel cell vehicles are being prepared for commercialization in 2015. Despite intensive research by the world's scientists and engineers and recent advances in our understanding of hydrogen behavior in materials, the only engineering phase technology which will be available for 2015 is high pressure storage. Thus industry has decided to implement the high pressure tank storage system. However the necessity of smart hydrogen storage is not decreasing but rather increasing because high market penetration of hydrogen fuel cell vehicles is expected from around 2025 onward. In order to bring more vehicles onto the market, cheaper and more compact hydrogen storage is inevitable. The year 2025 seems a long way away but considering the field tests and large scale preparation required, there is little time available for research. Finding smart materials within the next 5 years is very important to the success of fuel cells towards a low carbon sustainable world.

Tetra-n-butylammonium borohydride semiclathrate: a hybrid material for hydrogen storage.

PubMed

Shin, Kyuchul; Kim, Yongkwan; Strobel, Timothy A; Prasad, P S R; Sugahara, Takeshi; Lee, Huen; Sloan, E Dendy; Sum, Amadeu K; Koh, Carolyn A

2009-06-11

In this study, we demonstrate that tetra-n-butylammonium borohydride [(n-C(4)H(9))(4)NBH(4)] can be used to form a hybrid hydrogen storage material. Powder X-ray diffraction measurements verify the formation of tetra-n-butylammonium borohydride semiclathrate, while Raman spectroscopic and direct gas release measurements confirm the storage of molecular hydrogen within the vacant cavities. Subsequent to clathrate decomposition and the release of physically bound H(2), additional hydrogen was produced from the hybrid system via a hydrolysis reaction between the water host molecules and the incorporated BH(4)(-) anions. The additional hydrogen produced from the hydrolysis reaction resulted in a 170% increase in the gravimetric hydrogen storage capacity, or 27% greater storage than fully occupied THF + H(2) hydrate. The decomposition temperature of tetra-n-butylammonium borohydride semiclathrate was measured at 5.7 degrees C, which is higher than that for pure THF hydrate (4.4 degrees C). The present results reveal that the BH(4)(-) anion is capable of stabilizing tetraalkylammonium hydrates.

Light metal decoration on nitrogen/sulfur codoped graphyne: An efficient strategy for designing hydrogen storage media

NASA Astrophysics Data System (ADS)

Mohajeri, Afshan; Shahsavar, Azin

2018-07-01

Nitrogen/sulfur dual doped carbon materials have attracted a great deal of interest due to their fascinating applications in lithium ion batteries, hydrogen storage, and oxygen reduction reactions. Here, the hydrogen storage capacity of NS dual-doped graphyne (GYNS) decorated with Li or Na is theoretically explored. The NS-codoping leads to greater charge transfer and stronger binding between the alkali metal and graphyne surface giving rise to enhanced hydrogen storage capacity. We showed that the NS-codoping increases the hydrogen storage capacities of Li-decorated and Na-decorated GY by almost 30% and 60%, respectively. At high NS concentration, the hydrogen uptake capacities can reach to 8.98 wt% and 9.34 wt% for double-side Li- decorated GYNS and Na-decorated GYNS. Moreover, the average adsorption energies per H2 are -0.27 eV for 2Li/GYNS(33.3%) and -0.26 eV for 2Na/GYNS(33.3%) which lie in desirable range for practical applications at ambient conditions.

A comparative study for Hydrogen storage in metal decorated graphyne nanotubes and graphyne monolayers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu, Jinlian; Guo, Yanhua; Zhang, Yun

A comparative study for hydrogen storage in metal decorated graphyne nanotubes and graphyne monolayers has been investigated within the framework of first-principle calculations. Our results show that the binding energies of Li, Ca, Sc, Ti on graphyne nanotubes are stronger than that on graphyne monolayers. Such strong binding would prevent the formation of metal clusters on graphyne nanotubes. From the charge transfer and partial density of states, it is found that the curvature effect of nanotubes plays an important role for the strong binding strength of metal on graphyne nanotubes. And the hydrogen storage capacity is 4.82 wt%, 5.08 wt%,more » 4.88 wt%, 4.76 wt% for Li, Ca, Sc, Ti decorated graphyne nanotubes that promise a potential material for storing hydrogen. - Graphical abstract: Metal atoms (Li, Ca, Sc and Ti) can strongly bind to graphyne nanotubes to avoid the formation of metal clusters, and a capacity of Ca@graphyne nanotube is 5.08 wt% which is close to the requirement of DOE in 2015. Twenty-four hydrogen molecules absorb to Ti-decorated graphyne nanotube. - Highlights: • The binding strength for metal on graphyne nanotubes is much stronger than that on γ-graphyne monolayer. • Metal atoms can strongly bind to the curving triangle acetylenes rings to avoid the formation of metal clusters. • A capacity of Ca@graphyne nanotube is 5.08 wt% which is close to the requirement of DOE in 2015.« less

Structure-Kinetics Correlations in Isostructural Crystals of α-(ortho-Tolyl)-acetophenones: Pinning Down Electronic Effects Using Laser-Flash Photolysis in the Solid State.

PubMed

Ayitou, Anoklase J-L; Flynn, Kristen; Jockusch, Steffen; Khan, Saeed I; Garcia-Garibay, Miguel A

2016-03-02

Aqueous suspensions of nanocrystals in the 200-500 nm size range of isostructural α-(ortho-tolyl)-acetophenone (1a) and α-(ortho-tolyl)-para-methylacetophenone (1b) displayed good absorption characteristics for flash photolysis experiments in a flow system, with transient spectra and decay kinetics with a quality that is similar to that recorded in solution. In contrast to solution measurements, reactions in the solid state were characterized by a rate limiting hydrogen transfer reaction from the triplet excited state and a very short-lived biradical intermediate, which does not accumulate. Notably, the rate for δ-hydrogen atom transfer of 1a (2.7 × 10(7) s(-1)) in the crystalline phase is 18-fold larger than that of 1b (1.5 × 10(6) s(-1)). With nearly identical molecular and crystal structures, this decrease in the rate of δ-hydrogen abstraction can be assigned unambiguously to an electronic effect by the para-methyl group in 1b, which increases the contribution of the (3)π,π* configuration relative to the reactive (3)n,π* configuration in the lowest triplet excited state. These results highlight the potential of relating single crystal X-ray structural data with absolute kinetics from laser flash photolysis.

Anisotropic storage medium development in a full-scale, sodium alanate-based, hydrogen storage system

DOE PAGES

Jorgensen, Scott W.; Johnson, Terry A.; Payzant, E. Andrew; ...

2016-06-11

Deuterium desorption in an automotive-scale hydrogen storage tube was studied in-situ using neutron diffraction. Gradients in the concentration of the various alanate phases were observed along the length of the tube but no significant radial anisotropy was present. In addition, neutron radiography and computed tomography showed large scale cracks and density fluctuations, confirming the presence of these structures in an undisturbed storage system. These results demonstrate that large scale storage structures are not uniform even after many absorption/desorption cycles and that movement of gaseous hydrogen cannot be properly modeled by a simple porous bed model. In addition, the evidence indicatesmore » that there is slow transformation of species at one end of the tube indicating loss of catalyst functionality. These observations explain the unusually fast movement of hydrogen in a full scale system and shows that loss of capacity is not occurring uniformly in this type of hydrogen-storage system.« less

Metal hydride-based thermal energy storage systems

DOEpatents

Vajo, John J.; Fang, Zhigang

2017-10-03

The invention provides a thermal energy storage system comprising a metal-containing first material with a thermal energy storage density of about 1300 kJ/kg to about 2200 kJ/kg based on hydrogenation; a metal-containing second material with a thermal energy storage density of about 200 kJ/kg to about 1000 kJ/kg based on hydrogenation; and a hydrogen conduit for reversibly transporting hydrogen between the first material and the second material. At a temperature of 20.degree. C. and in 1 hour, at least 90% of the metal is converted to the hydride. At a temperature of 0.degree. C. and in 1 hour, at least 90% of the metal hydride is converted to the metal and hydrogen. The disclosed metal hydride materials have a combination of thermodynamic energy storage densities and kinetic power capabilities that previously have not been demonstrated. This performance enables practical use of thermal energy storage systems for electric vehicle heating and cooling.

Prediction of recrystallization behavior of troglitazone/polyvinylpyrrolidone solid dispersion by solid-state NMR.

PubMed

Ito, Atsutoshi; Watanabe, Tomoyuki; Yada, Shuichi; Hamaura, Takeshi; Nakagami, Hiroaki; Higashi, Kenjirou; Moribe, Kunikazu; Yamamoto, Keiji

2010-01-04

The purpose of this study was to elaborate the relationship between the (13)C CP/MAS NMR spectra and the recrystallization behavior during the storage of troglitazone solid dispersions. The solid dispersions were prepared by either the solvent method or by co-grinding. The recrystallization behavior under storage conditions at 40 degrees C/94% RH was evaluated by the Kolmogorov-Johnson-Mehl-Avrami (KJMA) equation. Solid dispersions prepared by the solvent method or by prolonged grinding brought about inhibition of the nucleation and the nuclei growth at the same time. No differences in the PXRD profiles were found in the samples prepared by the co-grinding and solvent methods, however, (13)C CP/MAS NMR showed significant differences in the spectra. The correlation coefficients using partial least square regression analysis between the PXRD profiles and the apparent nuclei-growth constant or induction period to nucleation were 0.1305 or 0.6350, respectively. In contrast, those between the (13)C CP/MAS NMR spectra and the constant or the period were 0.9916 or 0.9838, respectively. The (13)C CP/MAS NMR spectra had good correlation with the recrystallization kinetic parameters evaluated by the KJMA equation. Consequently, solid-state NMR was judged to be a useful tool for the prediction of the recrystallization behavior of solid dispersions.

Design tool for estimating chemical hydrogen storage system characteristics for light-duty fuel cell vehicles

DOE PAGES

Brooks, Kriston P.; Sprik, Samuel J.; Tamburello, David A.; ...

2018-04-07

The U.S. Department of Energy (DOE) developed a vehicle Framework model to simulate fuel cell-based light-duty vehicle operation for various hydrogen storage systems. This transient model simulates the performance of the storage system, fuel cell, and vehicle for comparison to Technical Targets established by DOE for four drive cycles/profiles. Chemical hydrogen storage models have been developed for the Framework for both exothermic and endothermic materials. Despite the utility of such models, they require that material researchers input system design specifications that cannot be estimated easily. To address this challenge, a design tool has been developed that allows researchers to directlymore » enter kinetic and thermodynamic chemical hydrogen storage material properties into a simple sizing module that then estimates system parameters required to run the storage system model. Additionally, the design tool can be used as a standalone executable file to estimate the storage system mass and volume outside of the Framework model. Here, these models will be explained and exercised with the representative hydrogen storage materials exothermic ammonia borane (NH 3BH 3) and endothermic alane (AlH 3).« less

Seasonal energy storage system based on hydrogen for self sufficient living

NASA Astrophysics Data System (ADS)

Bielmann, M.; Vogt, U. F.; Zimmermann, M.; Züttel, A.

SELF is a resource independent living and working environment. By on-board renewable electricity generation and storage, it accounts for all aspects of living, such as space heating and cooking as well as providing a purified rainwater supply and wastewater treatment, excluding food supply. Uninterrupted, on-demand energy and water supply are the key challenges. Off-grid renewable power supply fluctuations on daily and seasonal time scales impose production gaps that have to be served by local storage, a function normally fulfilled by the grid. While daily variations only obligate a small storage capacity, requirements for seasonal storage are substantial. The energy supply for SELF is reviewed based on real meteorological data and demand patterns for Zurich, Switzerland. A battery system with propane for cooking serves as a reference for battery-only and hybrid battery/hydrogen systems. In the latter, hydrogen is used for cooking and electricity generation. The analysis shows that hydrogen is ideal for long term bulk energy storage on a seasonal timescale, while batteries are best suited for short term energy storage. Although the efficiency penalty from hydrogen generation is substantial, in off-grid systems, this parameter is tolerable since the harvesting ratio of photovoltaic energy is limited by storage capacity.

Design tool for estimating chemical hydrogen storage system characteristics for light-duty fuel cell vehicles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brooks, Kriston P.; Sprik, Samuel J.; Tamburello, David A.

The U.S. Department of Energy (DOE) developed a vehicle Framework model to simulate fuel cell-based light-duty vehicle operation for various hydrogen storage systems. This transient model simulates the performance of the storage system, fuel cell, and vehicle for comparison to Technical Targets established by DOE for four drive cycles/profiles. Chemical hydrogen storage models have been developed for the Framework for both exothermic and endothermic materials. Despite the utility of such models, they require that material researchers input system design specifications that cannot be estimated easily. To address this challenge, a design tool has been developed that allows researchers to directlymore » enter kinetic and thermodynamic chemical hydrogen storage material properties into a simple sizing module that then estimates system parameters required to run the storage system model. Additionally, the design tool can be used as a standalone executable file to estimate the storage system mass and volume outside of the Framework model. Here, these models will be explained and exercised with the representative hydrogen storage materials exothermic ammonia borane (NH 3BH 3) and endothermic alane (AlH 3).« less

Key challenges and recent progress in batteries, fuel cells, and hydrogen storage for clean energy systems

NASA Astrophysics Data System (ADS)

Chalk, Steven G.; Miller, James F.

Reducing or eliminating the dependency on petroleum of transportation systems is a major element of US energy research activities. Batteries are a key enabling technology for the development of clean, fuel-efficient vehicles and are key to making today's hybrid electric vehicles a success. Fuel cells are the key enabling technology for a future hydrogen economy and have the potential to revolutionize the way we power our nations, offering cleaner, more efficient alternatives to today's technology. Additionally fuel cells are significantly more energy efficient than combustion-based power generation technologies. Fuel cells are projected to have energy efficiency twice that of internal combustion engines. However before fuel cells can realize their potential, significant challenges remain. The two most important are cost and durability for both automotive and stationary applications. Recent electrocatalyst developments have shown that Pt alloy catalysts have increased activity and greater durability than Pt catalysts. The durability of conventional fluorocarbon membranes is improving, and hydrocarbon-based membranes have also shown promise of equaling the performance of fluorocarbon membranes at lower cost. Recent announcements have also provided indications that fuel cells can start from freezing conditions without significant deterioration. Hydrogen storage systems for vehicles are inadequate to meet customer driving range expectations (>300 miles or 500 km) without intrusion into vehicle cargo or passenger space. The United States Department of Energy has established three centers of Excellence for hydrogen storage materials development. The centers are focused on complex metal hydrides that can be regenerated onboard a vehicle, chemical hydrides that require off-board reprocessing, and carbon-based storage materials. Recent developments have shown progress toward the 2010 DOE targets. In addition DOE has established an independent storage material testing center to verify storage capacity of promising materials. These developments point to a viable path to achieving the DOE/FreedomCAR cost and performance goals. The transition to hydrogen-powered fuel cell vehicles will occur over the next 10-15 years. In the interim, fossil fuel consumption will be reduced by increased penetration of battery/gasoline hybrid cars.

LANL Virtual Center for Chemical Hydrogen Storage: Chemical Hydrogen Storage Using Ultra-high Surface Area Main Group Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Susan M. Kauzlarich; Phillip P. Power; Doinita Neiner

The focus of the project was to design and synthesize light element compounds and nanomaterials that will reversibly store molecular hydrogen for hydrogen storage materials. The primary targets investigated during the last year were amine and hydrogen terminated silicon (Si) nanoparticles, Si alloyed with lighter elements (carbon (C) and boron (B)) and boron nanoparticles. The large surface area of nanoparticles should facilitate a favorable weight to volume ratio, while the low molecular weight elements such as B, nitrogen (N), and Si exist in a variety of inexpensive and readily available precursors. Furthermore, small NPs of Si are nontoxic and non-corrosive.more » Insights gained from these studies will be applied toward the design and synthesis of hydrogen storage materials that meet the DOE 2010 hydrogen storage targets: cost, hydrogen capacity and reversibility. Two primary routes were explored for the production of nanoparticles smaller than 10 nm in diameter. The first was the reduction of the elemental halides to achieve nanomaterials with chloride surface termination that could subsequently be replaced with amine or hydrogen. The second was the reaction of alkali metal Si or Si alloys with ammonium halides to produce hydrogen capped nanomaterials. These materials were characterized via X-ray powder diffraction, TEM, FTIR, TG/DSC, and NMR spectroscopy.« less

Poly(naphthalene diimide) vinylene: solid state red emission and semiconducting properties for transistors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liang, Xianfeng; Tan, Luxi; Liu, Zitong

Here in this work, a conjugated polymer PNV is developed, linking naphthalene diimide with a vinyl linkage. Owing to the C-H ∙∙∙O hydrogen bond between the carbonyl and the vinyl, PNV exhibits a high red emission with a quantum yield of 33.4% in the solid state while it shows n-type properties with an electron mobility up to 1.5 x 10 -3 cm 2 V -1 s -1 in organic field effect transistors, simultaneously.

Poly(naphthalene diimide) vinylene: solid state red emission and semiconducting properties for transistors

DOE PAGES

Liang, Xianfeng; Tan, Luxi; Liu, Zitong; ...

2017-04-06

Here in this work, a conjugated polymer PNV is developed, linking naphthalene diimide with a vinyl linkage. Owing to the C-H ∙∙∙O hydrogen bond between the carbonyl and the vinyl, PNV exhibits a high red emission with a quantum yield of 33.4% in the solid state while it shows n-type properties with an electron mobility up to 1.5 x 10 -3 cm 2 V -1 s -1 in organic field effect transistors, simultaneously.

Development of a Hydrogen Uptake-Release Mg-Based Alloy by Adding a Polymer CMC (Carboxymethylcellulose, Sodium Salt) via Reaction-Accompanying Milling

NASA Astrophysics Data System (ADS)

Kwak, Young Jun; Choi, Eunho; Song, Myoung Youp

2018-03-01

The addition of carboxymethylcellulose, sodium salt (CMC) might improve the hydrogen uptake and release properties of Mg since it has a relatively low melting point and the melting of CMC during milling in hydrogen (reaction-accompanying milling) may make the milled samples be in good states to absorb and release hydrogen rapidly and to have a large hydrogen-storage capacity. Samples with compositions of 95 w/o Mg + 5 w/o CMC (named Mg-5CMC) and 90 w/o Mg + 10 w/o CMC (named Mg-10CMC) were prepared by adding CMC via reaction-accompanying milling. Activation of Mg-10CMC was completed after about 3 hydrogen uptake-release cycles. Mg-10CMC had a higher initial hydrogen uptake rate and a larger amount of hydrogen absorbed in 60 min, U (60 min), than Mg-5CMC before and after activation. At the cycle number of three (CN = 3), Mg-10CMC had a very high initial hydrogen uptake rate (1.56 w/o H/min) and a large U (60 min) (5.57 w/o H) at 593 K in hydrogen of 12 bar, showing that the activated Mg-10CMC has an effective hydrogen-storage capacity of about 5.6 w/o at 593 K in hydrogen of 12 bar at CN = 3. At CN = 2, Mg-10CMC released 1.00 w/o H in 2.5 min, 4.67 w/o H in 10 min, and 4.76 w/o H in 60 min at 648 K in hydrogen of 1.0 bar. The milling in hydrogen of Mg with CMC is believed to generate imperfections and cracks and reduce the particle size. The addition of 10 w/o CMC was more effective on the initial hydrogen uptake rate and U (60 min) compared with the 10 w/o additions of NbF5, TaF5, Fe2O3, and MnO, and the 10 w/o simultaneous addition of Ni, Fe, and Ti. To the best of our knowledge, this study is the first in which a polymer CMC is added to Mg by reaction-accompanying milling to improve the hydrogen storage properties of Mg.

Prediction of thermodynamically reversible hydrogen storage reactions utilizing Ca-M(M = Li, Na, K)-B-H systems: a first-principles study.

PubMed

Guo, Yajuan; Ren, Ying; Wu, Haishun; Jia, Jianfeng

2013-12-01

Calcium borohydride is a potential candidate for onboard hydrogen storage because it has a high gravimetric capacity (11.5 wt.%) and a high volumetric hydrogen content (∼130 kg m(-3)). Unfortunately, calcium borohydride suffers from the drawback of having very strongly bound hydrogen. In this study, Ca(BH₄)₂ was predicted to form a destabilized system when it was mixed with LiBH₄, NaBH₄, or KBH₄. The release of hydrogen from Ca(BH₄)₂ was predicted to proceed via two competing reaction pathways (leading to CaB₆ and CaH₂ or CaB₁₂H₁₂ and CaH₂) that were found to have almost equal free energies. Using a set of recently developed theoretical methods derived from first principles, we predicted five new hydrogen storage reactions that are among the most attractive of those presently known. These combine high gravimetric densities (>6.0 wt.% H₂) with have low enthalpies [approximately 35 kJ/(mol(-1) H₂)] and are thermodynamically reversible at low pressure within the target window for onboard storage that is actively being considered for hydrogen storage applications. Thus, the first-principles theoretical design of new materials for energy storage in future research appears to be possible.

Tailoring the thermostability and hydrogen storage capacity of Li decorated carbon materials by heteroatom doping

NASA Astrophysics Data System (ADS)

Long, Jun; Li, Jieyuan; Nan, Fang; Yin, Shi; Li, Jianjun; Cen, Wanglai

2018-03-01

Li decorated graphene is supposed to be a promising material for the hydrogen storage, which can be further improved by heteroatom doping. But a unified promoting mechanism for various doping types and species are still lacking, which hinders the rational design of advanced materials. The potential of N/B doped Li decorated graphene for hydrogen storage is investigated with DFT calculations. A covalent interaction between Li and the graphene substrates is identified to control the thermostability and hydrogen storage capacity (HSC) of the Li decorated substrate, which is in turn subject to the electronegativity of doping species and the doping types. Additionally, a conceptual descriptor is proposed to predict the HSC of Li decorated graphene. These results provide a unified explanation and prediction of the effects of heteroatom doping on Li decorated carbon materials for hydrogen storage.

Vapor Pressure Measurements of LiBH4, NaBH 4 and Ca(BH4)2 using Knudsen Torsion Effusion Gravimetric Method

NASA Astrophysics Data System (ADS)

Danyan, Mohammad Masoumi

Hydrogen storage is one of the critical technologies needed on the path towards commercialization for mobile applications. In the past few years, a range of new light weight hydrogen containing material has been discovered with good storage properties. Among them, lithium borohydride (LiBH 4) sodium borohydride (NaBH4) and calcium borohydride (Ca(BH 4)2) have shown promising results to be used as solid state hydrogen storage material. In this work, we have determined equilibrium vapor pressures of LiBH 4 NaBH4 and Ca(BH4)2 obtained by Torsion effusion thermogravimetric method. Results for all the three hydrides exhibited that a small fraction of the materials showed congruency, and sublimed as gaseous compound, but the majority of the material showed incongruent vaporization. Two Knudsen cells of 0.3 and 0.6mm orifice size was employed to measure the total vapor pressures. A Whitman-Motzfeldt method is used to extrapolate the measured vapor pressures to zero orifice size to calculate the equilibrium vapor pressures. In the case of LiBH4 we found that 2% of the material evaporated congruently (LiBH4(s) → LiBH4(g)) according to the equation: logPLiBH4/P 0 =-3263.5 +/-309/T + (1.079 +/-0.69) and rest as incongruent vaporization to LiH, B, and hydrogen gas according to the equation logPeq/P0 =(-3263.5 +/-309)/T+ (2.458 +/-0.69) with DeltaH evap.= 62.47+/-5.9 kJ/mol of H2, DeltaSevap. = 47.05+/-13 J/mol of H2.K. The NaBH4 also had somewhat similar behavior, with 9% congruent evaporation and equilibrium vapor pressure equation of logPLiBH4=-7700+/-335/ T+ (6.7+/-1.5) and 91% incongruent decomposition to Na and Boron metal, and hydrogen gas. The enthalpy of vaporization; DeltaHevap. = 147.2+/-6.4kJ/molH2 and DeltaSevap.= 142 +/-28 kJ/molH2.K (550-650K). The Ca(BH4) 2 exhibited similar vaporization behavior with congruency of 3.2%. The decomposition products are CaH2 and Boron metal with evolution of hydrogen gas varying with the pressure equation as logPeq /P0 =(-1562.7 +/-177)/ T+ (2.57 +/-0.155). The enthalpy and entropy of vaporization, DeltaH evap.= 29.9+/-3.3kJ/molH2, DeltaSevap.=49.14 +/-2.9 J/molH2.K (400-650K) respectively. More details of the properties of the vaporization such partial pressures of effusing gases, Gibbs energies of vaporization, molecular weight of effusing gases, as well as decomposition products, evaporation reactions, thermodynamic modeling of the disproportionation of these three compounds are discussed in this dissertation.

Atomic hydrogen as a launch vehicle propellant

NASA Technical Reports Server (NTRS)

Palaszewski, Bryan A.

1990-01-01

An analysis of several atomic hydrogen launch vehicles was conducted. A discussion of the facilities and the technologies that would be needed for these vehicles is also presented. The Gross Liftoff Weights (GLOW) for two systems were estimated; their specific impulses (I sub sp) were 750 and 1500 lb (sub f)/s/lb(sub m). The atomic hydrogen launch vehicles were also compared to the currently planned Advanced Launch System design concepts. Very significant GLOW reductions of 52 to 58 percent are possible over the Advanced Launch System designs. Applying atomic hydrogen propellants to upper stages was also considered. Very high I(sub sp) (greater than 750 1b(sub f)/s/lb(sub m) is needed to enable a mass savings over advanced oxygen/hydrogen propulsion. Associated with the potential benefits of high I(sub sp) atomic hydrogen are several challenging problems. Very high magnetic fields are required to maintain the atomic hydrogen in a solid kilogauss (3 Tesla). Also the storage temperature of the propellant is 4 K. This very low temperature will require a large refrigeration facility for the launch vehicle. The design considerations for a very high recombination rate for the propellant are also discussed. A recombination rate of 210 cm/s is predicted for atomic hydrogen. This high recombination rate can produce very high acceleration for the launch vehicle. Unique insulation or segmentation to inhibit the propellant may be needed to reduce its recombination rate.

Defects in a nonlinear pseudo one-dimensional solid

NASA Astrophysics Data System (ADS)

Blanchet, Graciela B.; Fincher, C. R., Jr.

1985-03-01

These infrared studies of acetanilide together with the existence of two equivalent structures for the hydrogen-bonded chain suggest the possibility of a topological defect state rather than a Davydov soliton as suggested previously. Acetanilide is an example of a class of one-dimensional materials where solitons are a consequence of a twofold degenerate structure and the nonlinear dynamics of the hydrogen-bonded network.

Nickel hydrogen battery cell storage matrix test

NASA Technical Reports Server (NTRS)

Wheeler, James R.; Dodson, Gary W.

1993-01-01

Test were conducted to evaluate post storage performance of nickel hydrogen cells with various design variables, the most significant being nickel precharge versus hydrogen precharge. Test procedures and results are presented in outline and graphic form.

Modeling of composite hydrogen storage cylinders using finite element analysis

DOT National Transportation Integrated Search

2008-02-01

Pressurized hydrogen storage cylinders are critical components of hydrogen transportation systems. Composite cylinders have pressure/thermal relief devices that are activated in case of an emergency. The difficulty in accurately analyzing the behavio...

Nickel hydrogen capacity loss

NASA Technical Reports Server (NTRS)

Goualard, Jacques; Paugam, D.; Borthomieu, Y.

1993-01-01

The results of tests to assess capacity loss in nickel hydrogen cells are presented in outline form. The effects of long storage (greater than 1 month), high hydrogen pressure storage, high cobalt content, and recovery actions are addressed.

Chemical bridges for enhancing hydrogen storage by spillover and methods for forming the same

DOEpatents

Yang, Ralph T.; Li, Yingwei; Qi, Gongshin; Lachawiec, Jr., Anthony J.

2012-12-25

A composition for hydrogen storage includes a source of hydrogen atoms, a receptor, and a chemical bridge formed between the source and the receptor. The chemical bridge is formed from a precursor material. The receptor is adapted to receive hydrogen spillover from the source.

A comparative analysis of the cryo-compression and cryo-adsorption hydrogen storage methods

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petitpas, G; Benard, P; Klebanoff, L E

2014-07-01

While conventional low-pressure LH₂ dewars have existed for decades, advanced methods of cryogenic hydrogen storage have recently been developed. These advanced methods are cryo-compression and cryo-adsorption hydrogen storage, which operate best in the temperature range 30–100 K. We present a comparative analysis of both approaches for cryogenic hydrogen storage, examining how pressure and/or sorbent materials are used to effectively increase onboard H₂ density and dormancy. We start by reviewing some basic aspects of LH₂ properties and conventional means of storing it. From there we describe the cryo-compression and cryo-adsorption hydrogen storage methods, and then explore the relationship between them, clarifyingmore » the materials science and physics of the two approaches in trying to solve the same hydrogen storage task (~5–8 kg H₂, typical of light duty vehicles). Assuming that the balance of plant and the available volume for the storage system in the vehicle are identical for both approaches, the comparison focuses on how the respective storage capacities, vessel weight and dormancy vary as a function of temperature, pressure and type of cryo-adsorption material (especially, powder MOF-5 and MIL-101). By performing a comparative analysis, we clarify the science of each approach individually, identify the regimes where the attributes of each can be maximized, elucidate the properties of these systems during refueling, and probe the possible benefits of a combined “hybrid” system with both cryo-adsorption and cryo-compression phenomena operating at the same time. In addition the relationships found between onboard H₂ capacity, pressure vessel and/or sorbent mass and dormancy as a function of rated pressure, type of sorbent material and fueling conditions are useful as general designing guidelines in future engineering efforts using these two hydrogen storage approaches.« less

40 CFR 63.2550 - What definitions apply to this subpart?

Code of Federal Regulations, 2010 CFR

2010-07-01

... series of tanks with a fixed roof that contact emissions with a solid media (such as bark) and use... at any time the intermediate is placed in equipment used solely for storage. The storage equipment is...-state reactor is followed by an operation that is designed and operated to remove HAP solvent or...

Method and apparatus for offloading compute resources to a flash co-processing appliance

DOEpatents

Tzelnic, Percy; Faibish, Sorin; Gupta, Uday K.; Bent, John; Grider, Gary Alan; Chen, Hsing -bung

2015-10-13

Solid-State Drive (SSD) burst buffer nodes are interposed into a parallel supercomputing cluster to enable fast burst checkpoint of cluster memory to or from nearby interconnected solid-state storage with asynchronous migration between the burst buffer nodes and slower more distant disk storage. The SSD nodes also perform tasks offloaded from the compute nodes or associated with the checkpoint data. For example, the data for the next job is preloaded in the SSD node and very fast uploaded to the respective compute node just before the next job starts. During a job, the SSD nodes perform fast visualization and statistical analysis upon the checkpoint data. The SSD nodes can also perform data reduction and encryption of the checkpoint data.

Ultra-High Density Holographic Memory Module with Solid-State Architecture

NASA Technical Reports Server (NTRS)

Markov, Vladimir B.

2000-01-01

NASA's terrestrial. space, and deep-space missions require technology that allows storing. retrieving, and processing a large volume of information. Holographic memory offers high-density data storage with parallel access and high throughput. Several methods exist for data multiplexing based on the fundamental principles of volume hologram selectivity. We recently demonstrated that a spatial (amplitude-phase) encoding of the reference wave (SERW) looks promising as a way to increase the storage density. The SERW hologram offers a method other than traditional methods of selectivity, such as spatial de-correlation between recorded and reconstruction fields, In this report we present the experimental results of the SERW-hologram memory module with solid-state architecture, which is of particular interest for space operations.

Solid-state energy storage module employing integrated interconnect board

DOEpatents

Rouillard, Jean; Comte, Christophe; Daigle, Dominik; Hagen, Ronald A.; Knudson, Orlin B.; Morin, Andre; Ranger, Michel; Ross, Guy; Rouillard, Roger; St-Germain, Philippe; Sudano, Anthony; Turgeon, Thomas A.

2000-01-01

The present invention is directed to an improved electrochemical energy storage device. The electrochemical energy storage device includes a number of solid-state, thin-film electrochemical cells which are selectively interconnected in series or parallel through use of an integrated interconnect board. The interconnect board is typically disposed within a sealed housing which also houses the electrochemical cells, and includes a first contact and a second contact respectively coupled to first and second power terminals of the energy storage device. The interconnect board advantageously provides for selective series or parallel connectivity with the electrochemical cells, irrespective of electrochemical cell position within the housing. In one embodiment, a sheet of conductive material is processed by employing a known milling, stamping, or chemical etching technique to include a connection pattern which provides for flexible and selective interconnecting of individual electrochemical cells within the housing, which may be a hermetically sealed housing. Fuses and various electrical and electro-mechanical devices, such as bypass, equalization, and communication devices for example, may also be mounted to the interconnect board and selectively connected to the electrochemical cells.

Flexible solid-state symmetric supercapacitors based on MnO2 nanofilms with high rate capability and long cyclability

NASA Astrophysics Data System (ADS)

Wu, Lingxia; Li, Ruizhi; Guo, Junling; Zhou, Cheng; Zhang, Wenpei; Wang, Chong; Huang, Yu; Li, Yuanyuan; Liu, Jinping

2013-08-01

Flexible solid-state symmetric supercapacitor was fabricated using MnO2 nanofilms growing directly on carbon cloth as the electrodes and PVA/H3PO4 gel as the electrolyte/separator. The device can be operated at a stable cell-voltage up to 1.4 V, obviously larger than that of conventional solid-state symmetric supercapacitors (≤1 V). It exhibited excellent rate capability with a scan rate as high as 20 V s-1 and a long cyclability (˜60000 cycles) even under severe mechanical deformation. The charge storage mechanism at different scan rates was also quantitatively analyzed.

Engineering the Membrane/Electrode Interface To Improve the Performance of Solid-State Supercapacitors.

PubMed

Huang, Chun; Zhang, Jin; Snaith, Henry J; Grant, Patrick S

2016-08-17

This paper investigates the effect of adding a 450 nm layer based on porous TiO2 at the interface between a 4.5 μm carbon/TiO2 nanoparticle-based electrode and a polymer electrolyte membrane as a route to improve energy storage performance in solid-state supercapacitors. Electrochemical characterization showed that adding the interface layer reduced charge transfer resistance, promoted more efficient ion transfer across the interface, and significantly improved charge/discharge dynamics in a solid-state supercapacitor, resulting in an increased areal capacitance from 45.3 to 111.1 mF cm(-2) per electrode at 0.4 mA cm(-2).

Systems and methods for rapid processing and storage of data

DOEpatents

Stalzer, Mark A.

2017-01-24

Systems and methods of building massively parallel computing systems using low power computing complexes in accordance with embodiments of the invention are disclosed. A massively parallel computing system in accordance with one embodiment of the invention includes at least one Solid State Blade configured to communicate via a high performance network fabric. In addition, each Solid State Blade includes a processor configured to communicate with a plurality of low power computing complexes interconnected by a router, and each low power computing complex includes at least one general processing core, an accelerator, an I/O interface, and cache memory and is configured to communicate with non-volatile solid state memory.

Calix

PubMed

Frkanec; Visnjevac; Kojic-Prodic; Zinic

2000-02-04

Chiral calix[4]arene derivatives with four O-(N-acetyl-PhgOMe), (1), (Phg denotes R-phenylglycine), or O-(N-acetyl-LeuOMe) (2) strands have been synthesised. Both compounds exist in chloroform in stable cone conformations with a noncovalently organised cavity at the lower rim that is formed by circular interstrand amidic hydrogen bonds. Such organisation affects both the selectivity and extraction/transport properties of 1 and 2 toward metal cations. Calix[4]arene derivatives with one OCH2COPhgOMe strand (3), two OCH2COPhgOMe strands (5) and with 1,3-OMe-2,4-(O-CH2COPhgOMe) substituents (4) at the lower rim have also been prepared. For 3, a conformation stabilised by a circular hydrogen-bond arrangement is found in chloroform, while 4 exists as a time-averaged C2 conformation with two intramolecular NH ...OCH3 hydrogen bonds. Compound 5 has a unique hydrogen-bonding motif in solution and in the solid state with two three-centred NH-.. O and two OH...O hydrogen bonds at the lower rim. This motif keeps 5 in the flattened cone conformation in chloroform. The X-ray structure analysis of 1 revealed a molecular structure with C2 symmetry; this structure is organised in infinite chains by intra- and intermolecular H bonds. The solid-state and solution structures of the [1-Na]ClO4 complex are identical, C4 symmetric cone conformations.

Empirical Profiling of Cold Hydrogen Plumes Formed from Venting Of LH2 Storage Vessels: Preprint

DOE Office of Scientific and Technical Information (OSTI.GOV)

Buttner, William J; Rivkin, Carl H; Schmidt, Kara

Liquid hydrogen (LH2) storage is a viable approach to assuring 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 process. The behaviour of cold hydrogen plumes has not been well-characterized because empirical field data is essentially non-existent. The NFPA 2 Hydrogen Storage Safety Task Group, which consists of hydrogen producers, safety experts, and CFD modellers, has identified the lack of understanding of hydrogen dispersionmore » during LH2 venting of storage vessel as a critical gap for establishing safety distances at LH2 facilities, especially commercial hydrogen fuelling stations. To address this need, the NREL sensor laboratory, in collaboration with the NFPA 2 Safety Task Group developed the Cold Hydrogen Plume Analyzer to empirically characterize the hydrogen plume formed during LH2 storage tank venting. A prototype Analyzer was developed and field-deployed at an actual LH2 venting operation with critical findings that included: - H2 being detected as much as 2 m lower than the release point, which is not predicted by existing models - A small and inconsistent correlation between oxygen depletion and the hydrogen concentration - A negligible to non-existent correlation between in-situ temperature and the hydrogen concentration The Analyzer is currently being upgraded for enhanced metrological capabilities including improved real-time spatial and temporal profiling of the plume and tracking of prevailing weather conditions. Additional deployments are planned to monitor plume behaviour under different wind, humidity, and temperatures. This data will be shared with the NFPA 2 Safety Task Group and ultimately will be used support theoretical models and code requirements prescribed in NFPA 2.« less

Thermodynamic analysis of a combined-cycle solar thermal power plant with manganese oxide-based thermochemical energy storage

NASA Astrophysics Data System (ADS)

Lei, Qi; Bader, Roman; Kreider, Peter; Lovegrove, Keith; Lipiński, Wojciech

2017-11-01

We explore the thermodynamic efficiency of a solar-driven combined cycle power system with manganese oxide-based thermochemical energy storage system. Manganese oxide particles are reduced during the day in an oxygen-lean atmosphere obtained with a fluidized-bed reactor at temperatures in the range of 750-1600°C using concentrated solar energy. Reduced hot particles are stored and re-oxidized during night-time to achieve continuous power plant operation. The steady-state mass and energy conservation equations are solved for all system components to calculate the thermodynamic properties and mass flow rates at all state points in the system, taking into account component irreversibilities. The net power block and overall solar-to-electric energy conversion efficiencies, and the required storage volumes for solids and gases in the storage system are predicted. Preliminary results for a system with 100 MW nominal solar power input at a solar concentration ratio of 3000, designed for constant round-the-clock operation with 8 hours of on-sun and 16 hours of off-sun operation and with manganese oxide particles cycled between 750 and 1600°C yield a net power block efficiency of 60.0% and an overall energy conversion efficiency of 41.3%. Required storage tank sizes for the solids are estimated to be approx. 5-6 times smaller than those of state-of-the-art molten salt systems.

Effects of reducing temperatures on the hydrogen storage capacity of double-walled carbon nanotubes with Pd loading.

PubMed

Sheng, Qu; Wu, Huimin; Wexler, David; Liu, Huakun

2014-06-01

The effects of different temperatures on the hydrogen sorption characteristics of double-walled carbon nanotubes (DWCNTs) with palladium loading have been investigated. When we use different temperatures, the particle sizes and specific surface areas of the samples are different, which affects the hydrogen storage capacity of the DWCNTs. In this work, the amount of hydrogen storage capacity was determined (by AMC Gas Reactor Controller) to be 1.70, 1.85, 2.00, and 1.93 wt% for pristine DWCNTS and for 2%Pd/DWCNTs-300 degrees C, 2%Pd/DWCNTs-400 degrees C, and 2%Pd/DWCNTs-500 degrees C, respectively. We found that the hydrogen storage capacity can be enhanced by loading with 2% Pd nanoparticles and selecting a suitable temperature. Furthermore, the sorption can be attributed to the chemical reaction between atomic hydrogen and the dangling bonds of the DWCNTs.

Tuning the Hydrogen Storage in Magnesium Alloys

NASA Astrophysics Data System (ADS)

Er, Suleyman; de Wijs, Gilles A.; Brocks, Geert

2011-03-01

We investigate the hydrogen storage properties of promising magnesium alloys. Mg H2 (7.6 wt % H) would be a very useful storage material if the (de)hydrogenation kinetics can be improved and the desorption temperature is markedly lowered. Using first principles calculations, we show that hydrides of Mg-transition metal (TM) alloys adopt a structure that promotes faster (de)hydrogenation kinetics, as is also observed in experiment. Within the lightweight TMs, the most promising alloying element is titanium. Alloying Mg with Ti alone, however, is not sufficient to decrease the stability of the hydride phases, which is necessary to reduce the hydrogen desorption temperature. We find that adding aluminium or silicon markedly destabilizes Mg-Ti hydrides and stabilizes Mg-Ti alloys. Finally, we show that controlling the structure of Mg-Ti-Al(Si) system by growing it as multilayers, has a beneficial influence on the thermodynamic properties and makes it a stronger candidate for hydrogen storage.

Why solid oxide cells can be reversibly operated in solid oxide electrolysis cell and fuel cell modes?

PubMed

Chen, Kongfa; Liu, Shu-Sheng; Ai, Na; Koyama, Michihisa; Jiang, San Ping

2015-12-14

High temperature solid oxide cells (SOCs) are attractive for storage and regeneration of renewable energy by operating reversibly in solid oxide electrolysis cell (SOEC) and solid oxide fuel cell (SOFC) modes. However, the stability of SOCs, particularly the deterioration of the performance of oxygen electrodes in the SOEC operation mode, is the most critical issue in the development of high performance and durable SOCs. In this study, we investigate in detail the electrochemical activity and stability of La0.8Sr0.2MnO3 (LSM) oxygen electrodes in cyclic SOEC and SOFC modes. The results show that the deterioration of LSM oxygen electrodes caused by anodic polarization can be partially or completely recovered by subsequent cathodic polarization. Using in situ assembled LSM electrodes without pre-sintering, we demonstrate that the deteriorated LSM/YSZ interface can be repaired and regenerated by operating the cells under cathodic polarization conditions. This study for the first time establishes the foundation for the development of truly reversible and stable SOCs for hydrogen fuel production and electricity generation in cyclic SOEC and SOFC operation modes.

Development of solid-state NMR techniques for the characterisation of pharmaceutical compounds

NASA Astrophysics Data System (ADS)

Tatton, Andrew S.

Structural characterisation in the solid state is an important step in understanding the physical and chemical properties of a material. Solid-state NMR techniques applied to solid delivery forms are presented as an alternative to more established structural characterisation methods. The effect of homonuclear decoupling upon heteronuclear couplings is investigated using a combination of experimental and density-matrix simulation results acquired from a 13C-1H spinecho pulse sequence, modulated by scalar couplings. It is found that third-order cross terms under MAS and homonuclear decoupling contribute to strong dephasing effects in the NMR signal. Density-matrix simulations allow access to parameters currently unattainable in experiment, and demonstrate that higher homonuclear decoupling rf nutation frequencies reduce the magnitude of third-order cross terms. 15N-1H spinecho experiments were applied to pharmaceutically relevant samples to differentiate between the number of directly attached protons. Using this method, proton transfer in an acid-base reaction is proven in pharmaceutical salts. The indirect detection of 14N lineshapes via protons obtained using 2D 14N-1H HMQC experiments is presented, where coherence transfer is achieved via heteronuclear through-space dipolar couplings. The importance of fast MAS frequencies is demonstrated, and it is found that increasing the recoupling duration reveals longer range NH proximities. The 2D 14N-1H HMQC method is used to demonstrate the presence of specific hydrogen bonding interactions, and thus aid in identifying molecular association in a cocrystal and an amorphous dispersion. In addition, hydrogen bonding motifs were identified by observing the changes in the 14N quadrupolar parameters between individual molecular components relative to the respective solid delivery form. First-principles calculations of NMR chemical shifts and quadrupolar parameters using the GIPAW method were combined with 14N-1H experimental results to assist with spectral assignment and the identification of the hydrogen bonding interactions.

Novel thixotropic gel electrolytes based on dicationic bis-imidazolium salts for quasi-solid-state dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Kim, Jun Young; Kim, Tae Ho; Kim, Dong Young; Park, Nam-Gyu; Ahn, Kwang-Duk

Novel thixotropic gel electrolytes have been successfully prepared by utilizing oligomeric poly(ethylene oxide) (PEO)-based bis-imidazolium diiodide salts and hydrophilic silica nanoparticles for application in quasi-solid-state dye-sensitized solar cells (DSSCs). The thixotropic gel-state of the ionic liquid-based composite electrolytes is confirmed by observing the typical hysteresis loop and temporary hydrogen bonding. On using the PEO-based composite electrolyte, a quasi-solid-state DSSC exhibited highly improved properties such as easy penetration of the electrolyte into the cell without leakage, long-term stability, high open-circuit voltage without the use of 4- tert-butylpyridine, and a high energy-conversion efficiency of 5.25% under AM 1.5 illumination (100 mW cm -2).

Light metal decorated graphdiyne nanosheets for reversible hydrogen storage.

PubMed

Panigrahi, P; Dhinakaran, A K; Naqvi, S R; Gollu, S R; Ahuja, R; Hussain, T

2018-05-29

The sensitive nature of molecular hydrogen (H 2 ) interaction with the surfaces of pristine and functionalized nanostructures, especially two-dimensional materials, has been a subject of debate for a while now. An accurate approximation of the H 2 adsorption mechanism has vital significance for fields such as H 2 storage applications. Owing to the importance of this issue, we have performed a comprehensive density functional theory (DFT) study by means of several different approximations to investigate the structural, electronic, charge transfer and energy storage properties of pristine and functionalized graphdiyne (GDY) nanosheets. The dopants considered here include the light metals Li, Na, K, Ca, Sc and Ti, which have a uniform distribution over GDY even at high doping concentration due to their strong binding and charge transfer mechanism. Upon 11% of metal functionalization, GDY changes into a metallic state from being a small band-gap semiconductor. Such situations turn the dopants to a partial positive state, which is favorable for adsorption of H 2 molecules. The adsorption mechanism of H 2 on GDY has been studied and compared by different methods like generalized gradient approximation, van der Waals density functional and DFT-D3 functionals. It has been established that each functionalized system anchors multiple H 2 molecules with adsorption energies that fall into a suitable range regardless of the functional used for approximations. A significantly high H 2 storage capacity would guarantee that light metal-doped GDY nanosheets could serve as efficient and reversible H 2 storage materials.

Development of a kinetic model of hydrogen absorption and desorption in magnesium and analysis of the rate-determining step

NASA Astrophysics Data System (ADS)

Kitagawa, Yuta; Tanabe, Katsuaki

2018-05-01

Mg is promising as a new light-weight and low-cost hydrogen-storage material. We construct a numerical model to represent the hydrogen dynamics on Mg, comprising dissociative adsorption, desorption, bulk diffusion, and chemical reaction. Our calculation shows a good agreement with experimental data for hydrogen absorption and desorption on Mg. Our model clarifies the evolution of the rate-determining processes as absorption and desorption proceed. Furthermore, we investigate the optimal condition and materials design for efficient hydrogen storage in Mg. By properly understanding the rate-determining processes using our model, one can determine the design principle for high-performance hydrogen-storage systems.

Structure and physicochemical characterization of a naproxen–picolinamide cocrystal

PubMed Central

Kerr, Hannah E.; Softley, Lorna K.; Suresh, Kuthuru; Hodgkinson, Paul; Evans, Ivana Radosavljevic

2017-01-01

Naproxen (NPX) is a nonsteroidal anti-inflammatory drug with pain- and fever-relieving properties, currently marketed in the sodium salt form to overcome solubility problems; however, alternative solutions for improving its solubility across all pH values are desirable. NPX is suitable for cocrystal formation, with hydrogen-bonding possibilities via the COOH group. The crystal structure is presented of a 1:1 cocrystal of NPX with picolinamide as a coformer [systematic name: (S)-2-(6-meth­oxy­naphthalen-2-yl)propanoic acid–pyridine-2-carbox­amide (1/1), C14H14O3·C6H6N2O]. The pharmaceutically relevant physical properties were investigated and the intrinsic dissolution rate was found to be essentially the same as that of commercial naproxen. An NMR crystallography approach was used to investigate the H-atom positions in the two crystallographically unique COOH–CONH hydrogen-bonded dimers. 1H solid-state NMR distinguished the two carboxyl protons, despite the very similar crystallographic environments. The nature of the hydrogen bonding was confirmed by solid-state NMR and density functional theory calculations. PMID:28257010

Structure and physicochemical characterization of a naproxen-picolinamide cocrystal.

PubMed

Kerr, Hannah E; Softley, Lorna K; Suresh, Kuthuru; Hodgkinson, Paul; Evans, Ivana Radosavljevic

2017-03-01

Naproxen (NPX) is a nonsteroidal anti-inflammatory drug with pain- and fever-relieving properties, currently marketed in the sodium salt form to overcome solubility problems; however, alternative solutions for improving its solubility across all pH values are desirable. NPX is suitable for cocrystal formation, with hydrogen-bonding possibilities via the COOH group. The crystal structure is presented of a 1:1 cocrystal of NPX with picolinamide as a coformer [systematic name: (S)-2-(6-methoxynaphthalen-2-yl)propanoic acid-pyridine-2-carboxamide (1/1), C 14 H 14 O 3 ·C 6 H 6 N 2 O]. The pharmaceutically relevant physical properties were investigated and the intrinsic dissolution rate was found to be essentially the same as that of commercial naproxen. An NMR crystallography approach was used to investigate the H-atom positions in the two crystallographically unique COOH-CONH hydrogen-bonded dimers. 1 H solid-state NMR distinguished the two carboxyl protons, despite the very similar crystallographic environments. The nature of the hydrogen bonding was confirmed by solid-state NMR and density functional theory calculations.

Blowpipe Mineralogy for Physics/Environment: Highest-Possible-Tc SuperConductor (Beyond: (but via!!!) MgB2, Cuprates, Pnictides) Quest; BOTH PERMANENT FOREVER Carb-IDES SOLID-State Sequestration AND Drought(s)-Elimination

NASA Astrophysics Data System (ADS)

Segler, Kurt; Williams, Wendell; Siegel, Edward

2011-03-01

Detailed are old blowpipe new applications: charcoal-block reduction of borates to yield ("N-NW" of MgB2) Overhauser-[PR 35,1,411(1987); Intl.J.Mod.Phys.1, 2 & 4, 927(1987)]-"land" predicted high-EST-POSSIBLE Tc SC "LiD2"; very-early: Siegel[Phys.Stat.Sol.(a)11,45(1972);Semiconductors.and Insulators 5: 39,47,62(1979)] carb-IDES SOLID-state phase-TRANSITIONED CHEMICALLY-REDOX"-REACTED STABLE PERMANENT LONG-term NOT "CO2" BUT C-sequestration: PROFITABLE "Grab and Sell" TRUMPS "cap and trade"!!!; Mott alloying/vertical metal-insulator transitions in "borax-(GLASS)-beads"; and very-earlySiegel [{3rd Intl.Conf.Alt.Energy }(1980)-vol.5/p.459!!!] "FLYING-WATER" Hindenberg-effect (H2-UP;H2O-DOWN) via Hydrogen-maximal-Archimedes-buoyancy "chemical-rain-in-pipelines", only via Siegel proprietary "magnetic-hydrogen-valve"(MHV): Renewables-Hydrogen-Water flexible versatile agile scaleable retrofitable integrated operating-system for PERMANENT drought(s)-elimination FOREVER!!!

Oxygen- and Lithium-Doped Hybrid Boron-Nitride/Carbon Networks for Hydrogen Storage.

PubMed

Shayeganfar, Farzaneh; Shahsavari, Rouzbeh

2016-12-20

Hydrogen storage capacities have been studied on newly designed three-dimensional pillared boron nitride (PBN) and pillared graphene boron nitride (PGBN). We propose these novel materials based on the covalent connection of BNNTs and graphene sheets, which enhance the surface and free volume for storage within the nanomaterial and increase the gravimetric and volumetric hydrogen uptake capacities. Density functional theory and molecular dynamics simulations show that these lithium- and oxygen-doped pillared structures have improved gravimetric and volumetric hydrogen capacities at room temperature, with values on the order of 9.1-11.6 wt % and 40-60 g/L. Our findings demonstrate that the gravimetric uptake of oxygen- and lithium-doped PBN and PGBN has significantly enhanced the hydrogen sorption and desorption. Calculations for O-doped PGBN yield gravimetric hydrogen uptake capacities greater than 11.6 wt % at room temperature. This increased value is attributed to the pillared morphology, which improves the mechanical properties and increases porosity, as well as the high binding energy between oxygen and GBN. Our results suggest that hybrid carbon/BNNT nanostructures are an excellent candidate for hydrogen storage, owing to the combination of the electron mobility of graphene and the polarized nature of BN at heterojunctions, which enhances the uptake capacity, providing ample opportunities to further tune this hybrid material for efficient hydrogen storage.

Amorphous and nanocrystalline luminescent Si and Ge obtained via a solid-state chemical metathesis synthesis route

NASA Astrophysics Data System (ADS)

McMillan, Paul F.; Gryko, Jan; Bull, Craig; Arledge, Richard; Kenyon, Anthony J.; Cressey, Barbara A.

2005-03-01

A new solid-state metathesis synthesis route was applied to obtain bulk samples of amorphous or microcrystalline Si and Ge. The method involves reaction of Zintl phases such as NaSi or NaGe, with ammonium or metal (e.g., CuCl, CoBr 2) halides. The driving force for the solid-state reaction is provided by the formation of alkali halides and the transition metals or metal silicides, or gaseous ammonia and hydrogen. The semiconductors were purified by washing to remove other solid products. The amorphous semiconductors were obtained in bulk form from reactions carried out at 200-300 °C. Syntheses at higher temperatures gave rise to microcrystalline semiconductors, or to micro-/nanocrystalline particles contained within the amorphous material. Similar crystalline/amorphous composites were obtained after heat treatment of bulk amorphous materials.

Probing the Surface of Platinum during the Hydrogen Evolution Reaction in Alkaline Electrolyte

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stoerzinger, Kelsey A.; Favaro, Marco; Ross, Philip N.

Understanding the surface chemistry of electrocatalysts in operando can bring insight into the reaction mechanism, and ultimately the design of more efficient materials for sustainable energy storage and conversion. Recent progress in synchrotron based X-ray spectroscopies for in operando characterization allows us to probe the solid/liquid interface directly while applying an external potential, applied here to the model system of Pt in alkaline electrolyte for the hydrogen evolution reaction (HER). We employ ambient pressure X-ray photoelectron spectroscopy (AP-XPS) to identify the oxidation and reduction of Pt-oxides and hydroxides on the surface as a function of applied potential, and further assessmore » the potential for hydrogen adsorption and absorption (hydride formation) during and after the HER. This new window into the surface chemistry of Pt in alkaline brings insight into the nature of the rate limiting step, the extent of H ad/absorption and it’s persistence at more anodic potentials.« less

Polyaniline-Modified Oriented Graphene Hydrogel Film as the Free-Standing Electrode for Flexible Solid-State Supercapacitors.

PubMed

Du, Pengcheng; Liu, Huckleberry C; Yi, Chao; Wang, Kai; Gong, Xiong

2015-11-04

In this study, we report polyaniline (PANI)-modified oriented graphene hydrogel (OGH) films as the free-standing electrode for flexible solid-state supercapacitors (SCs). The OGH films are prepared by a facile filtration method using chemically converted graphene sheets and then introduced to PANI on the surface of OGH films by in situ chemical polymerization. The PANI-modified OGH films possess high flexibility, high electrical conductivity, and mechanical robustness. The flexible solid-state SCs based on the PANI-modified OGH films exhibit a specific capacitance of 530 F/g, keeping 80% of its original value up to 10 000 charge-discharge cycles at the current density of 10 A/g. Remarkably, the flexible solid-state SCs maintain ∼100% capacitance retention bent at 180° for 250 cycles. Moreover, the flexible solid-state SCs are further demonstrated to be able to light up a red-light-emitting diode. These results indicate that the flexible solid-state SCs based on PANI-modified OGH films as the free-standing electrode have potential applications as energy-storage devices.

Modular nonvolatile solid state recorder (MONSSTR) update

NASA Astrophysics Data System (ADS)

Klang, Mark R.; Small, Martin B.; Beams, Tom

2001-12-01

Solid state recorders have begun replacing traditional tape recorders in fulfilling the requirement to record images on airborne platforms. With the advances in electro-optical, IR, SAR, Multi and Hyper-spectral sensors and video recording requirements, solid state recorders have become the recorder of choice. Solid state recorders provide the additional storage, higher sustained bandwidth, less power, less weight and smaller footprint to meet the current and future recording requirements. CALCULEX, Inc., manufactures a non-volatile flash memory solid state recorder called the MONSSTR (Modular Non-volatile Solid State Recorder). MONSSTR is being used to record images from many different digital sensors on high performance aircraft such as the RF- 4, F-16 and the Royal Air Force Tornado. MONSSTR, with its internal multiplexer, is also used to record instrumentation data. This includes multiple streams of PCM and multiple channels of 1553 data. Instrumentation data is being recorded by MONSSTR systems in a range of platforms including F-22, F-15, F-16, Comanche Helicopter and US Navy torpedos. MONSSTR can also be used as a cockpit video recorder. This paper will provide an update of the MONSSTR.

Solid Hydrogen Experiments for Atomic Propellants: Image Analyses

NASA Technical Reports Server (NTRS)

Palaszewski, Bryan

2002-01-01

This paper presents the results of detailed analyses of the images from experiments that were conducted on the formation of solid hydrogen particles in liquid helium. Solid particles of hydrogen were frozen in liquid helium, and observed with a video camera. The solid hydrogen particle sizes, their agglomerates, and the total mass of hydrogen particles were estimated. Particle sizes of 1.9 to 8 mm (0.075 to 0.315 in.) were measured. The particle agglomerate sizes and areas were measured, and the total mass of solid hydrogen was computed. A total mass of from 0.22 to 7.9 grams of hydrogen was frozen. Compaction and expansion of the agglomerate implied that the particles remain independent particles, and can be separated and controlled. These experiment image analyses are one of the first steps toward visually characterizing these particles, and allow designers to understand what issues must be addressed in atomic propellant feed system designs for future aerospace vehicles.

Method of production of pure hydrogen near room temperature from aluminum-based hydride materials

DOEpatents

Pecharsky, Vitalij K.; Balema, Viktor P.

2004-08-10

The present invention provides a cost-effective method of producing pure hydrogen gas from hydride-based solid materials. The hydride-based solid material is mechanically processed in the presence of a catalyst to obtain pure gaseous hydrogen. Unlike previous methods, hydrogen may be obtained from the solid material without heating, and without the addition of a solvent during processing. The described method of hydrogen production is useful for energy conversion and production technologies that consume pure gaseous hydrogen as a fuel.

Hydrogen storage and generation system

DOEpatents

Dentinger, Paul M.; Crowell, Jeffrey A. W.

2010-08-24

A system for storing and generating hydrogen generally and, in particular, a system for storing and generating hydrogen for use in an H.sub.2/O.sub.2 fuel cell. The hydrogen storage system uses the beta particles from a beta particle emitting material to degrade an organic polymer material to release substantially pure hydrogen. In a preferred embodiment of the invention, beta particles from .sup.63Ni are used to release hydrogen from linear polyethylene.

14 CFR 420.66 - Separation distance requirements for storage of hydrogen peroxide, hydrazine, and liquid hydrogen...

Code of Federal Regulations, 2014 CFR

2014-01-01

... 14 Aeronautics and Space 4 2014-01-01 2014-01-01 false Separation distance requirements for storage of hydrogen peroxide, hydrazine, and liquid hydrogen and any incompatible energetic liquids stored within an intraline distance. 420.66 Section 420.66 Aeronautics and Space COMMERCIAL SPACE TRANSPORTATION...

14 CFR 420.66 - Separation distance requirements for storage of hydrogen peroxide, hydrazine, and liquid hydrogen...

Code of Federal Regulations, 2013 CFR

2013-01-01

... 14 Aeronautics and Space 4 2013-01-01 2013-01-01 false Separation distance requirements for storage of hydrogen peroxide, hydrazine, and liquid hydrogen and any incompatible energetic liquids stored within an intraline distance. 420.66 Section 420.66 Aeronautics and Space COMMERCIAL SPACE TRANSPORTATION...

Electronic Structure Calculations of Hydrogen Storage in Lithium-Decorated Metal-Graphyne Framework.

PubMed

Kumar, Sandeep; Dhilip Kumar, Thogluva Janardhanan

2017-08-30

Porous metal-graphyne framework (MGF) made up of graphyne linker decorated with lithium has been investigated for hydrogen storage. Applying density functional theory spin-polarized generalized gradient approximation with the Perdew-Burke-Ernzerhof functional containing Grimme's diffusion parameter with double numeric polarization basis set, the structural stability, and physicochemical properties have been analyzed. Each linker binds two Li atoms over the surface of the graphyne linker forming MGF-Li 8 by Dewar coordination. On saturation with hydrogen, each Li atom physisorbs three H 2 molecules resulting in MGF-Li 8 -H 24 . H 2 and Li interact by charge polarization mechanism leading to elongation in average H-H bond length indicating physisorption. Sorption energy decreases gradually from ≈0.4 to 0.20 eV on H 2 loading. Molecular dynamics simulations and computed sorption energy range indicate the high reversibility of H 2 in the MGF-Li 8 framework with the hydrogen storage capacity of 6.4 wt %. The calculated thermodynamic practical hydrogen storage at room temperature makes the Li-decorated MGF system a promising hydrogen storage material.

Hydrogen storage material and process using graphite additive with metal-doped complex hydrides

DOEpatents

Zidan, Ragaiy [Aiken, SC; Ritter, James A [Lexington, SC; Ebner, Armin D [Lexington, SC; Wang, Jun [Columbia, SC; Holland, Charles E [Cayce, SC

2008-06-10

A hydrogen storage material having improved hydrogen absorbtion and desorption kinetics is provided by adding graphite to a complex hydride such as a metal-doped alanate, i.e., NaAlH.sub.4. The incorporation of graphite into the complex hydride significantly enhances the rate of hydrogen absorbtion and desorption and lowers the desorption temperature needed to release stored hydrogen.

First principles study on electrochemical and chemical stability of solid electrolyte–electrode interfaces in all-solid-state Li-ion batteries

DOE PAGES

Zhu, Yizhou; He, Xingfeng; Mo, Yifei

2015-12-11

All-solid-state Li-ion batteries based on ceramic solid electrolyte materials are a promising next-generation energy storage technology with high energy density and enhanced cycle life. The poor interfacial conductance is one of the key limitations in enabling all-solid-state Li-ion batteries. However, the origin of this poor conductance has not been understood, and there is limited knowledge about the solid electrolyte–electrode interfaces in all-solid-state Li-ion batteries. In this paper, we performed first principles calculations to evaluate the thermodynamics of the interfaces between solid electrolyte and electrode materials and to identify the chemical and electrochemical stabilities of these interfaces. Our computation results revealmore » that many solid electrolyte–electrode interfaces have limited chemical and electrochemical stability, and that the formation of interphase layers is thermodynamically favorable at these interfaces. These formed interphase layers with different properties significantly affect the electrochemical performance of all-solid-state Li-ion batteries. The mechanisms of applying interfacial coating layers to stabilize the interface and to reduce interfacial resistance are illustrated by our computation. This study demonstrates a computational scheme to evaluate the chemical and electrochemical stability of heterogeneous solid interfaces. Finally, the enhanced understanding of the interfacial phenomena provides the strategies of interface engineering to improve performances of all-solid-state Li-ion batteries.« less

Air-stable magnesium nanocomposites provide rapid and high-capacity hydrogen storage without using heavy-metal catalysts

NASA Astrophysics Data System (ADS)

Jeon, Ki-Joon; Moon, Hoi Ri; Ruminski, Anne M.; Jiang, Bin; Kisielowski, Christian; Bardhan, Rizia; Urban, Jeffrey J.

2011-04-01

Hydrogen is a promising alternative energy carrier that can potentially facilitate the transition from fossil fuels to sources of clean energy because of its prominent advantages such as high energy density (142 MJ kg-1 ref. 1), great variety of potential sources (for example water, biomass, organic matter), light weight, and low environmental impact (water is the sole combustion product). However, there remains a challenge to produce a material capable of simultaneously optimizing two conflicting criteria—absorbing hydrogen strongly enough to form a stable thermodynamic state, but weakly enough to release it on-demand with a small temperature rise. Many materials under development, including metal-organic frameworks, nanoporous polymers, and other carbon-based materials, physisorb only a small amount of hydrogen (typically 1-2 wt%) at room temperature. Metal hydrides were traditionally thought to be unsuitable materials because of their high bond formation enthalpies (for example MgH2 has a ΔHf˜75 kJ mol-1), thus requiring unacceptably high release temperatures resulting in low energy efficiency. However, recent theoretical calculations and metal-catalysed thin-film studies have shown that microstructuring of these materials can enhance the kinetics by decreasing diffusion path lengths for hydrogen and decreasing the required thickness of the poorly permeable hydride layer that forms during absorption. Here, we report the synthesis of an air-stable composite material that consists of metallic Mg nanocrystals (NCs) in a gas-barrier polymer matrix that enables both the storage of a high density of hydrogen (up to 6 wt% of Mg, 4 wt% for the composite) and rapid kinetics (loading in <30 min at 200 °C). Moreover, nanostructuring of the Mg provides rapid storage kinetics without using expensive heavy-metal catalysts.

Charge Modulation in Graphitic Carbon Nitride as a Switchable Approach to High-Capacity Hydrogen Storage.

PubMed

Tan, Xin; Kou, Liangzhi; Tahini, Hassan A; Smith, Sean C

2015-11-01

Electrical charging of graphitic carbon nitride nanosheets (g-C4 N3 and g-C3 N4 ) is proposed as a strategy for high-capacity and electrocatalytically switchable hydrogen storage. Using first-principle calculations, we found that the adsorption energy of H2 molecules on graphitic carbon nitride nanosheets is dramatically enhanced by injecting extra electrons into the adsorbent. At full hydrogen coverage, the negatively charged graphitic carbon nitride achieves storage capacities up to 6-7 wt %. In contrast to other hydrogen storage approaches, the storage/release occurs spontaneously once extra electrons are introduced or removed, and these processes can be simply controlled by switching on/off the charging voltage. Therefore, this approach promises both facile reversibility and tunable kinetics without the need of specific catalysts. Importantly, g-C4 N3 has good electrical conductivity and high electron mobility, which can be a very good candidate for electron injection/release. These predictions may prove to be instrumental in searching for a new class of high-capacity hydrogen storage materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen gas storage in fluorinated ultramicroporous tunnel crystal

NASA Astrophysics Data System (ADS)

Kataoka, Keisuke; Katagiri, Toshimasa

2012-07-01

We report hydrogen storage at an ordinary pressure due to a bottle-neck effect of an ultramicroporous crystal. Stored hydrogen was kept at an ordinary pressure below -110 °C. The amounts of stored hydrogen gas linearly correlated with the initial pressures. These phenomena suggested the ultramicroporous tunnels worked as a molecular gas cylinder.We report hydrogen storage at an ordinary pressure due to a bottle-neck effect of an ultramicroporous crystal. Stored hydrogen was kept at an ordinary pressure below -110 °C. The amounts of stored hydrogen gas linearly correlated with the initial pressures. These phenomena suggested the ultramicroporous tunnels worked as a molecular gas cylinder. Electronic supplementary information (ESI) available. CCDC 246922. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c2nr30940h

Hydrogen storage methods.

PubMed

Züttel, Andreas

2004-04-01

Hydrogen exhibits the highest heating value per mass of all chemical fuels. Furthermore, hydrogen is regenerative and environmentally friendly. There are two reasons why hydrogen is not the major fuel of today's energy consumption. First of all, hydrogen is just an energy carrier. And, although it is the most abundant element in the universe, it has to be produced, since on earth it only occurs in the form of water and hydrocarbons. This implies that we have to pay for the energy, which results in a difficult economic dilemma because ever since the industrial revolution we have become used to consuming energy for free. The second difficulty with hydrogen as an energy carrier is its low critical temperature of 33 K (i.e. hydrogen is a gas at ambient temperature). For mobile and in many cases also for stationary applications the volumetric and gravimetric density of hydrogen in a storage material is crucial. Hydrogen can be stored using six different methods and phenomena: (1) high-pressure gas cylinders (up to 800 bar), (2) liquid hydrogen in cryogenic tanks (at 21 K), (3) adsorbed hydrogen on materials with a large specific surface area (at T<100 K), (4) absorbed on interstitial sites in a host metal (at ambient pressure and temperature), (5) chemically bonded in covalent and ionic compounds (at ambient pressure), or (6) through oxidation of reactive metals, e.g. Li, Na, Mg, Al, Zn with water. The most common storage systems are high-pressure gas cylinders with a maximum pressure of 20 MPa (200 bar). New lightweight composite cylinders have been developed which are able to withstand pressures up to 80 MPa (800 bar) and therefore the hydrogen gas can reach a volumetric density of 36 kg.m(-3), approximately half as much as in its liquid state. Liquid hydrogen is stored in cryogenic tanks at 21.2 K and ambient pressure. Due to the low critical temperature of hydrogen (33 K), liquid hydrogen can only be stored in open systems. The volumetric density of liquid hydrogen is 70.8 kg.m(-3), and large volumes, where the thermal losses are small, can cause hydrogen to reach a system mass ratio close to one. The highest volumetric densities of hydrogen are found in metal hydrides. Many metals and alloys are capable of reversibly absorbing large amounts of hydrogen. Charging can be done using molecular hydrogen gas or hydrogen atoms from an electrolyte. The group one, two and three light metals (e.g. Li, Mg, B, Al) can combine with hydrogen to form a large variety of metal-hydrogen complexes. These are especially interesting because of their light weight and because of the number of hydrogen atoms per metal atom, which is two in many cases. Hydrogen can also be stored indirectly in reactive metals such as Li, Na, Al or Zn. These metals easily react with water to the corresponding hydroxide and liberate the hydrogen from the water. Since water is the product of the combustion of hydrogen with either oxygen or air, it can be recycled in a closed loop and react with the metal. Finally, the metal hydroxides can be thermally reduced to metals in a solar furnace. This paper reviews the various storage methods for hydrogen and highlights their potential for improvement and their physical limitations.

Hydrogen storage methods

NASA Astrophysics Data System (ADS)

Züttel, Andreas

Hydrogen exhibits the highest heating value per mass of all chemical fuels. Furthermore, hydrogen is regenerative and environmentally friendly. There are two reasons why hydrogen is not the major fuel of today's energy consumption. First of all, hydrogen is just an energy carrier. And, although it is the most abundant element in the universe, it has to be produced, since on earth it only occurs in the form of water and hydrocarbons. This implies that we have to pay for the energy, which results in a difficult economic dilemma because ever since the industrial revolution we have become used to consuming energy for free. The second difficulty with hydrogen as an energy carrier is its low critical temperature of 33 K (i.e. hydrogen is a gas at ambient temperature). For mobile and in many cases also for stationary applications the volumetric and gravimetric density of hydrogen in a storage material is crucial. Hydrogen can be stored using six different methods and phenomena: (1) high-pressure gas cylinders (up to 800 bar), (2) liquid hydrogen in cryogenic tanks (at 21 K), (3) adsorbed hydrogen on materials with a large specific surface area (at T<100 K), (4) absorbed on interstitial sites in a host metal (at ambient pressure and temperature), (5) chemically bonded in covalent and ionic compounds (at ambient pressure), or (6) through oxidation of reactive metals, e.g. Li, Na, Mg, Al, Zn with water. The most common storage systems are high-pressure gas cylinders with a maximum pressure of 20 MPa (200 bar). New lightweight composite cylinders have been developed which are able to withstand pressures up to 80 MPa (800 bar) and therefore the hydrogen gas can reach a volumetric density of 36 kg.m-3, approximately half as much as in its liquid state. Liquid hydrogen is stored in cryogenic tanks at 21.2 K and ambient pressure. Due to the low critical temperature of hydrogen (33 K), liquid hydrogen can only be stored in open systems. The volumetric density of liquid hydrogen is 70.8 kg.m-3, and large volumes, where the thermal losses are small, can cause hydrogen to reach a system mass ratio close to one. The highest volumetric densities of hydrogen are found in metal hydrides. Many metals and alloys are capable of reversibly absorbing large amounts of hydrogen. Charging can be done using molecular hydrogen gas or hydrogen atoms from an electrolyte. The group one, two and three light metals (e.g. Li, Mg, B, Al) can combine with hydrogen to form a large variety of metal-hydrogen complexes. These are especially interesting because of their light weight and because of the number of hydrogen atoms per metal atom, which is two in many cases. Hydrogen can also be stored indirectly in reactive metals such as Li, Na, Al or Zn. These metals easily react with water to the corresponding hydroxide and liberate the hydrogen from the water. Since water is the product of the combustion of hydrogen with either oxygen or air, it can be recycled in a closed loop and react with the metal. Finally, the metal hydroxides can be thermally reduced to metals in a solar furnace. This paper reviews the various storage methods for hydrogen and highlights their potential for improvement and their physical limitations.

Atomic hydrogen as a launch vehicle propellant

NASA Technical Reports Server (NTRS)

Palaszewski, Bryan A.

1990-01-01

An analysis of several atomic hydrogen launch vehicles was conducted. A discussion of the facilities and the technologies that would be needed for these vehicles is also presented. The Gross Liftoff Weights (GLOW) for two systems were estimated; their specific impulses (I sub sp) were 750 and 1500 lb(sub f)/s/lb(sub m). The atomic hydrogen launch vehicles were also compared to the currently planned Advanced Launch System design concepts. Very significant GLOW reductions of 52 to 58 percent are possible over the Advanced Launch System designs. Applying atomic hydrogen propellants to upper stages was also considered. Very high I(sub sp) (greater than 750 lb(sub f)/s/lb(sub m)) is needed to enable a mass savings over advanced oxygen/hydrogen propulsion. Associated with the potential benefits of high I(sub sp) atomic hydrogen are several challenging problems. Very high magnetic fields are required to maintain the atomic hydrogen in a solid hydrogen matrix. The magnetic field strength was estimated to be 30 kilogauss (3 Tesla). Also the storage temperature of the propellant is 4 K. This very low temperature will require a large refrigeration facility for the launch vehicle. The design considerations for a very high recombination rate for the propellant are also discussed. A recombination rate of 210 cm/s is predicted for atomic hydrogen. This high recombination rate can produce very high acceleration for the launch vehicle. Unique insulation or segmentation to inhibit the propellant may be needed to reduce its recombination rate.

Redox Chemistry of Molybdenum Trioxide for Ultrafast Hydrogen-Ion Storage.

PubMed

Wang, Xianfu; Xie, Yiming; Tang, Kai; Wang, Chao; Yan, Chenglin

2018-05-11

Hydrogen ions are ideal charge carriers for rechargeable batteries due to their small ionic radius and wide availability. However, little attention has been paid to hydrogen-ion storage devices because they generally deliver relatively low Coulombic efficiency as a result of the hydrogen evolution reaction that occurs in an aqueous electrolyte. Herein, we successfully demonstrate that hydrogen ions can be electrochemically stored in an inorganic molybdenum trioxide (MoO 3 ) electrode with high Coulombic efficiency and stability. The as-obtained electrode exhibits ultrafast hydrogen-ion storage properties with a specific capacity of 88 mA hg -1 at an ultrahigh rate of 100 C. The redox reaction mechanism of the MoO 3 electrode in the hydrogen-ion cell was investigated in detail. The results reveal a conversion reaction of the MoO 3 electrode into H 0.88 MoO 3 during the first hydrogen-ion insertion process and reversible intercalation/deintercalation of hydrogen ions between H 0.88 MoO 3 and H 0.12 MoO 3 during the following cycles. This study reveals new opportunities for the development of high-power energy storage devices with lightweight elements. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Uncovering the intrinsic size dependence of hydriding phase transformations in nanocrystals.

PubMed

Bardhan, Rizia; Hedges, Lester O; Pint, Cary L; Javey, Ali; Whitelam, Stephen; Urban, Jeffrey J

2013-10-01

A quantitative understanding of nanocrystal phase transformations would enable more efficient energy conversion and catalysis, but has been hindered by difficulties in directly monitoring well-characterized nanoscale systems in reactive environments. We present a new in situ luminescence-based probe enabling direct quantification of nanocrystal phase transformations, applied here to the hydriding transformation of palladium nanocrystals. Our approach reveals the intrinsic kinetics and thermodynamics of nanocrystal phase transformations, eliminating complications of substrate strain, ligand effects and external signal transducers. Clear size-dependent trends emerge in nanocrystals long accepted to be bulk-like in behaviour. Statistical mechanical simulations show these trends to be a consequence of nanoconfinement of a thermally driven, first-order phase transition: near the phase boundary, critical nuclei of the new phase are comparable in size to the nanocrystal itself. Transformation rates are then unavoidably governed by nanocrystal dimensions. Our results provide a general framework for understanding how nanoconfinement fundamentally impacts broad classes of thermally driven solid-state phase transformations relevant to hydrogen storage, catalysis, batteries and fuel cells.

A Green Urban Mobility System Solution from the EU Ingrid project

NASA Astrophysics Data System (ADS)

D'Errico, Fabrizio; Screnci, Adamo; Romeo, Marco

With a mandate to reach 20/20/20 targets, new strategies are now focusing on the increased use of electricity to power transportation. Particularly in major urban areas of the EU, capillary use of electric vehicles are being encouraged, however, as these vehicles will be powered by the grid, there is always the risk that load peaks will occur. This work is just one of several being developed as part of the 23.9 MLN Euros INGRID European project started in July 2012, which combines solid-state high-density hydrogen storage systems with advanced ICT technologies for distribution grids. One possible solution which has been designed, is an off-grid utility to store renewable electricity captured from wind/solar sources and a re-charging point for full battery electric cars. This work shows the preliminary financial assessment of two business models for the Park-for-Recharging concept to promote green e-mobility as a more convenient and economical means of by-car transport.