Recent Progress in Development of Hydrogen Sorption Cryocoolers for Space Applications
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In January 2003, the administration announced a 5-year, $1.2 billion Hydrogen Fuel Initiative to perform research, development, and demonstration (R&D) for developing hydrogen fuel cells for use as a substitute for gasoline engines. Led by the Department of Energy (DOE), the initiative's goal is to develop the technologies by 2015 that will enable U.S. industry to make hydrogen-powered cars available to consumers by 2020. GAO examines the extent to which DOE has (1) made progress in meeting the initiative's targets, (2) worked with industry to set and meet targets, and (3) worked with other federal agencies to develop and demonstrate hydrogen technologies. GAO reviewed DOE's hydrogen R&D plans, attended DOE's annual review of each R&D project, and interviewed DOE managers, industry executives, and independent experts. The most recent report on the status of this program can be found at this website.
The H2@Scale concept is focused on developing hydrogen as an energy carrier and using hydrogen's properties to improve the national energy system. Specifically hydrogen has the abilities to (1) supply a clean energy source for industry and transportation and (2) increase the profitability of variable renewable electricity generators such as wind turbines and solar photovoltaic (PV) farms by providing value for otherwise potentially-curtailed electricity. Thus the concept also has the potential to reduce oil dependency by providing a low-carbon fuel for fuel cell electric vehicles (FCEVs), reduce emissions of carbon dioxide and pollutants such as NOx, and support domestic energy production, manufacturing, and U.S. economic competitiveness. The analysis reported here focuses on the potential market size and value proposition for the H2@Scale concept. It involves three analysis phases: 1. Initial phase estimating the technical potential for hydrogen markets and the resources required to meet them; 2. National-scale analysis of the economic potential for hydrogen and the interactions between willingness to pay by hydrogen users and the cost to produce hydrogen from various sources; and 3. In-depth analysis of spatial and economic issues impacting hydrogen production and utilization and the markets. Preliminary analysis of the technical potential indicates that the technical potential for hydrogen use is approximately 60 million metric tons (MMT) annually for light duty FCEVs, heavy duty vehicles, ammonia production, oil refining, biofuel hydrotreating, metals refining, and injection into the natural gas system. The technical potential of utility-scale PV and wind generation independently are much greater than that necessary to produce 60 MMT / year hydrogen. Uranium, natural gas, and coal reserves are each sufficient to produce 60 MMT / year hydrogen in addition to their current uses for decades to centuries. National estimates of the economic potential of hydrogen production using steam methane reforming of natural gas, high temperature electrolysis coupled with nuclear power plants, and low temperature electrolysis are reported. To generate the estimates, supply curves for those technologies are used. They are compared to demand curves that describe the market size for hydrogen uses and willingness to pay for that hydrogen. Scenarios are developed at prices where supply meets demand and are used to estimate energy use, emissions, and economic impacts.
This project will provide test data on the new Tatsuno coriolis flow meter. This flow meter has been developed by Tatsuno for the purpose of achieving improved flow meter performance for 70 mega pascal (MPA) hydrogen dispensing. Testing will be conducted at the National Renewable Laboratory (NREL) Hydrogen Infrastructure Testing and Research Facility (HITRF) facility utilizing the hydrogen flow meter benchmark testing apparatus. The benchmarking apparatus utilizes a gravimetric method for measuring flow for direct comparison with flow meter output. Using the NREL meter benchmarking apparatus will allow direct comparison with data taken on previous versions of the Tatsuno coriolis flow meter product. Flow meter accuracy at 70 MPA hydrogen dispensers is an issue that has generated a lot of effort by both standards organizations and the station providers.
Prototype atomic hydrogen maser standard for field operation
One of the challenges associated with transitioning our nation’s transportation economy to any alternative fuel is bringing fuel production, storage, transportation, and end-customer delivery infrastructure online. There are challenges associated with planning and implementing hydrogen fueling stations at locations relevant to the parallel effort of bringing the related transportation vehicles into the market. There are additional challenges associated with the operation of hydrogen fueling stations and reducing operating costs through energy reduction. Through calculation and design efforts it was concluded that elevating the pressure of a PEM cell stack and further developing hydrogen processing equipment that support elevated pressures while maintaining similar characteristics to their current production counterparts will yield in energy savings and by extension cost reductions. In this report, the design of a 57-bar (827-psig) electrolysis system and electrolysis cell stack is described. Furthermore, the fabrication, component verification, and integrated testing are summarized. Prior to this development effort, Proton had demonstrated thousand of hours of durability on 30-bar (435-psig) differential pressure PEM electrolysis hardware. Proton has sold and installed many of these 30-bar devices at customer sites. Through this project, Proton has developed and tested 57-bar PEM electrolysis, thereby extending the proven capability of PEM electrolysis as a hydrogen generation and electrochemical compression device. A design and validation effort to arrange hydrogen processioning equipment for refueling OEM vehicles was also undertaken within this project. By arranging equipment within two 6-meter ISO shipping containers and further developing NFPA 2 Hydrogen Technologies Code to support containerized hydrogen equipment, efforts to site, install, and commission, and approve hydrogen fueling stations were reduced and now provide a groundwork for future installations.
Element One, Inc. (www.elem.com), a small business with in Boulder, CO, has been developing hydrogen detection technology based upon a highly selective colorimetric indicator. In its native state, the indicator pigment is a pale gray color, but becomes black upon exposure to hydrogen. The colorimetric change can be readily observed by the naked eye without the need for supplemental electronics or other hardware. Recently, the colorimetric indicator was integrated into a pliable, self-adhesive tape that can readily wrap around pneumatic fittings to serve as a hydrogen leak detector. A prototype version of the Element One indicator tape was tested within an NREL hydrogen system and successfully identified the unexpected presence of a small leak; a summary document for this case study is presented in Appendix 1. The tape was subsequently configured into 10-foot rolls as a product prototype that has just recently been commercialized and marketed under the tradename DetecTape(R). Figure 1 shows the commercial version of DetecTape along with an indicator sample in its native state and one that had been exposed to hydrogen. DetecTape is a self-adhesive silicone-based tape impregnated with a proprietary hydrogen-sensitive indicator based on transition metal oxides. A length of the tape can be cut from the roll and stretched by a factor of two or three times around a fitting. Due to the self-adhesive property of the tape, this provides a tight seal around the fitting. The seal is not hermetic, and is not intended to prevent the release of a leaking gas. However, a portion of the hydrogen leaking from a wrapped fitting will pass through the tape and react with the active indicator impregnated within the tape, thereby inducing blackening.
A large scale gel production and storage facility and a small scale facility, the latter used for detailed visual examination of the gel/PPO foam interface, were developed. A subcontract was given to investigate techniques for the production of gelled liquid hydrogen, develop a process design for scale-up to a 1.89 cu m (500 gallon) gel production and storage facility, determine gel transfer characteristics, determine the solubility rate of gaseous helium in the gel, and investigate the gross gel/PPO foam interfacial phenomena. An inside-tank process for scaled-up production of gelled liquid hydrogen was selected. No detectable gel structure degradation occurred during repeated shearing. The viscosity of gelled liquid hydrogen at shear rates of 300/sec and higher is 2 to 5-fold greater than that of neat liquid hydrogen. No clogging problems were encountered during the transfer of gelled liquid hydrogen through warmed transfer lines. The solubility rate of helium in liquid hydrogen was significantly reduced by the presence of gel structure. The boil-off rates from gelled liquid hydrogen were reduced from 25 to 50 percent compared to those observed for the neat liquid hydrogen under compatible conditions. The polyphenylene oxide (PPO) foam insulation was found to be compatible with liquid ethane.
Fuel cell vehicles are entering the automotive market with significant potential to reduce harmful greenhouse emissions, facilitate energy security, and increase efficiency while providing expected driving range and fill times. One of the challenges for successful commercialization is transitioning the on-board fuel system from liquid gasoline to compressed hydrogen gas. Storing high pressurized hydrogen requires a specialized structural pressure vessel, significantly different in function from a gasoline container. In addition, the lower hydrogen energy combined with highly efficient fuel cell still requires a storage vessel that is four times the volume of a gasoline tank. In the late 1990s, the industry first developed hydrogen tanks based on traditional type 3 and 4 compressed natural gas (CNG) tanks designed for 250 bar service. As fuel cell vehicles developed along with the need for greater driving range, the OEMs increased the hydrogen storage pressure to 350 bar and then to 700 bar, which is currently the industry norm. However, the 700 bar pressure vessels continued to be manufactured using the materials and the design approach from the CNG tank technologies. In 2012 the U.S. Department of Energy, Office of Fuel Cell Technologies initiated a project to develop Enhanced Materials and Design Parameters for Reducing the Cost of Hydrogen Storage Tanks. The project took a holistic approach to improving performance by investigating: 1) the cost tradeoff of reduced composite mass at 500 bar versus the added insulation cost for cold gas operation at 200K, 2) using hybrid fiber layups to refine the tank composite design, 3) increasing the composite translation efficiency by adding nano-reinforcing particles to the resin, and 4) substituting a lower cost alternate resin in the filament winding process. This paper summarizes the effectiveness of these design modifications and considers the outlook for on-board 700 bar compressed hydrogen tank systems to achieve the commercialization goals for fuel cell vehicles.
Storage of hydrogen onboard vehicles is one of the critical technologies needed to create hydrogen-fueled transportation systems that can improve energy efficiency, resiliency, and energy independence reduce oil dependency. Stakeholders in developing hydrogen infrastructure (e.g., state governments, automotive original equipment manufacturers, station providers, and industrial gas suppliers) are currently focused on high-pressure storage at 350 bar and 700 bar, in part because no viable solid-phase storage material has emerged. Early-state research to develop foundational understanding of solid-state storage materials, including novel sorbents and highdensity hydrides, is of high importance because of their unique potential to meet all DOE Fuel Cell Technologies Office targets and deliver hydrogen with lower storage pressures and higher onboard densities. However, existing materials suffer from thermodynamic and kinetic limitations that prevent their application as practical H2 storage media. Sandia's overall objectives and responsibilities within HyMARC are to: (1) provide technical leadership to the Consortium at the Director level, as well as through leadership of Task 1 (Thermodynamics), Task 3 (Gas Surface Interactions), and Task 5 (Additives); (2) provide gas sorption and other property data required to develop and validate thermodynamic models of sorbents and metal hydride storage materials, including the effects of 350 bar and 700 bar H2 delivery pressures, serving as a resource for the consortium; (3) identify the structure, composition, and reactivity of gas surface and solid-solid hydride surfaces contributing to ratelimiting desorption and uptake; (4) provide metal hydrides and Metal-Organic Framework (MOF) sorbents in a variety of formats tailored for specific consortium tasks; (5) develop sample preparation methods and experimental protocols to enable facile use of the new characterization probes employed by the Consortium; (6) apply SNL multiscale codes to discover diffusion pathways and mechanisms of storage materials; and (7) elucidate the role of additives in promoting hydrogen storage reactions.
Rising energy demands and the imperative to reduce carbon dioxide (CO 2 ) emissions are driving research on biofuels development. Hydrogen gas (H 2 ) is one of the most promising biofuels and is seen as a future energy carrier by virtue of the fact that 1) it is renewable, 2) does not evolve the “greenhouse gas” CO 2 in combustion, 3) liberates large amounts of energy per unit weight in combustion (having about 3 times the energy content of gasoline), and 4) is easily converted to electricity by fuel cells. Among the various bioenergy strategies, environmental groups and others say that the concept of the direct manufacture of alternative fuels, such as H 2 , by photosynthetic organisms is the only biofuel alternative without significant negative criticism [1]. Biological H 2 production by photosynthetic microorganisms requires the use of a simple solar reactor such as a transparent closed box, with low energy requirements, and is considered as an attractive system to develop as a biocatalyst for H 2 production [2]. Various purple bacteria including Rhodopseudomonas palustris, can utilize organic substrates as electron donors to produce H 2 at the expense of solar energy. Because of the elimination of energy cost used for H 2 O oxidation and the prevention of the production of O 2 that inhibits the H 2 -producing enzymes, the efficiency of light energy conversion to H 2 by anoxygenic photosynthetic bacteria is in principle much higher than that by green algae or cyanobacteria, and is regarded as one of the most promising cultures for biological H 2 production [3]. Here implemented a simple and relatively straightforward strategy for hydrogen production by photosynthetic microorganisms using sunlight, sulfur- or iron-based inorganic substrates, and CO 2 as the feedstock. Carefully selected microorganisms with bioengineered beneficial traits act as the biocatalysts of the process designed to both enhance the system efficiency of CO 2 fixation and the net hydrogen production rate. Additionally we applied metabolic engineering approaches guided by computational modeling for the chosen model microorganisms to enable efficient hydrogen production.
Development of a high specific energy battery is one of the objectives of the lightweight nickel-hydrogen (Ni-H2) program at the NASA Glenn Research Center. The approach has been to improve the nickel electrode by continuing combined in-house and contract efforts to develop a lighter weight electrode for the nickel-hydrogen cell. Small fiber diameter nickel plaques are used as conductive supports for the nickel hydroxide active material. These plaques are commercial products and have an advantage of increased surface area available for the deposition of active material. Initial tests include activation and capacity measurements at five different discharge levels, C/2, 1.0 C, 1.37 C, 2.0 C, and 2.74 C. The electrodes are life cycle tested using a half-cell configuration at 40 and 80% depths-of-discharge (DOD) in a low-Earth-orbit regime. The electrodes that pass the initial tests are life cycle-tested in a boiler plate nickel-hydrogen cell before flight weight design are built and tested.
Radiolysis of water in nuclear waste storage generates hydrogen gas that can accumulate within sludge style waste and be rapidly released during agitation events, creating a significant flammability hazard. Engineering controls are therefore required to limit hydrogen concentrations during both quiescent storage and transient disturbances. Catalytic recombination of hydrogen in waste storage offgas is a proven mitigation strategy, maintaining hydrogen levels below flammability limits and managing sudden concentration spikes. Conventional recombiners rely on platinum and/or palladium catalysts, with development efforts focused on extending service life, increasing active surface area, and ensuring safe deployment in radioactive environments. Savannah River National Laboratory (SRNL) is evaluating a newly developed hydrogen recombiner catalyst from Canadian Nuclear Laboratories as a cost-effective and durable alternative for nuclear waste applications. Testing was conducted in SRNL’s Shielded Cells facility, which enables reduced-scale experimental modeling under radiation fields and near-use-case conditions relevant to radioactive waste storage. Catalyst performance was evaluated using a custom offgas characterization system designed for near-zero flow conditions. The experimental apparatus consisted of a gas-tight 2.7 L PTFE vessel equipped with temperature monitoring, gas flow controls, and a variable-speed mixer to simulate sludge agitation. Offgas composition was monitored using a dedicated gas chromatograph with argon carrier gas and a krypton internal standard. Measurements were obtained for an empty vessel, the vessel containing a well characterized radioactive tank waste sample, and the same configuration with the candidate catalyst installed. Results demonstrate that the new catalyst effectively reduced hydrogen concentrations in the offgas within the constraints of the experimental design. In addition to confirming catalytic activity, the testing provided valuable insights into experimental optimization and considerations for future performance evaluations. These findings support the potential scalability of the technology and highlight its applicability to broader nuclear waste management operations, offering improved safety and reduced operational costs through enhanced catalyst durability and lower replacement frequency.
In response to the urgent need to mitigate climate change via net-zero targets, many nations are renewing their interest in clean hydrogen as a net-zero energy carrier. Although clean hydrogen can be directly used in various sectors for deep decarbonization, the relatively low energy density and high production costs have raised doubts as to whether clean hydrogen development is worthwhile. Here, we improve on the GCAM model by including a more comprehensive and detailed representation of clean hydrogen production, distribution, and demand in all sectors of the global economy and simulate 25 scenarios to explore the cost-effectiveness of integrating clean hydrogen into the global energy system. We show that, due to costly technical obstacles, clean hydrogen can only provide 3%–9% of the 2050 global final energy use. Nevertheless, clean hydrogen deployment can reduce overall energy decarbonization costs by 15%–22%, mainly via powering “hard-to-electrify” sectors that would otherwise face high decarbonization expenditures. Our work provides practical references for cost-effective clean hydrogen planning.