A bio-inspired molecular water oxidation catalyst for renewable hydrogen generation: an examination of salt effects

NASA Astrophysics Data System (ADS)

Brimblecombe, Robin; Rotstein, Miriam; Koo, Annette; Dismukes, G. Charles; Swiegers, Gerhard F.; Spiccia, Leone

2009-08-01

Most transport fuels are derived from fossil fuels, generate greenhouse gases, and consume significant amounts of water in the extraction, purification, and/or burning processes. The generation of hydrogen using solar energy to split water, ideally from abundant water sources such as sea water or other non-potable sources, could potentially provide an unlimited, clean fuel for the future. Solar, electrochemical water splitting typically combines a photoanode at which water oxidation occurs, with a cathode for proton reduction to hydrogen. In recent work, we have found that a bioinspired tetra-manganese cluster catalyzes water oxidation at relatively low overpotentials (0.38 V) when doped into a Nafion proton conduction membrane deposited on a suitable electrode surface, and illuminated with visible light. We report here that this assembly is active in aqueous and organic electrolyte solutions containing a range of different salts in varying concentrations. Similar photocurrents were obtained using electrolytes containing 0.0 - 0.5 M sodium sulfate, sodium perchlorate or sodium chloride. A slight decline in photocurrent was observed for sodium perchlorate but only at and above 5.0 M concentration. In acetonitrile and acetone solutions containing 10% water, increasing the electrolyte concentration was found to result in leaching of the catalytic species from the membrane and a decrease in photocurrent. Leaching was not observed when the system was tested in an ionic liquid containing water, however, a lower photocurrent was generated than observed in aqueous electrolyte. We conclude that immersion of the membrane in an aqueous solution containing an electrolyte concentration of 0.05 - 0.5M represent good conditions for operation for the cubium/Nafion catalytic system.

Jumping liquid metal droplet in electrolyte triggered by solid metal particles

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

Tang, Jianbo; University of Chinese Academy of Sciences, Beijing 100049; Wang, Junjie

2016-05-30

We report the electron discharge effect due to point contact between liquid metal and solid metal particles in electrolyte. Adding nickel particles induces drastic hydrogen generating and intermittent jumping of a sub-millimeter EGaIn droplet in NaOH solution. Observations from different orientations disclose that such jumping behavior is triggered by pressurized bubbles under the assistance of interfacial interactions. Hydrogen evolution around particles provides clear evidence that such electric instability originates from the varied electric potential and morphology between the two metallic materials. The point-contact-induced charge concentration significantly enhances the near-surface electric field intensity at the particle tips and thus causes electricmore » breakdown of the electrolyte.« less

Sea water magnesium fuel cell power supply

NASA Astrophysics Data System (ADS)

Hahn, Robert; Mainert, Jan; Glaw, Fabian; Lang, K.-D.

2015-08-01

An environmentally friendly magnesium fuel cell system using seawater electrolyte and atmospheric oxygen was tested under practical considerations for use as maritime power supply. The hydrogen rate and therefore the power density of the system were increased by a factor of two by using hydrogen evolution cathodes with a gas separation membrane instead of submerged cathodes without gas separation. Commercial magnesium AZ31 rolled sheet anodes can be dissolved in seawater for hydrogen production, down to a thickness below 100 μm thickness, resulting in hydrogen generation efficiency of the anode of over 80%. A practical specific energy/energy density of the alloy of more than 1200 Wh/kg/3000 Wh/l was achieved when coupled to a fuel cell with atmospheric air breathing cathode. The performance of several AZ31 alloy anodes was tested as well as the influence of temperature, electrolyte concentration and anode - cathode separation. The excess hydrogen produced by the magnesium hydrogen evolving cell, due to the negative difference effect, is proportional to the cell current in case of the AZ31 alloys, which simplifies system control considerably. Stable long-term operation of the system was demonstrated at low pressures which can be maintained in an open-seawater-submerged hydrogen generator.

A preliminary systems-engineering study of an advanced nuclear-electrolytic hydrogen-production facility

NASA Technical Reports Server (NTRS)

Escher, W. J. D.; Donakowski, T. D.; Tison, R. R.

1975-01-01

An advanced nuclear-electrolytic hydrogen-production facility concept was synthesized at a conceptual level with the objective of minimizing estimated hydrogen-production costs. The concept is a closely-integrated, fully-dedicated (only hydrogen energy is produced) system whose components and subsystems are predicted on ''1985 technology.'' The principal components are: (1) a high-temperature gas-cooled reactor (HTGR) operating a helium-Brayton/ammonia-Rankine binary cycle with a helium reactor-core exit temperature of 980 C, (2) acyclic d-c generators, (3) high-pressure, high-current-density electrolyzers based on solid-polymer electrolyte technology. Based on an assumed 3,000 MWt HTGR the facility is capable of producing 8.7 million std cu m/day of hydrogen at pipeline conditions, 6,900 kPa. Coproduct oxygen is also available at pipeline conditions at one-half this volume. It has further been shown that the incorporation of advanced technology provides an overall efficiency of about 43 percent, as compared with 25 percent for a contemporary nuclear-electric plant powering close-coupled contemporary industrial electrolyzers.

Integrated photoelectrochemical cell and system having a liquid electrolyte

DOEpatents

Deng, Xunming; Xu, Liwei

2010-07-06

An integrated photoelectrochemical (PEC) cell generates hydrogen and oxygen from water while being illuminated with radiation. The PEC cell employs a liquid electrolyte, a multi-junction photovoltaic electrode, and a thin ion-exchange membrane. A PEC system and a method of making such PEC cell and PEC system are also disclosed.

Redox mediation and hydrogen-generation with bipyridinium reagents

DOEpatents

Wrighton, Mark S.; Bookbinder, Dana C.; Bruce, James A.; Dominey, Raymond N.; Lewis, Nathan S.

1984-03-27

A variety of redox mediating agents employing bipyridinium reagents and such reagents in conjunction with dispersed noble metals, such as platinium, are disclosed as coatings for substrates and electrodes. The agents may be charged by an applied voltage or by photoelectric effects or may be equilibrated with hydrogen. The agents are useful in reducing biological materials and electrolytic hydrogen production.

Development of a solid polymer electrolyte electrolysis cell module and ancillary components for a breadboard water electrolysis system

NASA Technical Reports Server (NTRS)

Porter, F. J., Jr.

1972-01-01

Solid polymer electrolyte technology in a water electrolysis system along with ancillary components to generate oxygen and hydrogen for a manned space station application are considered. Standard commercial components are utilized wherever possible. Presented are the results of investigations, surveys, tests, conclusions and recommendations for future development efforts.

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.

Hydrogen by electrolysis of water

NASA Technical Reports Server (NTRS)

1975-01-01

Hydrogen production by electrolytic decomposition of water is explained. Power efficiency, efficient energy utilization, and costs were emphasized. Four systems were considered: two were based on current electrolyzer technology using present efficiency values for electrical generation by fossil fired and nuclear thermal stations, and two using projected electrolyzer technology with advanced fossil and nuclear plants.

Energy Systems Integration Partnerships: NREL + GINER ELX

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

At current levels of renewable generation there are already periods when the supply of electrical power significantly exceeds the level of demand. The wide penetration of renewable energy sources (RES) requires an energy storage solution which can include hydrogen generated via Polymer Electrolyte Membrane (PEM) electrolysis.

Method for synthesis of titanium dioxide nanotubes using ionic liquids

DOEpatents

Qu, Jun; Luo, Huimin; Dai, Sheng

2013-11-19

The invention is directed to a method for producing titanium dioxide nanotubes, the method comprising anodizing titanium metal in contact with an electrolytic medium containing an ionic liquid. The invention is also directed to the resulting titanium dioxide nanotubes, as well as devices incorporating the nanotubes, such as photovoltaic devices, hydrogen generation devices, and hydrogen detection devices.

Progress in hydrogen energy; Proceedings of the National Workshop on Hydrogen Energy, New Delhi, India, July 4-6, 1985

NASA Astrophysics Data System (ADS)

Dahiya, R. P.

1987-06-01

The present conference on the development status of hydrogen energy technologies considers electrolytic hydrogen production, photoelectrolytic hydrogen production, microorganic hydrogen production, OTEC hydrogen production, solid-state materials for hydrogen storage, and a thin-film hydrogen storage system. Also discussed are the cryogenic storage of hydrogen; liquid hydrogen fuel for ground, air, and naval vehicles; hydrogen-fuel internal combustion engines; the use of hydrogen for domestic, commercial, and industrial applications; hydrogen fuel-cell development; enzyme electrodes for the use of hydrogen-rich fuels in biochemical fuel cells; an analysis of H2-O2 MHD generators; and hydrogen energy technology characterization and evaluation on the basis of an input-output structure.

Performance data for a terrestrial solar photovoltaic/water electrolysis experiment

NASA Technical Reports Server (NTRS)

Costogue, E. N.; Yasui, R. K.

1977-01-01

A description is presented of the equipment used in the experiment, taking into account the surplus solar panel from the Mariner 4 spacecraft which was used as a solar array source and an electrolytic hydrogen generator. Attention is also given to operational considerations and performance data, system considerations and aspects of optimization, and large-scale hydrogen production considerations.

Durability of PEM Fuel Cell Membranes

NASA Astrophysics Data System (ADS)

Huang, Xinyu; Reifsnider, Ken

Durability is still a critical limiting factor for the commercialization of polymer electrolyte membrane (PEM) fuel cells, a leading energy conversion technology for powering future hydrogen fueled automobiles, backup power systems (e.g., for base transceiver station of cellular networks), portable electronic devices, etc. Ionic conducting polymer (ionomer) electrolyte membranes are the critical enabling materials for the PEM fuel cells. They are also widely used as the central functional elements in hydrogen generation (e.g., electrolyzers), membrane cell for chlor-alkali production, etc. A perfluorosulfonic acid (PFSA) polymer with the trade name Nafion® developed by DuPont™ is the most widely used PEM in chlor-alkali cells and PEM fuel cells. Similar PFSA membranes have been developed by Dow Chemical, Asahi Glass, and lately Solvay Solexis. Frequently, such membranes serve the dual function of reactant separation and selective ionic conduction between two otherwise separate compartments. For some applications, the compromise of the "separation" function via the degradation and mechanical failure of the electrolyte membrane can be the life-limiting factor; this is particularly the case for PEM in hydrogen/oxygen fuel cells.

Production of hydrogen by electron transfer catalysis using conventional and photochemical means

NASA Technical Reports Server (NTRS)

Rillema, D. P.

1981-01-01

Alternate methods of generating hydrogen from the sulfuric acid thermal or electrochemical cycles are presented. A number of processes requiring chemical, electrochemical or photochemical methods are also presented. These include the design of potential photoelectrodes and photocatalytic membranes using Ru impregnated nafion tubing, and the design of experiments to study the catalyzed electrolytic formation of hydrogen and sulfuric acid from sulfur dioxide and water using quinones as catalysts. Experiments are carried out to determine the value of these approaches to energy conversion.

Hydrogen gas relief valve

DOEpatents

Whittlesey, Curtis C.

1985-01-01

An improved battery stack design for an electrochemical system having at least one cell from which a gas is generated and an electrolyte in communication with the cell is described. The improved battery stack design features means for defining a substantially closed compartment for containing the battery cells and at least a portion of the electrolyte for the system, and means in association with the compartment means for selectively venting gas from the interior of the compartment means in response to the level of the electrolyte within the compartment means. The venting means includes a relief valve having a float member which is actuated in response to the level of the electrolyte within the compartment means. This float member is adapted to close the relief valve when the level of the electrolyte is above a predetermined level and open the relief valve when the level of electrolyte is below this predetermined level.

Towards Versatile and Sustainable Hydrogen Production through Electrocatalytic Water Splitting: Electrolyte Engineering

PubMed Central

Shinagawa, Tatsuya

2017-01-01

Abstract Recent advances in power generation from renewable resources necessitate conversion of electricity to chemicals and fuels in an efficient manner. Electrocatalytic water splitting is one of the most powerful and widespread technologies. The development of highly efficient, inexpensive, flexible, and versatile water electrolysis devices is desired. This review discusses the significance and impact of the electrolyte on electrocatalytic performance. Depending on the circumstances under which the water splitting reaction is conducted, the required solution conditions, such as the identity and molarity of ions, may significantly differ. Quantitative understanding of such electrolyte properties on electrolysis performance is effective to facilitate the development of efficient electrocatalytic systems. The electrolyte can directly participate in reaction schemes (kinetics), affect electrode stability, and/or indirectly impact the performance by influencing the concentration overpotential (mass transport). This review aims to guide fine‐tuning of the electrolyte properties, or electrolyte engineering, for (photo)electrochemical water splitting reactions. PMID:27984671

Hybrid Composite Coatings for Durable and Efficient Solar Hydrogen Generation under Diverse Operating Conditions

DOE PAGES

Walczak, Karl A.; Segev, Gideon; Larson, David M.; ...

2017-02-17

Safe and practical solar-driven hydrogen generators must be capable of efficient and stable operation under diurnal cycling with full separation of gaseous H 2 and O 2 products. In this paper, a novel architecture that fulfills all of these requirements is presented. The approach is inherently scalable and provides versatility for operation under diverse electrolyte and lighting conditions. The concept is validated using a 1 cm 2 triple-junction photovoltaic cell with its illuminated photocathode protected by a composite coating comprising an organic encapsulant with an embedded catalytic support. The device is compatible with operation under conditions ranging from 1 Mmore » H 2SO 4 to 1 M KOH, enabling flexibility in selection of semiconductor, electrolyte, membrane, and catalyst. Stable operation at a solar-to-hydrogen conversion efficiency of >10% is demonstrated under continuous operation, as well as under diurnal light cycling for at least 4 d, with simulated sunlight. Operational characteristics are validated by extended time outdoor testing. A membrane ensures products are separated, with nonexplosive gas streams generated for both alkaline and acidic systems. Finally, analysis of operational characteristics under different lighting conditions is enabled by comparison of a device model to experimental data.« less

Anomalously enhanced hydration of aqueous electrolyte solution in hydrophobic carbon nanotubes to maintain stability.

PubMed

Ohba, Tomonori

2014-02-24

An understanding of the structure and behavior of electrolyte solutions in nanoenvironements is crucial not only for a wide variety of applications, but also for the development of physical, chemical, and biological processes. We demonstrate the structure and stability of electrolyte in carbon nanotubes using hybrid reverse Monte Carlo simulations of X-ray diffraction patterns. Hydrogen bonds between water are adequately formed in carbon nanotubes, although some hydrogen bonds are restricted by the interfaces of carbon nanotubes. The hydrogen bonding network of water in electrolyte in the carbon nanotubes is further weakened. On the other hand, formation of the ion hydration shell is significantly enhanced in the electrolyte in the carbon nanotubes in comparison to ion hydration in bulk electrolyte. The significant hydrogen bond and hydration shell formation are a result of gaining stability in the hydrophobic nanoenvironment. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A high-performance aluminum-feed microfluidic fuel cell stack

NASA Astrophysics Data System (ADS)

Wang, Yifei; Leung, Dennis Y. C.

2016-12-01

In this paper, a six-cell microfluidic fuel cell (MFC) stack is demonstrated. Low-cost aluminum is fed directly to the stack, which produces hydrogen fuel on site, through the Al-H2O reaction. This design is not only cost-efficient, but also eliminates the need for hydrogen storage. Unlike the conventional MFC stacks which generally require complex electrolyte distribution and management, the present Al-feed MFC stack requires only a single electrolyte stream, flowing successively through individual cells, which is finally utilized for hydrogen generation. In this manner, the whole system is greatly simplified while the operational robustness is also improved. With 2 M sodium hydroxide solution as electrolyte and kitchen foil Al as fuel, the present six-cell stack (in series) exhibits an open circuit voltage of nearly 6 V and a peak power density of 180.6 mWcm-2 at room temperature. In addition, an energy density of 1 Whg-1(Al) is achieved, which is quite high and comparable with its proton exchange membrane-based counterparts. Finally, pumpless operation of the present stack, together with its practical applications are successfully demonstrated, including lightening LED lights, driving an electric fan, and cell phone charging.

Electrolytic production of oxygen from lunar resources

NASA Technical Reports Server (NTRS)

Keller, Rudolf

1991-01-01

Some of the most promising approaches to extract oxygen from lunar resources involve electrochemical oxygen generation. In a concept called magma electrolysis, suitable oxides (silicates) which are molten at 1300 to 1500 C are then electrolyzed. Residual melt can be discarded after partial electrolysis. Alternatively, lunar soil may be dissolved in a molten salt and electrolyzed. In this approach, temperatures are lower and melt conductances higher, but electrolyte constituents need to be preserved. In a different approach ilmenite is reduced by hydrogen and the resulting water is electrolyzed.

Power generation in fuel cells using liquid methanol and hydrogen peroxide

NASA Technical Reports Server (NTRS)

Narayanan, Sekharipuram R. (Inventor); Valdez, Thomas I. (Inventor); Chun, William (Inventor)

2002-01-01

The invention is directed to an encapsulated fuel cell including a methanol source that feeds liquid methanol (CH.sub.3 OH) to an anode. The anode is electrical communication with a load that provides electrical power. The fuel cell also includes a hydrogen peroxide source that feeds liquid hydrogen peroxide (H.sub.2 O.sub.2) to the cathode. The cathode is also in communication with the electrical load. The anode and cathode are in contact with and separated by a proton-conducting polymer electrolyte membrane.

Solid polymer electrolyte water electrolysis system development. [to generate oxygen for manned space station applications

NASA Technical Reports Server (NTRS)

1975-01-01

Solid polymer electrolyte technology used in a water electrolysis system (WES) to generate oxygen and hydrogen for manned space station applications was investigated. A four-man rated, low pressure breadboard water electrolysis system with the necessary instrumentation and controls was fabricated and tested. A six man rated, high pressure, high temperature, advanced preprototype WES was developed. This configuration included the design and development of an advanced water electrolysis module, capable of operation at 400 psig and 200 F, and a dynamic phase separator/pump in place of a passive phase separator design. Evaluation of this system demonstrated the goal of safe, unattended automated operation at high pressure and high temperature with an accumulated gas generation time of over 1000 hours.

Nonsaturable microdryer

DOEpatents

Hirschfeld, Tomas B.

1985-01-01

A nonsaturable microdryer is provided for electrolytically removing moisture from sealed containers, particularly electronic equipment. An electrode/electrolyte assembly is disposed within a channel between the interior and exterior of a sealed container. A catalytic barrier disposed between the interior of the sealed container and the electrode/electrolyte assembly prevents the build-up of explosive concentrations of hydrogen by converting back-diffusing hydrogen and oxygen back into water, which is then recycled. A semipermeable membrane disposed between the exterior of the sealed container and the electrode/electrolyte assembly allows selective removal of hydrogen and prevents intake of water.

Nonsaturable microdryer

DOEpatents

Hirschfeld, T.B.

1984-05-23

A nonsaturable microdryer is provided for electrolytically removing moisture from sealed containers, particularly electronic equipment. An electrode/electrolyte assembly is disposed within a channel between the interior and exterior of a sealed container. A catalytic barrier disposed between the interior of the sealed container and the electrode/electrolyte assembly prevents the build-up of explosive concentrations of hydrogen by converting back-diffusing hydrogen and oxygen back into water, which is then recycled. A semipermeable membrane disposed between the exterior of the sealed container and the electrode/electrolyte assembly allows selective removal of hydrogen and prevents intake of water.

Mechanisms of Furfural Reduction on Metal Electrodes: Distinguishing Pathways for Selective Hydrogenation of Bioderived Oxygenates.

PubMed

Chadderdon, Xiaotong H; Chadderdon, David J; Matthiesen, John E; Qiu, Yang; Carraher, Jack M; Tessonnier, Jean-Philippe; Li, Wenzhen

2017-10-11

Electrochemical reduction of biomass-derived platform molecules is an emerging route for the sustainable production of fuels and chemicals. However, understanding gaps between reaction conditions, underlying mechanisms, and product selectivity have limited the rational design of active, stable, and selective catalyst systems. In this work, the mechanisms of electrochemical reduction of furfural, an important biobased platform molecule and model for aldehyde reduction, are explored through a combination of voltammetry, preparative electrolysis, thiol-electrode modifications, and kinetic isotope studies. It is demonstrated that two distinct mechanisms are operable on metallic Cu electrodes in acidic electrolytes: (i) electrocatalytic hydrogenation (ECH) and (ii) direct electroreduction. The contributions of each mechanism to the observed product distribution are clarified by evaluating the requirement for direct chemical interactions with the electrode surface and the role of adsorbed hydrogen. Further analysis reveals that hydrogenation and hydrogenolysis products are generated by parallel ECH pathways. Understanding the underlying mechanisms enables the manipulation of furfural reduction by rationally tuning the electrode potential, electrolyte pH, and furfural concentration to promote selective formation of important biobased polymer precursors and fuels.

Mechanisms of Furfural Reduction on Metal Electrodes: Distinguishing Pathways for Selective Hydrogenation of Bioderived Oxygenates

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

Chadderdon, Xiaotong H.; Chadderdon, David J.; Matthiesen, John E.

Electrochemical reduction of biomass-derived platform molecules is an emerging route for the sustainable production of fuels and chemicals. Understanding gaps between reaction conditions, underlying mechanisms, and product selectivity have limited the rational design of active, stable, and selective catalyst systems. Here, the mechanisms of electrochemical reduction of furfural, an important biobased platform molecule and model for aldehyde reduction, are explored through a combination of voltammetry, preparative electrolysis, thiol-electrode modifications, and kinetic isotope studies. It is demonstrated that two distinct mechanisms are operable on metallic Cu electrodes in acidic electrolytes: (i) electrocatalytic hydrogenation (ECH) and (ii) direct electroreduction. The contributions ofmore » each mechanism to the observed product distribution are clarified by evaluating the requirement for direct chemical interactions with the electrode surface and the role of adsorbed hydrogen. Further analysis reveals that hydrogenation and hydrogenolysis products are generated by parallel ECH pathways. By understanding the underlying mechanisms it enables the manipulation of furfural reduction by rationally tuning the electrode potential, electrolyte pH, and furfural concentration to promote selective formation of important biobased polymer precursors and fuels.« less

Mechanisms of Furfural Reduction on Metal Electrodes: Distinguishing Pathways for Selective Hydrogenation of Bioderived Oxygenates

DOE PAGES

Chadderdon, Xiaotong H.; Chadderdon, David J.; Matthiesen, John E.; ...

2017-09-13

Electrochemical reduction of biomass-derived platform molecules is an emerging route for the sustainable production of fuels and chemicals. Understanding gaps between reaction conditions, underlying mechanisms, and product selectivity have limited the rational design of active, stable, and selective catalyst systems. Here, the mechanisms of electrochemical reduction of furfural, an important biobased platform molecule and model for aldehyde reduction, are explored through a combination of voltammetry, preparative electrolysis, thiol-electrode modifications, and kinetic isotope studies. It is demonstrated that two distinct mechanisms are operable on metallic Cu electrodes in acidic electrolytes: (i) electrocatalytic hydrogenation (ECH) and (ii) direct electroreduction. The contributions ofmore » each mechanism to the observed product distribution are clarified by evaluating the requirement for direct chemical interactions with the electrode surface and the role of adsorbed hydrogen. Further analysis reveals that hydrogenation and hydrogenolysis products are generated by parallel ECH pathways. By understanding the underlying mechanisms it enables the manipulation of furfural reduction by rationally tuning the electrode potential, electrolyte pH, and furfural concentration to promote selective formation of important biobased polymer precursors and fuels.« less

Nuclear driven water decomposition plant for hydrogen production

NASA Technical Reports Server (NTRS)

Parker, G. H.; Brecher, L. E.; Farbman, G. H.

1976-01-01

The conceptual design of a hydrogen production plant using a very-high-temperature nuclear reactor (VHTR) to energize a hybrid electrolytic-thermochemical system for water decomposition has been prepared. A graphite-moderated helium-cooled VHTR is used to produce 1850 F gas for electric power generation and 1600 F process heat for the water-decomposition process which uses sulfur compounds and promises performance superior to normal water electrolysis or other published thermochemical processes. The combined cycle operates at an overall thermal efficiency in excess of 45%, and the overall economics of hydrogen production by this plant have been evaluated predicated on a consistent set of economic ground rules. The conceptual design and evaluation efforts have indicated that development of this type of nuclear-driven water-decomposition plant will permit large-scale economic generation of hydrogen in the 1990s.

Self-assembling hydrogel scaffolds for photocatalytic hydrogen production

DOE PAGES

Weingarten, Adam S.; Kazantsev, Roman V.; Palmer, Liam C.; ...

2014-10-05

Integration into a soft material of all the molecular components necessary to generate storable fuels is an interesting target in supramolecular chemistry. The concept is inspired by the internal structure of photosynthetic organelles, such as plant chloroplasts, which colocalize molecules involved in light absorption, charge transport and catalysis to create chemical bonds using light energy. We report in this paper on the light-driven production of hydrogen inside a hydrogel scaffold built by the supramolecular self-assembly of a perylene monoimide amphiphile. The charged ribbons formed can electrostatically attract a nickel-based catalyst, and electrolyte screening promotes gelation. We found the emergent phenomenonmore » that screening by the catalyst or the electrolytes led to two-dimensional crystallization of the chromophore assemblies and enhanced the electronic coupling among the molecules. Finally, photocatalytic production of hydrogen is observed in the three-dimensional environment of the hydrogel scaffold and the material is easily placed on surfaces or in the pores of solid supports.« less

Towards Versatile and Sustainable Hydrogen Production through Electrocatalytic Water Splitting: Electrolyte Engineering.

PubMed

Shinagawa, Tatsuya; Takanabe, Kazuhiro

2017-04-10

Recent advances in power generation from renewable resources necessitate conversion of electricity to chemicals and fuels in an efficient manner. Electrocatalytic water splitting is one of the most powerful and widespread technologies. The development of highly efficient, inexpensive, flexible, and versatile water electrolysis devices is desired. This review discusses the significance and impact of the electrolyte on electrocatalytic performance. Depending on the circumstances under which the water splitting reaction is conducted, the required solution conditions, such as the identity and molarity of ions, may significantly differ. Quantitative understanding of such electrolyte properties on electrolysis performance is effective to facilitate the development of efficient electrocatalytic systems. The electrolyte can directly participate in reaction schemes (kinetics), affect electrode stability, and/or indirectly impact the performance by influencing the concentration overpotential (mass transport). This review aims to guide fine-tuning of the electrolyte properties, or electrolyte engineering, for (photo)electrochemical water splitting reactions. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Anhydrous hydrogen fluoride electrolyte battery. [Patent application

DOEpatents

Not Available

1972-06-26

It is an object of the invention to provide a primary cell or battery using ammonium fluoride--anhydrous hydrogen fluoride electrolyte having improved current and power production capabilities at low temperatures. It is operable at temperatures substantially above the boiling point of hydrogen fluoride. (GRA)

Growth and detachment of single hydrogen bubbles in a magnetohydrodynamic shear flow

NASA Astrophysics Data System (ADS)

Baczyzmalski, Dominik; Karnbach, Franziska; Mutschke, Gerd; Yang, Xuegeng; Eckert, Kerstin; Uhlemann, Margitta; Cierpka, Christian

2017-09-01

This study investigates the effect of a magnetohydrodynamic (MHD) shear flow on the growth and detachment of single sub-millimeter-sized hydrogen gas bubbles. These bubbles were electrolytically generated at a horizontal Pt microelectrode (100 μ m in diameter) in an acidic environment (1 M H2SO4 ). The inherent electric field was superimposed by a homogeneous electrode-parallel magnetic field of up to 700 mT to generate Lorentz forces in the electrolyte, which drive the MHD flow. The growth and motion of the hydrogen bubble was analyzed by microscopic high-speed imaging and measurements of the electric current, while particle tracking velocimetry (μ PTV ) and particle image velocimetry (μ PIV ) were applied to measure the surrounding electrolyte flow. In addition, numerical flow simulations were performed based on the experimental conditions. The results show a significant reduction of the bubble growth time and detachment diameter with increasing magnetic induction, which is known to improve the efficiency of water electrolysis. In order to gain further insight into the bubble detachment mechanism, an analysis of the forces acting on the bubble was performed. The strong MHD-induced drag force causes the bubble to slowly slide away from the center of the microelectrode before its detachment. This motion increases the active electrode area and enhances the bubble growth rate. The results further indicate that at large current densities the coalescence of tiny bubbles formed at the foot of the main bubble might play an important role for the bubble detachment. Moreover, the occurrence of Marangoni stresses at the gas-liquid interface is discussed.

Nickel-hydrogen battery with oxygen and electrolyte management features

DOEpatents

Sindorf, John F.

1991-10-22

A nickel-hydrogen battery or cell having one or more pressure vessels containing hydrogen gas and a plurality of cell-modules therein. Each cell-module includes a configuration of cooperatively associated oxygen and electrolyte mangement and component alignment features. A cell-module having electrolyte includes a negative electrode, a positive electrode adapted to facilitate oxygen diffusion, a separator disposed between the positive and negative electrodes for separating them and holding electrolyte for ionic conductivity, an absorber engaging the surface of the positive electrode facing away from the separator for providing electrolyte to the positive electrode, and a pair of surface-channeled diffusion screens for enclosing the positive and negative electrodes, absorber, and separator and for maintaining proper alignment of these components. The screens, formed in the shape of a pocket by intermittently sealing the edges together along as many as three sides, permit hydrogen gas to diffuse therethrough to the negative electrodes, and prevent the edges of the separator from swelling. Electrolyte is contained in the cell-module, absorbhed by the electrodes, the separator and the absorber.

Performance model of a recirculating stack nickel hydrogen cell

NASA Technical Reports Server (NTRS)

Zimmerman, Albert H.

1994-01-01

A theoretical model of the nickel hydrogen battery cell has been utilized to describe the chemical and physical changes during charge and overcharge in a recirculating stack nickel hydrogen cell. In particular, the movement of gas and electrolyte have been examined as a function of the amount of electrolyte put into the cell stack during cell activation, and as a function of flooding in regions of the gas screen in this cell design. Additionally, a two-dimensional variation on this model has been utilized to describe the effects of non-uniform loading in the nickel-electrode on the movement of gas and electrolyte within the recirculating stack nickel hydrogen cell. The type of nonuniform loading that has been examined here is that associated with higher than average loading near the surface of the sintered nickel electrode, a condition present to some degree in many nickel electrodes made by electrochemical impregnation methods. The effects of high surface loading were examined primarily under conditions of overcharge, since the movement of gas and electrolyte in the overcharging condition was typically where the greatest effects of non-uniform loading were found. The results indicate that significant changes in the capillary forces between cell components occur as the percentage of free volume in the stack filled by electrolyte becomes very high. These changes create large gradients in gas-filled space and oxygen concentrations near the boundary between the separator and the hydrogen electrode when the electrolyte fill is much greater than about 95 percent of the stack free volume. At lower electrolyte fill levels, these gaseous and electrolyte gradients become less extreme, and shift through the separator towards the nickel electrode. Similarly, flooding of areas in the gas screen cause higher concentrations of oxygen gas to approach the platinum/hydrogen electrode that is opposite the back side of the nickel electrode. These results illustrate the need for appropriate pore size distributions, and the maintenance of both convective electrolyte and gas flow paths through the stack, if the recirculating stack nickel hydrogen cell design is to work properly.

Electrochemical hydrogenation of thiophene on SPE electrodes

NASA Astrophysics Data System (ADS)

Huang, Haiyan; Yuan, Penghui; Yu, Ying; Chung, Keng H.

2017-01-01

Electrochemical reduction desulfurization is a promising technology for petroleum refining which is environmental friendly, low cost and able to achieve a high degree of automation. Electrochemical hydrogenation of thiophene was performed in a three-electrode system which SPE electrode was the working electrode. The electrochemical desulfurization was studied by cyclic voltammetry and bulk electrolysis with coulometry (BEC) techniques. The results of cyclic voltammetry showed that the electrochemical hydrogenation reduction reaction occurred at -0.4V. The BEC results showed that the currents generated from thiophene hydrogenation reactions increased with temperature. According to Arrhenius equation, activation energy of thiophene electrolysis was calculated and lower activation energy value indicated it was diffusion controlled reaction. From the products of electrolytic reactions, the mechanisms of electrochemical hydrogenation of thiophene were proposed, consisting of two pathways: openingring followed by hydrogenation, and hydrogenation followed by ring opening.

Development and Application of a Sample Holder for In Situ Gaseous TEM Studies of Membrane Electrode Assemblies for Polymer Electrolyte Fuel Cells.

PubMed

Kamino, Takeo; Yaguchi, Toshie; Shimizu, Takahiro

2017-10-01

Polymer electrolyte fuel cells hold great potential for stationary and mobile applications due to high power density and low operating temperature. However, the structural changes during electrochemical reactions are not well understood. In this article, we detail the development of the sample holder equipped with gas injectors and electric conductors and its application to a membrane electrode assembly of a polymer electrolyte fuel cell. Hydrogen and oxygen gases were simultaneously sprayed on the surfaces of the anode and cathode catalysts of the membrane electrode assembly sample, respectively, and observation of the structural changes in the catalysts were simultaneously carried out along with measurement of the generated voltages.

NREL Establishes World Record for Solar Hydrogen Production | News | News |

Science.gov Websites

acid/water solution (electrolyte) where the water-splitting reaction occurs to form hydrogen and oxygen efficiency and to partially protect the critical underlying layers from the corrosive electrolyte solution

In Situ Potentiodynamic Analysis of the Electrolyte/Silicon Electrodes Interface Reactions - A Sum Frequency Generation Vibrational Spectroscopy Study

DOE PAGES

Horowitz, Yonatan; Han, Hui-Ling; Ross, Philip N.; ...

2015-12-11

The key factor in long-term use of batteries is the formation of an electrically insulating solid layer that allows lithium ion transport but stops further electrolyte redox reactions on the electrode surface, hence solid electrolyte interphase (SEI). In this paper, we have studied a common electrolyte, 1.0 M LiPF 6/ethylene carbonate (EC)/diethyl carbonate (DEC), reduction products on crystalline silicon (Si) electrodes in a lithium (Li) half-cell system under reaction conditions. We employed in situ sum frequency generation vibrational spectroscopy (SFG-VS) with interface sensitivity in order to probe the molecular composition of the SEI surface species under various applied potentials wheremore » electrolyte reduction is expected. We found that, with a Si(100)-hydrogen terminated wafer, a Si-ethoxy (Si-OC 2H 5) surface intermediate forms due to DEC decomposition. Our results suggest that the SEI surface composition varies depending on the termination of Si surface, i.e., the acidity of the Si surface. We provide the evidence of specific chemical composition of the SEI on the anode surface under reaction conditions. This supports an electrochemical electrolyte reduction mechanism in which the reduction of the DEC molecule to an ethoxy moiety plays a key role. Finally, these findings shed new light on the formation mechanism of SEI on Si anodes in particular and on SEI formation in general.« less

Prospects on hydrogen production for a generalized domestic, industrial and automotive, usage

NASA Astrophysics Data System (ADS)

Dini, D.

Assuming the availability of advanced nuclear and solar systems as prime energy sources for electrolytic production of hydrogen, an assessment is made of high pressure electrolytic gasification, liquefaction and storage work requirements. Also, a pipeline network and associated equipment for the delivery and storage of hydrogen are considered in the context of a future replacement of all fossil fuels by hydrogen. Attention is given to space-based systems and terrestrial photovoltaics.

Microelectrode generator-collector systems for electrolytic titration: theoretical and practical considerations.

PubMed

Bell, Christopher G; Seelanan, Parinya; O'Hare, Danny

2017-10-23

Electochemical generator-collector systems, where one electrode is used to generate a reagent, have a potentially large field of application in sensing and measurement. We present a new theoretical description for coplanar microelectrode disc-disc systems where the collector is passive (such as a potentiometric sensor) and the generator is operating at constant flux. This solution is then used to develop a leading order solution for such a system where the reagent reacts reversibly in solution, such as in acid-base titration, where a hydrogen ion flux is generated by electrolysis of water. The principal novel result of the theory is that such devices are constrained by a maximum reagent flux. The hydrogen ion concentration at the collector will only reflect the buffer capacity of the bulk solution if this constraint is met. Both mathematical solutions are evaluated with several microfabricated devices and reasonable agreement with theory is demonstrated.

Photoelectrochemical generation of hydrogen and electricity from hydrazine hydrate using BiVO4 electrodes.

PubMed

Pilli, Satyananda Kishore; Summers, Kodi; Chidambaram, Dev

2015-06-07

This study demonstrates solar driven oxidation of hydrazine hydrate and the simultaneous production of hydrogen and electricity in photoelectrochemical cells and photofuel cells, respectively, using a visible light active molybdenum doped BiVO4 photoelectrode. The developed photoelectrodes exhibited tremendous efficiency towards anodic oxidation of hydrous hydrazine with continuous and stable hydrogen evolution at the Pt cathode under benign pH and zero bias conditions. Significantly, the photofuel cell containing hydrazine hydrate fuel has generated electricity with a high open circuit potential of 0.8 V. The presence of bicarbonate ions in the electrolyte has played a significant role in enhancing the kinetics of photoelectrochemical oxidation of hydrazine and improved the hydrogen and electricity generation efficiency thus avoiding the integration of an oxidation electrocatalyst. In addition, molybdenum doped BiVO4 as a possible photoelectrochemical hydrazine sensor has been investigated and the electrode photocurrent was found to be linearly dependent on the concentration of the hydrazine hydrate in the range of 20-90 mM with a correlation coefficient of 0.9936.

Optimizing investments in coupled offshore wind -electrolytic hydrogen storage systems in Denmark

NASA Astrophysics Data System (ADS)

Hou, Peng; Enevoldsen, Peter; Eichman, Joshua; Hu, Weihao; Jacobson, Mark Z.; Chen, Zhe

2017-08-01

In response to electricity markets with growing levels of wind energy production and varying electricity prices, this research examines incentives for investments in integrated renewable energy power systems. A strategy for using optimization methods for a power system consisting of wind turbines, electrolyzers, and hydrogen fuel cells is explored. This research reveals the investment potential of coupling offshore wind farms with different hydrogen systems. The benefits in terms of a return on investment are demonstrated with data from the Danish electricity markets. This research also investigates the tradeoffs between selling the hydrogen directly to customers or using it as a storage medium to re-generate electricity at a time when it is more valuable. This research finds that the most beneficial configuration is to produce hydrogen at a time that complements the wind farm and sell the hydrogen directly to end users.

New, efficient and viable system for ethanol fuel utilization on combined electric/internal combustion engine vehicles

NASA Astrophysics Data System (ADS)

Sato, André G.; Silva, Gabriel C. D.; Paganin, Valdecir A.; Biancolli, Ana L. G.; Ticianelli, Edson A.

2015-10-01

Although ethanol can be directly employed as fuel on polymer-electrolyte fuel cells (PEMFC), its low oxidation kinetics in the anode and the crossover to the cathode lead to a substantial reduction of energy conversion efficiency. However, when fuel cell driven vehicles are considered, the system may include an on board steam reformer for converting ethanol into hydrogen, but the hydrogen produced contains carbon monoxide, which limits applications in PEMFCs. Here, we present a system consisting of an ethanol dehydrogenation catalytic reactor for producing hydrogen, which is supplied to a PEMFC to generate electricity for electric motors. A liquid by-product effluent from the reactor can be used as fuel for an integrated internal combustion engine, or catalytically recycled to extract more hydrogen molecules. Power densities comparable to those of a PEMFC operating with pure hydrogen are attained by using the hydrogen rich stream produced by the ethanol dehydrogenation reactor.

Optimizing investments in coupled offshore wind-electrolytic hydrogen storage systems in Denmark

DOE PAGES

Hou, Peng; Enevoldsen, Peter; Eichman, Joshua; ...

2017-05-25

In response to electricity markets with growing levels of wind energy production and varying electricity prices, this research examines incentives for investments in integrated renewable energy power systems. A strategy for using optimization methods for a power system consisting of wind turbines, electrolyzers, and hydrogen fuel cells is explored. This research reveals the investment potential of coupling offshore wind farms with different hydrogen systems. The benefits in terms of a return on investment are demonstrated with data from the Danish electricity markets. This research also investigates the tradeoffs between selling the hydrogen directly to customers or using it as amore » storage medium to re-generate electricity at a time when it is more valuable. Finally, this research finds that the most beneficial configuration is to produce hydrogen at a time that complements the wind farm and sell the hydrogen directly to end users.« less

The application of diffusion theory to the analysis of hydrogen desorption data at 25 deg C

NASA Technical Reports Server (NTRS)

Danford, M. D.

1985-01-01

The application of diffusion theory to the analysis of hydrogen desorption data (coulombs of H2 desorbed versus time) has been studied. From these analyses, important information concerning hydrogen solubilities and the nature of the hydrogen distributions in the metal has been obtained. Two nickel base alloys, Rene' 41 and Waspaloy, and one ferrous alloy, 4340 steel, are studied in this work. For the nickel base alloys, it is found that the hydrogen distributions after electrolytic charging conforms closely to those which would be predicted by diffusion theory. For Waspaloy samples charged at 5,000 psi, it is found that the hydrogen distributions are essentially the same as those obtained by electrolytic charging. The hydrogen distributions in electrolytically charged 4340 steel, on the other hand, are essentially uniform in nature, which would not be predicted by diffusion theory. A possible explanation has been proposed. Finally, it is found that the hydrogen desorption is completely explained by the nature of the hydrogen distribution in the metal, and that the fast hydrogen is not due to surface and sub-surface hydride formation, as was originally proposed.

Hydrogen storage and fuel cells

NASA Astrophysics Data System (ADS)

Liu, Di-Jia

2018-01-01

Global warming and future energy supply are two major challenges facing American public today. To overcome such challenges, it is imperative to maximize the existing fuel utilization with new conversion technologies while exploring alternative energy sources with minimal environmental impact. Hydrogen fuel cell represents a next-generation energy-efficient technology in transportation and stationary power productions. In this presentation, a brief overview of the current technology status of on-board hydrogen storage and polymer electrolyte membrane fuel cell in transportation will be provided. The directions of the future researches in these technological fields, including a recent "big idea" of "H2@Scale" currently developed at the U. S. Department of Energy, will also be discussed.

InGaN working electrodes with assisted bias generated from GaAs solar cells for efficient water splitting.

PubMed

Liu, Shu-Yen; Sheu, J K; Lin, Yu-Chuan; Chen, Yu-Tong; Tu, S J; Lee, M L; Lai, W C

2013-11-04

Hydrogen generation through water splitting by n-InGaN working electrodes with bias generated from GaAs solar cell was studied. Instead of using an external bias provided by power supply, a GaAs-based solar cell was used as the driving force to increase the rate of hydrogen production. The water-splitting system was tuned using different approaches to set the operating points to the maximum power point of the GaAs solar cell. The approaches included changing the electrolytes, varying the light intensity, and introducing the immersed ITO ohmic contacts on the working electrodes. As a result, the hybrid system comprising both InGaN-based working electrodes and GaAs solar cells operating under concentrated illumination could possibly facilitate efficient water splitting.

DEGRADATION ISSUES IN SOLID OXIDE CELLS DURING HIGH TEMPERATURE ELECTROLYSIS

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

M. S. Sohal; J. E. O'Brien; C. M. Stoots

2012-02-01

Idaho National Laboratory (INL) is performing high-temperature electrolysis research to generate hydrogen using solid oxide electrolysis cells (SOECs). The project goals are to address the technical and degradation issues associated with the SOECs. This paper provides a summary of various ongoing INL and INL sponsored activities aimed at addressing SOEC degradation. These activities include stack testing, post-test examination, degradation modeling, and a list of issues that need to be addressed in future. Major degradation issues relating to solid oxide fuel cells (SOFC) are relatively better understood than those for SOECs. Some of the degradation mechanisms in SOFCs include contact problemsmore » between adjacent cell components, microstructural deterioration (coarsening) of the porous electrodes, and blocking of the reaction sites within the electrodes. Contact problems include delamination of an electrode from the electrolyte, growth of a poorly (electronically) conducting oxide layer between the metallic interconnect plates and the electrodes, and lack of contact between the interconnect and the electrode. INL's test results on high temperature electrolysis (HTE) using solid oxide cells do not provide a clear evidence whether different events lead to similar or drastically different electrochemical degradation mechanisms. Post-test examination of the solid oxide electrolysis cells showed that the hydrogen electrode and interconnect get partially oxidized and become non-conductive. This is most likely caused by the hydrogen stream composition and flow rate during cool down. The oxygen electrode side of the stacks seemed to be responsible for the observed degradation due to large areas of electrode delamination. Based on the oxygen electrode appearance, the degradation of these stacks was largely controlled by the oxygen electrode delamination rate. University of Utah (Virkar) has developed a SOEC model based on concepts in local thermodynamic equilibrium in systems otherwise in global thermodynamic non-equilibrium. This model is under continued development. It shows that electronic conduction through the electrolyte, however small, must be taken into account for determining local oxygen chemical potential, within the electrolyte. The chemical potential within the electrolyte may lie out of bounds in relation to values at the electrodes in the electrolyzer mode. Under certain conditions, high pressures can develop in the electrolyte just under the oxygen electrode (anode)/electrolyte interface, leading to electrode delamination. This theory is being further refined and tested by introducing some electronic conduction in the electrolyte.« less

DEGRADATION ISSUES IN SOLID OXIDE CELLS DURING HIGH TEMPERATURE ELECTROLYSIS

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

J. E. O'Brien; C. M. Stoots; V. I. Sharma

2010-06-01

Idaho National Laboratory (INL) is performing high-temperature electrolysis research to generate hydrogen using solid oxide electrolysis cells (SOECs). The project goals are to address the technical and degradation issues associated with the SOECs. This paper provides a summary of various ongoing INL and INL sponsored activities aimed at addressing SOEC degradation. These activities include stack testing, post-test examination, degradation modeling, and a list of issues that need to be addressed in future. Major degradation issues relating to solid oxide fuel cells (SOFC) are relatively better understood than those for SOECs. Some of the degradation mechanisms in SOFCs include contact problemsmore » between adjacent cell components, microstructural deterioration (coarsening) of the porous electrodes, and blocking of the reaction sites within the electrodes. Contact problems include delamination of an electrode from the electrolyte, growth of a poorly (electronically) conducting oxide layer between the metallic interconnect plates and the electrodes, and lack of contact between the interconnect and the electrode. INL’s test results on high temperature electrolysis (HTE) using solid oxide cells do not provide a clear evidence whether different events lead to similar or drastically different electrochemical degradation mechanisms. Post-test examination of the solid oxide electrolysis cells showed that the hydrogen electrode and interconnect get partially oxidized and become non-conductive. This is most likely caused by the hydrogen stream composition and flow rate during cool down. The oxygen electrode side of the stacks seemed to be responsible for the observed degradation due to large areas of electrode delamination. Based on the oxygen electrode appearance, the degradation of these stacks was largely controlled by the oxygen electrode delamination rate. University of Utah (Virkar) has developed a SOEC model based on concepts in local thermodynamic equilibrium in systems otherwise in global thermodynamic non-equilibrium. This model is under continued development. It shows that electronic conduction through the electrolyte, however small, must be taken into account for determining local oxygen chemical potential, within the electrolyte. The chemical potential within the electrolyte may lie out of bounds in relation to values at the electrodes in the electrolyzer mode. Under certain conditions, high pressures can develop in the electrolyte just under the oxygen electrode (anode)/electrolyte interface, leading to electrode delamination. This theory is being further refined and tested by introducing some electronic conduction in the electrolyte.« less

New spectrophotometric methods for the determinations of hydrogen sulfide present in the samples of lake water, industrial effluents, tender coconut, sugarcane juice and egg

NASA Astrophysics Data System (ADS)

Shyla, B.; Nagendrappa, G.

2012-10-01

The new methods are working on the principle that iron(III) is reduced to iron(II) by hydrogen sulfide, catechol and p-toluidine the system 1/hydrogen sulfide the system 2, in acidic medium followed by the reduced iron forming complex with 1,10-phenanthroline with λmax 510 nm. The other two methods are based on redox reactions between electrolytically generated manganese(III) sulfate taken in excess and hydrogen sulfide followed by the unreacted oxidant oxidizing diphenylamine λmax 570 the system 3/barium diphenylamine sulphonate λmax 540 nm, the system 4. The increase/decrease in the color intensity of the dye products of the systems 1 and 2 or 3 and 4 are proportional to the concentration of hydrogen sulfide with its quantification range 0.035-1.40 μg ml-1/0.14-1.40 μg ml-1.

Method and apparatus for hydrogen production from water

NASA Technical Reports Server (NTRS)

Muradov, Nazim Z. (Inventor)

2012-01-01

A method, apparatuses and chemical compositions are provided for producing high purity hydrogen from water. Metals or alloys capable of reacting with water and producing hydrogen in aqueous solutions at ambient conditions are reacted with one or more inorganic hydrides capable of releasing hydrogen in aqueous solutions at ambient conditions, one or more transition metal compounds are used to catalyze the reaction and, optionally, one or more alkali metal-based compounds. The metal or alloy is preferably aluminum. The inorganic hydride is from a family of complex inorganic hydrides; most preferably, NaBH.sub.4. The transition metal catalyst is from the groups VIII and IB; preferably, Cu and Fe. The alkali metal-based compounds are preferably NaOH, KOH, and the like. Hydrogen generated has a purity of at least 99.99 vol. % (dry basis), and is used without further purification in all types of fuel cells, including the polymer electrolyte membrane (PEM) fuel cell.

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.

Molecular metal-Oxo catalysts for generating hydrogen from water

DOEpatents

Long, Jeffrey R; Chang, Christopher J; Karunadasa, Hemamala I

2015-02-24

A composition of matter suitable for the generation of hydrogen from water is described, the positively charged cation of the composition having the general formula [(PY5W.sub.2)MO].sup.2+, wherein PY5W.sub.2 is (NC.sub.5XYZ)(NC.sub.5H.sub.4).sub.4C.sub.2W.sub.2, M is a transition metal, and W, X, Y, and Z can be H, R, a halide, CF.sub.3, or SiR.sub.3, where R can be an alkyl or aryl group. The two accompanying counter anions, in one embodiment, can be selected from the following Cl.sup.-, I.sup.-, PF.sub.6.sup.-, and CF.sub.3SO.sub.3.sup.-. In embodiments of the invention, water, such as tap water containing electrolyte or straight sea water can be subject to an electric potential of between 1.0 V and 1.4 V relative to the standard hydrogen electrode, which at pH 7 corresponds to an overpotential of 0.6 to 1.0 V, with the result being, among other things, the generation of hydrogen with an optimal turnover frequency of ca. 1.5 million mol H.sub.2/mol catalyst per h.

Solid oxide fuel cell power plant having a bootstrap start-up system

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

Lines, Michael T

The bootstrap start-up system (42) achieves an efficient start-up of the power plant (10) that minimizes formation of soot within a reformed hydrogen rich fuel. A burner (48) receives un-reformed fuel directly from the fuel supply (30) and combusts the fuel to heat cathode air which then heats an electrolyte (24) within the fuel cell (12). A dilute hydrogen forming gas (68) cycles through a sealed heat-cycling loop (66) to transfer heat and generated steam from an anode side (32) of the electrolyte (24) through fuel processing system (36) components (38, 40) and back to an anode flow field (26)more » until fuel processing system components (38, 40) achieve predetermined optimal temperatures and steam content. Then, the heat-cycling loop (66) is unsealed and the un-reformed fuel is admitted into the fuel processing system (36) and anode flow (26) field to commence ordinary operation of the power plant (10).« less

Cell and method for electrolysis of water and anode

NASA Technical Reports Server (NTRS)

Aylward, J. R. (Inventor)

1981-01-01

An electrolytic cell for converting water vapor to oxygen and hydrogen include an anode comprising a foraminous conductive metal substrate with a 65-85 weight percent iridium oxide coating and 15-35 weight percent of a high temperature resin binder. A matrix member contains an electrolyte to which a cathode substantially inert. The foraminous metal member is most desirably expanded tantalum mesh, and the cell desirably includes reservoir elements of porous sintered metal in contact with the anode to receive and discharge electrolyte to the matrix member as required. Upon entry of a water vapor containing airstream into contact with the outer surface of the anode and thence into contact with iridium oxide coating, the water vapor is electrolytically converted to hydrogen ions and oxygen with the hydrogen ions migrating through the matrix to the cathode and the oxygen gas produced at the anode to enrich the air stream passing by the anode.

Hierarchical Ni-Mo-S nanosheets on carbon fiber cloth: A flexible electrode for efficient hydrogen generation in neutral electrolyte.

PubMed

Miao, Jianwei; Xiao, Fang-Xing; Yang, Hong Bin; Khoo, Si Yun; Chen, Jiazang; Fan, Zhanxi; Hsu, Ying-Ya; Chen, Hao Ming; Zhang, Hua; Liu, Bin

2015-08-01

A unique functional electrode made of hierarchal Ni-Mo-S nanosheets with abundant exposed edges anchored on conductive and flexible carbon fiber cloth, referred to as Ni-Mo-S/C, has been developed through a facile biomolecule-assisted hydrothermal method. The incorporation of Ni atoms in Mo-S plays a crucial role in tuning its intrinsic catalytic property by creating substantial defect sites as well as modifying the morphology of Ni-Mo-S network at atomic scale, resulting in an impressive enhancement in the catalytic activity. The Ni-Mo-S/C electrode exhibits a large cathodic current and a low onset potential for hydrogen evolution reaction in neutral electrolyte (pH ~7), for example, current density of 10 mA/cm(2) at a very small overpotential of 200 mV. Furthermore, the Ni-Mo-S/C electrode has excellent electrocatalytic stability over an extended period, much better than those of MoS2/C and Pt plate electrodes. Scanning and transmission electron microscopy, Raman spectroscopy, x-ray diffraction, x-ray photoelectron spectroscopy, and x-ray absorption spectroscopy were used to understand the formation process and electrocatalytic properties of Ni-Mo-S/C. The intuitive comparison test was designed to reveal the superior gas-evolving profile of Ni-Mo-S/C over that of MoS2/C, and a laboratory-scale hydrogen generator was further assembled to demonstrate its potential application in practical appliances.

Recent Progress in Energy-Driven Water Splitting.

PubMed

Tee, Si Yin; Win, Khin Yin; Teo, Wee Siang; Koh, Leng-Duei; Liu, Shuhua; Teng, Choon Peng; Han, Ming-Yong

2017-05-01

Hydrogen is readily obtained from renewable and non-renewable resources via water splitting by using thermal, electrical, photonic and biochemical energy. The major hydrogen production is generated from thermal energy through steam reforming/gasification of fossil fuel. As the commonly used non-renewable resources will be depleted in the long run, there is great demand to utilize renewable energy resources for hydrogen production. Most of the renewable resources may be used to produce electricity for driving water splitting while challenges remain to improve cost-effectiveness. As the most abundant energy resource, the direct conversion of solar energy to hydrogen is considered the most sustainable energy production method without causing pollutions to the environment. In overall, this review briefly summarizes thermolytic, electrolytic, photolytic and biolytic water splitting. It highlights photonic and electrical driven water splitting together with photovoltaic-integrated solar-driven water electrolysis.

Recent Progress in Energy‐Driven Water Splitting

PubMed Central

Tee, Si Yin; Win, Khin Yin; Teo, Wee Siang; Koh, Leng‐Duei; Liu, Shuhua; Teng, Choon Peng

2017-01-01

Hydrogen is readily obtained from renewable and non‐renewable resources via water splitting by using thermal, electrical, photonic and biochemical energy. The major hydrogen production is generated from thermal energy through steam reforming/gasification of fossil fuel. As the commonly used non‐renewable resources will be depleted in the long run, there is great demand to utilize renewable energy resources for hydrogen production. Most of the renewable resources may be used to produce electricity for driving water splitting while challenges remain to improve cost‐effectiveness. As the most abundant energy resource, the direct conversion of solar energy to hydrogen is considered the most sustainable energy production method without causing pollutions to the environment. In overall, this review briefly summarizes thermolytic, electrolytic, photolytic and biolytic water splitting. It highlights photonic and electrical driven water splitting together with photovoltaic‐integrated solar‐driven water electrolysis. PMID:28546906

Effect of KOH concentration on LEO cycle life of IPV nickel-hydrogen flight cells. An update

NASA Technical Reports Server (NTRS)

Smithrick, John J.; Hall, Stephen W.

1991-01-01

An update of validation test results confirming the breakthrough in LEO cycle life of nickel-hydrogen cells containing 26 percent potassium hydroxide (KOH) electrolyte is presented. A breakthrough in the LEO cycle life of individual pressure vessel nickel-hydrogen cells is reported. The cycle life of boiler plate cells containing 26 percent KOH electrolyte was about 40,000 LEO cycles compared to 3500 cycles for cells containing 31 percent KOH.

Effect of KOH concentration on LEO cycle life of IPV nickel-hydrogen flight cells - An update

NASA Technical Reports Server (NTRS)

Smithrick, John J.; Hall, Stephen W.

1991-01-01

An update of validation test results confirming the breakthrough in LEO cycle life of nickel-hydrogen cells containing 26 percent potassium hydroxide (KOH) electrolyte is presented. A breakthrough in the LEO cycle life of individual pressure vessel nickel-hydrogen cells is reported. The cycle life of boiler plate cells containing 26 percent KOH electrolyte was about 40,000 LEO cycles compared to 3500 cycles for cells containing 31 percent KOH.

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

An update of validation test results confirming the breakthrough in LEO cycle life of nickel-hydrogen cells containing 26 percent potassium hydroxide (KOH) electrolyte is presented. A breakthrough in the LEO cycle life of individual pressure vessel nickel-hydrogen cells is reported. The cycle life of boiler plate cells containing 26 percent KOH electrolyte was about 40,000 LEO cycles compared to 3500 cycles for cells containing 31 percent KOH.

A ketone/alcohol polymer for cycle of electrolytic hydrogen-fixing with water and releasing under mild conditions

PubMed Central

Kato, Ryo; Yoshimasa, Keisuke; Egashira, Tatsuya; Oya, Takahiro; Oyaizu, Kenichi; Nishide, Hiroyuki

2016-01-01

Finding a safe and efficient carrier of hydrogen is a major challenge. Recently, hydrogenated organic compounds have been studied as hydrogen storage materials because of their ability to stably and reversibly store hydrogen by forming chemical bonds; however, these compounds often suffer from safety issues and are usually hydrogenated with hydrogen at high pressure and/or temperature. Here we present a ketone (fluorenone) polymer that can be moulded as a plastic sheet and fixes hydrogen via a simple electrolytic hydrogenation at −1.5 V (versus Ag/AgCl) in water at room temperature. The hydrogenated alcohol derivative (the fluorenol polymer) reversibly releases hydrogen by heating (80 °C) in the presence of an aqueous iridium catalyst. Both the use of a ketone polymer and the efficient hydrogen fixing with water as a proton source are completely different from other (de)hydrogenated compounds and hydrogenation processes. The easy handling and mouldable polymers could suggest a pocketable hydrogen carrier. PMID:27687772

The effects of cations and anions on hydrogen chemisorption at Pt

NASA Technical Reports Server (NTRS)

Huang, J. C.; Ogrady, W. E.; Yeager, E.

1977-01-01

Experimental evidence based on linear sweep voltammetry is presented to substantiate the view that ionic adsorption substantially shifts electrode potentials in addition to the relative heights of the hydrogen adsorption peaks. HClO4 and HF are chosen as better reference electrolytes for anion studies. The voltammetry curves for 0.1M HF and 0.1M HClO4 as well as the effect of adding successively increasing amounts of H2SO4 to these electrolytes are discussed. The measurements are also extended to alkaline solutions. Mechanisms whereby the addition of various cations and anions to electrolytes such as HF and HClO4 can induce changes in the structure of the hydrogen adsorption region in the voltammetry curves are identified: (1) blocking of sites by anion adsorption and coupling of hydrogen adsorption and anion desorption, (2) modification in the hydrogen adsorption energies for sites adjacent to adsorbed anions, (3) changes in the potential distribution across the interface, and (4) surface restructuring.

Chemically Modified Metal Oxide Nanostructure for Photoelectrochemical Water Splitting

NASA Astrophysics Data System (ADS)

Wang, Gongming

Hydrogen gas is chemical fuel with high energy density, and represents a clean, renewable and carbon-free burning fuel, which has the potential to solve the more and more urgent energy crisis in today's society. Inspired by natural photosynthesis, artificial photosynthesis to generate hydrogen energy has attracted a lot of attentions in the field of chemistry, physics and material. Photoelectrochemical water splitting based on semiconductors represents a green and low cost method to generate hydrogen fuel. However, the current overall efficiency of solar to hydrogen is quite low, due to some intrinsic limitations such as bandgap, diffusion distance, carrier lifetime and photostability of semiconductors. Although nanostructured semiconductors can improve their photoelectrochemical water splitting performance to some extent, by increasing electrolyte accessible area and shortening minority carrier diffusion distance, nanostructure engineering cannot change their intrinsic electronic properties. Recent development in chemically modified nanostructures such as surface catalyst decoration, element doping, plasmonic modification and interfacial hetero-junction design have led to significant advancement in the photoelectrochemical water splitting, by improving surface reaction kinetics and charge separation, transportation and collection efficiency. In this thesis, I will give a detailed discussion on the chemically modified metal oxide nanostructures for photoelectrocemical hydrogen generation, with a focus on the element doping, hydrogen treatment and catalyst modification. I have demonstrated nitrogen doping on ZnO and Ti doping on hematite can improve their photoelectrochemical performance. In addition, we found hydrogen treatment is a general and effective method to improve the photocatalytic performance, by increasing their carrier desities. Hydrogen treatment has been demonstrated on TiO2, WO3 and BiVO4. In the end, we also used electrochemical catalyt to modify these metal oxide photoelectrode for waste water treatment and chemical fuel generation.

Effect of Hydrogen Charging on the Stress Corrosion Behavior of 2205 Duplex Stainless Steel Under 3.5 wt.% NaCl Thin Electrolyte Layer

NASA Astrophysics Data System (ADS)

Zhao, Tianliang; Liu, Zhiyong; Hu, Shanshan; Du, Cuiwei; Li, Xiaogang

2017-05-01

The effect of hydrogen charging on the stress corrosion cracking (SCC) behavior of 2205 duplex stainless steel (DSS) under 3.5 wt.% NaCl thin electrolyte layer was investigated on precharged samples through hydrogen determination, electrochemical measurement, and slow strain rate tensile test. Results show that hydrogen charging weakens the passive film without inducing any obvious trace of localized anodic dissolution. Therefore, hydrogen charging increases the SCC susceptibility of 2205 DSS mainly through mechanism of hydrogen embrittlement rather than mechanism of localized anodic dissolution. 2205 DSS shows a more susceptibility to hydrogen under the TEL when hydrogen charging current density (HCCD) is between 20 and 50 mA cm-2. The increasing trend is remarkable when hydrogen charging current density increases from 20 to 50 mA cm-2 and fades after 50 mA cm-2.

New vistas in the determination of hydrogen in aerospace engine metal alloys

NASA Technical Reports Server (NTRS)

Danford, M. D.

1986-01-01

The application of diffusion theory to the analysis of hydrogen desorption data has been studied. From these analyses, important information concerning hydrogen solubilities and the nature of the hydrogen distributions in the metal has been obtained. Two nickel base alloys, Rene' 41 and Waspaloy, and one ferrous alloy, 4340 steel, were studied in this work. For the nickel base alloys, it was found that the hydrogen distributions after electrolytic charging conformed closely to those which would be predicted by diffusion theory. The hydrogen distributions in electrolytically charged 4340 steel, on the other hand, were essentially uniform in nature, which would not be predicted by diffusion theory. Finally, it has been found that the hydrogen desorption is completely explained by the nature of the hydrogen distribution in the metal, and that the 'fast' hydrogen is not due to surface and subsurface hydride formation, as was originally proposed.

Development of planar solid oxide fuel cells for power generation applications

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

Minh, N.Q.

1996-04-01

Planar solid oxide fuel cells (SOFCs) are presently being developed for a variety of electric power generation application. The planar design offers simple cell geometry, high power density, and multiple fabrication and gas manifolding options. Planar SOFC technology has received much attention recently, and significant progress has been made in this area. Recent effort at AlliedSignal has focused on the development of high-performance, lightweight planar SOFCs, having thin-electrolyte films, that can be operated efficiently at reduced temperatures (< 1000{degrees}C). The advantages of reduced-temperature operation include wider material choice (including use of metallic interconnects), expected longer cell life, reduced thermal stress,more » improved reliability, and reduced fuel cell cost. The key aspect in the development of thin-film SIFCs is to incorporate the thin electrolyte layer into the desired structure of cells in a manner that yields the required characteristics. AlliedSignal has developed a simple and cost-effective method based on tape calendering for the fabrication of thin-electrolyte SOFCs. Thin-electrolyte cells made by tape calendering have shown extraordinary performance, e.g., producing more than 500mW/cm{sup 2} at 700{degrees}C and 800mW/cm{sup 2} at 800{degrees}C with hydrogen as fuel and air is oxidant. thin-electrolyte single cells have been incorporated into a compliant metallic stack structure and operated at reduced and operated at reduced-temperature conditions.« less

Electrochemical process and production of novel complex hydrides

DOEpatents

Zidan, Ragaiy

2013-06-25

A process of using an electrochemical cell to generate aluminum hydride (AlH.sub.3) is provided. The electrolytic cell uses a polar solvent to solubilize NaAlH.sub.4. The resulting electrochemical process results in the formation of AlH.sub.3. The AlH.sub.3 can be recovered and used as a source of hydrogen for the automotive industry. The resulting spent aluminum can be regenerated into NaAlH.sub.4 as part of a closed loop process of AlH.sub.3 generation.

Design of a microbial fuel cell and its transition to microbial electrolytic cell for hydrogen production by electrohydrogenesis.

PubMed

Gupta, Pratima; Parkhey, Piyush; Joshi, Komal; Mahilkar, Anjali

2013-10-01

Anaerobic bacteria were isolated from industrial wastewater and soil samples and tested for exoelectrogenic activity by current production in double chambered microbial fuel cell (MFC), which was further transitioned into a single chambered microbial electrolytic cell to test hydrogen production by electrohydrogenesis. Of all the cultures, the isolate from industrial water sample showed the maximum values for current = 0.161 mA, current density = 108.57 mA/m2 and power density = 48.85 mW/m2 with graphite electrode. Maximum voltage across the cell, however, was reported by the isolate from sewage water sample (506 mv) with copper as electrode. Tap water with KMnO4 was the best cathodic electrolyte as the highest values for all the measured MFC parameters were reported with it. Once the exoelectrogenic activity of the isolates was confirmed by current production, these were tested for hydrogen production in a single chambered microbial electrolytic cell (MEC) modified from the MFC. Hydrogen production was reported positive from co-culture of isolates of both the water samples and co-culture of one soil and one water sample. The maximum rate and yield of hydrogen production was 0.18 m3H2/m3/d and 3.2 mol H2/mol glucose respectively with total hydrogen production of 42.4 mL and energy recovery of 57.4%. Cumulative hydrogen production for a five day cycle of MEC operation was 0.16 m3H2/m3/d.

Method for hydrogen production and metal winning, and a catalyst/cocatalyst composition useful therefor

DOEpatents

Dhooge, Patrick M.

1987-10-13

A catalyst/cocatalyst/organics composition of matter is useful in electrolytically producing hydrogen or electrowinning metals. Use of the catalyst/cocatalyst/organics composition causes the anode potential and the energy required for the reaction to decrease. An electrolyte, including the catalyst/cocatalyst composition, and a reaction medium composition further including organic material are also described.

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

Gottesfeld, S.

The fuel cell is the most efficient device for the conversion of hydrogen fuel to electric power. As such, the fuel cell represents a key element in efforts to demonstrate and implement hydrogen fuel utilization for electric power generation. The low temperature, polymer electrolyte membrane fuel cell (PEMFC) has recently been identified as an attractive option for stationary power generation, based on the relatively simple and benign materials employed, the zero-emission character of the device, and the expected high power density, high reliability and low cost. However, a PEMFC stack fueled by hydrogen with the combined properties of low cost,more » high performance and high reliability has not yet been demonstrated. Demonstration of such a stack will remove a significant barrier to implementation of this advanced technology for electric power generation from hydrogen. Work done in the past at LANL on the development of components and materials, particularly on advanced membrane/electrode assemblies (MEAs), has contributed significantly to the capability to demonstrate in the foreseeable future a PEMFC stack with the combined characteristics described above. A joint effort between LANL and an industrial stack manufacturer will result in the demonstration of such a fuel cell stack for stationary power generation. The stack could operate on hydrogen fuel derived from either natural gas or from renewable sources. The technical plan includes collaboration with a stack manufacturer (CRADA). It stresses the special requirements from a PEMFC in stationary power generation, particularly maximization of the energy conversion efficiency, extension of useful life to the 10 hours time scale and tolerance to impurities from the reforming of natural gas.« less

In-Situ Formed Hydroxide Accelerating Water Dissociation Kinetics on Co3N for Hydrogen Production in Alkaline Solution.

PubMed

Xu, Zhe; Li, Wenchao; Yan, Yadong; Wang, HongXu; Zhu, Heng; Zhao, Meiming; Yan, Shicheng; Zou, Zhigang

2018-06-21

Sluggish water dissociation kinetics on nonprecious metal electrocatalysts limits the development of economical hydrogen production from water-alkali electrolyzers. Here, using Co 3 N electrocatalyst as a prototype, we find that during water splitting in alkaline electrolyte a cobalt-containing hydroxide formed on the surface of Co 3 N, which greatly decreased the activation energy of water dissociation (Volmer step, a main rate-determining step for water splitting in alkaline electrolytes). Combining the cobalt ion poisoning test and theoretical calculations, the efficient hydrogen production on Co 3 N electrocatalysts would benefit from favorable water dissociation on in-situ formed cobalt-containing hydroxide and low hydrogen production barrier on the nitrogen sites of Co 3 N. As a result, the Co 3 N catalyst exhibits a low water-splitting activation energy (26.57 kJ mol -1 ) that approaches the value of platinum electrodes (11.69 kJ mol -1 ). Our findings offer new insight into understanding the catalytic mechanism of nitride electrocatalysts, thus contributing to the development of economical hydrogen production in alkaline electrolytes.

Apparatus and method for the electrolysis of water

DOEpatents

Greenbaum, Elias

2015-04-21

An apparatus for the electrolytic splitting of water into hydrogen and/or oxygen, the apparatus comprising: (i) at least one lithographically-patternable substrate having a surface; (ii) a plurality of microscaled catalytic electrodes embedded in said surface; (iii) at least one counter electrode in proximity to but not on said surface; (iv) means for collecting evolved hydrogen and/or oxygen gas; (v) electrical powering means for applying a voltage across said plurality of microscaled catalytic electrodes and said at least one counter electrode; and (vi) a container for holding an aqueous electrolyte and housing said plurality of microscaled catalytic electrodes and said at least one counter electrode. Electrolytic processes using the above electrolytic apparatus or functional mimics thereof are also described.

Tensile properties of titanium electrolytically charged with hydrogen

NASA Technical Reports Server (NTRS)

Smith, R. J.; Otterson, D. A.

1971-01-01

Yield strength, ultimate tensile strength, and elongation were studied for annealed titanium electrolytically charged with hydrogen. The hydrogen was present as a surface hydride layer. These tensile properties were generally lower for uncharged titanium than for titanium with a continuous surface hydride; they were greater for uncharged titanium than for titanium with an assumed discontinuous surface hydride. We suggest that the interface between titanium and titanium hydride is weak. And the hydride does not necessarily impair strength and ductility of annealed titanium. The possibility that oxygen and/or nitrogen can embrittle titanium hydride is discussed.

Efficient Electron Transfer across a ZnO-MoS2 -Reduced Graphene Oxide Heterojunction for Enhanced Sunlight-Driven Photocatalytic Hydrogen Evolution.

PubMed

Kumar, Suneel; Reddy, Nagappagari Lakshmana; Kushwaha, Himmat Singh; Kumar, Ashish; Shankar, Muthukonda Venkatakrishnan; Bhattacharyya, Kaustava; Halder, Aditi; Krishnan, Venkata

2017-09-22

The development of noble metal-free catalysts for hydrogen evolution is required for energy applications. In this regard, ternary heterojunction nanocomposites consisting of ZnO nanoparticles anchored on MoS 2 -RGO (RGO=reduced graphene oxide) nanosheets as heterogeneous catalysts show highly efficient photocatalytic H 2 evolution. In the photocatalytic process, the catalyst dispersed in an electrolytic solution (S 2- and SO 3 2- ions) exhibits an enhanced rate of H 2 evolution, and optimization experiments reveal that ZnO with 4.0 wt % of MoS 2 -RGO nanosheets gives the highest photocatalytic H 2 production of 28.616 mmol h -1  g cat -1 under sunlight irradiation; approximately 56 times higher than that on bare ZnO and several times higher than those of other ternary photocatalysts. The superior catalytic activity can be attributed to the in situ generation of ZnS, which leads to improved interfacial charge transfer to the MoS 2 cocatalyst and RGO, which has plenty of active sites available for photocatalytic reactions. Recycling experiments also proved the stability of the optimized photocatalyst. In addition, the ternary nanocomposite displayed multifunctional properties for hydrogen evolution activity under electrocatalytic and photoelectrocatalytic conditions owing to the high electrode-electrolyte contact area. Thus, the present work provides very useful insights for the development of inexpensive, multifunctional catalysts without noble metal loading to achieve a high rate of H 2 generation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

New spectrophotometric methods for the determinations of hydrogen sulfide present in the samples of lake water, industrial effluents, tender coconut, sugarcane juice and egg.

PubMed

Shyla, B; Nagendrappa, G

2012-10-01

The new methods are working on the principle that iron(III) is reduced to iron(II) by hydrogen sulfide, catechol and p-toluidine the system 1/hydrogen sulfide the system 2, in acidic medium followed by the reduced iron forming complex with 1,10-phenanthroline with λ(max) 510 nm. The other two methods are based on redox reactions between electrolytically generated manganese(III) sulfate taken in excess and hydrogen sulfide followed by the unreacted oxidant oxidizing diphenylamine λ(max) 570 the system 3/barium diphenylamine sulphonate λ(max) 540 nm, the system 4. The increase/decrease in the color intensity of the dye products of the systems 1 and 2 or 3 and 4 are proportional to the concentration of hydrogen sulfide with its quantification range 0.035-1.40 μg ml(-1)/0.14-1.40 μg ml(-1). Copyright © 2012 Elsevier B.V. All rights reserved.

Common pressure vessel development for the nickel hydrogen technology

NASA Technical Reports Server (NTRS)

Holleck, G.

1981-01-01

The design of a pressure vessel nickel hydrogen cell is described. The cell has the following key features: it eliminates electrolyte bridging; provides for independent electrolyte management for each unit stack; provides for independent oxygen management for each unit stack; has good heat dissipation; has a mechanically sound and practical interconnection; and has the maximum in common with state of the art individual pressure vessel technology.

Synthetic carbonaceous fuels and feedstocks

DOEpatents

Steinberg, Meyer

1980-01-01

This invention relates to the use of a three compartment electrolytic cell in the production of synthetic carbonaceous fuels and chemical feedstocks such as gasoline, methane and methanol by electrolyzing an aqueous sodium carbonate/bicarbonate solution, obtained from scrubbing atmospheric carbon dioxide with an aqueous sodium hydroxide solution, whereby the hydrogen generated at the cathode and the carbon dioxide liberated in the center compartment are combined thermocatalytically into methanol and gasoline blends. The oxygen generated at the anode is preferably vented into the atmosphere, and the regenerated sodium hydroxide produced at the cathode is reused for scrubbing the CO.sub.2 from the atmosphere.

Performance evaluation of SPE electrolyzer for Space Station life support

NASA Technical Reports Server (NTRS)

Erickson, A. C.; Puskar, M. C.; Zagaja, J. A.; Miller, P. S.

1987-01-01

An static water-vapor feed electrolyzer has been developed as a candidate for Space Station life-support oxygen generation. The five-cell electrolysis module has eliminated the need for phase separation devices, pumps, and deionizers by transporting only water vapor to the solid polymer electrolyte cells. The introduction of an innovative electrochemical hydrogen pump allows the use of low-pressure reclaimed water to generate gas pressures of up to 230 psia. The electrolyzer has been tested in a computer-controlled test stand featuring continuous, cyclic, and standby operation (including automatic shutdown with fault detection).

Hydrogen Generation Via Fuel Reforming

NASA Astrophysics Data System (ADS)

Krebs, John F.

2003-07-01

Reforming is the conversion of a hydrocarbon based fuel to a gas mixture that contains hydrogen. The H2 that is produced by reforming can then be used to produce electricity via fuel cells. The realization of H2-based power generation, via reforming, is facilitated by the existence of the liquid fuel and natural gas distribution infrastructures. Coupling these same infrastructures with more portable reforming technology facilitates the realization of fuel cell powered vehicles. The reformer is the first component in a fuel processor. Contaminants in the H2-enriched product stream, such as carbon monoxide (CO) and hydrogen sulfide (H2S), can significantly degrade the performance of current polymer electrolyte membrane fuel cells (PEMFC's). Removal of such contaminants requires extensive processing of the H2-rich product stream prior to utilization by the fuel cell to generate electricity. The remaining components of the fuel processor remove the contaminants in the H2 product stream. For transportation applications the entire fuel processing system must be as small and lightweight as possible to achieve desirable performance requirements. Current efforts at Argonne National Laboratory are focused on catalyst development and reactor engineering of the autothermal processing train for transportation applications.

Al2O3 Disk Supported Si3N4 Hydrogen Purification Membrane for Low Temperature Polymer Electrolyte Membrane Fuel Cells

PubMed Central

Liu, Xiaoteng; Christensen, Paul A.; Kelly, Stephen M.; Rocher, Vincent; Scott, Keith

2013-01-01

Reformate gas, a commonly employed fuel for polymer electrolyte membrane fuel cells (PEMFCs), contains carbon monoxide, which poisons Pt-containing anodes in such devices. A novel, low-cost mesoporous Si3N4 selective gas separation material was tested as a hydrogen clean-up membrane to remove CO from simulated feed gas to single-cell PEMFC, employing Nafion as the polymer electrolyte membrane. Polarization and power density measurements and gas chromatography showed a clear effect of separating the CO from the gas mixture; the performance and durability of the fuel cell was thereby significantly improved. PMID:24957065

High temperature electrolytic recovery of oxygen from gaseous effluents from the carbo-chlorination of lunar anorthite and the hydrogenation of ilmenite: A theoretical study

NASA Technical Reports Server (NTRS)

Erstfield, T. E.; Williams, R. J.

1979-01-01

A thermodynamic analysis discusses the compositions of gaseous effluents from the reaction of carbon and chlorine and of hydrogen with lunar anorthite and ilmenite, respectively. The computations consider the effects of the indigenous volatiles on the solid/gas reactions and on the composition of the effluent gases. A theoretical parameterization of the high temperature electrolysis of such gases is given for several types of solid ceramic electrolytes, and the effect of oxygen removal on the effluents is computed. Potential chemical interactions between the gases and the ceramic electrolytes are analyzed and discussed.

Al2O3 Disk Supported Si3N4 Hydrogen Purification Membrane for Low Temperature Polymer Electrolyte Membrane Fuel Cells.

PubMed

Liu, Xiaoteng; Christensen, Paul A; Kelly, Stephen M; Rocher, Vincent; Scott, Keith

2013-12-05

Reformate gas, a commonly employed fuel for polymer electrolyte membrane fuel cells (PEMFCs), contains carbon monoxide, which poisons Pt-containing anodes in such devices. A novel, low-cost mesoporous Si3N4 selective gas separation material was tested as a hydrogen clean-up membrane to remove CO from simulated feed gas to single-cell PEMFC, employing Nafion as the polymer electrolyte membrane. Polarization and power density measurements and gas chromatography showed a clear effect of separating the CO from the gas mixture; the performance and durability of the fuel cell was thereby significantly improved.

[Accelerated senescence of fresh-cut Chinese water chestnut tissues in relation to hydrogen peroxide accumulation].

PubMed

Peng, Li-Tao; Jiang, Yue-Ming; Yang, Shu-Zhen; Pan, Si-Yi

2005-10-01

Accelerated senescence of fresh-cut Chinese water chestnut (CWC) tissues in relation to active oxygen species (AOS) metabolism was investigated. Fresh-cut CWC (2 mm thick) and intact CWC were stored at 4 degrees C in trays wrapped with plastic films. Changes in superoxide anion production rate, activities of superoxide dismutase (SOD), catalase (CAT) and ascorbate peroxidase (APX) were monitored, while contents of hydrogen peroxide, ascorbic acid, MDA as well as electrolyte leakage were measured. Fresh-cutting of CWC induced activities of SOD, CAT and APX to a certain extent (Fig. 2B and Fig. 3), but simultaneously stimulated superoxide anion production markedly (Fig. 2A), enhanced hydrogen peroxide accumulation and accelerated loss in ascorbic acid (Figs. 4 and 5), which resulted in increased lipid peroxidation indicated by malondialdehyde (MDA) content and electrolyte leakage (Fig. 1). Statistics analysis indicated that there was a significantly positive correlation among hydrogen peroxide accumulation, MDA content and electrolyte leakage (Table 1). Histochemical detection with 3, 3'-diaminobenzidine further demonstrated that hydrogen peroxide accumulation increased in fresh-cut CWC during storage (Fig. 5). AOS production rate and activities of SOD, CAT and APX changed little while no obvious hydrogen peroxide accumulation was observed, in intact CWC during storage.

Factors Affecting Nickel-oxide Electrode Capacity in Nickel-hydrogen Cells

NASA Technical Reports Server (NTRS)

Ritterman, P. F.

1984-01-01

The nickel-oxide electrode common to the nickel hydrogen and nickel cadmium cell is by design the limiting or capacity determining electrode on both charge and discharge. The useable discharge capacity from this electrode, and since it is the limiting electrode, the useable discharge capacity of the cell as well, can and is optimized by rate of charge, charge temperature and additives to electrode and electrolyte. Recent tests with nickel hydrogen cells and tests performed almost 25 years ago with nickel cadmium cells indicate an improvement of capacity as a result of using increased electrolyte concentration.

40 CFR 61.51 - Definitions.

Code of Federal Regulations, 2013 CFR

2013-07-01

... produce chlorine gas, hydrogen gas, and alkali metal hydroxide. (f) Mercury chlor-alkali electrolyzer... converted to alkali metal hydroxide, mercury, and hydrogen gas in a short-circuited, electrolytic reaction. (h) Hydrogen gas stream means a hydrogen stream formed in the chlor-alkali cell denuder. (i) End box...

40 CFR 61.51 - Definitions.

Code of Federal Regulations, 2011 CFR

2011-07-01

... produce chlorine gas, hydrogen gas, and alkali metal hydroxide. (f) Mercury chlor-alkali electrolyzer... converted to alkali metal hydroxide, mercury, and hydrogen gas in a short-circuited, electrolytic reaction. (h) Hydrogen gas stream means a hydrogen stream formed in the chlor-alkali cell denuder. (i) End box...

40 CFR 61.51 - Definitions.

Code of Federal Regulations, 2010 CFR

2010-07-01

... produce chlorine gas, hydrogen gas, and alkali metal hydroxide. (f) Mercury chlor-alkali electrolyzer... converted to alkali metal hydroxide, mercury, and hydrogen gas in a short-circuited, electrolytic reaction. (h) Hydrogen gas stream means a hydrogen stream formed in the chlor-alkali cell denuder. (i) End box...

40 CFR 61.51 - Definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... produce chlorine gas, hydrogen gas, and alkali metal hydroxide. (f) Mercury chlor-alkali electrolyzer... converted to alkali metal hydroxide, mercury, and hydrogen gas in a short-circuited, electrolytic reaction. (h) Hydrogen gas stream means a hydrogen stream formed in the chlor-alkali cell denuder. (i) End box...

40 CFR 61.51 - Definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

... produce chlorine gas, hydrogen gas, and alkali metal hydroxide. (f) Mercury chlor-alkali electrolyzer... converted to alkali metal hydroxide, mercury, and hydrogen gas in a short-circuited, electrolytic reaction. (h) Hydrogen gas stream means a hydrogen stream formed in the chlor-alkali cell denuder. (i) End box...

APPARATUS FOR CONVERTING HEAT INTO ELECTRICITY

DOEpatents

Crouthamel, C.E.; Foster, M.S.

1964-01-28

This patent shows an apparatus for converting heat to electricity. It includes a galvanic cell having an anodic metal anode, a fused salt electrolyte, and a hydrogen cathode having a diffusible metal barrier of silver-- palladium alloy covered with sputtered iron on the side next to the fused electrolyte. Also shown is a regenerator for regenerating metal hydride produced by the galvanic cell into hydrogen gas and anodic metal, both of which are recycled. (AEC)

Pore size engineering applied to starved electrochemical cells and batteries

NASA Technical Reports Server (NTRS)

Abbey, K. M.; Thaller, L. H.

1982-01-01

To maximize performance in starved, multiplate cells, the cell design should rely on techniques which widen the volume tolerance characteristics. These involve engineering capillary pressure differences between the components of an electrochemical cell and using these forces to promote redistribution of electrolyte to the desired optimum values. This can be implemented in practice by prescribing pore size distributions for porous back-up plates, reservoirs, and electrodes. In addition, electrolyte volume management can be controlled by incorporating different pore size distributions into the separator. In a nickel/hydrogen cell, the separator must contain pores similar in size to the small pores of both the nickel and hydrogen electrodes in order to maintain an optimum conductive path for the electrolyte. The pore size distributions of all components should overlap in such a way as to prevent drying of the separator and/or flooding of the hydrogen electrode.

NREL, Giner Evaluated Polymer Electrolyte Membrane for Maximizing Renewable

Science.gov Websites

Energy on Grid | Energy Systems Integration Facility | NREL Giner NREL, Giner Evaluated Polymer -scale polymer electrolyte membrane (PEM) stack designed to maximize renewable energy on the grid by converting it to hydrogen when supply exceeds demand. Photo of a polymer electrolyte membrane stack in a

Validation test of advanced technology for IPV nickel-hydrogen flight cells - Update

NASA Technical Reports Server (NTRS)

Smithrick, John J.; Hall, Stephen W.

1992-01-01

Individual pressure vessel (IPV) nickel-hydrogen technology was advanced at NASA Lewis and under Lewis contracts with the intention of improving cycle life and performance. One advancement was to use 26 percent potassium hydroxide (KOH) electrolyte to improve cycle life. Another advancement was to modify the state-of-the-art cell design to eliminate identified failure modes. The modified design is referred to as the advanced design. A breakthrough in the LEO cycle life of IPV nickel-hydrogen cells has been previously reported. The cycle life of boiler plate cells containing 26 percent KOH electrolyte was about 40,000 LEO cycles compared to 3,500 cycles for cells containing 31 percent KOH. The boiler plate test results are in the process of being validated using flight hardware and real time LEO testing. The primary function of the advanced cell is to store and deliver energy for long-term, LEO spacecraft missions. The new features of this design are: (1) use of 26 percent rather than 31 percent KOH electrolyte; (2) use of a patented catalyzed wall wick; (3) use of serrated-edge separators to facilitate gaseous oxygen and hydrogen flow within the cell, while still maintaining physical contact with the wall wick for electrolyte management; and (4) use of a floating rather than a fixed stack (state-of-the-art) to accommodate nickel electrode expansion due to charge/discharge cycling. The significant improvements resulting from these innovations are: extended cycle life; enhanced thermal, electrolyte, and oxygen management; and accommodation of nickel electrode expansion.

Chemical and electrochemical oxidation of small organic molecules

NASA Astrophysics Data System (ADS)

Smart, Marshall C.

Direct oxidation fuel cells using proton-exchange membrane electrolytes have long been recognized as being an attractive mode of power generation. The current work addresses the electro-oxidation characteristics of a number of potential fuels on Pt-based electrodes which can be used in direct oxidation fuel cells, including hydrocarbons and oxygenated molecules, such as alcohols, formates, ethers, and acetals. Promising alternative fuels which were identified, such as trimethoxymethane and dimethoxymethane, were then investigated in liquid-feed PEM-based fuel cells. In addition to investigating the nature of the anodic electro-oxidation of organic fuels, effort was also devoted to developing novel polymer electrolyte membranes which have low permeability to organic molecules, such as methanol. This research was initiated with the expectation of reducing the extent of fuel crossover from the anode to the cathode in the liquid-feed design fuel cell which results in lower fuel efficiency and performance. Other work involving efforts to improve the performance of direct oxidation fuel cell includes research focused upon improving the kinetics of oxygen reduction. There is continued interest in the identification of new, safe, non-toxic, and inexpensive reagents which can be used in the oxidation of organic compounds. Urea-hydrogen peroxide (UHP), a hydrogen bonded adduct, has been shown to serve as a valuable source of hydrogen peroxide in a range of reactions. UHP has been shown to be ideal for the monohydroxylation of aromatics, including toluene, ethylbenzene, p-xylene, m-xylene, and mesitylene, as well as benzene, in the presence of trifluoromethanesulfonic acid. It was also found that aniline was converted to a mixture containing primarily azobenzene, azoxybenzene and nitrobenzene when reacted with UHP in glacial acetic acid. A number of aniline derivatives have been investigated and it was observed that the corresponding azoxybenzene derivatives could be generated as the major products in good to excellent yields. The oxidation of other organic substrates was also investigated using urea-hydrogen peroxide as an oxidation reagent, including cyclohexylamine, 1-adamantaneamine, and adamantane.

Shift of the reactive species in the Sb-SnO2-electrocatalyzed inactivation of e. coli and degradation of phenol: effects of nickel doping and electrolytes.

PubMed

Yang, So Young; Kim, Dongseog; Park, Hyunwoong

2014-01-01

The electrocatalytic behavior and anodic performance of Sb-SnO2 and nickel-doped Sb-SnO2 (Ni-Sb-SnO2) in sodium sulfate and sodium chloride electrolytes were compared. Nickel-doping increased the service lifetime by a factor of 9 and decreased the charge transfer resistance of the Sb-SnO2 electrodes by 65%. More importantly, Ni doping improved the electrocatalytic performance of Sb-SnO2 for the remediation of aqueous phenol and the inactivation of E. coli by a factor of more than 600% and ∼20%, respectively. In the sulfate electrolyte, the primary reactive oxygen species (ROS) identified were OH radicals (Faradaic efficiency η = 2.4%) with trace levels of ozone and hydrogen peroxide (η < 0.01%) at Sb-SnO2. In contrast, the primary ROS at Ni-Sb-SnO2 was ozone (η = 9.3%) followed by OH radicals (η = 3.7%). In the chloride electrolyte, the production of hypochlorite (OCl(-)) was higher (η = 0.73%) than that of ozone (η = 0.13%) at Sb-SnO2, whereas the level of ozone (η = 13.6%) was much higher than that of hypochlorite (η = 0.24%) at Ni-Sb-SnO2. Based on the shift of the reactive species, the primary effect of Ni doping is to catalyze the six-electron oxidation of water to ozone and inhibit the competing one or two-electron oxidation of water (generation of OH radicals, hydrogen peroxides, and hypochlorites). A range of electrochemical and surface analyses were performed, and a detailed mechanism was proposed.

21 CFR 184.1366 - Hydrogen peroxide.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Hydrogen peroxide. 184.1366 Section 184.1366 Food... Specific Substances Affirmed as GRAS § 184.1366 Hydrogen peroxide. (a) Hydrogen peroxide (H2O2, CAS Reg. No. 7722-84-1) is also referred to as hydrogen dioxide. It is made by the electrolytic oxidation of...

21 CFR 184.1366 - Hydrogen peroxide.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Hydrogen peroxide. 184.1366 Section 184.1366 Food... Specific Substances Affirmed as GRAS § 184.1366 Hydrogen peroxide. (a) Hydrogen peroxide (H2O2, CAS Reg. No. 7722-84-1) is also referred to as hydrogen dioxide. It is made by the electrolytic oxidation of...

21 CFR 184.1366 - Hydrogen peroxide.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Hydrogen peroxide. 184.1366 Section 184.1366 Food... Specific Substances Affirmed as GRAS § 184.1366 Hydrogen peroxide. (a) Hydrogen peroxide (H2O2, CAS Reg. No. 7722-84-1) is also referred to as hydrogen dioxide. It is made by the electrolytic oxidation of...

21 CFR 184.1366 - Hydrogen peroxide.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Hydrogen peroxide. 184.1366 Section 184.1366 Food... GRAS § 184.1366 Hydrogen peroxide. (a) Hydrogen peroxide (H2O2, CAS Reg. No. 7722-84-1) is also referred to as hydrogen dioxide. It is made by the electrolytic oxidation of sulfuric acid or a sulfate to...

Renewable Fuels-to-Grid Integration | Energy Systems Integration Facility |

Science.gov Websites

hydrogen, other than electrolysis. Read more about this research. Partnerships Photo of a polymer electrolyte membrane stack in a laboratory Giner NREL helped evaluate a large-scale polymer electrolyte

Electrocatalysts for oxygen electrodes in fuel cells and water electrolyzers for space applications

NASA Technical Reports Server (NTRS)

Prakash, Jai; Tryk, Donald; Yeager, Ernest

1989-01-01

In most instances separate electrocatalysts are needed to promote the reduction of O2 in the fuel cell mode and to generate O2 in the energy storage-water electrolysis mode in aqueous electrochemical systems operating at low and moderate temperatures (T greater than or equal to 200 C). Interesting exceptions are the lead and bismuth ruthenate pyrochlores in alkaline electrolytes. These catalysts on high area carbon supports have high catalytic activity for both O2 reduction and generation (1,2). Rotating ring-disk electrode measurements provide evidence that the O2 reduction proceeds by a parallel four-electron pathway. The ruthenates can also be used as self-supported catalysts to avoid the problems associated with carbon oxidation, but the electrode performance so far achieved in the research at Case Western Reserve University (CWRU) is considerably less. At the potentials involved in the anodic mode the ruthenate pyrochlores have substantial equilibrium solubility in concentrated alkaline electrolyte. This results in the loss of catalyst into the bulk solution and a decline in catalytic activity. Furthermore, the hydrogen generation counter electrode may become contaminated with reduction products from the pyrochlores (lead, ruthenium). A possible approach to this problem is to immobilize the pyrochlore catalyst within an ionic-conducting solid polymer, which would replace the fluid electrolyte within the porous gas diffusion O2 electrode. For bulk alkaline electrolyte, an anion-exchange polymer is needed with a transference number close to unity for the Oh(-) ion. Preliminary short-term measurements with lead ruthenates using a commercially available partially-fluorinated anion-exchange membrane as an overlayer on the porous gas-fed electrode indicate lower anodic polarization and virtually unchanged cathodic polarization.

Electrochemical sensor for monitoring electrochemical potentials of fuel cell components

DOEpatents

Kunz, Harold R.; Breault, Richard D.

1993-01-01

An electrochemical sensor comprised of wires, a sheath, and a conduit can be utilized to monitor fuel cell component electric potentials during fuel cell shut down or steady state. The electrochemical sensor contacts an electrolyte reservoir plate such that the conduit wicks electrolyte through capillary action to the wires to provide water necessary for the electrolysis reaction which occurs thereon. A voltage is applied across the wires of the electrochemical sensor until hydrogen evolution occurs at the surface of one of the wires, thereby forming a hydrogen reference electrode. The voltage of the fuel cell component is then determined with relation to the hydrogen reference electrode.

A Hydrogen-Evolving Hybrid-Electrolyte Battery with Electrochemical/Photoelectrochemical Charging from Water Oxidation.

PubMed

Jin, Zhaoyu; Li, Panpan; Xiao, Dan

2017-02-08

Decoupled hydrogen and oxygen production were successfully embedded into an aqueous dual-electrolyte (acid-base) battery for simultaneous energy storage and conversion. A three-electrode configuration was adopted, involving an electrocatalytic hydrogen-evolving electrode as cathode, an alkaline battery-type or capacitor-type anode as shuttle, and a charging-assisting electrode for electro-/photoelectrochemically catalyzing water oxidation. The conceptual battery not only synergistically outputs electricity and chemical fuels with tremendous specific energy and power densities, but also supports various approaches to be charged by pure or solar-assisted electricity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transient analysis of gas transport in anode channel of a polymer electrolyte membrane fuel cell with dead-ended anode under pressure swing operation

NASA Astrophysics Data System (ADS)

Ichikawa, Yasushi; Oshima, Nobuyuki; Tabuchi, Yuichiro; Ikezoe, Keigo

2014-12-01

Further cost reduction is a critical issue for commercialization of fuel-cell electric vehicles (FCEVs) based on polymer electrolyte fuel cells (PEFCs). The cost of the fuel-cell system is driven by the multiple parts required to maximize stack performance and maintain durability and robustness. The fuel-cell system of the FCEV must be simplified while maintaining functionality. The dead-ended anode is considered as a means of simplification in this study. Generally, if hydrogen is supplied under constant pressure during dead-ended operation, stable power generation is impossible because of accumulation of liquid water produced by power generation and of nitrogen via leakage from the cathode through the membrane. Herein, pressure oscillation is applied to address this issue. Empirical and CFD data are employed to elucidate the mechanism of stable power generation using the pressure swing supply. Simultaneous and time-continuous measurements of the current distribution and gas concentration distribution are also conducted. The results demonstrate that the nitrogen concentration in the anode channel under pressure constant operation differs from that under pressure swing supply conditions. The transient two-dimensional CFD results indicate that oscillatory flow is generated by pressure swing supply, which periodically sweeps out nitrogen from the active area, resulting in stable power generation.

Improvement of efficiency in graphene/gallium nitride nanowire on Silicon photoelectrode for overall water splitting

NASA Astrophysics Data System (ADS)

Bae, Hyojung; Rho, Hokyun; Min, Jung-Wook; Lee, Yong-Tak; Lee, Sang Hyun; Fujii, Katsushi; Lee, Hyo-Jong; Ha, Jun-Seok

2017-11-01

Gallium nitride (GaN) nanowires are one of the most promising photoelectrode materials due to their high stability in acidic and basic electrolytes, and tunable band edge potentials. In this study, GaN nanowire arrays (GaN NWs) were prepared by molecular beam epitaxy (MBE); their large surface area enhanced the solar to hydrogen conversion efficiency. More significantly, graphene was grown by chemical vapor deposition (CVD), which enhanced the electron transfer between NWs for water splitting and protected the GaN NW surface. Structural characterizations of the prepared composite were performed using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The photocurrent density of Gr/GaN NWs exhibited a two-fold increase over pristine GaN NWs and sustained water splitting up to 70 min. These improvements may accelerate possible applications for hydrogen generation with high solar to hydrogen conversion efficiency.

Validation test of advanced technology for IPV nickel-hydrogen flight cells: Update

NASA Technical Reports Server (NTRS)

Smithrick, John J.; Hall, Stephen W.

1992-01-01

Individual pressure vessel (IPV) nickel-hydrogen technology was advanced at NASA Lewis and under Lewis contracts with the intention of improving cycle life and performance. One advancement was to use 26 percent potassium hydroxide (KOH) electrolyte to improve cycle life. Another advancement was to modify the state-of-the-art cell design to eliminate identified failure modes. The modified design is referred to as the advanced design. A breakthrough in the low-earth-orbit (LEO) cycle life of IPV nickel-hydrogen cells has been previously reported. The cycle life of boiler plate cells containing 26 percent KOH electrolyte was about 40,000 LEO cycles compared to 3,500 cycles for cells containing 31 percent KOH. The boiler plate test results are in the process of being validated using flight hardware and real time LEO testing at the Naval Weapons Support Center (NWSC), Crane, Indiana under a NASA Lewis Contract. An advanced 125 Ah IPV nickel-hydrogen cell was designed. The primary function of the advanced cell is to store and deliver energy for long-term, LEO spacecraft missions. The new features of this design are: (1) use of 26 percent rather than 31 percent KOH electrolyte; (2) use of a patented catalyzed wall wick; (3) use of serrated-edge separators to facilitate gaseous oxygen and hydrogen flow within the cell, while still maintaining physical contact with the wall wick for electrolyte management; and (4) use of a floating rather than a fixed stack (state-of-the-art) to accommodate nickel electrode expansion due to charge/discharge cycling. The significant improvements resulting from these innovations are: extended cycle life; enhanced thermal, electrolyte, and oxygen management; and accommodation of nickel electrode expansion. The advanced cell design is in the process of being validated using real time LEO cycle life testing of NWSC, Crane, Indiana. An update of validation test results confirming this technology is presented.

Zinc halogen battery electrolyte composition with lead additive

DOEpatents

Henriksen, Gary L.

1981-01-01

This disclosure relates to a zinc halogen battery electrolyte composition containing an additive providing improved zinc-on-zinc recyclability. The improved electrolyte composition involves the use of a lead additive to inhibit undesirable irregular plating and reduce nodular or dendritic growth on the electrode surface. The lead-containing electrolyte composition of the present invention appears to influence not only the morphology of the base plate zinc, but also the morphology of the zinc-on-zinc replate. In addition, such lead-containing electrolyte compositions appear to reduce hydrogen formation.

The Conceptual Design of an Integrated Nuclearhydrogen Production Plant Using the Sulfur Cycle Water Decomposition System

NASA Technical Reports Server (NTRS)

Farbman, G. H.

1976-01-01

A hydrogen production plant was designed based on a hybrid electrolytic-thermochemical process for decomposing water. The sulfur cycle water decomposition system is driven by a very high temperature nuclear reactor that provides 1,283 K helium working gas. The plant is sized to approximately ten million standard cubic meters per day of electrolytically pure hydrogen and has an overall thermal efficiently of 45.2 percent. The economics of the plant were evaluated using ground rules which include a 1974 cost basis without escalation, financing structure and other economic factors. Taking into account capital, operation, maintenance and nuclear fuel cycle costs, the cost of product hydrogen was calculated at $5.96/std cu m for utility financing. These values are significantly lower than hydrogen costs from conventional water electrolysis plants and competitive with hydrogen from coal gasification plants.

Method for producing electricity from a fuel cell having solid-oxide ionic electrolyte

DOEpatents

Mason, David M.

1984-01-01

Stabilized quadrivalent cation oxide electrolytes are employed in fuel cells at elevated temperatures with a carbon and/or hydrogen containing fuel anode and an oxygen cathode. The fuel cell is operated at elevated temperatures with conductive metallic coatings as electrodes and desirably having the electrolyte surface blackened. Of particular interest as the quadrivalent oxide is zirconia.

A hydrogen-ferric ion rebalance cell operating at low hydrogen concentrations for capacity restoration of iron-chromium redox flow batteries

NASA Astrophysics Data System (ADS)

Zeng, Y. K.; Zhao, T. S.; Zhou, X. L.; Zou, J.; Ren, Y. X.

2017-06-01

To eliminate the adverse impacts of hydrogen evolution on the capacity of iron-chromium redox flow batteries (ICRFBs) during the long-term operation and ensure the safe operation of the battery, a rebalance cell that reduces the excessive Fe(III) ions at the positive electrolyte by using the hydrogen evolved from the negative electrolyte is designed, fabricated and tested. The effects of the flow field, hydrogen concentration and H2/N2 mixture gas flow rate on the performance of the hydrogen-ferric ion rebalance cell have been investigated. Results show that: i) an interdigitated flow field based rebalance cell delivers higher limiting current densities than serpentine flow field based one does; ii) the hydrogen utilization can approach 100% at low hydrogen concentrations (≤5%); iii) the apparent exchange current density of hydrogen oxidation reaction in the rebalance cell is proportional to the square root of the hydrogen concentration at the hydrogen concentration from 1.3% to 50%; iv) a continuous rebalance process is demonstrated at the current density of 60 mA cm-2 and hydrogen concentration of 2.5%. Moreover, the cost analysis shows that the rebalance cell is just approximately 1% of an ICRFB system cost.

Fuel cell with electrolyte feed system

DOEpatents

Feigenbaum, Haim

1984-01-01

A fuel cell having a pair of electrodes at the sites of electrochemical reactions of hydrogen and oxygen and a phosphoric acid electrolyte provided with an electrolyte supporting structure in the form of a laminated matrix assembly disposed between the electrodes. The matrix assembly is formed of a central layer disposed between two outer layers, each being permeable to the flow of the electrolyte. The central layer is provided with relatively large pores while the outer layers are provided with relatively small pores. An external reservoir supplies electrolyte via a feed means to the central layer to compensate for changes in electrolyte volume in the matrix assembly during the operation of fuel cell.

Electrocatalysis for oxygen electrodes in fuel cells and water electrolyzers for space applications

NASA Technical Reports Server (NTRS)

Prakash, Jai; Tryk, Donald; Yeager, Ernest

1989-01-01

In most instances separate electrocatalysts are needed to promote the reduction of O2 in the fuel cell mode and to generate O2 in the energy storage-water electrolysis mode in aqueous electrochemical systems operating at low and moderate temperatures (T greater than or equal to 200 C). Interesting exceptions are the lead and bismuth ruthenate pyrochlores in alkaline electrolytes. These catalysts on high area carbon supports have high catalytic activity for both O2 reduction and generation. Rotating ring-disk electrode measurements provide evidence that the O2 reduction proceeds by a parallel four-electron pathway. The ruthenates can also be used as self-supported catalysts to avoid the problems associated with carbon oxidation, but the electrode performance so far achieved in the research at Case Western Reserve University (CWRU) is considerably less. At the potentials involved in the anodic mode the ruthenate pyrochlores have substantial equilibrium solubility in concentrated alkaline electrolyte. This results in the loss of catalyst into the bulk solution and a decline in catalytic activity. Furthermore, the hydrogen generation counter electrode may become contaminated with reduction products from the pyrochlores (lead, ruthenium).

Systems and methods for rebalancing redox flow battery electrolytes

DOEpatents

Pham, Ai Quoc; Chang, On Kok

2015-03-17

Various methods of rebalancing electrolytes in a redox flow battery system include various systems using a catalyzed hydrogen rebalance cell configured to minimize the risk of dissolved catalyst negatively affecting flow battery performance. Some systems described herein reduce the chance of catalyst contamination of RFB electrolytes by employing a mediator solution to eliminate direct contact between the catalyzed membrane and the RFB electrolyte. Other methods use a rebalance cell chemistry that maintains the catalyzed electrode at a potential low enough to prevent the catalyst from dissolving.

An electrochemical study of hydrogen uptake and elimination by bare and gold-plated waspaloy

NASA Technical Reports Server (NTRS)

Danford, M. D.; Deramus, G. E., Jr.; Lowery, J. R.

1984-01-01

Two electrochemical methods for the determination of hydrogen concentrations in metals are discussed and evaluated. The take-up of hydrogen at a pressure of 5000 psi by Waspaloy metal was determined experimentally at 24 C. It was found that the metal becomes saturated with hydrogen after an exposure time of about 1 hr. For samples charged with hydrogen at high pressure, most of the hydrogen is contained in the interstitial solid solution of the metal. For electrolytically charged samples, most of the hydrogen is contained as surface and subsurface hydrides. Hydrogen elimination rates were determined for these two cases, with the rate for electrolytically charged samples being greater by over a factor of two. Theoretical effects of high temperature and pressure on hydrogen take-up and elimination by bare and gold plated Waspaloy metal was considered. The breakthrough point for hydrogen at 5000 psi, determined experimentally, lies between a gold thickness of 0.0127 mm (0.0005 in.) and 0.0254 mm (0.001 in.) at 24 C. Electropolishing was found to greatly reduce the uptake of hydrogen at high pressure by Waspaloy metal at 24 C. Possible implications of the results obtained, as they apply to the turbine disk of the space shuttle main engine, are discussed.

Cosolvent electrolytes for electrochemical devices

DOEpatents

Wessells, Colin Deane; Firouzi, Ali; Motallebi, Shahrokh; Strohband, Sven

2018-01-23

A method for stabilizing electrodes against dissolution and/or hydrolysis including use of cosolvents in liquid electrolyte batteries for three purposes: the extension of the calendar and cycle life time of electrodes that are partially soluble in liquid electrolytes, the purpose of limiting the rate of electrolysis of water into hydrogen and oxygen as a side reaction during battery operation, and for the purpose of cost reduction.

Cosolvent electrolytes for electrochemical devices

DOEpatents

Wessells, Colin Deane; Firouzi, Ali; Motallebi, Shahrokh; Strohband, Sven

2018-02-13

A system and method for stabilizing electrodes against dissolution and/or hydrolysis including use of cosolvents in liquid electrolyte batteries for three purposes: the extension of the calendar and cycle life time of electrodes that are partially soluble in liquid electrolytes, the purpose of limiting the rate of electrolysis of water into hydrogen and oxygen as a side reaction during battery operation, and for the purpose of cost reduction.

Cosolvent electrolytes for electrochemical devices

DOEpatents

Wessells, Colin Deane; Firouzi, Ali; Motallebi, Shahrokh; Strohband, Sven

2018-05-15

A system and method for stabilizing electrodes against dissolution and/or hydrolysis including use of cosolvents in liquid electrolyte batteries for three purposes: the extension of the calendar and cycle life time of electrodes that are partially soluble in liquid electrolytes, the purpose of limiting the rate of electrolysis of water into hydrogen and oxygen as a side reaction during battery operation, and for the purpose of cost reduction.

Microscopic mechanisms of graphene electrolytic delamination from metal substrates

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

Fisichella, G.; Department of Electronic Engineering, University of Catania, Viale A. Doria, 6 – 95125 Catania; Di Franco, S.

In this paper, hydrogen bubbling delamination of graphene (Gr) from copper using a strong electrolyte (KOH) water solution was performed, focusing on the effect of the KOH concentration (C{sub KOH}) on the Gr delamination rate. A factor of ∼10 decrease in the time required for the complete Gr delamination from Cu cathodes with the same geometry was found increasing C{sub KOH} from ∼0.05 M to ∼0.60 M. After transfer of the separated Gr membranes to SiO{sub 2} substrates by a highly reproducible thermo-compression printing method, an accurate atomic force microscopy investigation of the changes in Gr morphology as a function of C{submore » KOH} was performed. Supported by these analyses, a microscopic model of the delamination process has been proposed, where a key role is played by graphene wrinkles acting as nucleation sites for H{sub 2} bubbles at the cathode perimeter. With this approach, the H{sub 2} supersaturation generated at the electrode for different electrolyte concentrations was estimated and the inverse dependence of t{sub d} on C{sub KOH} was quantitatively explained. Although developed in the case of Cu, this analysis is generally valid and can be applied to describe the electrolytic delamination of graphene from several metal substrates.« less

Extraction of Carbon Dioxide and Hydrogen from Seawater By an Electrolytic Cation Exchange Module (E-CEM) Part 5: E-CEM Effluent Discharge Composition as a Function of Electrode Water Composition

DTIC Science & Technology

2017-08-01

Naval Research Laboratory Washington, DC 20375-5320 NRL/MR/6360--17-9743 Extraction of Carbon Dioxide and Hydrogen from Seawater by an Electrolytic...Cation Exchange Module (E-CEM) Part V: E-CEM Effluent Discharge Composition as a Function of Electrode Water Composition August 1, 2017 Approved for...Office of Naval Research Arlington, Virginia Dennis r. HarDy Nova Research Inc. Alexandria, Virginia i REPORT DOCUMENTATION PAGE Form

Proton conduction in electrolyte made of manganese dioxide for hydrogen gas sensor

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

Koyanaka, Hideki; Ueda, Yoshikatsu; Takeuchi, K

2012-01-01

We propose a network model of oxygen-pairs to store and conduct protons on the surface of manganese dioxide with a weak covalent bond like protons stored in pressured ice. The atomic distances of oxygen-pairs were estimated between 2.57 and 2.60 angstroms in crystal structures of ramsdellite-type and lambda-type manganese dioxides by using protonated samples and inelastic neutron scattering measurements. Good properties for a hydrogen gas sensor using electrolytes made of manganese dioxides that contain such oxygen-pairs were confirmed experimentally.

Fuel cell technology program

NASA Technical Reports Server (NTRS)

1972-01-01

A fuel cell technology program was established to advance the state-of-the art of hydrogen oxygen fuel cells using low temperature, potassium hydroxide electrolyte technology as the base. Cell and component testing confirmed that low temperature, potassium hydroxide electrolyte technology is compatible with the requirements of the space shuttle Phase B contractors. Testing of the DM-1 powerplant demonstrated all of the important requirements of the shuttle except operating life. Testing also identified DM-1 powerplant life limiting mechanisms; hydrogen pump gear wear and pressurization of the cell stack over its design limits.

An alternative to hydrogenation processes. Electrocatalytic hydrogenation of benzophenone.

PubMed

Mozo Mulero, Cristina; Sáez, Alfonso; Iniesta, Jesús; Montiel, Vicente

2018-01-01

The electrocatalytic hydrogenation of benzophenone was performed at room temperature and atmospheric pressure using a polymer electrolyte membrane electrochemical reactor (PEMER). Palladium (Pd) nanoparticles were synthesised and supported on a carbonaceous matrix (Pd/C) with a 28 wt % of Pd with respect to carbon material. Pd/C was characterised by transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). Cathodes were prepared using Pd electrocatalytic loadings (L Pd ) of 0.2 and 0.02 mg cm -2 . The anode consisted of hydrogen gas diffusion for the electrooxidation of hydrogen gas, and a 117 Nafion exchange membrane acted as a cationic polymer electrolyte membrane. Benzophenone solution was electrochemically hydrogenated in EtOH/water (90/10 v/v) plus 0.1 M H 2 SO 4 . Current densities of 10, 15 and 20 mA cm -2 were analysed for the preparative electrochemical hydrogenation of benzophenone and such results led to the highest fractional conversion (X R ) of around 30% and a selectivity over 90% for the synthesis of diphenylmethanol upon the lowest current density. With regards to an increase by ten times the Pd electrocatalytic loading the electrocatalytic hydrogenation led neither to an increase in fractional conversion nor to a change in selectivity.

An alternative to hydrogenation processes. Electrocatalytic hydrogenation of benzophenone

PubMed Central

Mozo Mulero, Cristina; Iniesta, Jesús; Montiel, Vicente

2018-01-01

The electrocatalytic hydrogenation of benzophenone was performed at room temperature and atmospheric pressure using a polymer electrolyte membrane electrochemical reactor (PEMER). Palladium (Pd) nanoparticles were synthesised and supported on a carbonaceous matrix (Pd/C) with a 28 wt % of Pd with respect to carbon material. Pd/C was characterised by transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). Cathodes were prepared using Pd electrocatalytic loadings (LPd) of 0.2 and 0.02 mg cm−2. The anode consisted of hydrogen gas diffusion for the electrooxidation of hydrogen gas, and a 117 Nafion exchange membrane acted as a cationic polymer electrolyte membrane. Benzophenone solution was electrochemically hydrogenated in EtOH/water (90/10 v/v) plus 0.1 M H2SO4. Current densities of 10, 15 and 20 mA cm−2 were analysed for the preparative electrochemical hydrogenation of benzophenone and such results led to the highest fractional conversion (XR) of around 30% and a selectivity over 90% for the synthesis of diphenylmethanol upon the lowest current density. With regards to an increase by ten times the Pd electrocatalytic loading the electrocatalytic hydrogenation led neither to an increase in fractional conversion nor to a change in selectivity. PMID:29623115

Space water electrolysis: Space Station through advance missions

NASA Technical Reports Server (NTRS)

Davenport, Ronald J.; Schubert, Franz H.; Grigger, David J.

1991-01-01

Static Feed Electrolyzer (SFE) technology can satisfy the need for oxygen (O2) and Hydrogen (H2) in the Space Station Freedom and future advanced missions. The efficiency with which the SFE technology can be used to generate O2 and H2 is one of its major advantages. In fact, the SFE is baselined for the Oxygen Generation Assembly within the Space Station Freedom's Environmental Control and Life Support System (ECLSS). In the conventional SFE process an alkaline electrolyte is contained within the matrix and is sandwiched between two porous electrodes. The electrodes and matrix make up a unitized cell core. The electrolyte provides the necessary path for the transport of water and ions between the electrodes, and forms a barrier to the diffusion of O2 and H2. A hydrophobic, microporous membrane permits water vapor to diffuse from the feed water to the cell core. This membrane separates the liquid feed water from the product H2, and, therefore, avoids direct contact of the electrodes by the feed water. The feed water is also circulated through an external heat exchanger to control the temperature of the cell.

Capacitance, charge dynamics, and electrolyte-surface interactions in functionalized carbide-derived carbon electrodes

DOE PAGES

Dyatkin, Boris; Mamontov, Eugene; Cook, Kevin M.; ...

2015-12-24

Our study analyzed the dynamics of ionic liquid electrolyte inside of defunctionalized, hydrogenated, and aminated pores of carbide-derived carbon supercapacitor electrodes. The approach tailors surface functionalities and tunes nanoporous structures to decouple the influence of pore wall composition on capacitance, ionic resistance, and long-term cyclability. Moreover, quasi-elastic neutron scattering probes the self-diffusion properties and electrode-ion interactions of electrolyte molecules confined in functionalized pores. Room-temperature ionic liquid interactions in confined pores are strongest when the hydrogen-containing groups are present on the surface. This property translates into higher capacitance and greater ion transport through pores during electrochemical cycling. Aminated pores, unlike hydrogenatedmore » pores, do not favorably interact with ionic liquid ions and, subsequently, are outperformed by defunctionalized surfaces.« less

Mediated electrochemical oxidation of organic wastes without electrode separators

DOEpatents

Farmer, Joseph C.; Wang, Francis T.; Hickman, Robert G.; Lewis, Patricia R.

1996-01-01

An electrochemical cell/electrolyte/mediator combination for the efficient destruction of organic contaminants using metal salt mediators in a sulfuric acid electrolyte, wherein the electrodes and mediator are chosen such that hydrogen gas is produced at the cathode and no cell membrane is required.

Electroflotation

NASA Astrophysics Data System (ADS)

Chen, Xueming; Chen, Guohua

Electroflotation (EF) is the flotation using electrolytically generated bubbles of hydrogen and oxygen for separating suspended substances from aqueous phases. This process was first proposed by Elmore in 1905 for flotation of valuable minerals from ores. Compared with the conventional dissolved air flotation (DAF), EF has many advantages, including high flotation efficiency, compact units, easy operation, and less maintenance. Therefore, EF is an attractive alternative to DAF. This technique has been proven very effective in treating oily wastewater or oil-water emulsion, mining wastewater, groundwater, food processing wastewater, restaurant wastewater, industrial sewage, heavy metals containing effluent, and many other water and wastewaters.

Organic hydrogen peroxide-driven low charge potentials for high-performance lithium-oxygen batteries with carbon cathodes

PubMed Central

Wu, Shichao; Qiao, Yu; Yang, Sixie; Ishida, Masayoshi; He, Ping; Zhou, Haoshen

2017-01-01

Reducing the high charge potential is a crucial concern in advancing the performance of lithium-oxygen batteries. Here, for water-containing lithium-oxygen batteries with lithium hydroxide products, we find that a hydrogen peroxide aqueous solution added in the electrolyte can effectively promote the decomposition of lithium hydroxide compounds at the ultralow charge potential on a catalyst-free Ketjen Black-based cathode. Furthermore, for non-aqueous lithium-oxygen batteries with lithium peroxide products, we introduce a urea hydrogen peroxide, chelating hydrogen peroxide without any water in the organic, as an electrolyte additive in lithium-oxygen batteries with a lithium metal anode and succeed in the realization of the low charge potential of ∼3.26 V, which is among the best levels reported. In addition, the undesired water generally accompanying hydrogen peroxide solutions is circumvented to protect the lithium metal anode and ensure good battery cycling stability. Our results should provide illuminating insights into approaches to enhancing lithium-oxygen batteries. PMID:28585527

Effects of sour crude oil on fatigue properties of steel plates for shipbuilding

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

Ouchi, H.; Kobayashi, J.; Ishikawa, T.

1994-12-31

The concentration of diffusible hydrogen introduced into steel was measured, and fatigue crack growth tests and fatigue life tests were carried out in sour crude oil containing a high concentration of hydrogen sulfide and under electrolytic hydrogen-charging conditions in neutral solution, using a high strength steel produced by the thermo-mechanical control process (TMCP) and a mild steel which are steels for hull plates. Comparison of the results demonstrated that a very small amount of hydrogen such as that introduced into steel from sour crude oil under atmospheric pressure accelerated the fatigue crack growth in the high {Delta}K regime and shortenedmore » the fatigue life in the high stress range region, but did not shorten the fatigue life in the low stress region. The electrolytic hydrogen-charging condition appeared to be appropriate as a fatigue-crack-growth test environment to simulate sour crude oil. The deterioration of fatigue characteristics of the TMCP high strength steel was similar with that of the mild steel.« less

Organic hydrogen peroxide-driven low charge potentials for high-performance lithium-oxygen batteries with carbon cathodes

NASA Astrophysics Data System (ADS)

Wu, Shichao; Qiao, Yu; Yang, Sixie; Ishida, Masayoshi; He, Ping; Zhou, Haoshen

2017-06-01

Reducing the high charge potential is a crucial concern in advancing the performance of lithium-oxygen batteries. Here, for water-containing lithium-oxygen batteries with lithium hydroxide products, we find that a hydrogen peroxide aqueous solution added in the electrolyte can effectively promote the decomposition of lithium hydroxide compounds at the ultralow charge potential on a catalyst-free Ketjen Black-based cathode. Furthermore, for non-aqueous lithium-oxygen batteries with lithium peroxide products, we introduce a urea hydrogen peroxide, chelating hydrogen peroxide without any water in the organic, as an electrolyte additive in lithium-oxygen batteries with a lithium metal anode and succeed in the realization of the low charge potential of ~3.26 V, which is among the best levels reported. In addition, the undesired water generally accompanying hydrogen peroxide solutions is circumvented to protect the lithium metal anode and ensure good battery cycling stability. Our results should provide illuminating insights into approaches to enhancing lithium-oxygen batteries.

Rechargeable Metal-Air Proton-Exchange Membrane Batteries for Renewable Energy Storage.

PubMed

Nagao, Masahiro; Kobayashi, Kazuyo; Yamamoto, Yuta; Yamaguchi, Togo; Oogushi, Akihide; Hibino, Takashi

2016-02-01

Rechargeable proton-exchange membrane batteries that employ organic chemical hydrides as hydrogen-storage media have the potential to serve as next-generation power sources; however, significant challenges remain regarding the improvement of the reversible hydrogen-storage capacity. Here, we address this challenge through the use of metal-ion redox couples as energy carriers for battery operation. Carbon, with a suitable degree of crystallinity and surface oxygenation, was used as an effective anode material for the metal redox reactions. A Sn 0.9 In 0.1 P 2 O 7 -based electrolyte membrane allowed no crossover of vanadium ions through the membrane. The V 4+ /V 3+ , V 3+ /V 2+ , and Sn 4+ /Sn 2+ redox reactions took place at a more positive potential than that for hydrogen reduction, so that undesired hydrogen production could be avoided. The resulting electrical capacity reached 306 and 258 mAh g -1 for VOSO 4 and SnSO 4 , respectively, and remained at 76 and 91 % of their respective initial values after 50 cycles.

Showcasing electrode-electrolyte interfacial potential as a vital parameter in the hydrogen generation by metal oxides electrodes

NASA Astrophysics Data System (ADS)

Niveditha, C. V.; Nizamudeen, A. C.; Ramanarayanan, Rajita; Jabeen Fatima, M. J.; Swaminathan, Sindhu

2018-03-01

This investigation presents a new insight by experimentally demonstrating electrode-electrolyte interface potential that is flat band potential as a determinant in photoelectrochemical splitting of water. Two different metal oxides namely n type, nitrogen doped titania and p type copper oxides have been synthesized for the study. The flat band potential values of these oxide systems were obtained from Mott-Schottky analysis. The obtained flat band potential is used as a marker to fix the working potential in water splitting experiment. To obtain optimum photocurrent a potential more positive than flatband is applied to n-type N-TiO2 and vice-versa for p-type Cu2O. The findings are well supported by I-t curves derived from chronoamperometric measurements. Finally the mechanisms behind interfacial potential dynamics have been discussed in this work.

Polymer electrolyte fuel cell mini power unit for portable application

NASA Astrophysics Data System (ADS)

Urbani, F.; Squadrito, G.; Barbera, O.; Giacoppo, G.; Passalacqua, E.; Zerbinati, O.

This paper describes the design, realisation and test of a power unit based on a polymer electrolyte fuel cell, operating at room temperature, for portable application. The device is composed of an home made air breathing fuel cell stack, a metal hydride tank for H 2 supply, a dc-dc converter for power output control and a fan for stack cooling. The stack is composed by 10 cells with an active surface of 25 cm 2 and produces a rated power of 15 W at 6 V and 2 A. The stack successfully runs with end-off fed hydrogen without appreciable performance degradation during the time. The final assembled system is able to generate 12 W at 9.5 V, and power a portable DVD player for 3 h in continuous. The power unit has collected about 100 h of operation without maintenance.

Hydrogen evolution using palladium sulfide (PdS) nanocorals as photoanodes in aqueous solution.

PubMed

Barawi, M; Ferrer, I J; Ares, J R; Sánchez, C

2014-11-26

Palladium sulfide (PdS) nanostructures are proposed to be used as photoanodes in photoelectrochemical cells (PECs) for hydrogen evolution due to their adequate transport and optical properties shown in previous works. Here, a complete morphological and electrochemical characterization of PdS films has been performed by different techniques. PdS flatband potential (Vfb=-0.65±0.05 V vs NHE) was determined by electrochemical impedance spectroscopy measurements in aqueous Na2SO3 electrolyte, providing a description of the energy levels scheme at the electrolyte-semiconductor interface. This energy levels scheme confirms PdS as a compound able to photogenerate hydrogen in a PEC. At last, photogenerated hydrogen rates are measured continuously by mass spectrometry as a function of the external bias potential under illumination, reaching values up to 4.4 μmolH2/h at 0.3 V vs Ag/AgCl.

Hydrogen-via-electricity concept. Critique report

NASA Technical Reports Server (NTRS)

Escher, W. J. D.

1981-01-01

The hydrogen-via-electricity (HvE) concept is the prospective use of hydrogen fuel produced electrolytically from the electric utility grid as a means of responding to conventional fuels shortages. The two sets of comments and critiques of this concept solicited from the Government/Government contractor group and from the electric utility companies are presented.

The effect of hydrogen embrittlement on the localized plastic deformation of aluminum alloy

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

Bochkareva, Anna, E-mail: avb@ispms.tsc.ru; Lunev, Aleksey, E-mail: agl@ispms.tsc.ru; National Research Tomsk Polytechnic University, Tomsk, 634050

2015-10-27

The effect of hydrogen embrittlement on the localized plastic deformation of aluminum alloy D1 was investigated. The studies were performed for the test samples of aluminum alloy subjected to electrolytic hydrogenation. It is found that the mechanical properties and localized plastic deformation parameters of aluminum alloy are affected adversely by hydrogen embrittlement. The hydrogenated counterpart of alloy has a lower degree of ductility relative to the original alloy; however, the plastic flow behavior of material remains virtually unaffected. Using scanning electron and atomic force microscopy methods, the changes in the fracture surface were investigated. The deformation diagrams were examined formore » the deformed samples of aluminum alloy. These are found to show all the plastic flow stages: the linear, parabolic and pre-failure stages would occur for the respective values of the exponent n from the Ludwik-Holomon equation. Using digital speckle image technique, the local strain patterns were being registered for the original alloy D1 and the counterpart subjected to electrolytic hydrogenation for 100 h.« less

Situ treatment of contaminated groundwater

DOEpatents

McNab, Jr., Walt W.; Ruiz, Roberto; Pico, Tristan M.

2001-01-01

A system for treating dissolved halogenated organic compounds in groundwater that relies upon electrolytically-generated hydrogen to chemically reduce the halogenated compounds in the presence of a suitable catalyst. A direct current is placed across at least a pair, or an array, of electrodes which are housed within groundwater wells so that hydrogen is generated at the cathode and oxygen at the anode. A pump is located within the well housing in which the cathode(s) is(are) located and draws in groundwater where it is hydrogenated via electrolysis, passes through a well-bore treatment unit, and then transported to the anode well(s) for reinjection into the ground. The well-bore treatment involves a permeable cylinder located in the well bore and containing a packed bed of catalyst material that facilitates the reductive dehalogenation of the halogenated organic compounds by hydrogen into environmentally benign species such as ethane and methane. Also, electro-osmatic transport of contaminants toward the cathode also contributes to contaminant mass removal. The only above ground equipment required are the transfer pipes and a direct circuit power supply for the electrodes. The electrode wells in an array may be used in pairs or one anode well may be used with a plurality of cathode wells. The DC current flow between electrode wells may be periodically reversed which controls the formation of mineral deposits in the alkaline cathode well-bore water, as well as to help rejuvenate the catalysis.

Polymer electrolyte membrane water electrolysis: Restraining degradation in the presence of fluctuating power

NASA Astrophysics Data System (ADS)

Rakousky, Christoph; Reimer, Uwe; Wippermann, Klaus; Kuhri, Susanne; Carmo, Marcelo; Lueke, Wiebke; Stolten, Detlef

2017-02-01

Polymer electrolyte membrane (PEM) water electrolysis generates 'green' hydrogen when conducted with electricity from renewable - but fluctuating - sources like wind or solar photovoltaic. Unfortunately, the long-term stability of the electrolyzer performance is still not fully understood under these input power profiles. In this study, we contrast the degradation behavior of our PEM water electrolysis single cells that occurs under operation with constant and intermittent power and derive preferable operating states. For this purpose, five different current density profiles are used, of which two were constant and three dynamic. Cells operated at 1 A cm-2 show no degradation. However, degradation was observed for the remaining four profiles, all of which underwent periods of high current density (2 A cm-2). Hereby, constant operation at 2 A cm-2 led to the highest degradation rate (194 μV h-1). Degradation can be greatly reduced when the cells are operated with an intermittent profile. Current density switching has a positive effect on durability, as it causes reversible parts of degradation to recover and results in a substantially reduced degradation per mole of hydrogen produced. Two general degradation phenomena were identified, a decreased anode exchange current density and an increased contact resistance at the titanium porous transport layer (Ti-PTL).

Mediated electrochemical oxidation of organic wastes without electrode separators

DOEpatents

Farmer, J.C.; Wang, F.T.; Hickman, R.G.; Lewis, P.R.

1996-05-14

An electrochemical cell/electrolyte/mediator combination is described for the efficient destruction of organic contaminants using metal salt mediators in a sulfuric acid electrolyte, wherein the electrodes and mediator are chosen such that hydrogen gas is produced at the cathode and no cell membrane is required. 3 figs.

Sulfonated polysulfone battery membrane for use in corrosive environments

DOEpatents

Arnold, Jr., Charles; Assink, Roger

1987-01-01

For batteries containing strong oxidizing electrolyte and a membrane separating two electrolyte solutions, e.g., a zinc ferricyanide battery, an improved membrane is provided comprising an oxidative resistant, conductive, ion-selective membrane fabricated from a catenated aromatic polymer having an absence of tertiary hydrogens, e.g., a sulfonated polysulfone.

The effects of platinum on nickel electrodes in the nickel hydrogen cell

NASA Technical Reports Server (NTRS)

Zimmerman, Albert H.

1991-01-01

Interactions of platinum and platinum compounds with the nickel electrode that are possible in the nickel hydrogen cell, where both the nickel electrode and a platinum catalyst hydrogen electrode are in intimate contact with the alkaline electrolyte, are examined. Additionally, a mechanism of nickel cobalt oxyhydroxide formation in NiH2 cells is presented.

Evaluating Hydrogen Evolution and Oxidation in Alkaline Media to Establish Baselines

DOE PAGES

Alia, Shaun M.; Pivovar, Bryan S.

2018-04-28

This paper fills a significant gap in the literature for alkaline hydrogen evolution (HER) and oxidation (HOR) baseline performance, while reviewing the different variables that influence observed properties. Although high-performing HER-HOR catalysts in acidic electrolytes are too active to measure kinetic in rotating disk electrode (RDE) half-cells, under alkaline conditions RDE kinetics evaluations are relevant and half-cell performances are comparable to hydrogen pump data. This paper focuses on best practices to ensure that half-cell tests don't unnecessarily lower platinum group metal (PGM) performance or improve non-PGM performance. Specific aspects examined include experiments on PGMs minimizing the impact of impurities (electrolyte,more » cell material) and experiments on non-PGMs minimizing the impact from test protocols (counter electrode).« less

Evaluating Hydrogen Evolution and Oxidation in Alkaline Media to Establish Baselines

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

Alia, Shaun M.; Pivovar, Bryan S.

This paper fills a significant gap in the literature for alkaline hydrogen evolution (HER) and oxidation (HOR) baseline performance, while reviewing the different variables that influence observed properties. Although high-performing HER-HOR catalysts in acidic electrolytes are too active to measure kinetic in rotating disk electrode (RDE) half-cells, under alkaline conditions RDE kinetics evaluations are relevant and half-cell performances are comparable to hydrogen pump data. This paper focuses on best practices to ensure that half-cell tests don't unnecessarily lower platinum group metal (PGM) performance or improve non-PGM performance. Specific aspects examined include experiments on PGMs minimizing the impact of impurities (electrolyte,more » cell material) and experiments on non-PGMs minimizing the impact from test protocols (counter electrode).« less

Nanostructured hematite thin films for photoelectrochemical water splitting

NASA Astrophysics Data System (ADS)

Maabong, Kelebogile; Machatine, Augusto G. J.; Mwankemwa, Benard S.; Braun, Artur; Bora, Debajeet K.; Toth, Rita; Diale, Mmantsae

2018-04-01

Nanostructured hematite thin films prepared by dip coating technique were investigated for their photoelectrochemical activity for generation of hydrogen from water splitting. Structural, morphological and optical analyses of the doped/undoped films were performed by X-ray diffraction, high resolution field emission-scanning electron microscopy, UV-vis spectrophotometry and Raman spectroscopy. The photoelectrochemical measurements of the films showed enhanced photoresponse and cathodic shift of the onset potential upon Ti doping indicating improved transfer of photoholes at the semiconductor-electrolyte interface. Films doped with 1 at% Ti produced 0.72 mA/cm2 at 1.23 V vs RHE which is 2 times higher than current density for the pure film (0.30 mA/cm2, at 1.23 V vs RHE). Gas chromatography analysis of the films also showed enhanced hydrogen evolution at 1 at% Ti with respect to pure film.

Interruption of Hydrogen Bonding Networks of Water in Carbon Nanotubes Due to Strong Hydration Shell Formation.

PubMed

Oya, Yoshifumi; Hata, Kenji; Ohba, Tomonori

2017-10-24

We present the structures of NaCl aqueous solution in carbon nanotubes with diameters of 1, 2, and 3 nm based on an analysis performed using X-ray diffraction and canonical ensemble Monte Carlo simulations. Anomalously longer nearest-neighbor distances were observed in the electrolyte for the 1-nm-diameter carbon nanotubes; in contrast, in the 2 and 3 nm carbon nanotubes, the nearest-neighbor distances were shorter than those in the bulk electrolyte. We also observed similar properties for water in carbon nanotubes, which was expected because the main component of the electrolyte was water. However, the nearest-neighbor distances of the electrolyte were longer than those of water in all of the carbon nanotubes; the difference was especially pronounced in the 2-nm-diameter carbon nanotubes. Thus, small numbers of ions affected the entire structure of the electrolyte in the nanopores of the carbon nanotubes. The formation of strong hydration shells between ions and water molecules considerably interrupted the hydrogen bonding between water molecules in the nanopores of the carbon nanotubes. The hydration shell had a diameter of approximately 1 nm, and hydration shells were thus adopted for the nanopores of the 2-nm-diameter carbon nanotubes, providing an explanation for the large difference in the nearest-neighbor distances between the electrolyte and water in these nanopores.

Electrocoagulation of palm oil mill effluent as wastewater treatment and hydrogen production using electrode aluminum.

PubMed

Nasution, M Ansori; Yaakob, Z; Ali, Ehsan; Tasirin, S M; Abdullah, S R S

2011-01-01

Palm oil mill effluent (POME) is highly polluting wastewater generated from the palm oil milling process. Palm oil mill effluent was used as an electrolyte without any additive or pretreatment to perform electrocoagulation (EC) using electricity (direct current) ranging from 2 to 4 volts in the presence of aluminum electrodes with a reactor volume of 20 L. The production of hydrogen gas, removal of chemical oxygen demand (COD), and turbidity as a result of electrocoagulation of POME were determined. The results show that EC can reduce the COD and turbidity of POME by 57 and 62%, respectively, in addition to the 42% hydrogen production. Hydrogen production was also helpful to remove the lighter suspended solids toward the surface. The production of Al(OH)XHO at the aluminum electrode (anode) was responsible for the flocculation-coagulation process of suspended solids followed by sedimentation under gravity. The production of hydrogen gas from POME during EC was also compared with hydrogen gas production by electrolysis of tap water at pH 4 and tap water without pH adjustment under the same conditions. The main advantage of this study is to produce hydrogen gas while treating POME with EC to reduce COD and turbidity effectively. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Polymerization Effect of Electrolytes on Hydrogen-Bonding Cryoprotectants: Ion–Dipole Interactions between Metal Ions and Glycerol

PubMed Central

2015-01-01

Protectants which are cell membrane permeable, such as glycerol, have been used effectively in the cryopreservation field for a number of decades, for both slow cooling and vitrification applications. In the latter case, the glass transition temperature (Tg) of the vitrification composition is key to its application, dictating the ultimate storage conditions. It has been observed that the addition of some electrolytes to glycerol, such as MgCl2, could elevate the Tg of the mixture, thus potentially providing more storage condition flexibility. The microscopic mechanisms that give rise to the Tg-enhancing behavior of these electrolytes are not yet well understood. The current study focuses on molecular dynamics simulation of glycerol mixed with a variety of metal chlorides (i.e., NaCl, KCl, MgCl2, and CaCl2), covering a temperature range that spans both the liquid and glassy states. The characteristics of the ion–dipole interactions between metal cations and hydroxyl groups of glycerol were analyzed. The interruption of the original hydrogen-bonding network among glycerol molecules by the addition of ions was also investigated in the context of hydrogen-bonding quantity and lifetime. Divalent metal cations were found to significantly increase the Tg by strengthening the interacting network in the electrolyte/glycerol mixture via strong cation–dipole attractions. In contrast, monovalent cations increased the Tg insignificantly, as the cation–dipole attraction was only slightly stronger than the original hydrogen-bonding network among glycerol molecules. The precursor of crystallization of NaCl and KCl was also observed in these compositions, potentially contributing to weak Tg-enhancing ability. The Tg-enhancing mechanisms elucidated in this study suggest a structure-enhancing role for divalent ions that could be of benefit in the design of protective formulations for biopreservation purposes. PMID:25405831

Nickel-silver alloy electrocatalysts for hydrogen evolution and oxidation in an alkaline electrolyte.

PubMed

Tang, Maureen H; Hahn, Christopher; Klobuchar, Aidan J; Ng, Jia Wei Desmond; Wellendorff, Jess; Bligaard, Thomas; Jaramillo, Thomas F

2014-09-28

The development of improved catalysts for the hydrogen evolution reaction (HER) and hydrogen oxidation reaction (HOR) in basic electrolytes remains a major technical obstacle to improved fuel cells, water electrolyzers, and other devices for electrochemical energy storage and conversion. Based on the free energy of adsorbed hydrogen intermediates, theory predicts that alloys of nickel and silver are active for these reactions. In this work, we synthesize binary nickel-silver bulk alloys across a range of compositions and show that nickel-silver alloys are indeed more active than pure nickel for hydrogen evolution and, possibly, hydrogen oxidation. To overcome the mutual insolubility of silver and nickel, we employ electron-beam physical vapor codeposition, a low-temperature synthetic route to metastable alloys. This method also produces flat and uniform films that facilitate the measurement of intrinsic catalytic activity with minimal variations in the surface area, ohmic contact, and pore transport. Rotating-disk-electrode measurements demonstrate that the hydrogen evolution activity per geometric area of the most active catalyst in this study, Ni0.75Ag0.25, is approximately twice that of pure nickel and has comparable stability and hydrogen oxidation activity. Our experimental results are supported by density functional theory calculations, which show that bulk alloying of Ni and Ag creates a variety of adsorption sites, some of which have near-optimal hydrogen binding energy.

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

Zidan, Ragaiy

A process of using an electrochemical cell to generate aluminum hydride (AlH.sub.3) and other high capacity hydrides is provided. The electrolytic cell uses an electro-catalytic-additive within a polar non-salt containing solvent to solubilize an ionic hydride such as NaAlH.sub.4 or LiAlH.sub.4. The resulting electrochemical process results in the formation of AlH.sub.3 adduct. AlH.sub.3 is obtained from the adduct by heating under vacuum. The AlH.sub.3 can be recovered and used as a source of hydrogen for the automotive industry. The resulting spent aluminum can be regenerated into NaAlH.sub.4 or LiAlH.sub.4 as part of a closed loop process of AlH.sub.3 generation.

Electrochemical process for the preparation of nitrogen fertilizers

DOEpatents

Aulich, Ted R [Grand Forks, ND; Olson, Edwin S [Grand Forks, ND; Jiang, Junhua [Grand Forks, ND

2012-04-10

The present invention provides methods and apparatus for the preparation of nitrogen fertilizers including ammonium nitrate, urea, urea-ammonium nitrate, and/or ammonia, at low temperature and pressure, preferably at ambient temperature and pressure, utilizing a source of carbon, a source of nitrogen, and/or a source of hydrogen or hydrogen equivalent. Implementing an electrolyte serving as ionic charge carrier, (1) ammonium nitrate is produced via the reduction of a nitrogen source at the cathode and the oxidation of a nitrogen source at the anode; (2) urea or its isomers are produced via the simultaneous cathodic reduction of a carbon source and a nitrogen source; (3) ammonia is produced via the reduction of nitrogen source at the cathode and the oxidation of a hydrogen source or a hydrogen equivalent such as carbon monoxide or a mixture of carbon monoxide and hydrogen at the anode; and (4) urea-ammonium nitrate is produced via the simultaneous cathodic reduction of a carbon source and a nitrogen source, and anodic oxidation of a nitrogen source. The electrolyte can be aqueous, non-aqueous, or solid.

Kinetics of hydrogen-evolution reaction on lead and lead-alloy electrodes in sulfuric acid electrolyte with phosphoric acid and antimony additives

NASA Astrophysics Data System (ADS)

Venugopalan, S.

1994-03-01

The kinetics of the hydrogen-evolution reaction (HER) on smooth Pb, PbCaSn and PbSbSe alloy electrodes is studied in H 2SO 4 (3-10 M) electrolyte that contains phosphoric acid (0-40 g l -1) and antimony (0-10 mg l -1) using galvanostatic polarization in the Tafel domain. A direct correlation is found between iO,H and icor on lead and lead-alloy electrodes with varying concentrations of H 3PO 4 and Sb(III) in H 2SO 4. The maximum suppression of the HER occurs with 20 g l -1 H 3PO 4 in H 2SO 4 for both lead and lead alloys. The data are explained in the light of a model that employs adsorption of H 3PO 4 at the electrode/ electrolyte interface.

Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte

DOE PAGES

Zhuang, Zhongbin; Giles, Stephen A.; Zheng, Jie; ...

2016-01-14

The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizesmore » the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Here, owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells.« less

Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte

PubMed Central

Zhuang, Zhongbin; Giles, Stephen A.; Zheng, Jie; Jenness, Glen R.; Caratzoulas, Stavros; Vlachos, Dionisios G.; Yan, Yushan

2016-01-01

The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizes the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells. PMID:26762466

Durability evaluation of reversible solid oxide cells

NASA Astrophysics Data System (ADS)

Zhang, Xiaoyu; O'Brien, James E.; O'Brien, Robert C.; Housley, Gregory K.

2013-11-01

An experimental investigation on the performance and durability of single solid oxide cells (SOCs) is under way at the Idaho National Laboratory. Reversible operation of SOCs includes electricity generation in the fuel cell mode and hydrogen generation in the electrolysis mode. Degradation is a more significant issue when operating SOCs in the electrolysis mode. In order to understand and mitigate the degradation issues in high temperature electrolysis, single SOCs with different configurations from several manufacturers have been evaluated for initial performance and long-term durability. Cells were obtained from four industrial partners. Cells from Ceramatec Inc. and Materials and Systems Research Inc. (MSRI) showed improved durability in electrolysis mode compared to previous stack tests. Cells from Saint Gobain Advanced Materials Inc. (St. Gobain) and SOFCPower Inc. demonstrated stable performance in the fuel cell mode, but rapid degradation in the electrolysis mode, especially at high current density. Electrolyte-electrode delamination was found to have a significant impact on degradation in some cases. Enhanced bonding between electrolyte and electrode and modification of the electrode microstructure helped to mitigate degradation. Polarization scans and AC impedance measurements were performed during the tests to characterize cell performance and degradation.

Theoretical performance of hydrogen-bromine rechargeable SPE fuel cell. [Solid Polymer Electrolyte

NASA Technical Reports Server (NTRS)

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

1988-01-01

A mathematical model was formulated to describe the performance of a hydrogen-bromine fuel cell. Porous electrode theory was applied to the carbon felt flow-by electrode and was coupled to theory describing the solid polymer electrolyte (SPE) system. Parametric studies using the numerical solution to this model were performed to determine the effect of kinetic, mass transfer, and design parameters on the performance of the fuel cell. The results indicate that the cell performance is most sensitive to the transport properties of the SPE membrane. The model was also shown to be a useful tool for scale-up studies.

Properties of solid polymer electrolyte fluorocarbon film. [used in hydrogen/oxygen fuel cells

NASA Technical Reports Server (NTRS)

Alston, W. B.

1973-01-01

The ionic fluorocarbon film used as the solid polymer electrolyte in hydrogen/oxygen fuel cells was found to exhibit delamination failures. Polarized light microscopy of as-received film showed a lined region at the center of the film thickness. It is shown that these lines were not caused by incomplete saponification but probably resulted from the film extrusion process. The film lines could be removed by an annealing process. Chemical, physical, and tensile tests showed that annealing improved or sustained the water contents, spectral properties, thermo-oxidative stability, and tensile properties of the film. The resistivity of the film was significantly decreased by the annealing process.

Parasitic Currents Caused by Different Ionic and Electronic Conductivities in Fuel Cell Anodes.

PubMed

Schalenbach, Maximilian; Zillgitt, Marcel; Maier, Wiebke; Stolten, Detlef

2015-07-29

The electrodes in fuel cells simultaneously realize electric and ionic conductivity. In the case of acidic polymer electrolytes, the electrodes are typically made of composites of carbon-supported catalyst and Nafion polymer electrolyte binder. In this study, the interaction of the proton conduction, the electron conduction, and the electrochemical hydrogen conversion in such composite electrode materials was examined. Exposed to a hydrogen atmosphere, these composites displayed up to 10-fold smaller resistivities for the proton conduction than that of Nafion membranes. This effect was ascribed to the simultaneously occurring electrochemical hydrogen oxidation and evolution inside the composite samples, which are driven by different proton and electron resistivities. The parasitic electrochemical currents resulting were postulated to occur in the anode of fuel cells with polymer, solid oxide, or liquid alkaline electrolytes, when the ohmic drop of the ion conduction in the anode is higher with the anodic kinetic overvoltage (as illustrated in the graphical abstract). In this case, the parasitic electrochemical currents increase the anodic kinetic overpotential and the ohmic drop in the anode. Thinner fuel cell anodes with smaller ohmic drops for the ion conduction may reduce the parasitic electrochemical currents.

Tris(trimethylsilyl) phosphite (TMSPi) and triethyl phosphite (TEPi) as electrolyte additives for lithium ion batteries: Mechanistic insights into differences during LiNi 0.5Mn 0.3Co 0.2O 2- Graphite full cell cycling

DOE PAGES

Peebles, Cameron; Sahore, Ritu; Gilbert, James A.; ...

2017-05-27

Here, tris(trimethylsilyl) phosphite (TMSPi) has emerged as an useful electrolyte additive for lithium ion cells. This work examines the use of TMSPi and a structurally analogous compound, triethyl phosphite (TEPi), in LiNi 0.5Mn 0.3Co 0.2O 2-graphite full cells, containing a (baseline) electrolyte with 1.2 M LiPF6 in EC: EMC (3:7 w/w) and operating between 3.0-4.4 V. Galvanostatic cycling data reveal a measurable difference in capacity fade between the TMSPi and TEPi cells. Furthermore, lower impedance rise is observed for the TMSPi cells, because of the formation of a P-and O-rich surface film on the positive electrode that was revealed bymore » X-ray photoelectron spectroscopy data. Elemental analysis on negative electrodes harvested from cycled cells show lower contents of transition metal (TM) elements for the TMSPi cells than for the baseline and TEPi cells. Our findings indicate that removal of TMS groups from the central P-O core of the TMSPi additive enables formation of the oxide surface film. This film is able to block the generation of reactive TM-oxygen radical species, suppress hydrogen abstraction from the electrolyte solvent, and minimize oxidation reactions at the positive electrode-electrolyte interface. In contrast, oxidation of TEPi does not yield a protective positive electrode film, which results in inferior electrochemical performance.« less

Tris(trimethylsilyl) phosphite (TMSPi) and triethyl phosphite (TEPi) as electrolyte additives for lithium ion batteries: Mechanistic insights into differences during LiNi 0.5Mn 0.3Co 0.2O 2- Graphite full cell cycling

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

Peebles, Cameron; Sahore, Ritu; Gilbert, James A.

Here, tris(trimethylsilyl) phosphite (TMSPi) has emerged as an useful electrolyte additive for lithium ion cells. This work examines the use of TMSPi and a structurally analogous compound, triethyl phosphite (TEPi), in LiNi 0.5Mn 0.3Co 0.2O 2-graphite full cells, containing a (baseline) electrolyte with 1.2 M LiPF6 in EC: EMC (3:7 w/w) and operating between 3.0-4.4 V. Galvanostatic cycling data reveal a measurable difference in capacity fade between the TMSPi and TEPi cells. Furthermore, lower impedance rise is observed for the TMSPi cells, because of the formation of a P-and O-rich surface film on the positive electrode that was revealed bymore » X-ray photoelectron spectroscopy data. Elemental analysis on negative electrodes harvested from cycled cells show lower contents of transition metal (TM) elements for the TMSPi cells than for the baseline and TEPi cells. Our findings indicate that removal of TMS groups from the central P-O core of the TMSPi additive enables formation of the oxide surface film. This film is able to block the generation of reactive TM-oxygen radical species, suppress hydrogen abstraction from the electrolyte solvent, and minimize oxidation reactions at the positive electrode-electrolyte interface. In contrast, oxidation of TEPi does not yield a protective positive electrode film, which results in inferior electrochemical performance.« less

Configuring a fuel cell based residential combined heat and power system

NASA Astrophysics Data System (ADS)

Ahmed, Shabbir; Papadias, Dionissios D.; Ahluwalia, Rajesh K.

2013-11-01

The design and performance of a fuel cell based residential combined heat and power (CHP) system operating on natural gas has been analyzed. The natural gas is first converted to a hydrogen-rich reformate in a steam reformer based fuel processor, and the hydrogen is then electrochemically oxidized in a low temperature polymer electrolyte fuel cell to generate electric power. The heat generated in the fuel cell and the available heat in the exhaust gas is recovered to meet residential needs for hot water and space heating. Two fuel processor configurations have been studied. One of the configurations was explored to quantify the effects of design and operating parameters, which include pressure, temperature, and steam-to-carbon ratio in the fuel processor, and fuel utilization in the fuel cell. The second configuration applied the lessons from the study of the first configuration to increase the CHP efficiency. Results from the two configurations allow a quantitative comparison of the design alternatives. The analyses showed that these systems can operate at electrical efficiencies of ∼46% and combined heat and power efficiencies of ∼90%.

Electrochemical methane sensor

DOEpatents

Zaromb, S.; Otagawa, T.; Stetter, J.R.

1984-08-27

A method and instrument including an electrochemical cell for the detection and measurement of methane in a gas by the oxidation of methane electrochemically at a working electrode in a nonaqueous electrolyte at a voltage about 1.4 volts vs R.H.E. (the reversible hydrogen electrode potential in the same electrolyte), and the measurement of the electrical signal resulting from the electrochemical oxidation.

Liquid junction schottky barrier solar cell

DOEpatents

Williams, Richard

1980-01-01

A mixture of ceric ions (Ce.sup.+4) and cerous ions (Ce.sup.+3) in an aqueous electrolyte solution forms a Schottky barrier at the interface between an active region of silicon and the electrolyte solution. The barrier height obtained for hydrogenated amorphous silicon using the Ce.sup.+4 /Ce.sup.+3 redox couple is about 1.7 eV.

Development of a Novel Efficient Solid-Oxide Hybrid for Co-generation of Hydrogen and Electricity Using Nearby Resources for Local Application

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

Tao, Greg, G.; Virkar, Anil, V.; Bandopadhyay, Sukumar

2009-06-30

Developing safe, reliable, cost-effective, and efficient hydrogen-electricity co-generation systems is an important step in the quest for national energy security and minimized reliance on foreign oil. This project aimed to, through materials research, develop a cost-effective advanced technology cogenerating hydrogen and electricity directly from distributed natural gas and/or coal-derived fuels. This advanced technology was built upon a novel hybrid module composed of solid-oxide fuel-assisted electrolysis cells (SOFECs) and solid-oxide fuel cells (SOFCs), both of which were in planar, anode-supported designs. A SOFEC is an electrochemical device, in which an oxidizable fuel and steam are fed to the anode and cathode,more » respectively. Steam on the cathode is split into oxygen ions that are transported through an oxygen ion-conducting electrolyte (i.e. YSZ) to oxidize the anode fuel. The dissociated hydrogen and residual steam are exhausted from the SOFEC cathode and then separated by condensation of the steam to produce pure hydrogen. The rationale was that in such an approach fuel provides a chemical potential replacing the external power conventionally used to drive electrolysis cells (i.e. solid oxide electrolysis cells). A SOFC is similar to the SOFEC by replacing cathode steam with air for power generation. To fulfill the cogeneration objective, a hybrid module comprising reversible SOFEC stacks and SOFC stacks was designed that planar SOFECs and SOFCs were manifolded in such a way that the anodes of both the SOFCs and the SOFECs were fed the same fuel, (i.e. natural gas or coal-derived fuel). Hydrogen was produced by SOFECs and electricity was generated by SOFCs within the same hybrid system. A stand-alone 5 kW system comprising three SOFEC-SOFC hybrid modules and three dedicated SOFC stacks, balance-of-plant components (including a tailgas-fired steam generator and tailgas-fired process heaters), and electronic controls was designed, though an overall integrated system assembly was not completed because of limited resources. An inexpensive metallic interconnects fabrication process was developed in-house. BOP components were fabricated and evaluated under the forecasted operating conditions. Proof-of-concept demonstration of cogenerating hydrogen and electricity was performed, and demonstrated SOFEC operational stability over 360 hours with no significant degradation. Cost analysis was performed for providing an economic assessment of the cost of hydrogen production using the targeted hybrid technology, and for guiding future research and development.« less

Electrolyte management considerations in modern nickel hydrogen and nickel cadmium cell and battery designs

NASA Technical Reports Server (NTRS)

Thaller, L. H.; Zimmerman, A. H.

1995-01-01

In the early 1980's the NASA Lewis group addressed the topic of designing nickel hydrogen cells for LEO applications. As published in 1984, the design addressed the topics of gas management, liquid management, plate expansion, and the recombination of oxygen during overcharge. This design effort followed principles set forth in an earlier Lewis paper that addressed the topic of pore size engineering. At about that same time, the beneficial effect on cycle life of lower electrolyte concentrations was verified by Hughes Aircraft as part of a Lewis funded study. A succession of life cycle tests of these concepts have been carried out that essentially verified all of this earlier work. During these past two decades, some of the mysteries involved in the active material of the nickel electrode have been resolved by careful research efforts carried out at several laboratories. At The Aerospace Corporation, Dr. Zimmerman has been developing a sophisticated model of an operating nickel hydrogen cell which will be used to model certain mechanisms that have contributed to premature failures in nickel hydrogen and nickel cadmium cells. During the course of trying to understand and model abnormal nickel hydrogen cell behaviors, we have noted that not enough attention has been paid to the potassium ion content in these cells, and more recently batteries. Several of these phenomenon have been well known in the area of alkaline fuel cells, but only recently have they been examined as they might impact alkaline cell designs. This paper will review three general areas where the potassium ion content can impact the performance and life of nickel hydrogen and nickel cadmium devices, Once these phenomenon are understood conceptually, the impact of potassium content on a potential cell design can be evaluated with the aid of an accurate model of an operating cell or battery. All three of these areas are directly related to the volume tolerance and pore size engineering aspects of the components used in the cell or battery design: (1) The gamma phase uptake of potassium ion can result in a lowering of the electrolyte concentration. This leads to a higher electrolyte resistance as well as electrolyte diffusional limitations on the discharge rate. This phenomenon will also impact the response of the cell to a reconditioning cycle. (2) The impact of low level shunt currents in multi-cell con figurations will result in the movement of potassium ion from one part of the battery to another. This will impact the electrolyte volume/vapor pressure relationships within the cell or battery. (3) The transport of water vapor from place to place under the driving force of a tempetature gradient has already impacted cells for the case where water vapor is condensed on a colder cell wall. The paper will explore the convective and diffusive movement of gases saturated with water vapor from a warmer plate pack to a cooler one - both with and without liquid communication.

A study of water electrolysis using ionic polymer-metal composite for solar energy storage

NASA Astrophysics Data System (ADS)

Keow, Alicia; Chen, Zheng

2017-04-01

Hydrogen gas can be harvested via the electrolysis of water. The gas is then fed into a proton exchange membrane fuel cell (PEMFC) to produce electricity with clean emission. Ionic polymer-metal composite (IPMC), which is made from electroplating a proton-conductive polymer film called Nafion encourages ion migration and dissociation of water under application of external voltage. This property has been proven to be able to act as catalyst for the electrolysis of pure water. This renewable energy system is inspired by photosynthesis. By using solar panels to gather sunlight as the source of energy, the generation of electricity required to activate the IPMC electrolyser is acquired. The hydrogen gas is collected as storable fuel and can be converted back into energy using a commercial fuel cell. The goal of this research is to create a round-trip energy efficient system which can harvest solar energy, store them in the form of hydrogen gas and convert the stored hydrogen back to electricity through the use of fuel cell with minimal overall losses. The effect of increasing the surface area of contact is explored through etching of the polymer electrolyte membrane (PEM) with argon plasma or manually sanding the surface and how it affects the increase of energy conversion efficiency of the electrolyser. In addition, the relationship between temperature and the IPMC is studied. Experimental results demonstrated that increases in temperature of water and changes in surface area contact correlate with gas generation.

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.

Improved Durability of SOEC Stacks for High Temperature Electrolysis

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

James E. O'Brien; Robert C. O'Brien; Xiaoyu Zhang

2013-01-01

High temperature steam electrolysis is a promising technology for efficient and sustainable large-scale hydrogen production. Solid oxide electrolysis cells (SOECs) are able to utilize high temperature heat and electric power from advanced high-temperature nuclear reactors or renewable sources to generate carbon-free hydrogen at large scale. However, long term durability of SOECs needs to be improved significantly before commercialization of this technology can be realized. A degradation rate of 1%/khr or lower is proposed as a threshold value for commercialization of this technology. Solid oxide electrolysis stack tests have been conducted at Idaho National Laboratory to demonstrate recent improvements in long-termmore » durability of SOECs. Electrolyte-supported and electrode-supported SOEC stacks were provided by Ceramatec Inc. and Materials and Systems Research Inc. (MSRI), respectively, for these tests. Long-term durability tests were generally operated for a duration of 1000 hours or more. Stack tests based on technologies developed at Ceramatec and MSRI have shown significant improvement in durability in the electrolysis mode. Long-term degradation rates of 3.2%/khr and 4.6%/khr were observed for MSRI and Ceramatec stacks, espectively. One recent Ceramatec stack even showed negative degradation (performance improvement) over 1900 hours of operation. Optimization of electrode materials, interconnect coatings, and electrolyte-electrode interface microstructures contribute to better durability of SOEC stacks.« less

New Gas Polarographic Hydrogen Sensor

NASA Technical Reports Server (NTRS)

Dominguez, Jesus A.; Barile, Ron

2004-01-01

Polarography is the measurement of the current that flows in solution as a function of an applied voltage. The actual form of the observed polarographic current depends upon the manner in which the voltage is applied and on the characteristics of the working electrode. The new gas polarographic H2 sensor shows a current level increment with concentration of the gaseous H2 similar to those relating to metal ions in liquid electrolytes in well-known polarography. This phenomenon is caused by the fact that the diffusion of the gaseous H2 through a gas diffusion hole built in the sensor is a rate-determining step in the gaseous-hydrogen sensing mechanism. The diffusion hole artificially limits the diffusion of the gaseous H2 toward the electrode located at the sensor cavity. This gas polarographic H2 sensor. is actually an electrochemical-pumping cell since the gaseous H2 is in fact pumped via the electrochemical driving force generated between the electrodes. Gaseous H2 enters the diffusion hole and reaches the first electrode (anode) located in the sensor cavity to be transformed into an H+ ions or protons; H+ ions pass through the electrolyte and reach the second electrode (cathode) to be reformed to gaseous H2. Gas polarographic 02 sensors are commercially available; a gas polarographic 02 sensor was used to prove the feasibility of building a new gas polarographic H2 sensor.

Particle size dependence of CO tolerance of anode PtRu catalysts for polymer electrolyte fuel cells

NASA Astrophysics Data System (ADS)

Yamanaka, Toshiro; Takeguchi, Tatsuya; Wang, Guoxiong; Muhamad, Ernee Noryana; Ueda, Wataru

An anode catalyst for a polymer electrolyte fuel cell must be CO-tolerant, that is, it must have the function of hydrogen oxidation in the presence of CO, because hydrogen fuel gas generated by the steam reforming process of natural gas contains a small amount of CO. In the present study, PtRu/C catalysts were prepared with control of the degree of Pt-Ru alloying and the size of PtRu particles. This control has become possible by a new method of heat treatment at the final step in the preparation of catalysts. The CO tolerances of PtRu/C catalysts with the same degree of Pt-Ru alloying and with different average sizes of PtRu particles were thus compared. Polarization curves were obtained with pure H 2 and CO/H 2 (CO concentrations of 500-2040 ppm). It was found that the CO tolerance of highly dispersed PtRu/C (high dispersion (HD)) with small PtRu particles was much higher than that of poorly dispersed PtRu/C (low dispersion (LD)) with large metal particles. The CO tolerance of PtRu/C (HD) was higher than that of any commercial PtRu/C. The high CO tolerance of PtRu/C (HD) is thought to be due to efficient concerted functions of Pt, Ru, and their alloy.

PEM Electrolysis H2A Production Case Study Documentation

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

James, Brian; Colella, Whitney; Moton, Jennie

2013-12-31

This report documents the development of four DOE Hydrogen Analysis (H2A) case studies for polymer electrolyte membrane (PEM) electrolysis. The four cases characterize PEM electrolyzer technology for two hydrogen production plant sizes (Forecourt and Central) and for two technology development time horizons (Current and Future).

High-performance low-temperature solid oxide fuel cell with novel BSCF cathode

NASA Astrophysics Data System (ADS)

Liu, Q. L.; Khor, K. A.; Chan, S. H.

An anode-supported solid oxide fuel cell (SOFC), consisting of a dense 10 μm Gd 0.1Ce 0.9O 1.95 (GDC) electrolyte, a porous Ba 0.5Sr 0.5Co 0.8Fe 0.2O 3- δ (BSCF) cathode and a porous Ni-GDC cermet anode, is successfully assembled and electrochemically characterized. With humidified (3% water vapour) hydrogen as the fuel and air as the oxidant, the cell exhibits open-circuit voltages of 0.903 and 0.984 V when operating at 600 and 500 °C, respectively. The cell produces peak power densities of 1329, 863, 454, 208 and 83 mW cm -2 at 600, 550, 500, 450 and 400 °C, respectively. These results are impressive and demonstrate the potential of BSCF for use as the cathode material in new-generation SOFCs with GDC as the electrolyte. In addition, the sustained performance at temperatures below 600 °C warrants commercial exploitation of this SOFC in stationary and mobile applications.

Real-time imaging, spectroscopy, and structural investigation of cathodic plasma electrolytic oxidation of molybdenum

NASA Astrophysics Data System (ADS)

Stojadinović, Stevan; Tadić, Nenad; Šišović, Nikola M.; Vasilić, Rastko

2015-06-01

In this paper, the results of the investigation of cathodic plasma electrolytic oxidation (CPEO) of molybdenum at 160 V in a mixed solution of borax, water, and ethylene glycol are presented. Real-time imaging and optical emission spectroscopy were used for the characterization of the CPEO. During the process, vapor envelope is formed around the cathode and strong electric field within the envelope caused the generation of plasma discharges. The spectral line shape analysis of hydrogen Balmer line Hβ (486.13 nm) shows that plasma discharges are characterized by the electron number density of about 1.4 × 1021 m-3. The electron temperature of 15 000 K was estimated by measuring molybdenum atomic lines intensity. Surface morphology, chemical, and phase composition of coatings formed by CPEO were characterized by scanning electron microscopy with energy dispersive x-ray spectroscopy and x-ray diffraction. The elemental components of CPEO coatings are Mo and O and the predominant crystalline form is MoO3.

Modeling complex dispersed energy and clean water systems for the United States/Mexico border

NASA Astrophysics Data System (ADS)

Herrera, Hugo Francisco Lopez

As world population grows, and its technology evolves, the demand for electricity inexorably increases. Until now most of this electricity has been produced via fossil fuels, non-renewable energy resources that are irreversibly deteriorating our environment. On the economical aspect it does not get any better. Let's not forget market rules, the higher the demand and lower the offer, the higher the price we will have to pay. Oil is an excellent example. Some countries try to solve this situation with Pharaohnic projects, i.e. investing absurd amounts of money in 'green electricity' building monstrous dams to power equally monstrous hydroelectric power plants. The only problem with this is that it is not green at all---it does have an enormous environmental impact---it is extremely complicated and expensive to implement. It is important to point out, that this research project does not try to solve world's thirst for electricity. It is rather aimed to help solve this problematic at a much lower scale---it should be considered as an extremely small step in the right direction. It focuses on satisfying the local electricity needs with renewable, non-contaminating and locally available resources. More concisely, this project focuses on the attainment and use of hydrogen as an alternate energy source in El Paso/Juarez region. Clean technology is nowadays available to produce hydrogen and oxygen, i.e. the photoelectrolysis process. Photovoltaic cells coupled with electrolytic devices can be used to produce hydrogen and oxygen in a sustainable manner. In this research, simulation models of hybrid systems were designed and developed. They were capable to compare, predict and evaluate different options for hydrogen generation. On the other hand, with the produced hydrogen from the electrolysis process it was possible to generate electricity through fuel cells. The main objectives of the proposed research were to define how to use the resources for the attainment of hydrogen and distribution of it in El Paso/Juarez region. More precisely, the goals were the conversion of brines and waste-waters to hydrogen via electrolysis, and the generation of electricity through fuel cells. Thereafter, the specific objectives were to (1) design a simulation model for hydrogen generation, (2) design and simulate a model of photovoltaic (PV) array capable to generate the required energy for the process, (3) simulate fuel cells in order to be used as electricity power supply in remote houses, and (4) simulate a complete remote house hybrid system. The results of this research gave us information about the feasibility of high-volume hydrogen generation with the diverse resources of the region. On the other hand, this research has shown the alternatives of local energy generation, and efficiency of a remote house hybrid system located in El Paso/Juarez area. Experiences obtained from this research will also provide information for future investigations in the field of alternate energy sources, in order to get a clean environment through sustainable development.

The effect of grain size on aluminum anodes for Al-air batteries in alkaline electrolytes

NASA Astrophysics Data System (ADS)

Fan, Liang; Lu, Huimin

2015-06-01

Aluminum is an ideal material for metallic fuel cells. In this research, different grain sizes of aluminum anodes are prepared by equal channel angular pressing (ECAP) at room temperature. Microstructure of the anodes is examined by electron backscatter diffraction (EBSD) in scanning electron microscope (SEM). Hydrogen corrosion rates of the Al anodes in 4 mol L-1 NaOH are determined by hydrogen collection method. The electrochemical properties of the aluminum anodes are investigated in the same electrolyte using electrochemical impedance spectroscopy (EIS) and polarization curves. Battery performance is also tested by constant current discharge at different current densities. Results confirm that the electrochemical properties of the aluminum anodes are related to grain size. Finer grain size anode restrains hydrogen evolution, improves electrochemical activity and increases anodic utilization rate. The proposed method is shown to effectively improve the performance of Al-air batteries.

Polarization loss correction derived from hydrogen local-resistance measurement in low Pt-loaded polymer-electrolyte fuel cells

DOE PAGES

Freiberg, Anna T. S.; Tucker, Michael C.; Weber, Adam Z.

2017-04-12

The reduction of platinum-loading on the cathode side of polymer-electrolyte fuel cells leads to a poorly understood increase in mass-transport resistance (MTR) at high current densities. This local resistance was measured using a facile hydrogen-pump technique with dilute active gases for membrane-electrode assemblies with catalyst layers of varying platinum-loading (0.03-0.40 mgPt/cm²). Furthermore, polarization curves in H 2/air were measured and corrected for the overpotential caused by the increased MTR for low loadings on the air side due to the reduced concentration of reactant gas at the catalyst surface. The difference in performance after correction for all resistances including the MTRmore » is minor, suggesting its origin to be diffusive in nature, and proving the meaningfulness of the facile hydrogen-pump technique for the characterization of the cathode catalyst layer under defined operation conditions.« less

Survey of hydrogen production and utilization methods. Volume 1: Executive summary

NASA Technical Reports Server (NTRS)

Gregory, D. P.; Pangborn, J. B.; Gillis, J. C.

1975-01-01

The use of hydrogen as a synthetic fuel is considered. Processes for the production of hydrogen are described along with the present and future industrial uses of hydrogen as a fuel and as a chemical feedstock. Novel and unconventional hydrogen-production techniques are evaluated, with emphasis placed on thermochemical and electrolytic processes. Potential uses for hydrogen as a fuel in industrial and residential applications are identified and reviewed in the context of anticipated U.S. energy supplies and demands. A detailed plan for the period from 1975 to 1980 prepared for research on and development of hydrogen as an energy carrier is included.

Can a fermentation gas mainly produced by rumen Isotrichidae ciliates be a potential source of biohydrogen and a fuel for a chemical fuel cell?

PubMed

Piela, Piotr; Michałowski, Tadeusz; Miltko, Renata; Szewczyk, Krzysztof; Sikora, Radosław; Grzesiuk, Elzbieta; Sikora, Anna

2010-07-01

Bacteria, fungi and protozoa inhabiting the rumen, the largest chamber of the ruminants' stomach, release large quantities of hydrogen during the fermentation of carbohydrates. The hydrogen is used by coexisting methanogens to produce methane in energy-yielding processes. This work shows, for the first time, a fundamental possibility of using a hydrogen-rich fermentation gas produced by selected rumen ciliates to feed a low-temperature hydrogen fuel cell. A biohydrogen fuel cell (BHFC) was constructed consisting of (i) a bioreactor, in which a hydrogen-rich gas was produced from glucose by rumen ciliates, mainly of the Isotrichidae family, deprived of intra- and extracellular bacteria, methanogens, and fungi, and (ii) a chemical fuel cell of the polymer-electrolyte type (PEFC). The fuel cell was used as a tester of the technical applicability of the fermentation gas produced by the rumen ciliates for power generation. The average estimated hydrogen yield was ca. 1.15 mol H2 per mol of fermented glucose. The BHFC performance was equal to the performance of the PEFC running on pure hydrogen. No fuel cell poisoning effects were detected. A maximum power density of 1.66 kW/m2 (PEFC geometric area) was obtained at room temperature. The maximum volumetric power density was 128 W/m3 but the coulombic efficiency was only ca. 3.8%. The configuration of the bioreactor limited the continuous operation time of this BHFC to ca. 14 hours.

Micro reactor integrated μ-PEM fuel cell system: a feed connector and flow field free approach

NASA Astrophysics Data System (ADS)

Balakrishnan, A.; Mueller, C.; Reinecke, H.

2013-12-01

A system level microreactor concept for hydrogen generation with Sodium Borohydride (NaBH4) is demonstrated. The uniqueness of the system is the transport and distribution feature of fuel (hydrogen) to the anode of the fuel cell without any external feed connectors and flow fields. The approach here is to use palladium film instead of feed connectors and the flow fields; palladium's property to adsorb and desorb the hydrogen at ambient and elevated condition. The proof of concept is demonstrated with a polymethyl methacrylate (PMMA) based complete system integration which includes microreactor, palladium transport layer and the self-breathing polymer electrolyte membrane (PEM) fuel cell. The hydrolysis of NaBH4 was carried out in the presence of platinum supported by nickel (NiPt). The prototype functionality is tested with NaBH4 chemical hydride. The characterization of the integrated palladium layer and fuel cell is tested with constant and switching load. The presented integrated fuel cell is observed to have a maximum power output and current of 60 mW and 280 mA respectively.

Engineering MoSx/Ti/InP Hybrid Photocathode for Improved Solar Hydrogen Production

NASA Astrophysics Data System (ADS)

Li, Qiang; Zheng, Maojun; Zhong, Miao; Ma, Liguo; Wang, Faze; Ma, Li; Shen, Wenzhong

2016-07-01

Due to its direct band gap of ~1.35 eV, appropriate energy band-edge positions, and low surface-recombination velocity, p-type InP has attracted considerable attention as a promising photocathode material for solar hydrogen generation. However, challenges remain with p-type InP for achieving high and stable photoelectrochemical (PEC) performances. Here, we demonstrate that surface modifications of InP photocathodes with Ti thin layers and amorphous MoSx nanoparticles can remarkably improve their PEC performances. A high photocurrent density with an improved PEC onset potential is obtained. Electrochemical impedance analyses reveal that the largely improved PEC performance of MoSx/Ti/InP is attributed to the reduced charge-transfer resistance and the increased band bending at the MoSx/Ti/InP/electrolyte interface. In addition, the MoSx/Ti/InP photocathodes function stably for PEC water reduction under continuous light illumination over 2 h. Our study demonstrates an effective approach to develop high-PEC-performance InP photocathodes towards stable solar hydrogen production.

Inhibition of tafel kinetics for electrolytic hydrogen evolution on isolated micron scale electrocatalysts on semiconductor interfaces

DOE PAGES

Coridan, Robert H.; Schichtl, Zebulon G.; Sun, Tao; ...

2016-08-30

Semiconductor-liquid junctions are ubiquitous in photoelectrochemical approaches for solar-to-fuels energy conversion. Electrocatalysts are added to the interface to improve catalytic efficiency, but they can also impair the photovoltage-generating energetics of the electrode without appropriate microscopic organization of catalytically active area on the surface. This balance is more complicated when gas products are evolved, like hydrogen on water splitting electrodes. Discrete catalysts can be blocked by the gas liquid-solid boundary of a bubble stuck to the surface. Here, we study the kinetics of hydrogen evolution on semiconductor electrodes fabricated with an isolated, micronscale platinum electrocatalyst pad. Movies of in operando bubblemore » evolution were recorded with synchrotron-based high-speed x-ray phase-contrast imaging in a compatible electrochemical cell. The self-limited growth of a bubble residing on the isolated electrocatalyst was measured by tracking the evolution of the gas-liquid boundary through the sequence of images in the movie. As a result, the effect of pad size on the catalytic currents and the issues with reactant transport can be inferred from these dynamics.« less

Engineering MoSx/Ti/InP Hybrid Photocathode for Improved Solar Hydrogen Production

PubMed Central

Li, Qiang; Zheng, Maojun; Zhong, Miao; Ma, Liguo; Wang, Faze; Ma, Li; Shen, Wenzhong

2016-01-01

Due to its direct band gap of ~1.35 eV, appropriate energy band-edge positions, and low surface-recombination velocity, p-type InP has attracted considerable attention as a promising photocathode material for solar hydrogen generation. However, challenges remain with p-type InP for achieving high and stable photoelectrochemical (PEC) performances. Here, we demonstrate that surface modifications of InP photocathodes with Ti thin layers and amorphous MoSx nanoparticles can remarkably improve their PEC performances. A high photocurrent density with an improved PEC onset potential is obtained. Electrochemical impedance analyses reveal that the largely improved PEC performance of MoSx/Ti/InP is attributed to the reduced charge-transfer resistance and the increased band bending at the MoSx/Ti/InP/electrolyte interface. In addition, the MoSx/Ti/InP photocathodes function stably for PEC water reduction under continuous light illumination over 2 h. Our study demonstrates an effective approach to develop high-PEC-performance InP photocathodes towards stable solar hydrogen production. PMID:27431993

Engineering MoSx/Ti/InP Hybrid Photocathode for Improved Solar Hydrogen Production.

PubMed

Li, Qiang; Zheng, Maojun; Zhong, Miao; Ma, Liguo; Wang, Faze; Ma, Li; Shen, Wenzhong

2016-07-19

Due to its direct band gap of ~1.35 eV, appropriate energy band-edge positions, and low surface-recombination velocity, p-type InP has attracted considerable attention as a promising photocathode material for solar hydrogen generation. However, challenges remain with p-type InP for achieving high and stable photoelectrochemical (PEC) performances. Here, we demonstrate that surface modifications of InP photocathodes with Ti thin layers and amorphous MoSx nanoparticles can remarkably improve their PEC performances. A high photocurrent density with an improved PEC onset potential is obtained. Electrochemical impedance analyses reveal that the largely improved PEC performance of MoSx/Ti/InP is attributed to the reduced charge-transfer resistance and the increased band bending at the MoSx/Ti/InP/electrolyte interface. In addition, the MoSx/Ti/InP photocathodes function stably for PEC water reduction under continuous light illumination over 2 h. Our study demonstrates an effective approach to develop high-PEC-performance InP photocathodes towards stable solar hydrogen production.

Inhibition of tafel kinetics for electrolytic hydrogen evolution on isolated micron scale electrocatalysts on semiconductor interfaces

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

Coridan, Robert H.; Schichtl, Zebulon G.; Sun, Tao

Semiconductor-liquid junctions are ubiquitous in photoelectrochemical approaches for solar-to-fuels energy conversion. Electrocatalysts are added to the interface to improve catalytic efficiency, but they can also impair the photovoltage-generating energetics of the electrode without appropriate microscopic organization of catalytically active area on the surface. This balance is more complicated when gas products are evolved, like hydrogen on water splitting electrodes. Discrete catalysts can be blocked by the gas liquid-solid boundary of a bubble stuck to the surface. Here, we study the kinetics of hydrogen evolution on semiconductor electrodes fabricated with an isolated, micronscale platinum electrocatalyst pad. Movies of in operando bubblemore » evolution were recorded with synchrotron-based high-speed x-ray phase-contrast imaging in a compatible electrochemical cell. The self-limited growth of a bubble residing on the isolated electrocatalyst was measured by tracking the evolution of the gas-liquid boundary through the sequence of images in the movie. As a result, the effect of pad size on the catalytic currents and the issues with reactant transport can be inferred from these dynamics.« less

Actions of Hydrogen Sulfide on Sodium Transport Processes across Native Distal Lung Epithelia (Xenopus laevis)

PubMed Central

Erb, Alexandra; Althaus, Mike

2014-01-01

Hydrogen sulfide (H2S) is well known as a highly toxic environmental chemical threat. Prolonged exposure to H2S can lead to the formation of pulmonary edema. However, the mechanisms of how H2S facilitates edema formation are poorly understood. Since edema formation can be enhanced by an impaired clearance of electrolytes and, consequently, fluid across the alveolar epithelium, it was questioned whether H2S may interfere with transepithelial electrolyte absorption. Electrolyte absorption was electrophysiologically measured across native distal lung preparations (Xenopus laevis) in Ussing chambers. The exposure of lung epithelia to H2S decreased net transepithelial electrolyte absorption. This was due to an impairment of amiloride-sensitive sodium transport. H2S inhibited the activity of the Na+/K+-ATPase as well as lidocaine-sensitive potassium channels located in the basolateral membrane of the epithelium. Inhibition of these transport molecules diminishes the electrochemical gradient which is necessary for transepithelial sodium absorption. Since sodium absorption osmotically facilitates alveolar fluid clearance, interference of H2S with the epithelial transport machinery provides a mechanism which enhances edema formation in H2S-exposed lungs. PMID:24960042

Process for electrochemically gasifying coal using electromagnetism

DOEpatents

Botts, Thomas E.; Powell, James R.

1987-01-01

A process for electrochemically gasifying coal by establishing a flowing stream of coal particulate slurry, electrolyte and electrode members through a transverse magnetic field that has sufficient strength to polarize the electrode members, thereby causing them to operate in combination with the electrolyte to electrochemically reduce the coal particulate in the slurry. Such electrochemical reduction of the coal produces hydrogen and carbon dioxide at opposite ends of the polarized electrode members. Gas collection means are operated in conjunction with the process to collect the evolved gases as they rise from the slurry and electrolyte solution.

Optimal control of fuel overpressure in a polymer electrolyte membrane fuel cell with hydrogen transfer leak during load change

NASA Astrophysics Data System (ADS)

Ebadighajari, Alireza; DeVaal, Jake; Golnaraghi, Farid

2017-02-01

Formation of membrane pinholes is a common defect in fuel cells, inflicting more cost and making less durable cells. This work focuses on mitigating this issue, and offers a continuous online treatment instead of attempting to dynamically model the hydrogen transfer leak rate. This is achieved by controlling the differential pressure between the anode and cathode compartments at the inlet side of the fuel cell stack, known as the fuel overpressure. The model predictive control approach is used to attain the objectives in a Ballard 9-cell Mk1100 polymer electrolyte membrane fuel cell (PEMFC) with inclusion of hydrogen transfer leak. Furthermore, the pneumatic modeling technique is used to model the entire anode side of a fuel cell station. The hydrogen transfer leak is embedded in the model in a novel way, and is considered as a disturbance during the controller design. Experimental results for different sizes of hydrogen transfer leaks are provided to show the benefits of fuel overpressure control system in alleviating the effects of membrane pinholes, which in turn increases membrane longevity, and reduces hydrogen emissions in the eventual presence of transfer leaks. Moreover, the model predictive controller provides an optimal control input while satisfying the problem constraints.

Evaluation of AA5052 alloy anode in alkaline electrolyte with organic rare-earth complex additives for aluminium-air batteries

NASA Astrophysics Data System (ADS)

Wang, Dapeng; Li, Heshun; Liu, Jie; Zhang, Daquan; Gao, Lixin; Tong, Lin

2015-10-01

Behaviours of the AA5052 aluminium alloy anode of the alkaline aluminium-air battery are studied by the hydrogen evolution test, the electrochemical measurements and the surface analysis method. The combination of amino-acid and rare earth as electrolyte additives effectively retards the self-corrosion of AA5052 aluminium alloy in 4 M NaOH solution. It shows that the combination of L-cysteine and cerium nitrate has a synergistic effect owing to the formation of a complex film on AA5052 alloy surface. The organic rare-earth complex can decrease the anodic polarisation, suppress the hydrogen evolution and increase the anodic utilization rate.

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).

Redox shuttles for overcharge protection of lithium batteries

DOEpatents

Amine, Khalil; Chen, Zonghai; Wang, Qingzheng

2010-12-14

The present invention is generally related to electrolytes containing novel redox shuttles for overcharge protection of lithium-ion batteries. The redox shuttles are capable of thousands hours of overcharge tolerance and have a redox potential at about 3-5.5 V vs. Li and particularly about 4.4-4.8 V vs. Li. Accordingly, in one aspect the invention provides electrolytes comprising an alkali metal salt; a polar aprotic solvent; and a redox shuttle additive that is an aromatic compound having at least one aromatic ring with four or more electronegative substituents, two or more oxygen atoms bonded to the aromatic ring, and no hydrogen atoms bonded to the aromatic ring; and wherein the electrolyte solution is substantially non-aqueous. Further there are provided electrochemical devices employing the electrolyte and methods of making the electrolyte.

The effect of urea on microstructures of Ni{sub 3}S{sub 2} on nickel foam and its hydrogen evolution reaction

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

Jinlong, Lv, E-mail: ljltsinghua@126.com; State Key Lab of New Ceramic and Fine Processing, Tsinghua University, Beijing 100084; Tongxiang, Liang, E-mail: txliang@mail.tsinghua.edu.cn

The effects of urea concentration on microstructures of Ni{sub 3}S{sub 2}formed on nickel foam and its hydrogen evolution reaction were investigated. The Ni{sub 3}S{sub 2} nanosheets with porous structure were formed on nickel foam during hydrothermal process due to low urea concentration. While high urea concentration facilitated the forming of Ni{sub 3}S{sub 2} nanotube arrays. The resulting Ni{sub 3}S{sub 2} nanotube arrays exhibited higher catalytic activity than Ni3S2nanosheets for hydrogen evolution reaction. This was mainly attributed to a fact that Ni{sub 3}S{sub 2} nanotube arrays facilitated diffusion of electrolyte for hydrogen evolution reaction. - Graphical abstract: The resulting Ni{sub 3}S{submore » 2} nanotube arrays exhibited higher catalytic activity than Ni{sub 3}S{sub 2} nanosheets for hydrogen evolution reaction. This was mainly attributed to a fact that Ni{sub 3}S{sub 2} nanotube arrays facilitated diffusion of electrolyte for hydrogen evolution reaction and hydrogen evolution. - Highlights: • Urea promoted to forming more Ni{sub 3}S{sub 2} nanotube arrays on nickel foam. • Ni{sub 3}S{sub 2} nanotube arrays showed higher catalytic activity in alkaline solution. • Ni{sub 3}S{sub 2} nanotube arrays promoted electron transport and reaction during the HER.« less

Novel aqueous dual-channel aluminum-hydrogen peroxide battery

NASA Astrophysics Data System (ADS)

Marsh, Catherine; Licht, Stuart

1994-06-01

A dual-channel aluminum hydrogen peroxide battery is introduced with an open-circuit voltage of 1.9 volts, polarization losses of 0.9 mV cm(exp 2) mA(exp -1), and power densities of 1 W/cm(exp 2). Catholyte and anolyte cell compartments are separated by an Ir/Pd modified porous nickel cathode. Separation of catholyte and anolyte chambers prevents hydrogen peroxide poisoning of the aluminum anode. The battery is expressed by aluminum oxidation and aqueous solution phase hydrogen peroxide reduction for an overall battery discharge consisting of 2Al + 3H2O2 + 2OH(-) yields 2AlO2(-) + 4H2O E = 2.3 V. The search for electrical propulsion sources which fit the requirements for electrically powered vehicles has blurred the standard characteristics associated with electrochemical storage systems. Presently, electrochemical systems comprised of mechanically rechargeable primary batteries, secondary batteries, and fuel cells are candidates for electrochemical propulsion sources. While important advances in energy and power density continue for nonaqueous and molten electrolytes, aqueous electrolyte batteries often have an advantage in simplicity, conductivity, cost effectiveness, and environmental impact. Systems coupling aluminum anodes and aqueous electrolytes have been investigated. These systems include: aluminum/silver oxide, aluminum/manganese dioxide, aluminum air, aluminum/hydrogen peroxide aqueous batteries, and the recently introduced aluminum/ferricyanide and aluminum sulfur aqueous batteries. Conventional aqueous systems such as the nickel cadmium and lead-acid batteries are characterized by their relatively low energy densities and adverse environmental impact. Other systems have substantially higher theoretical energy capacities. While aluminum-silver oxide has demonstrated the highest steady-state power density, its high cost is an impediment for widespread utilization for electric propulsion.

Ion Transport via Structural Relaxations in Polymerized Ionic Liquids

NASA Astrophysics Data System (ADS)

Ganesan, Venkat; Mogurampelly, Santosh

We study the mechanisms underlying ion transport in poly(1-butyl-3-vinylimidazolium-hexafluorophosphate) polymer electrolytes. We consider polymer electrolytes of varying polymerized ionic liquid to ionic liquid (polyIL:IL) ratios and use atomistic molecular dynamics (MD) simulations to probe the dynamical and structural characteristics of the electrolyte. Our results reveal that anion diffusion along polymer backbone occurs primarily viathe formation and breaking of ion-pairs involving threepolymerized cationic monomers of twodifferent polymer chains. Moreover, we observe that the ionic diffusivities exhibit a direct correlation with the structural relaxation times of the ion-pairs and hydrogen bonds (H-bonds). These results provide new insights into the mechanisms underlying ion transport in polymerized ionic liquid electrolytes.

The effect of crystal orientation on the aluminum anodes of the aluminum-air batteries in alkaline electrolytes

NASA Astrophysics Data System (ADS)

Fan, Liang; Lu, Huimin; Leng, Jing; Sun, Zegao; Chen, Chunbo

2015-12-01

Recently, aluminum-air (Al-air) batteries have received attention from researchers as an exciting option for safe and efficient batteries. The electrochemical performance of Aluminum anode remains an active area of investigation. In this paper, the electrochemical properties of polycrystalline Al, Al (001), (110) and (111) single crystals are investigated using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) in 4 M NaOH and KOH. Hydrogen corrosion rates of the Al anodes are determined by hydrogen collection. Battery performance using the anodes is tested by constant current discharge at 10 mA cm-2. This is the first report showing that the electrochemical properties of Al are closely related to the crystallographic orientation in alkaline electrolytes. The (001) crystallographic plane has good corrosion resistance but (110) is more sensitive. Al (001) single crystals display higher anode efficiency and capacity density. Controlling the crystallographic orientation of the Al anode is another way to improve the performance of Al-air batteries in alkaline electrolytes.

Non-aqueous electrolyte for lithium-ion battery

DOEpatents

Amine, Khalil; Zhang, Lu; Zhang, Zhengcheng

2016-01-26

A substantially non-aqueous electrolyte solution includes an alkali metal salt, a polar aprotic solvent, and an organophosphorus compound of Formula IA, IB, or IC: ##STR00001## where R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are each independently hydrogen, halogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl, heteroaryl, alkoxy, alkenoxy, alkynoxy, cycloalkoxy, aryloxy, heterocyclyloxy, heteroaryloxy, siloxyl, silyl, or organophosphatyl; R.sup.5 and R.sup.6 are each independently alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl, or heteroaryl; R.sup.7 is ##STR00002## and R.sup.8, R.sup.9 and R.sup.10 are each independently alkyl, cycloalkyl, aryl, heterocyclyl, or heteroaryl; provided that if the organophosphorus compound is of Formula IB, then at least one of R.sup.5, and R.sup.6 are other than hydrogen, alkyl, or alkenyl; and if the organophosphorus compound is of Formula IC, then the electrolyte solution does not include 4-methylene-1,3-dioxolan-2-one or 4,5-dimethylene-1,3-dioxolan-2-one.

Electrolyte management considerations in modern nickel/hydrogen and nickel/cadmium cell and battery designs

NASA Astrophysics Data System (ADS)

Thaller, Lawrence H.; Zimmerman, Albert H.

In the early 1980s, the battery group at the NASA Lewis Research Center (LeRC) reviewed the design issues associated with nickel/hydrogen cells for low-earth orbit applications. In 1984, these issues included gas management, liquid management, plate expansion, and the recombination of oxygen during overcharge. The design effort by that group followed principles set forth in an earlier LeRC paper that introduced the topic of pore size engineering. Also in 1984, the beneficial effect of lower electrolyte concentrations on cycle life was verified by Hughes Aircraft as part of a LeRC-funded study. Subsequent life cycle tests of these concepts have been carried out that essentially have verified all of this earlier work. During the past decade, some of the mysteries involved in the active material of the nickel electrode have been resolved by careful research done at several laboratories. While attention has been paid to understanding and modeling abnormal nickel/hydrogen cell behaviors, not enough attention has been paid to the potassium ion content in these cells, and more recently, in batteries. Examining the potassium ion content of different portions of the cell or battery is a convenient way of following the conductivity, mass transport properties, and electrolyte volume in each of the cell or battery portions under consideration. Several of the consequences of solvent and solute changes within fuel cells have been well known for some time. However, only recently have these consequences been applied to nickel/hydrogen and nickel/cadmium cell designs. As a result of these studies, several unusual cell performance signatures can now be satisfactorily explained in terms of movement of the solvent and solute components in the electrolyte. This paper will review three general areas where the potassium ion content can impact the performance and life of nickel/hydrogen and nickel/cadmium cells. Sample calculations of the concentration or volume changes that can take place within operating cells will be presented. With the aid of an accurate model of an operating cell or battery, the impact of changes of potassium ion content within a potential cell design can be estimated. All three of these areas are directly related to the volume tolerance and pore size engineering aspects of the components used in the cell or battery design. The three areas follow. (i) The gamma phase uptake of potassium ion can result in a lowering of the electrolyte concentration. This leads to a higher electrolyte resistance as well as electrolyte diffusional limitations on the discharge rate. This phenomenon also impacts the response of the cell to a reconditioning cycle. (ii) The transport of water vapor from a warmer to a cooler portion of the cell or battery under the driving force of a vapor pressure gradient has already impacted cells when water vapor condenses on a colder cell wall. This paper will explore the convective and diffusive movement of gases saturated with water vapor from a warmer plate pack to a cooler one, both with and without liquid communication. (iii) The impact of low-level shunt currents in multicell configurations results in the net movement of potassium hydroxide from one part of the battery to another. This movement impacts the electrolyte volume/vapor pressure relationships within the cell or battery.

Ionic liquids as electrolytes for non-aqueous solutions electrochemical supercapacitors in a temperature range of 20 °C-80 °C

NASA Astrophysics Data System (ADS)

Zhang, Lei; Tsay, Ken; Bock, Christina; Zhang, Jiujun

2016-08-01

To increase the operating temperature of the supercapacitors (SCs) without compromising their high cycle-life, several typical fluoro- and non-fluoro containing ionic liquids (EMI-mesylate, EMI-hydrogen sulfate, PP13-triflate, PP13-TFSI, and EMI-TFSI, as shown in Fig. 1) are studied as the electrolytes to prepare organic solutions for SC performance measurements using a two-electrode cell. Both cyclic voltammograms and charge/discharge curves at various temperatures such as 20, 40, 60 and 80 °C are collected. At 60 °C, the increased performance order in both rating and cyclability measurements are found to be as follows: 1) EMI-hydrogen sulfate < PP13-TFSI < EMI-mesylate < PP13-triflate < EMI-TFSI for rating; and 2) EMI-hydrogen sulfate < EMI-mesylate < PP13-Triflate < PP13-TFSI < EMI-TFSI for life-time. The fluoro-containing group of ILs, i.e., PP13-Triflate, PP13-TFSI and EMI-TFSI can give a specific capacitance between 100 and 170 F/g for various scan rates for a conventional carbon electrode, and an extended lifetime test of 10, 000 cycles with a capacitance degradation of less than 10%, indicating that these two ion liquids can be used for SC electrolytes operated at high temperature.

Hydrogen-oxygen proton-exchange membrane fuel cells and electrolyzers

NASA Technical Reports Server (NTRS)

Baldwin, R.; Pham, M.; Leonida, A.; Mcelroy, J.; Nalette, T.

1989-01-01

Hydrogen-oxygen solid polymer electrolyte (SPE) fuel cells and SPE electrolyzers (products of Hamilton Standard) both use a Proton-Exchange Membrane (PEM) as the sole electrolyte. These solid electrolyte devices have been under continuous development for over 30 years. This experience has resulted in a demonstrated ten-year SPE cell life capability under load conditions. Ultimate life of PEM fuel cells and electrolyzers is primarily related to the chemical stability of the membrane. For perfluorocarbon proton exchange membranes an accurate measure of the membrane stability is the fluoride loss rate. Millions of cell hours have contributed to establishing a relationship between fluoride loss rates and average expected ultimate cell life. This relationship is shown. Several features have been introduced into SPE fuel cells and SPE electrolyzers such that applications requiring greater than or equal to 100,000 hours of life can be considered. Equally important as the ultimate life is the voltage stability of hydrogen-oxygen fuel cells and electrolyzers. Here again the features of SPE fuel cells and SPE electrolyzers have shown a cell voltage stability in the order of 1 microvolt per hour. That level of stability has been demonstrated for tens of thousands of hours in SPE fuel cells at up to 500 amps per square foot (ASF) current density.

Air-cooled, hydrogen-air fuel cell

NASA Technical Reports Server (NTRS)

Shelekhin, Alexander B. (Inventor); Bushnell, Calvin L. (Inventor); Pien, Michael S. (Inventor)

1999-01-01

An air-cooled, hydrogen-air solid polymer electrolyte (SPE) fuel cell with a membrane electrode assembly operatively associated with a fluid flow plate having at least one plate cooling channel extending through the plate and at least one air distribution hole extending from a surface of the cathode flow field into the plate cooling channel.

Influence of phosphoric acid on the electrochemistry of lead electrodes in sulfuric acid electrolyte containing antimony

NASA Astrophysics Data System (ADS)

Venugopalan, S.

The influence of phosphoric acid (0 to 40 g 1 -1) on the Pb/PbSO 4 reaction and the kinetics of hydrogen evolution on pure, smooth lead and lead alloy electrodes is studied via galvanostatic polarization in the linear and Tafel domains with and without antimony (0 to 10 mg 1 -1) addition to the H 2SO 4 (3 to 10 M) electrolyte. Phosphoric acid is found to offset significantly the adverse effect of antimony. H 3PO 4 is also found to increase the hydrogen overpotential without affecting the Pb/PbSO 4 reaction. This implies that the open-circuit corrosion of lead and the consequent hydrogen evolution rate on lead are reduced in the presence of H 3PO 4. The beneficial effects of H 3PO 4 additive are found to be optimum at around 20 g 1 -1. Suppression of hydrogen evolution on the negative electrode, a crucial criterion for sealed cell operation, can be achieved using a H 3PO 4 additive.

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.

Yttria-stabilized zirconia solid oxide electrolyte fuel cells: Monolithic solid oxide fuel cells

NASA Astrophysics Data System (ADS)

1990-10-01

The monolithic solid oxide fuel cell (MSOFC) is currently under development for a variety of applications including coal-based power generation. The MSOFC is a design concept that places the thin components of a solid oxide fuel cell in lightweight, compact, corrugated structure, and so achieves high efficiency and excellent performance simultaneously with high power density. The MSOFC can be integrated with coal gasification plants and is expected to have high overall efficiency in the conversion of the chemical energy of coal to electrical energy. This report describes work aimed at: (1) assessing manufacturing costs for the MSOFC and system costs for a coal-based plant; (2) modifying electrodes and electrode/electrolyte interfaces to improve the electrochemical performance of the MSOFC; and (3) testing the performance of the MSOFC on hydrogen and simulated coal gas. Manufacturing costs for both the coflow and crossflow MSOFC's were assessed based on the fabrication flow charts developed by direct scaleup of tape calendering and other laboratory processes. Integrated coal-based MSOFC systems were investigated to determine capital costs and costs of electricity. Design criteria were established for a coal-fueled 200-Mw power plant. Four plant arrangements were evaluated, and plant performance was analyzed. Interfacial modification involved modification of electrodes and electrode/electrolyte interfaces to improve the MSOFC electrochemical performance. Work in the cathode and cathode/electrolyte interface was concentrated on modification of electrode porosity, electrode morphology, electrode material, and interfacial bonding. Modifications of the anode and anode/electrolyte interface included the use of additives and improvement of nickel distribution. Single cells have been tested for their electrochemical performance. Performance data were typically obtained with humidified H2 or simulated coal gas and air or oxygen.

Iron-Air Rechargeable Battery

NASA Technical Reports Server (NTRS)

Narayan, Sri R. (Inventor); Kindler, Andrew (Inventor); Prakash, G.K. Surya (Inventor)

2014-01-01

Embodiments include an iron-air rechargeable battery having a composite electrode including an iron electrode and a hydrogen electrode integrated therewith. An air electrode is spaced from the iron electrode and an electrolyte is provided in contact with the air electrode and the iron electrodes. Various additives and catalysts are disclosed with respect to the iron electrode, air electrode, and electrolyte for increasing battery efficiency and cycle life.

Method of determining methane and electrochemical sensor therefor

DOEpatents

Zaromb, Solomon; Otagawa, Takaaki; Stetter, Joseph R.

1986-01-01

A method and instrument including an electrochemical cell for the detection and measurement of methane in a gas by the oxidation of methane electrochemically at a working electrode in a nonaqueous electrolyte at a voltage about about 1.4 volts versus R.H.E. (the reversible hydrogen electrode potential in the same electrolyte), and the measurement of the electrical signal resulting from the electrochemical oxidation.

Modification of the surface adsorption properties of alumina-supported Pd catalysts for the electrocatalytic hydrogenation of phenol.

PubMed

Cirtiu, Ciprian Mihai; Hassani, Hicham Oudghiri; Bouchard, Nicolas-Alexandre; Rowntree, Paul A; Ménard, Hugues

2006-07-04

The electrocatalytic hydrogenation (ECH) of phenol has been studied using palladium supported on gamma-alumina (10% Pd-Al2O3) catalysts. The catalyst powders were suspended in aqueous supporting electrolyte solutions containing methanol and short-chain aliphatic acids (acetic acid, propionic acid, or butyric acid) and were dynamically circulated through a reticulated vitreous carbon cathode. The efficiency of the hydrogenation process was measured as a function of the total electrolytic charge and was compared for different types of supporting electrolyte and for various solvent compositions. Our results show that these experimental parameters strongly affect the overall ECH efficiency of phenol. The ECH efficiency and yields vary inversely with the quantity of methanol present in the electrolytic solutions, whereas the presence of aliphatic carboxylic acids increased the ECH efficiency in proportion to the chain length of the specific acids employed. In all cases, ECH efficiency was directly correlated with the adsorption properties of phenol onto the Pd-alumina catalyst in the studied electrolyte solution, as measured independently using dynamic adsorption isotherms. It is shown that the alumina surface binds the aliphatic acids via the carboxylate terminations and transforms the catalyst into an organically functionalized material. Temperature-programmed mass spectrometry analysis and diffuse-reflectance infrared spectroscopy measurements confirm that the organic acids are stably bound to the alumina surface below 200 degrees C, with coverages that are independent of the acid chain length. These reproducibly functionalized alumina surfaces control the adsorption/desorption equilibrium of the target phenol molecules and allow us to prepare new electrocatalytic materials to enhance the efficiency of the ECH process. The in situ grafting of specific aliphatic acids on general purpose Pd-alumina catalysts offers a new and flexible mechanism to control the ECH process to enhance the selectivity, efficiency, and yields according to the properties of the specific target molecule.

Chemically durable polymer electrolytes for solid-state alkaline water electrolysis

NASA Astrophysics Data System (ADS)

Park, Eun Joo; Capuano, Christopher B.; Ayers, Katherine E.; Bae, Chulsung

2018-01-01

Generation of high purity hydrogen using electrochemical splitting of water is one of the most promising methods for sustainable fuel production. The materials to be used as solid-state electrolytes for alkaline water electrolyzer require high thermochemical stability against hydroxide ion attack in alkaline environment during the operation of electrolysis. In this study, two quaternary ammonium-tethered aromatic polymers were synthesized and investigated for anion exchange membrane (AEM)-based alkaline water electrolyzer. The membranes properties including ion exchange capacity (IEC), water uptake, swelling degree, and anion conductivity were studied. The membranes composed of all C-C bond polymer backbones and flexible side chain terminated by cation head groups exhibited remarkably good chemical stability by maintaining structural integrity in 1 M NaOH solution at 95 °C for 60 days. Initial electrochemical performance and steady-state operation performance were evaluated, and both membranes showed a good stabilization of the cell voltage during the steady-state operation at the constant current density at 200 mA/cm2. Although both membranes in current form require improvement in mechanical stability to afford better durability in electrolysis operation, the next generation AEMs based on this report could lead to potentially viable AEM candidates which can provide high electrolysis performance under alkaline operating condition.

CO2-Free Power Generation on an Iron Group Nanoalloy Catalyst via Selective Oxidation of Ethylene Glycol to Oxalic Acid in Alkaline Media

NASA Astrophysics Data System (ADS)

Matsumoto, Takeshi; Sadakiyo, Masaaki; Ooi, Mei Lee; Kitano, Sho; Yamamoto, Tomokazu; Matsumura, Syo; Kato, Kenichi; Takeguchi, Tatsuya; Yamauchi, Miho

2014-07-01

An Fe group ternary nanoalloy (NA) catalyst enabled selective electrocatalysis towards CO2-free power generation from highly deliverable ethylene glycol (EG). A solid-solution-type FeCoNi NA catalyst supported on carbon was prepared by a two-step reduction method. High-resolution electron microscopy techniques identified atomic-level mixing of constituent elements in the nanoalloy. We examined the distribution of oxidised species, including CO2, produced on the FeCoNi nanoalloy catalyst in the EG electrooxidation under alkaline conditions. The FeCoNi nanoalloy catalyst exhibited the highest selectivities toward the formation of C2 products and to oxalic acid, i.e., 99 and 60%, respectively, at 0.4 V vs. the reversible hydrogen electrode (RHE), without CO2 generation. We successfully generated power by a direct EG alkaline fuel cell employing the FeCoNi nanoalloy catalyst and a solid-oxide electrolyte with oxygen reduction ability, i.e., a completely precious-metal-free system.

Hydrogen depolarized carbon dioxide concentrator performance improvements and cell pair structural tests. [for manned space station

NASA Technical Reports Server (NTRS)

Huddleston, J. D.; Aylward, J. R.

1973-01-01

The investigations and testing associated with the CO2 removal efficiency and voltage degradation of a hydrogen depolarized carbon oxide concentrator are reported. Also discussed is the vibration testing of a water vapor electrolysis cell pair. Performance testing of various HDC cell pairs with Cs2CO3 electrolyte provided sufficient parametric and endurance data to size a six man space station prototype CO2 removal system as having 36 HDC cell pairs, and to verify a life capability exceeding six moths. Testing also demonstrated that tetramethylammonium carbonate is an acceptable HDC electrolyte for operating over the relative humidity range of 30 to 90 percent and over a temperature range of 50 to 80 F.

Process for electrochemically gasifying coal

DOEpatents

Botts, T.E.; Powell, J.R.

1985-10-25

A process is claimed for electrochemically gasifying coal by establishing a flowing stream of coal particulate slurry, electrolyte and electrode members through a transverse magnetic field that has sufficient strength to polarize the electrode members, thereby causing them to operate in combination with the electrolyte to electrochemically reduce the coal particulate in the slurry. Such electrochemical reduction of the coal produces hydrogen and carbon dioxide at opposite ends of the polarized electrode members. Gas collection means are operated in conjunction with the process to collect the evolved gases as they rise from the slurry and electrolyte solution. 7 figs.

Performance of fuel cell for energy supply of passive house

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

Badea, G.; Felseghi, R. A., E-mail: Raluca.FELSEGHI@insta.utcluj.ro; Mureşan, D.

2015-12-23

Hydrogen technology and passive house represent two concepts with a remarkable role for the efficiency and decarbonisation of energy systems in the residential buildings area. Through design and functionality, the passive house can make maximum use of all available energy resources. One of the solutions to supply energy of these types of buildings is the fuel cell, using this technology integrated into a system for generating electricity from renewable primary sources, which take the function of backup power (energy reserve) to cover peak load and meteorological intermittents. In this paper is presented the results of the case study that providemore » an analysis of the energy, environmental and financial performances regarding energy supply of passive house by power generation systems with fuel cell fed with electrolytic hydrogen produced by harnessing renewable energy sources available. Hybrid systems have been configured and operate in various conditions of use for five differentiated locations according to the main areas of solar irradiation from the Romanian map. Global performance of hybrid systems is directly influenced by the availability of renewable primary energy sources - particular geo-climatic characteristics of the building emplacement.« less

Amperometric detector for gas chromatography based on a silica sol-gel solid electrolyte.

PubMed

Steinecker, William H; Miecznikowski, Krzysztof; Kulesza, Pawel J; Sandlin, Zechariah D; Cox, James A

2017-11-01

An electrochemical cell comprising a silica sol-gel solid electrolyte, a working electrode that protrudes into a gas phase, and reference and counter electrodes that contact the solid electrolyte comprises an amperometric detector for gas chromatography. Under potentiostatic conditions, a current related to the concentration of an analyte in the gas phase is produced by its oxidation at the three-phase boundary among the sol-gel, working electrode, and the gas phase. The sol-gel is processed to contain an electrolyte that also serves as a humidistat to maintain a constant water activity even in the presence the gas chromatographic mobile phase. Response was demonstrated toward a diverse set of analytes, namely hydrogen, 1,2-ethandithiol, phenol, p-cresol, and thioanisole. Using flow injection amperometry of hydrogen with He as the carrier gas, 90% of the steady-state current was achieved in < 1s at a flow rate of 20mLmin -1 . A separation of 1,2-ethandithiol, phenol, p-cresol, and thioanisole at a 2.2mLmin -1 flow rate was achieved with respective detection limits (k = 3 criterion) of 4, 1, 3, and 70 ppmv when the working electrode potential was 800mV. Copyright © 2017 Elsevier B.V. All rights reserved.

NaTi2(PO4)3 as an Aqueous Anode: Degradation Mechanisms and Mitigation Techniques

NASA Astrophysics Data System (ADS)

Mohamed, Alexander I.

With the proliferation of renewable energy sources, there has been a growing interest in battery chemistries for grid scale energy storage. Aqueous sodium ion batteries are particularly interesting for large scale energy storage because of their low cost and high safety, however, they tend to show poor long term stability. NaTi2(PO4)3 (NTP) shows promise as an anode for these systems with excellent long term stability when cycled quickly. When cycled slowly, NaTi2(PO4) 3 shows rapid capacity fade. The reasons for this rate depend capacity fade is poorly understood and is the topic of this document. It has been found that the products of the hydrogen evolution reaction, H2(g) and OH-, are the two largest contributors to capacity fade. High electrolyte pH caused by generation of OH- promotes dissolution of NTP during extend cycling, this is exacerbated when the pH increase above 11. The single greatest cause of apparent capacity fade for this material is loss of electrochemical surface area due to hydrogen gas entrapment within the porous structure of the electrode. Capacity lost in this manner can be recovered through reinfiltration of the electrode. The detrimental effects of gas entrapment within the electrode can be partially mitigated through compositing of the electrode with activated carbon and enhancing the wettability of the pores through addition of a surfactant to the electrolyte.

Thermal Design for Extra-Terrestrial Regenerative Fuel Cell System

NASA Technical Reports Server (NTRS)

Gilligan, R.; Guzik, M.; Jakupca, I.; Bennett, W.; Smith, P.; Fincannon, J.

2017-01-01

The Advanced Exploration Systems (AES) Advanced Modular Power Systems (AMPS) Project is investigating different power systems for various lunar and Martian mission concepts. The AMPS Fuel Cell (FC) team has created two system-level models to evaluate the performance of regenerative fuel cell (RFC) systems employing different fuel cell chemistries. Proton Exchange Membrane fuel cells PEMFCs contain a polymer electrolyte membrane that separates the hydrogen and oxygen cavities and conducts hydrogen cations (protons) across the cell. Solid Oxide fuel cells (SOFCs) operate at high temperatures, using a zirconia-based solid ceramic electrolyte to conduct oxygen anions across the cell. The purpose of the modeling effort is to down select one fuel cell chemistry for a more detailed design effort. Figures of merit include the system mass, volume, round trip efficiency, and electrolyzer charge power required. PEMFCs operate at around 60 C versus SOFCs which operate at temperatures greater than 700 C. Due to the drastically different operating temperatures of the two chemistries the thermal control systems (TCS) differ. The PEM TCS is less complex and is characterized by a single pump cooling loop that uses deionized water coolant and rejects heat generated by the system to the environment via a radiator. The solid oxide TCS has its own unique challenges including the requirement to reject high quality heat and to condense the steam produced in the reaction. This paper discusses the modeling of thermal control systems for an extraterrestrial RFC that utilizes either a PEM or solid oxide fuel cell.

Component variations and their effects on bipolar nickel-hydrogen cell performance

NASA Technical Reports Server (NTRS)

Manzo, Michelle A.; Gahn, Randall F.; Gonzalez-Sanabria, Olga D.; Cataldo, Robert L.; Gemeiner, Russel P.

1987-01-01

A 50 cell bipolar nickel-hydrogen battery was assembled to demonstrate the feasibility of constructing a high voltage stack of cells. Various component combinations were tested in this battery. The battery had approximately 1 ampere-hour of capacity and was constructed from components with an active area of 2 x 2 inches. The components were parametrically varied to give a comparison of nickel electrodes, hydrogen electrodes, separators, fill procedures and electrolyte reservoir plate thicknesses. Groups of five cells were constructed using the same components; ten combinations were tested in all. The battery was thoroughly characterized at various change and discharge rates as well as with various pulse patterns and rates. Over a period of 1400 40-percent DOD LEO cycles some of the groups began to exhibit performance differences. In general, only separator variations had a significant effect on cell performance. It also appears that shunt currents may have been operating within the stack, resulting in electrolyte transfer from one cell to another, thus contributing to cell performance variations.

Component variations and their effects on bipolar nickel-hydrogen cell performance

NASA Technical Reports Server (NTRS)

Manzo, Michelle A.; Gahn, Randall F.; Gonzalez-Sanabria, Olga D.; Cataldo, Robert L.; Gemeiner, Russel P.

1987-01-01

A 50 cell bipolar nickel-hydrogen battery was assembled to demonstrate the feasibility of constructing a high voltage stack of cells. Various component combinations were tested in this battery. The battery had approximately 1 ampere-hour of capacity and was constructed from components with an active area of 2" X 2". The components were parametrically varied to give a comparison of nickel electrodes, hydrogen electrodes, separators, fill procedures and electrolyte reservoir plate thicknesses. Groups of five cells were constructed using the same components; ten combinations were tested in all. The battery was thoroughly characterized at various change and discharge rates as well as with various pulse patterns and rates. Over a period of 1400 40% DOD LEO cycles some of the groups began to exhibit performance differences. In general, only separator variations had a significant effect on cell performance. It also appears that shunt currents may have been operating within the stack, resulting in electrolyte transfer from one cell to another, thus contributing to cell performance variations.

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

Dispatchable hydrogen production at the forecourt for electricity grid balancing

NASA Astrophysics Data System (ADS)

Rahil, Abdulla; Gammon, Rupert; Brown, Neil

2017-02-01

The rapid growth of renewable energy (RE) generation and its integration into electricity grids has been motivated by environmental issues and the depletion of fossil fuels. For the same reasons, an alternative to hydrocarbon fuels is needed for vehicles; hence the anticipated uptake of electric and fuel cell vehicles. High penetrations of RE generators with variable and intermittent output threaten to destabilise electricity networks by reducing the ability to balance electricity supply and demand. This can be greatly mitigated by the use of energy storage and demand-side response (DSR) techniques. Hydrogen production by electrolysis is a promising option for providing DSR as well as an emission-free vehicle fuel. Tariff structures can be used to incentivise the operating of electrolysers as controllable (dispatchable) loads. This paper compares the cost of hydrogen production by electrolysis at garage forecourts under both dispatchable and continuous operation, while ensuring no interruption of fuel supply to fuel cell vehicles. An optimisation algorithm is applied to investigate a hydrogen refueling station in both dispatchable and continuous operation. Three scenarios are tested to see whether a reduced off-peak electricity price could lower the cost of electrolytic hydrogen. These scenarios are: 1) "Standard Continuous", where the electrolyser is operated continuously on a standard all-day tariff of 12p/kWh; 2) "Off-peak Only", where it runs only during off-peak periods in a 2-tier tariff system at the lower price of 5p/kWh; and 3) "2-Tier Continuous", operating continuously and paying a low tariff at off- peak times and a high tariff at other times. This study uses the Libyan coastal city of Derna as a case study. The cheapest electricity cost per kg of hydrogen produced was £2.8, which occurred in Scenario 2. The next cheapest, at £5.8 - £6.3, was in Scenario 3, and the most expensive was £6.8/kg in Scenario 1.

Kinetic Characteristics of Hydrogen Transfer Through Palladium-Modified Membrane

NASA Astrophysics Data System (ADS)

Petriev, I. S.; Frolov, V. Yu.; Bolotin, S. N.; Baryshev, M. G.; Kopytov, G. F.

2018-01-01

The paper deals with hydrogen transfer through Pd-23%Ag alloy membrane, the surface of which is modified by the electrolytic deposition of highly dispersed palladium. The dependence between the density of hydrogen flow and its excess pressure on the input surface of membrane is well approximated by the first-order curve. This fact indicates that the process of hydrogen permeability is defined by its dissociation on the input surface. Activation energy of this process is 47.9 kJ/mol which considerably exceeds that of the process of hydrogen transfer through palladium (22-30 kJ/mol). This confirms the fact that the chemisorption is a rate-controlling step of the hydrogen transfer through membrane.

Hydrogen as an energy medium

NASA Technical Reports Server (NTRS)

Cox, K. E.

1976-01-01

Coal, though abundant in certain geographical locations of the USA poses environmental problems associated with its mining and combustion. Also, nuclear fission energy appears to have problems regarding safety and radioactive waste disposal that are as yet unresolved. The paper discusses hydrogen use and market projection along with energy sources for hydrogen production. Particular attention is given to hydrogen production technology as related to electrolysis and thermochemical water decomposition. Economics of hydrogen will ultimately be determined by the price and availability of future energy carriers such as electricity and synthetic natural gas. Thermochemical methods of hydrogen production appear to offer promise largely in the efficiency of energy conversion and in capital costs over electrolytic methods.

Separation and/or sequestration apparatus and methods

DOEpatents

Rieke, Peter C; Towne, Silas A; Coffey, Greg W; Appel, Aaron M

2015-02-03

Apparatus for separating CO.sub.2 from an electrolyte solution are provided. Example apparatus can include: a vessel defining an interior volume and configured to house an electrolyte solution; an input conduit in fluid communication with the interior volume; an output conduit in fluid communication with the interior volume; an exhaust conduit in fluid communication with the interior volume; and an anode located within the interior volume. Other example apparatus can include: an elongated vessel having two regions; an input conduit extending outwardly from the one region; an output conduit extending outwardly from the other region; an exhaust conduit in fluid communication with the one region; and an anode located within the one region. Methods for separating CO.sub.2 from an electrolyte solution are provided. Example methods can include: providing a CO.sub.2 rich electrolyte solution to a vessel containing an anode; and distributing hydrogen from the anode to acidify the electrolyte solution.

Characteristics and performance of lanthanum gallate electrolyte-supported SOFC under ethanol steam and hydrogen

NASA Astrophysics Data System (ADS)

Huang, Bo; Zhu, Xin-Jian; Hu, Wan-Qi; Yu, Qing-Chun; Tu, Heng-Yong

This study is focused on the electrochemical performance of perovskite-type materials based on doped LaGaO 3. La 0.8Sr 0.2Ga 0.8Mg 0.2O 3- δ (LSGM) and La 0.8Sr 0.2Ga 0.8Mg 0.115Co 0.085O 3- δ (LSGMC) were used as electrolytes and (Pr 0.7Ca 0.3) 0.9MnO 3 (PCM) and La 0.75Sr 0.25Cr 0.5Mn 0.5O 3- δ (LSCM) as cathode and anode material, respectively. LSGM and LSGMC electrolytes were prepared by tape casting with a thickness of about 600 μm. The performance of LSCM/LSGMC/PCM was slightly superior to that obtained on LSCM/LSGM/PCM at different temperatures in both humidified hydrogen and ethanol steam atmospheres, good values of power output in LSCM/LSGMC/PCM were 182 and 169 mW cm -2 using humidified hydrogen and ethanol steam as fuel, respectively, and oxygen as oxidant at 850 °C. Cell stability tests indicate no significant degradation in performance after 60 h of cell testing when LSCM anode was exposed to ethanol steam at 750 °C. Almost no carbon deposits were detected after testing in ethanol steam at 750 °C for >60 h on the LSCM anodes, suggesting that carbon deposition was limited during cell operation.

The molecular basis of the solution properties of hyaluronan investigated by confocal fluorescence recovery after photobleaching.

PubMed Central

Gribbon, P; Heng, B C; Hardingham, T E

1999-01-01

Hyaluronan (HA) is a highly hydrated polyanion, which is a network-forming and space-filling component in the extracellular matrix of animal tissues. Confocal fluorescence recovery after photobleaching (confocal-FRAP) was used to investigate intramolecular hydrogen bonding and electrostatic interactions in hyaluronan solutions. Self and tracer lateral diffusion coefficients within hyaluronan solutions were measured over a wide range of concentrations (c), with varying electrolyte and at neutral and alkaline pH. The free diffusion coefficient of fluoresceinamine-labeled HA of 500 kDa in PBS was 7.9 x 10(-8) cm(2) s(-1) and of 830 kDa HA was 5.6 x 10(-8) cm(2) s(-1). Reductions in self- and tracer-diffusion with c followed a stretched exponential model. Electrolyte-induced polyanion coil contraction and destiffening resulted in a 2.8-fold increase in self-diffusion between 0 and 100 mM NaCl. Disruption of hydrogen bonds by strong alkali (0.5 M NaOH) resulted in further larger increases in self- and tracer-diffusion coefficients, consistent with a more dynamic and permeable network. Concentrated hyaluronan solution properties were attributed to hydrodynamic and entanglement interactions between domains. There was no evidence of chain-chain associations. At physiological electrolyte concentration and pH, the greatest contribution to the intrinsic stiffness of hyaluronan appeared to be due to hydrogen bonds between adjacent saccharides. PMID:10512840

Hydrogen dissolution in palladium: A resistometric study under pressure

NASA Astrophysics Data System (ADS)

Magnouche, A.; Fromageau, R.

1984-09-01

The hydrogen solubility in palladium in equilibrium with H2 gas has been measured, between room temperature and 540 °C, using a resistometric method, for pressures ranging between 0.01 and 10 MPa. In these conditions, the experimentally determined values of the solubility and of the dissolution enthalpy exhibit very close agreement with those obtained by other methods (calorimetry, volumetry, etc.), or after electrolytic charging. This good agreement demonstrates the validity of the resistometric method for determination of the solubility of hydrogen in metals.

A thermodynamic description for water, hydrogen fluoride and hydrogen dissolutions in cryolite-base molten salts.

PubMed

Wang, Kun; Chartrand, Patrice

2018-06-15

This paper presents a quantitative thermodynamic description for water, hydrogen fluoride and hydrogen dissolutions in cryolite-base molten salts, which is of technological importance to the Hall-Héroult electrolytic aluminum extraction cell. The Modified Quasichemical Model in the Quadruplet Approximation (MQMQA), as used to treat a large variety of molten salt systems, was adopted to thermodynamically describe the present liquid phase; all solid solutions were modeled using the Compound Energy Formalism (CEF); the gas phase was thermodynamically treated as an ideal mixture of all possible species. The model parameters were mainly obtained by critical evaluations and optimizations of thermodynamic and phase equilibrium data available from relative experimental measurements and theoretical predictions (first-principles calculations and empirical estimations) for the lower-order subsystems. These optimized model parameters were thereafter merged within the Kohler/Toop interpolation scheme, facilitating the prediction of gas solubility (H2O, HF and H2) in multicomponent cryolite-base molten salts using the FactSage thermochemical software. Several interesting diagrams were finally obtained in order to provide useful information for the industrial partners dedicated to the Hall-Héroult electrolytic aluminum production or other molten-salt technologies (the purification process and electroslag refining).

Functionalization of super-aligned carbon nanotube film using hydrogen peroxide solution and its application in copper electrodeposition.

PubMed

Xiong, Lunqiao; Shuai, Jing; Hou, Zecheng; Zhu, Lin; Li, Wenzhen

2017-07-15

In order to make super-aligned carbon nanotubes (SACNT) homogeneously spread in electrolytes, a swift and effective method was devised for surface functionalization of SACNT film by ohmic heating using hydrogen peroxide solution. Controllable generation of defects and notable graft of oxygen functional groups on the sidewall of SACNTs were induced as proven by X-ray photoelectron spectroscopy and Raman spectroscopy. Differently from the harsh wet chemical oxidation, the super-aligned morphology and structural integrity of carbon nanotubes in the SACNT film were found to be well preserved by electron microscopy analysis. The functionalized treatment can remove extraneous material contaminating SACNT film and improve its conductivity. The grafting of polar ionizable groups has been proved to effectively eliminate the agglomeration of SACNTs. When the oxidized SACNT film was used as host material for electrodeposition of copper, the composite film of well-bonded SACNTs and Cu was successfully prepared. Copyright © 2017 Elsevier Inc. All rights reserved.

Photocurrent Enhancement by a Rapid Thermal Treatment of Nanodisk-Shaped SnS Photocathodes.

PubMed

Patel, Malkeshkumar; Kumar, Mohit; Kim, Joondong; Kim, Yu Kwon

2017-12-21

Photocathodes made from the earth-abundant, ecofriendly mineral tin monosulfide (SnS) can be promising candidates for p/n-type photoelectrochemical cells because they meet the strict requirements of energy band edges for each individual photoelectrode. Herein we fabricated SnS-based cell that exhibited a prolonged photocurrent for 3 h at -0.3 V vs the reversible hydrogen electrode (RHE) in a 0.1 M HCl electrolyte. An enhancement of the cathodic photocurrent from 2 to 6 mA cm -2 is observed through a rapid thermal treatment. Mott-Schottky analysis of SnS samples revealed an anodic shift of 0.7 V in the flat band potential under light illumination. Incident photon-to-current conversion efficiency (IPCE) analysis indicates that an efficient charge transfer appropriate for solar hydrogen generation occurs at the -0.3 V vs RHE potential. This work shows that SnS is a promising material for photocathode in PEC cells and its performance can be enhanced via simple postannealing.

Analysis of Ni-HYDRIDE Thin Film after Surface Plasmon Generation by Laser Technique

NASA Astrophysics Data System (ADS)

Violante, V.; Castagna, E.; Sibilia, C.; Paoloni, S.; Sarto, F.

2005-12-01

A nickel hydride thin film was studied by the attenuated total reflection method. The differences in behavior between a "black" film, and a pure nickel film "blank," are shown. The black nickel hydride film has been obtained by a short electrolysis with 1 M Li2SO4 electrolyte in light water, A shift in the minimum of the observed reflected light occurs, together with a change in the minimum shape (i.e. its half-height width increases). These two phenomenon are due to the change in the electronic band structure of the metal induced by electrons added to the lattice by hydrogen. The change of the electronic structure, revealed by the laser coupling conditions, leads us to consider that a hydride phase was created. Both the blank (not hydrogenated) and black (hydrogenated) specimens were taken under He-Ne laser beam at the reflectance minimum angle for about three hours. A SIMS analysis was also implemented to reveal differences in the isotopic composition of Cu, as marker element between the blank and black films, in order to study the coupled effect of electrolysis and plasmon-polariton excitation on LENR processes in condensed matter.

Dynamic Photoelectrochemical Device Using an Electrolyte-Permeable NiO x/SiO2/Si Photocathode with an Open-Circuit Potential of 0.75 V.

PubMed

Jung, Jin-Young; Yu, Jin-Young; Lee, Jung-Ho

2018-03-07

As a thermodynamic driving force obtained from sunlight, the open-circuit potential (OCP) in photoelectrochemical cells is typically limited by the photovoltage ( V ph ). In this work, we establish that the OCP can exceed the value of V ph when an electrolyte-permeable NiO x thin film is employed as an electrocatalyst in a Si photocathode. The built-in potential developed at the NiO x /Si junction is adjusted in situ according to the progress of the NiO x hydration for the hydrogen evolution reaction (HER). As a result of decoupling of the OCP from V ph , a high OCP value of 0.75 V (vs reversible hydrogen electrode) is obtained after 1 h operation of HER in an alkaline electrolyte (pH = 14), thus outperforming the highest value (0.64 V) reported to date with conventional Si photoelectrodes. This finding might offer insight into novel photocathode designs such as those based on tandem water-splitting systems.

Ammonium Additives to Dissolve Lithium Sulfide through Hydrogen Binding for High-Energy Lithium-Sulfur Batteries.

PubMed

Pan, Huilin; Han, Kee Sung; Vijayakumar, M; Xiao, Jie; Cao, Ruiguo; Chen, Junzheng; Zhang, Jiguang; Mueller, Karl T; Shao, Yuyan; Liu, Jun

2017-02-08

In rechargeable Li-S batteries, the uncontrollable passivation of electrodes by highly insulating Li 2 S limits sulfur utilization, increases polarization, and decreases cycling stability. Dissolving Li 2 S in organic electrolyte is a facile solution to maintain the active reaction interface between electrolyte and sulfur cathode, and thus address the above issues. Herein, ammonium salts are demonstrated as effective additives to promote the dissolution of Li 2 S to 1.25 M in DMSO solvent at room temperature. NMR measurements show that the strong hydrogen binding effect of N-H groups plays a critical role in dissolving Li 2 S by forming complex ligands with S 2- anions coupled with the solvent's solvating surrounding. Ammonium additives in electrolyte can also significantly improve the oxidation kinetics of Li 2 S, and therefore enable the direct use of Li 2 S as cathode material in Li-S battery system in the future. This provides a new approach to manage the solubility of lithium sulfides through cation coordination with sulfide anion.

Ammonium Additives to Dissolve Lithium Sulfide through Hydrogen Binding for High-Energy Lithium–Sulfur Batteries

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

Pan, Huilin; Han, Kee Sung; Vijayakumar, M.

In rechargeable Li-S batteries, the uncontrollable passivation of electrodes by highly insulating Li2S limits sulfur utilization, increases polarization and decreases cycling stability. Dissolving Li2S in organic electrolyte is a facile solution to maintain the active reaction interface between electrolyte and sulfur cathode, and thus address the above issues. Herein, ammonium salts are demonstrated as effective additives to promote the dissolution of Li2S to 1.25 M in DMSO solvent at room temperature. NMR measurements show that the strong hydrogen binding effect of N-H groups plays a critical role in dissolving Li2S by forming complex ligands with S2- anions coupled with themore » solvent’s solvating surrounding. Ammonium additives in electrolyte can also significantly improve the oxidation kinetics of Li2S, therefore enables the direct use of Li2S as cathode material in Li-S battery system in the future. This provides a new approach to manage the solubility of lithium sulfides through cation coordination with sulfide anion.« less

Critical Research for Cost-Effective Photoelectrochemical Production of Hydrogen

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

Xu, Liwei; Deng, Xunming; Abken, Anka

2014-10-29

The objective of this project is to develop critical technologies required for cost-effective production of hydrogen from sunlight and water using a-Si triple junction solar cell based photo-electrodes. In this project, Midwest Optoelectronics, LLC (MWOE) and its collaborating organizations utilize triple junction a-Si thin film solar cells as the core element to fabricate photoelectrochemical (PEC) cells. Triple junction a-Si/a-SiGe/a-SiGe solar cell is an ideal material for making cost-effective PEC system which uses sun light to split water and generate hydrogen. It has the following key features: 1) It has an open circuit voltage (Voc ) of ~ 2.3V and hasmore » an operating voltage around 1.6V. This is ideal for water splitting. There is no need to add a bias voltage or to inter-connect more than one solar cell. 2) It is made by depositing a-Si/a-SiGe/aSi-Ge thin films on a conducting stainless steel substrate which can serve as an electrode. When we immerse the triple junction solar cells in an electrolyte and illuminate it under sunlight, the voltage is large enough to split the water, generating oxygen at the Si solar cell side (for SS/n-i-p/sunlight structure) and hydrogen at the back, which is stainless steel side. There is no need to use a counter electrode or to make any wire connection. 3) It is being produced in large rolls of 3ft wide and up to 5000 ft long stainless steel web in a 25MW roll-to-roll production machine. Therefore it can be produced at a very low cost. After several years of research with many different kinds of material, we have developed promising transparent, conducting and corrosion resistant (TCCR) coating material; we carried out extensive research on oxygen and hydrogen generation catalysts, developed methods to make PEC electrode from production-grade a-Si solar cells; we have designed and tested various PEC module cases and carried out extensive outdoor testing; we were able to obtain a solar to hydrogen conversion efficiency (STH) about 5.7% and a running time about 480 hrs, which are very promising results; we have also completed a techno-economic analysis of our PEC system, which indicates that a projected hydrogen generation cost of $2/gge is achievable with a 50 Ton-per-day (TPD) scale under certain conditions.« less

Real-time imaging, spectroscopy, and structural investigation of cathodic plasma electrolytic oxidation of molybdenum

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

Stojadinović, Stevan, E-mail: sstevan@ff.bg.ac.rs; Tadić, Nenad; Šišović, Nikola M.

2015-06-21

In this paper, the results of the investigation of cathodic plasma electrolytic oxidation (CPEO) of molybdenum at 160 V in a mixed solution of borax, water, and ethylene glycol are presented. Real-time imaging and optical emission spectroscopy were used for the characterization of the CPEO. During the process, vapor envelope is formed around the cathode and strong electric field within the envelope caused the generation of plasma discharges. The spectral line shape analysis of hydrogen Balmer line H{sub β} (486.13 nm) shows that plasma discharges are characterized by the electron number density of about 1.4 × 10{sup 21 }m{sup −3}. The electron temperaturemore » of 15 000 K was estimated by measuring molybdenum atomic lines intensity. Surface morphology, chemical, and phase composition of coatings formed by CPEO were characterized by scanning electron microscopy with energy dispersive x-ray spectroscopy and x-ray diffraction. The elemental components of CPEO coatings are Mo and O and the predominant crystalline form is MoO{sub 3}.« less

In situ S-K XANES study of polymer electrolyte fuel cells: changes in the chemical states of sulfonic groups depending on humidity.

PubMed

Isegawa, Kazuhisa; Nagami, Tetsuo; Jomori, Shinji; Yoshida, Masaaki; Kondoh, Hiroshi

2016-09-14

Changes in the chemical states of sulfonic groups of Nafion in polymer electrolyte fuel cells (PEFCs) under gas-flowing conditions were studied using in situ S-K XANES spectroscopy. The applied potential to the electrodes and the humidity of the cell were changed under flowing H 2 gas in the anode and He gas in the cathode. While the potential shows no significant effect on the S-K XANES spectra, the humidity is found to induce reversible changes in the spectra. Comparison of the spectral changes with simulations based on the density functional theory calculations indicates that the humidity influences the chemical state of the sulfonic group; under wet conditions the sulfonic group is in the form of a sulfonate ion. By drying treatment the sulfonate ion binds to hydrogen and becomes sulfonic acid. Furthermore, a small fraction of the sulfonic acid irreversibly decomposes to atomic sulfur. The peak energy of the atomic sulfur suggests that the generated atomic sulfur is adsorbed on the Pt catalyst surfaces.

Atomic Layer Deposition of Bismuth Vanadates for Solar Energy Materials.

PubMed

Stefik, Morgan

2016-07-07

The fabrication of porous nanocomposites is key to the advancement of energy conversion and storage devices that interface with electrolytes. Bismuth vanadate, BiVO4 , is a promising oxide for solar water splitting where the controlled fabrication of BiVO4 layers within porous, conducting scaffolds has remained a challenge. Here, the atomic layer deposition of bismuth vanadates is reported from BiPh3 , vanadium(V) oxytriisopropoxide, and water. The resulting films have tunable stoichiometry and may be crystallized to form the photoactive scheelite structure of BiVO4 . A selective etching process was used with vanadium-rich depositions to enable the synthesis of phase-pure BiVO4 after spinodal decomposition. BiVO4 thin films were measured for photoelectrochemical performance under AM 1.5 illumination. The average photocurrents were 1.17 mA cm(-2) at 1.23 V versus the reversible hydrogen electrode using a hole-scavenging sulfite electrolyte. The capability to deposit conformal bismuth vanadates will enable a new generation of nanocomposite architectures for solar water splitting. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrolytic hydriding of LaFe(13-x)Si(x) alloys for energy efficient magnetic cooling.

PubMed

Lyubina, Julia; Hannemann, Ullrich; Ryan, Mary P; Cohen, Lesley F

2012-04-17

An effective, low-temperature and readily available electrochemical method for tuning the operation temperature of LaFe(13-x)Si(x)-type alloys is demonstrated. Electrolytically hydrided materials have the same high level magnetic properties as in high temperature gas-phase processed materials and offer an advantage of higher hydrogen absorption rate in the ferromagnetic state. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The effect of hydrogen on the parameters of plastic deformation localization in low carbon steel

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

Lunev, Aleksey G., E-mail: agl@ispms.tsc.ru, E-mail: nadjozhkin@ispms.tsc.ru; Nadezhkin, Mikhail V., E-mail: agl@ispms.tsc.ru, E-mail: nadjozhkin@ispms.tsc.ru; Shlyakhova, Galina V., E-mail: shgv@ispms.tsc.ru

2014-11-14

In the present study, the effect of interstitial hydrogen atoms on the mechanical properties and plastic strain localization patterns in tensile tested polycrystals of low-carbon steel Fe-0.07%C has been studied using double exposure speckle photography technique. The main parameters of plastic flow localization at various stages of deformation hardening have been determined in polycrystals of steel electrolytically saturated with hydrogen in a three-electrode electrochemical cell at a controlled constant cathode potential. Also, the effect of hydrogen on changing of microstructure by using optical microscopy has been demonstrated.

Modelling heterogeneous interfaces for solar water splitting

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

Pham, Tuan Anh; Ping, Yuan; Galli, Giulia

2017-01-09

The generation of hydrogen from water and sunlight others a promising approach for producing scalable and sustainable carbon-free energy. The key of a successful solar-to-fuel technology is the design of efficient, long-lasting and low-cost photoelectrochemical cells, which are responsible for absorbing sunlight and driving water splitting reactions. To this end, a detailed understanding and control of heterogeneous interfaces between photoabsorbers, electrolytes and catalysts present in photoelectrochemical cells is essential. Here we review recent progress and open challenges in predicting physicochemical properties of heterogeneous interfaces for solar water splitting applications using first-principles-based approaches, and highlights the key role of these calculationsmore » in interpreting increasingly complex experiments.« less

The influence of electrolyte additives on the anodic dissolution of aluminum in alkaline solutions

NASA Astrophysics Data System (ADS)

Boehnstedt, W.

1980-09-01

The paper describes the effect of electrolyte additives on the anodic dissolution of aluminum in alkaline solutions. The dissolution is accelerated by the addition of small quantities of gallium or indium ions to the electrolyte indicated by the shift of the zero current potential by about 250 mV on the current-potential curve. Scanning electron microscope studies showed that gallium ions produce many small cracks in the aluminum electrode and collect at the grain boundary areas, increasing the electrode surface; this enlargement, in combination with increased electrolyte agitation due to greater hydrogen evolution, provides higher current densities at the same potential. It is concluded that this process will widen the possibilities of using aluminum and its alloys in high-rate batteries.

In Situ Analysis of Gas Generation in Lithium-Ion Batteries with Different Carbonate-Based Electrolytes.

PubMed

Teng, Xin; Zhan, Chun; Bai, Ying; Ma, Lu; Liu, Qi; Wu, Chuan; Wu, Feng; Yang, Yusheng; Lu, Jun; Amine, Khalil

2015-10-21

Gas generation in lithium-ion batteries is one of the critical issues limiting their safety performance and lifetime. In this work, a set of 900 mAh pouch cells were applied to systematically compare the composition of gases generated from a serial of carbonate-based composite electrolytes, using a self-designed gas analyzing system. Among electrolytes used in this work, the composite γ-butyrolactone/ethyl methyl carbonate (GBL/EMC) exhibited remarkably less gassing because of the electrochemical stability of the GBL, which makes it a promising electrolyte for battery with advanced safety and lifetime.

Facile Fabrication of Ethoxy-Functional Polysiloxane Wrapped LiNi0.6Co0.2Mn0.2O2 Cathode with Improved Cycling Performance for Rechargeable Li-Ion Battery.

PubMed

Wang, Hao; Ge, Wujie; Li, Wen; Wang, Feng; Liu, Wenjing; Qu, Mei-Zhen; Peng, Gongchang

2016-07-20

Dealing with the water molecule on the surface of LiNi0.6Co0.2Mn0.2O2 (NCM) cathode and hydrogen fluoride in the electrolyte is one of the most difficult challenges in Li-ion battery research. In this paper, the surface polymerization of tetraethyl orthosilicate (TEOS) on NCM to generate ethoxy-functional polysiloxane (EPS) wrapped NCM (E-NCM) cathode under mild conditions and without any additions is utilized to solve this intractable problem. The differential scanning calorimetry, transmission electron microscopy, and X-ray photoelectron spectroscopy results show that the formed amorphous coating can provide a protective shell to improve the NCM thermal stability, suppress the thickening of the solid electrolyte interphase (SEI) layer, and scavenge HF in the electrolyte. The E-NCM composite with 2 mol % EPS delivers a high discharge capacity retention of 84.9% after 100 cycles at a 1 C discharge rate in the 2.8-4.3 V potential range at 55 °C. Moreover, electrochemical impedance spectroscopy measurements reveal that the EPS coating could alleviate the impedance rise during cycling especially at an elevated temperature. Therefore, the fabricated E-NCM cathode with long-term cycling and thermal stability is a promising candidate for use in a high-energy Li-ion battery.

High-Efficiency Artificial Photosynthesis Using a Novel Alkaline Membrane Cell

NASA Technical Reports Server (NTRS)

Narayan, Sri; Haines, Brennan; Blosiu, Julian; Marzwell, Neville

2009-01-01

A new cell designed to mimic the photosynthetic processes of plants to convert carbon dioxide into carbonaceous products and oxygen at high efficiency, has an improved configuration using a polymer membrane electrolyte and an alkaline medium. This increases efficiency of the artificial photosynthetic process, achieves high conversion rates, permits the use of inexpensive catalysts, and widens the range of products generated by this type of process. The alkaline membrane electrolyte allows for the continuous generation of sodium formate without the need for any additional separation system. The electrolyte type, pH, electrocatalyst type, and cell voltage were found to have a strong effect on the efficiency of conversion of carbon dioxide to formate. Indium electrodes were found to have higher conversion efficiency compared to lead. Bicarbonate electrolyte offers higher conversion efficiency and higher rates than water solutions saturated with carbon dioxide. pH values between 8 and 9 lead to the maximum values of efficiency. The operating cell voltage of 2.5 V, or higher, ensures conversion of the carbon dioxide to formate, although the hydrogen evolution reaction begins to compete strongly with the formate production reaction at higher cell voltages. Formate is produced at indium and lead electrodes at a conversion efficiency of 48 mg of CO2/kilojoule of energy input. This efficiency is about eight times that of natural photosynthesis in green plants. The electrochemical method of artificial photosynthesis is a promising approach for the conversion, separation and sequestration of carbon dioxide for confined environments as in space habitats, and also for carbon dioxide management in the terrestrial context. The heart of the reactor is a membrane cell fabricated from an alkaline polymer electrolyte membrane and catalyst- coated electrodes. This cell is assembled and held in compression in gold-plated hardware. The cathode side of the cell is supplied with carbon dioxide-saturated water or bicarbonate solution. The anode side of the cell is supplied with sodium hydroxide solution. The solutions are circulated past the electrodes in the electrochemical cell using pumps. A regulated power supply provides the electrical energy required for the reactions. Photovoltaic cells can be used to better mimic the photosynthetic reaction. The current flowing through the electrochemical cell, and the cell voltage, are monitored during experimentation. The products of the electrochemical reduction of carbon dioxide are allowed to accumulate in the cathode reservoir. Samples of the cathode solution are withdrawn for product analysis. Oxygen is generated on the anode side and is allowed to vent out of the reservoir.

Catalytic partial oxidation reforming of hydrocarbon fuels.

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

Ahmed, S.

1998-09-21

The polymer electrolyte fuel cell (PEFC) is the primary candidate as the power source for light-duty transportation systems. On-board conversion of fuels (reforming) to supply the required hydrogen has the potential to provide the driving range that is typical of today's automobiles. Petroleum-derived fuels, gasoline or some distillate similar to it, are attractive because of their existing production, distribution, and retailing infrastructure. The fuel may be either petroleum-derived or other alternative fuels such as methanol, ethanol, natural gas, etc. [1]. The ability to use a variety of fuels is also attractive for stationary distributed power generation [2], such as inmore » buildings, or for portable power in remote locations. Argonne National Laboratory has developed a catalytic reactor based on partial oxidation reforming that is suitable for use in light-duty vehicles powered by fuel cells. The reactor has shown the ability to convert a wide variety of fuels to a hydrogen-rich gas at less than 800 C, temperatures that are several hundreds of degrees lower than alternative noncatalytic processes. The fuel may be methanol, ethanol, natural gas, or petroleum-derived fuels that are blends of various hydrocarbons such as paraffins, olefins, aromatics, etc., as in gasoline. This paper will discuss the results obtained from a bench-scale (3-kWe) reactor., where the reforming of gasoline and natural gas generated a product gas that contained 38% and 42% hydrogen on a dry basis at the reformer exit, respectively.« less

Validation test of 125 Ah advanced design IPV nickel-hydrogen flight cells

NASA Technical Reports Server (NTRS)

Smithrick, John J.; Hall, Stephen W.

1993-01-01

An update of validation test results confirming the advanced design nickel-hydrogen cell is presented. An advanced 125 Ah individual pressure vessel (IPV) nickel-hydrogen cell was designed. The primary function of the advanced cell is to store and deliver energy for long-term, Low-Earth-Orbit (LEO) spacecraft missions. The new features of this design, which are not incorporated in state-of-the-art design cells, are: (1) use of 26 percent rather than 31 percent potassium hydroxide (KOH) electrolyte; (2) use of a patented catalyzed wall wick; (3) use of serrated-edge separators to facilitate gaseous oxygen and hydrogen flow within the cell, while still maintaining physical contact with the wall wick for electrolyte management; and (4) use of a floating rather than a fixed stack (state-of-the-art) to accommodate nickel electrode expansion due to charge/discharge cycling. The significant improvements resulting from these innovations are extended cycle life; enhanced thermal, electrolyte, and oxygen management; and accommodation of nickel electrode expansion. Six 125 Ah flight cells based on this design were fabricated by Eagle-Picher. Three of the cells contain all of the advanced features (test cells) and three are the same as the test cells except they do not have catalyst on the wall wick (control cells). All six cells are in the process of being evaluated in a LEO cycle life test at the Naval Weapons Support Center, Crane, IN, under a NASA Lewis Research Center contract. The catalyzed wall wick cells have been cycled for over 19000 cycles with no cell failures in the continuing test. Two of the noncatalyzed wall wick cells failed (cycles 9588 and 13,900).

Coupling thermoelectricity and electrocatalysis for hydrogen production via PbTesbnd PbS/TiO2 heterojunction

NASA Astrophysics Data System (ADS)

Liu, Zhongqing; Cao, Xiaohao; Wang, Bin; Xia, Min; Lin, Sidney; Guo, Zhanhu; Zhang, Xiaoming; Gao, Shiyuan

2017-02-01

PbTesbnd PbS/TiO2 electrodes are produced via wet chemical routes for splitting water into hydrogen at the ambient temperatures. PbTe nano-crystals are firstly deposited via the successive ionic layer adsorption and reaction (SILAR) treatment onto TiO2 nanotube arrays (TNAs) prepared by anodic oxidation of Ti substrates. Subsequently, linear sweep voltammetry (LSV) is employed to convert the outer PbTe into PbS, producing PbTesbnd PbS/TiO2 electrodes with a gradient p-n-n band configuration. With the external electric field, the vector charge transfer effect of the TNAs and the gradient energy band structure of PbTesbnd PbS/TNAs, the two electrode system in which PbTesbnd PbS/TNAs functions as the anode illustrates excellent hydrogen production activities. The whole electrochemical system consisted of anode, cathode, electrolyte serves as a hot side while the endothermic electrochemical reactions in hydrogen production as an in situ cold side. At 70 °C and 1.0 V bath voltage, the system registers 6.1 mL cm-2 h-1 rate of hydrogen generation, consuming electric power of 26.2 kW h kg-1 H2, with an energy efficiency of 88.5% and a heat efficiency of 49.9%. This method demonstrates a novel pathway to produce chemical energy from low quality waste heat, benefitting from thermoelectric and electrocatalytic coupling.

Investigation of advanced nanostructured multijunction photoanodes for enhanced solar hydrogen generation via water splitting

NASA Astrophysics Data System (ADS)

Ishihara, Hidetaka

As the worldwide demand for fossil-based fuel increases every day and the fossil reserve continues to be depleted, the need for alternative/renewable energy sources has gained momentum. Electric, hybrid, and hydrogen cars have been at the center of discussion lately among consumers, automobile manufacturers, and politicians, alike. The development of a fuel-cell based engine using hydrogen has been an ambitious research area over the last few decades-ever since Fujishima showed that hydrogen can be generated via the solar-energy driven photo-electrolytic splitting of water. Such solar cells are known as Photo-Electro-Chemical (PEC) solar cells. In order to commercialize this technology, various challenges associated with photo-conversion efficiency, chemical corrosion resistance, and longevity need to be overcome. In general, metal oxide semiconductors such as titanium dioxide (TiO 2, titania) are excellent candidates for PEC solar cells. Titania nanotubes have several advantages, including biocompatibility and higher chemical stability. Nevertheless, they can absorb only 5-7% of the solar spectrum which makes it difficult to achieve the higher photo-conversion efficiency required for successful commercial applications. A two-prong approach was employed to enhance photo-conversion efficiency: 1) surface modification of titania nanotubes using plasma treatment and 2) nano-capping of the titania nanotubes using titanium disilicide. The plasma surface treatment with N2 was found to improve the photo-current efficiency of titania nanotubes by 55%. Similarly, a facile, novel approach of nano-capping titania nanotubes to enhance their photocurrent response was also investigated. Electrochemically anodized titania nanotubes were capped by coating a 25 nm layer of titanium disilicide using RF magnetron sputtering technique. The optical properties of titania nanotubes were not found to change due to the capping; however, a considerable increase (40%) in the photocurrent density was observed for the nano-capped titania nanotubes due to the enhanced charge transfer process. Similarly, another metal oxide semiconductor was investigated tungsten trioxide (WO3), which has a much higher absorption capability (12%) in the solar spectrum. The WO3 porous nanostructures suffered from surface corrosion resulting in a large reduction in the photocurrent density as a function of time in the alkaline electrolytes. However, with a protective coating of Indium Tin Oxide (100 nm), the surface corrosion of WO3 porous nanostructures was reduced. A large increase in the photocurrent density of as much as 340% was observed after the ITO was applied to the WO3 porous nanostructures

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

Corrosion test cell for bipolar plates

DOEpatents

Weisbrod, Kirk R.

2002-01-01

A corrosion test cell for evaluating corrosion resistance in fuel cell bipolar plates is described. The cell has a transparent or translucent cell body having a pair of identical cell body members that seal against opposite sides of a bipolar plate. The cell includes an anode chamber and an cathode chamber, each on opposite sides of the plate. Each chamber contains a pair of mesh platinum current collectors and a catalyst layer pressed between current collectors and the plate. Each chamber is filled with an electrolyte solution that is replenished with fluid from a much larger electrolyte reservoir. The cell includes gas inlets to each chamber for hydrogen gas and air. As the gases flow into a chamber, they pass along the platinum mesh, through the catalyst layer, and to the bipolar plate. The gas exits the chamber through passageways that provide fluid communication between the anode and cathode chambers and the reservoir, and exits the test cell through an exit port in the reservoir. The flow of gas into the cell produces a constant flow of fresh electrolyte into each chamber. Openings in each cell body is member allow electrodes to enter the cell body and contact the electrolyte in the reservoir therein. During operation, while hydrogen gas is passed into one chamber and air into the other chamber, the cell resistance is measured, which is used to evaluate the corrosion properties of the bipolar plate.

Unique Three-Dimensional InP Nanopore Arrays for Improved Photoelectrochemical Hydrogen Production.

PubMed

Li, Qiang; Zheng, Maojun; Ma, Liguo; Zhong, Miao; Zhu, Changqing; Zhang, Bin; Wang, Faze; Song, Jingnan; Ma, Li; Shen, Wenzhong

2016-08-31

Ordered three-dimensional (3D) nanostructure arrays hold promise for high-performance energy harvesting and storage devices. Here, we report the fabrication of InP nanopore arrays (NPs) in unique 3D architectures with excellent light trapping characteristic and large surface areas for use as highly active photoelectrodes in photoelectrochemical (PEC) hydrogen evolution devices. The ordered 3D NPs were scalably synthesized by a facile two-step etching process of (1) anodic etching of InP in neutral 3 M NaCl electrolytes to realize nanoporous structures and (2) wet chemical etching in HCl/H3PO4 (volume ratio of 1:3) solutions for removing the remaining top irregular layer. Importantly, we demonstrated that the use of neutral electrolyte of NaCl instead of other solutions, such as HCl, in anodic etching of InP can significantly passivate the surface states of 3D NPs. As a result, the maximum photoconversion efficiency obtained with ∼15.7 μm thick 3D NPs was 0.95%, which was 7.3 and 1.4 times higher than that of planar and 2D NPs. Electrochemical impedance spectroscopy and photoluminescence analyses further clarified that the improved PEC performance was attributed to the enhanced charge transfer across 3D NPs/electrolyte interfaces, the improved charge separation at 3D NPs/electrolyte junction, and the increased PEC active surface areas with our unique 3D NP arrays.

Highly Selective TiN-Supported Highly Dispersed Pt Catalyst: Ultra Active toward Hydrogen Oxidation and Inactive toward Oxygen Reduction.

PubMed

Luo, Junming; Tang, Haibo; Tian, Xinlong; Hou, Sanying; Li, Xiuhua; Du, Li; Liao, Shijun

2018-01-31

The severe dissolution of the cathode catalyst, caused by an undesired oxygen reduction reaction at the anode during startup and shutdown, is a fatal challenge to practical applications of polymer electrolyte membrane fuel cells. To address this important issue, according to the distinct structure-sensitivity between the σ-type bond in H 2 and the π-type bond in O 2 , we design a HD-Pt/TiN material by highly dispersing Pt on the TiN surface to inhibit the unwanted oxygen reduction reaction. The highly dispersed Pt/TiN catalyst exhibits excellent selectivity toward hydrogen oxidation and oxygen reduction reactions. With a Pt loading of 0.88 wt %, our catalyst shows excellent hydrogen oxidation reaction activity, close to that of commercial 20 wt % Pt/C catalyst, and much lower oxygen reduction reaction activity than the commercial 20 wt % Pt/C catalyst. The lack of well-ordered Pt facets is responsible for the excellent selectivity of the HD-Pt/TiN materials toward hydrogen oxidation and oxygen reduction reactions. Our work provides a new and cost-effective solution to design selective catalysts toward hydrogen oxidation and oxygen reduction reactions, making the strategy of using oxygen-tolerant anode catalyst to improve the stability of polymer electrolyte membrane fuel cells during startup and shutdown more affordable and practical.

Lorentz force on sodium and chlorine ions in a salt water solution flow under a transverse magnetic field

NASA Astrophysics Data System (ADS)

DeLuca, R.

2009-05-01

It is shown that, by applying elementary concepts in electromagnetism and electrochemistry to a system consisting of salt water flowing in a thin rectangular pipe at an average velocity vA under the influence of a transverse magnetic field B0, an electromotive force generator can be conceived. In fact, the Lorentz force acting on the sodium and chlorine ions in a water solution gives rise to a so-called Faraday voltage across the two metal electrodes, positioned at the sides of the pipe. The effect is carried along the following chemical reactions at the electrodes: at the cathode, water is reduced (instead of sodium ions) and hydrogen gas is generated; at the anode, chlorine gas is produced. In college physics teaching, this interdisciplinary subject can be adopted to stress analogies and differences between the Hall voltage in conductors and the Faraday voltage in electrolyte solutions.

Silicon based multilayer photoelectrodes for photoelectrolysis of water to produce hydrogen from the sun

NASA Astrophysics Data System (ADS)

Faruque, Faisal

The main objective of this work is to study different materials for the direct photosynthesis of hydrogen from water. A variety of photocatalysts such as titanium dioxide, titanium oxy-nitride, silicon carbide, and gallium nitride are being investigated by others for the clean production of hydrogen for fuel cells and hydrogen economy. Our approach was to deposit suitable metallic regions on photocatalyst nanoparticles to direct the efficient synthesis of hydrogen to a particular site for convenient collection. We studied different electrode metals such as gold, platinum, titanium, palladium, and tungsten. We also studied different solar cell materials such as silicon (p- and n-types), silicon carbide and titanium dioxide semiconductors in order to efficiently generate electrons under illumination. We introduced a novel silicon-based multilayer photosynthesis device to take advantage of suitable properties of silicon and tungsten to efficiently produce hydrogen. The device consisted of a silicon (0.5mm) substrate, a deposited atomic layer of Al2O 3 (1nm), a doped polysilicon (0.1microm), and finally a tungsten nanoporous (5-10nm) layer acting as an interface electrode with water. The Al2O 3 layer was introduced to reduce leakage current and to prevent the spreading of the diffused p-n junction layer between the silicon and doped polysilicon layers. The surface of the photoelectrode was coated with nanotextured tungsten nanopores (TNP), which increased the surface area of the electrodes to the electrolyte, assisting in electron-hole mobility, and acting as a photocatalyst. The reported device exhibited a fill factor (%FF) of 27.22% and solar-to-hydrogen conversion efficiency of 0.03174%. This thesis describes the structures of the device, and offers a characterization and comparison between different photoelectrodes.

Correlating hydrogen oxidation and evolution activity on platinum at different pH with measured hydrogen binding energy

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

Sheng, WC; Zhuang, ZB; Gao, MR

2015-01-08

The hydrogen oxidation/evolution reactions are two of the most fundamental reactions in distributed renewable electrochemical energy conversion and storage systems. The identification of the reaction descriptor is therefore of critical importance for the rational catalyst design and development. Here we report the correlation between hydrogen oxidation/evolution activity and experimentally measured hydrogen binding energy for polycrystalline platinum examined in several buffer solutions in a wide range of electrolyte pH from 0 to 13. The hydrogen oxidation/evolution activity obtained using the rotating disk electrode method is found to decrease with the pH, while the hydrogen binding energy, obtained from cyclic voltammograms, linearlymore » increases with the pH. Correlating the hydrogen oxidation/evolution activity to the hydrogen binding energy renders a monotonic decreasing hydrogen oxidation/evolution activity with the hydrogen binding energy, strongly supporting the hypothesis that hydrogen binding energy is the sole reaction descriptor for the hydrogen oxidation/evolution activity on monometallic platinum.« less

Visible light-induced water oxidation on mesoscopic alpha-Fe2O3 films made by ultrasonic spray pyrolysis.

PubMed

Duret, Alexis; Grätzel, Michael

2005-09-15

Alpha-Fe(2)O(3) films having a mesoscopic leaflet type structure were produced for the first time by ultrasonic spray pyrolysis (USP) to explore their potential as oxygen-evolving photoanodes. The target of these studies is to use translucent hematite films deposited on conducting fluorine doped tin oxide (FTO) glass as top electrodes in a tandem cell that accomplishes the cleavage of water into hydrogen and oxygen by sunlight. The properties of layers made by USP were compared to those deposited by conventional spray pyrolysis (SP). Although both types of films show similar XRD and UV-visible and Raman spectra, they differ greatly in their morphology. The mesoscopic alpha-Fe(2)O(3) layers produced by USP consist mainly of 100 nm-sized platelets with a thickness of 5-10 nm. These nanosheets are oriented mainly perpendicularly to the FTO support, their flat surface exposing (001) facets. The mesoscopic leaflet structure has the advantage that it allows for efficient harvesting of visible light, while offering at the same time the very short distance required for the photogenerated holes to reach the electrolyte interface before recombining with conduction band electrons. This allows for water oxidation by the valence band holes even though their diffusion length is only a few nanometers. Distances are longer in the particles produced by SP favoring recombination of photoinduced charge carriers. Open-circuit photovoltage measurements indicate a lower surface state density for the nanoplatelets as compared to the round particles. These factors explain the much higher photoactivity of the USP compared to the SP deposited alpha-Fe(2)O(3) layers. Addition of hydrogen peroxide to the alkaline electrolyte further improves the photocurrent-voltage characteristics of films generated by USP indicating the hole transfer from the valence band of the semiconductor oxide to the adsorbed water to be the rate-limiting kinetic step in the oxygen generation reaction.

Hypervelocity Impact Testing of Nickel Hydrogen Battery Cells

NASA Technical Reports Server (NTRS)

Frate, David T.; Nahra, Henry K.

1996-01-01

Nickel-Hydrogen (Ni/H2) battery cells have been used on several satellites and are planned for use on the International Space Station. In January 1992, the NASA Lewis Research Center (LeRC) conducted hypervelocity impact testing on Ni/H2 cells to characterize their failure modes. The cell's outer construction was a 24 mil-thick Inconel 718 pressure vessel. A sheet of 1.27 cm thick honeycomb was placed in front of the battery cells during testing to simulate the on-orbit box enclosure. Testing was conducted at the NASA White Sands Test Facility (WSTF). The hypervelocity gun used was a 7.6 mm (0.30 caliber) two-stage light gas gun. Test were performed at speeds of 3, 6, and 7 km/sec using aluminum 2017 spherical particles of either 4.8 or 6.4 mm diameter as the projectile. The battery cells were electrically charged to about 75 percent of capacity, then back-filled with hydrogen gas to 900 psi simulating the full charge condition. High speed film at 10,000 frames/sec was taken of the impacts. Impacts in the dome area (top) and the electrode area (middle) of the battery cells were investigated. Five tests on battery cells were performed. The results revealed that in all of the test conditions investigated, the battery cells simply vented their hydrogen gas and some electrolyte, but did not burst or generate any large debris fragments.

Semi-empirical equation of limiting current for cobalt electrodeposition in the presence of magnetic field and additive electrolyte

NASA Astrophysics Data System (ADS)

Sudibyo, Aziz, N.

2016-02-01

One of the available methods to solve a roughening in cobalt electrodeposition is magneto electrodeposition (MED) in the presence of additive electrolyte. Semi-empirical equation of limiting current under a magnetic field for cobalt MED in the presence of boric acid as an additive electrolyte was successfully developed. This semi empirical equation shows the effects of the electrode area (A), the concentration of the electro active species (C), the diffusion coefficient of the electro active species (D), the kinematic viscosity of the electrolyte (v), magnetic strength (B) and the number of electrons involved in the redox process (n). The presence of boric acid led to decrease in the limiting current, but the acid was found useful as a buffer to avoid the local pH rise caused by parallel hydrogen evolution reaction (HER).

40 CFR 63.9075 - What definitions apply to this subpart?

Code of Federal Regulations, 2013 CFR

2013-07-01

... hydroxide are produced as co-products and hydrogen is produced as a by-product in an electrolytic process using either mercury cells, diaphragm cells, or membrane cells. Continuous monitoring system, for...

40 CFR 63.9075 - What definitions apply to this subpart?

Code of Federal Regulations, 2012 CFR

2012-07-01

... hydroxide are produced as co-products and hydrogen is produced as a by-product in an electrolytic process using either mercury cells, diaphragm cells, or membrane cells. Continuous monitoring system, for...

40 CFR 63.9075 - What definitions apply to this subpart?

Code of Federal Regulations, 2014 CFR

2014-07-01

... hydroxide are produced as co-products and hydrogen is produced as a by-product in an electrolytic process using either mercury cells, diaphragm cells, or membrane cells. Continuous monitoring system, for...

Lithium-ion battery electrolyte emissions analyzed by coupled thermogravimetric/Fourier-transform infrared spectroscopy

NASA Astrophysics Data System (ADS)

Bertilsson, Simon; Larsson, Fredrik; Furlani, Maurizio; Albinsson, Ingvar; Mellander, Bengt-Erik

2017-10-01

In the last few years the use of Li-ion batteries has increased rapidly, powering small as well as large applications, from electronic devices to power storage facilities. The Li-ion battery has, however, several safety issues regarding occasional overheating and subsequent thermal runaway. During such episodes, gas emissions from the electrolyte are of special concern because of their toxicity, flammability and the risk for gas explosion. In this work, the emissions from heated typical electrolyte components as well as from commonly used electrolytes are characterized using FT-IR spectroscopy and FT-IR coupled with thermogravimetric (TG) analysis, when heating up to 650 °C. The study includes the solvents EC, PC, DEC, DMC and EA in various single, binary and ternary mixtures with and without the LiPF6 salt, a commercially available electrolyte, (LP71), containing EC, DEC, DMC and LiPF6 as well as extracted electrolyte from a commercial 6.8 Ah Li-ion cell. Upon thermal heating, emissions of organic compounds and of the toxic decomposition products hydrogen fluoride (HF) and phosphoryl fluoride (POF3) were detected. The electrolyte and its components have also been extensively analyzed by means of infrared spectroscopy for identification purposes.

Electrochemical and structural characterization of polymer gel electrolytes based on a PEO copolymer and an imidazolium-based ionic liquid for dye-sensitized solar cells.

PubMed

Freitas, Flavio S; de Freitas, Jilian N; Ito, Bruno I; De Paoli, Marco-A; Nogueira, Ana F

2009-12-01

Polymer electrolytes based on mixtures of poly(ethylene oxide-co-propylene oxide) and 1-methyl-3-propyl-imidazolium iodide (MPII) were investigated, aiming at their application in dye-sensitized solar cells (DSSC). The interactions between the copolymer and the ionic liquid were analyzed by infrared spectroscopy and (1)H NMR. The results show interactions between the ether oxygen in the polymer and the hydrogen in the imidazolium cations. The ionic conductivities, electrochemical behaviors, and thermal properties of the electrolytes containing different concentrations of MPII were investigated. The electrolyte containing 70 wt % MPII presented the highest ionic conductivity (2.4 x 10(-3) S cm(-1)) and a diffusion coefficient of 1.9 x 10(-7) cm(2) s(-1). The influence of LiI addition to the electrolytes containing different concentrations of MPII was also investigated. The DSSC assembled with the electrolyte containing 70 wt % MPII showed an efficiency of 3.84% at 100 mW cm(-2). The stability of the devices for a period of 30 days was also evaluated using sealed cells. The devices assembled with the electrolyte containing less ionic liquid showed to be more stable.

Pore size engineering applied to the design of separators for nickel-hydrogen cells and batteries

NASA Technical Reports Server (NTRS)

Abbey, K. M.; Britton, D. L.

1983-01-01

Pore size engineering in starved alkaline multiplate cells involves adopting techniques to widen the volume tolerance of individual cells. Separators with appropriate pore size distributions and wettability characteristics (capillary pressure considerations) to have wider volume tolerances and an ability to resist dimensional changes in the electrodes were designed. The separators studied for potential use in nickel-hydrogen cells consist of polymeric membranes as well as inorganic microporous mats. In addition to standard measurements, the resistance and distribution of electrolyte as a function of total cell electrolyte content were determined. New composite separators consisting of fibers, particles and/or binders deposited on Zircar cloth were developed in order to engineer the proper capillary pressure characteristics in the separator. These asymmetric separators were prepared from a variety of fibers, particles and binders.

High voltage AC/AC electrochemical capacitor operating at low temperature in salt aqueous electrolyte

NASA Astrophysics Data System (ADS)

Abbas, Qamar; Béguin, François

2016-06-01

We demonstrate that an activated carbon (AC)-based electrochemical capacitor implementing aqueous lithium sulfate electrolyte in 7:3 vol:vol water/methanol mixture can operate down to -40 °C with good electrochemical performance. Three-electrode cell investigations show that the faradaic contributions related with hydrogen chemisorption in the negative AC electrode are thermodynamically unfavored at -40 °C, enabling the system to work as a typical electrical double-layer (EDL) capacitor. After prolonged floating of the AC/AC capacitor at 1.6 V and -40°C, the capacitance, equivalent series resistance and efficiency remain constant, demonstrating the absence of ageing related with side redox reactions at this temperature. Interestingly, when temperature is increased back to 24 °C, the redox behavior due to hydrogen storage reappears and the system behaves as a freshly prepared one.

Spermidine sprays alleviate the water deficit-induced oxidative stress in finger millet (Eleusine coracana L. Gaertn.) plants.

PubMed

Satish, Lakkakula; Rency, Arockiam Sagina; Ramesh, Manikandan

2018-01-01

Severe drought stress (water deficit) in finger millet ( Eleusine coracana L. Gaertn.) plants significantly reduced total leaf chlorophyll and relative water content in shoots and roots, whereas electrolyte leakage, concentrations of proline and hydrogen peroxide, as well as caspase-like activity were significantly increased. The role of spermidine in plant defence to water-stress was investigated after subjected to various drought treatments. Three weeks of daily spermidine sprays (0.2 mM) at early flowering stage significantly changed shoot and root growth, in both fresh and dry weights terms. At 75% of water deficit stress, leaves accumulated twice as much proline as unstressed plants, and roots accumulated thrice. Plants treated with spermidine under water stress showed lower electrolyte leakage, hydrogen peroxide and caspase-like activity than unstressed and untreated control.

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.

U.S. Clean Energy Hydrogen and Fuel Cell Technologies: A Competitiveness Analysis

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

Fullenkamp, Patrick; Holody, Diane; James, Brian

The objectives of this project are a 1) Global Competitiveness Analysis of hydrogen and fuel cell systems and components manufactured including 700 bar compressed hydrogen storage system in the U.S., Europe, Asia, and other key areas to be identified to determine the global cost leaders, the best current manufacturing processes, the key factors determining competitiveness, and the potential means of cost reductions; and an 2) Analysis to assess the status of global hydrogen and fuel cell markets. The analysis of units, megawatts by country and by application will focus on polymer electrolyte membrane (PEM) fuel cell systems (automotive and stationary).

Conceptual design study of a six-man solid electrolyte system for oxygen reclamation

NASA Technical Reports Server (NTRS)

Morris, J. P.; Wu, C. K.; Elikan, L.; Bifano, N. J.; Holman, R. R.

1972-01-01

A six-man solid electrolyte oxygen regeneration system (SEORS) that will produce 12.5 lbs/day of oxygen has been designed. The SEORS will simultaneously electrolyze both carbon dioxide and water vapor and be suitable for coupling with a carbon dioxide concentration system of either molecular sieve, solid amine or hydrogen depolarized electrochemical type. The total system will occupy approximately 19 cu ft (34.5 in. x .26 in. x 36 in. high) and will weigh approximately 500 pounds. It is estimated that the total electrical power required will be 1783 watts. The system consists of three major components; electrolyzer, hydrogen diffuser, and carbon deposition reactor. There are 108 electrolysis stacks of 12 cells each in the electrolyzer. Only 2/3 of the 108 stacks will be operated at a time; the remainder will be held in reserve. The design calls for 96 palladium membranes for hydrogen removal to give 60 percent redundancy. Four carbon deposition reactors are employed. The iron catalyst tube in each reactor weighs 7.1 lb and 100 percent redundancy is allowed.

Thermal System Modeling for Lunar and Martian Surface Regenerative Fuel Cell Systems

NASA Technical Reports Server (NTRS)

Gilligan, Ryan Patrick; Smith, Phillip James; Jakupca, Ian Joseph; Bennett, William Raymond; Guzik, Monica Christine; Fincannon, Homer J.

2017-01-01

The Advanced Exploration Systems (AES) Advanced Modular Power Systems (AMPS) Project is investigating different power systems for various lunar and Martian mission concepts. The AMPS Fuel Cell (FC) team has created two system-level models to evaluate the performance of regenerative fuel cell (RFC) systems employing different fuel cell chemistries. Proton Exchange Membrane fuel cells PEMFCs contain a polymer electrolyte membrane that separates the hydrogen and oxygen cavities and conducts hydrogen cations (protons) across the cell. Solid Oxide fuel cells (SOFCs) operate at high temperatures, using a zirconia-based solid ceramic electrolyte to conduct oxygen anions across the cell. The purpose of the modeling effort is to down select one fuel cell chemistry for a more detailed design effort. Figures of merit include the system mass, volume, round trip efficiency, and electrolyzer charge power required. PEMFCs operate at around 60 degrees Celsius versus SOFCs which operate at temperatures greater than 700 degrees Celsius. Due to the drastically different operating temperatures of the two chemistries the thermal control systems (TCS) differ. The PEM TCS is less complex and is characterized by a single pump cooling loop that uses deionized water coolant and rejects heat generated by the system to the environment via a radiator. The solid oxide TCS has its own unique challenges including the requirement to reject high quality heat and to condense the steam produced in the reaction. This paper discusses the modeling of thermal control systems for an extraterrestrial RFC that utilizes either a PEM or solid oxide fuel cell.

CO2-Free Power Generation on an Iron Group Nanoalloy Catalyst via Selective Oxidation of Ethylene Glycol to Oxalic Acid in Alkaline Media

PubMed Central

Matsumoto, Takeshi; Sadakiyo, Masaaki; Ooi, Mei Lee; Kitano, Sho; Yamamoto, Tomokazu; Matsumura, Syo; Kato, Kenichi; Takeguchi, Tatsuya; Yamauchi, Miho

2014-01-01

An Fe group ternary nanoalloy (NA) catalyst enabled selective electrocatalysis towards CO2-free power generation from highly deliverable ethylene glycol (EG). A solid-solution-type FeCoNi NA catalyst supported on carbon was prepared by a two-step reduction method. High-resolution electron microscopy techniques identified atomic-level mixing of constituent elements in the nanoalloy. We examined the distribution of oxidised species, including CO2, produced on the FeCoNi nanoalloy catalyst in the EG electrooxidation under alkaline conditions. The FeCoNi nanoalloy catalyst exhibited the highest selectivities toward the formation of C2 products and to oxalic acid, i.e., 99 and 60%, respectively, at 0.4 V vs. the reversible hydrogen electrode (RHE), without CO2 generation. We successfully generated power by a direct EG alkaline fuel cell employing the FeCoNi nanoalloy catalyst and a solid-oxide electrolyte with oxygen reduction ability, i.e., a completely precious-metal-free system. PMID:25004118

Decomposition of the fluoroethylene carbonate additive and the glue effect of lithium fluoride products for the solid electrolyte interphase: an ab initio study.

PubMed

Okuno, Yukihiro; Ushirogata, Keisuke; Sodeyama, Keitaro; Tateyama, Yoshitaka

2016-03-28

Additives in the electrolyte solution of lithium-ion batteries (LIBs) have a large impact on the performance of the solid electrolyte interphase (SEI) that forms on the anode and is a key to the stability and durability of LIBs. We theoretically investigated effects of fluoroethylene carbonate (FEC), a representative additive, that has recently attracted considerable attention for the enhancement of cycling stability of silicon electrodes and the improvement of reversibility of sodium-ion batteries. First, we intensively examined the reductive decompositions by ring-opening, hydrogen fluoride (HF) elimination to form a vinylene carbonate (VC) additive and intermolecular chemical reactions of FEC in the ethylene carbonate (EC) electrolyte, by using density functional theory (DFT) based molecular dynamics and the blue-moon ensemble technique for the free energy profile. The results show that the most plausible product of the FEC reductive decomposition is lithium fluoride (LiF), and that the reactivity of FEC to anion radicals is found to be inert compared to the VC additive. We also investigated the effects of the generated LiF on the SEI by using two model systems; (1) LiF molecules distributed in a model aggregate of organic SEI film components (SFCs) and (2) a LiF aggregate interfaced with the SFC aggregate. DFT calculations of the former system show that F atoms form strong bindings with the Li atoms of multiple organic SFC molecules and play as a joint connecting them. In the latter interface system, the LiF aggregate adsorbs the organic SFCs through the F-Li bindings. These results suggest that LiF moieties play the role of glue in the organic SFC within the SEI film. We also examined the interface structure between a LiF aggregate and a lithiated silicon anode, and found that they are strongly bound. This strong binding is likely to be related to the effectiveness of the FEC additive in the electrolyte for the silicon anode.

Spectrally- and Time-Resolved Sum Frequency Generation (STiR-SFG): a new tool for ultrafast hydrogen bond dynamics at interfaces.

NASA Astrophysics Data System (ADS)

Benderskii, Alexander; Bordenyuk, Andrey; Weeraman, Champika

2006-03-01

The recently developed spectrally- and time-resolved Sum Frequency Generation (STiR-SFG) is a surface-selective 3-wave mixing (IR+visible) spectroscopic technique capable of measuring ultrafast spectral evolution of vibrational coherences. A detailed description of this measurement will be presented, and a noniterative method or deconvolving the laser pulses will be introduced to obtain the molecular response function. STiR-SFG, combined with the frequency-domain SFG spectroscopy, was applied to study hydrogen bonding dynamics at aqueous interfaces (D2O/CaF2). Spectral dynamics of the OD-stretch on the 50-150 fs time scale provides real-time observation of ultrafast H-bond rearrangement. Tuning the IR wavelength to the blue or red side of the OD-stretch transition, we selectively monitor the dynamics of different sub-ensembles in the distribution of the H-bond structures. The blue-side excitation (weaker H-bonding) shows monotonic red-shift of the OD-frequency. In contrast, the red-side excitation (stronger H-bonding structures) produces a blue-shift and a recursion, which may indicate the presence of an underdamped intermolecular mode of interfacial water. Effect of electrolyte concentration on the H-bond dynamics will be discussed.

Bubble template synthesis of hollow gold nanoparticles and their applications as theranostic agents

NASA Astrophysics Data System (ADS)

Huang, Chienwen

Hollow gold nanoparticle with a sub-30nm polycrystalline shell and a 50 nm hollow core has been successfully synthesized through the reduction of sodium gold sulfite by electrochemically evolved hydrogen. Such hollow gold nanoparticles exhibit unique plasmonic properties. They strongly scatter and absorb near infrared light. In this thesis we seek to understand the formation mechanism of hollow gold nanoparticles in this new synthesis process and their plasmonic properties. Also, we explore their biomedical applications as theranostic agents (therapeutic and diagnostic imaging). A lithographically patterned electrode consisting of Ag stripes on a glass substrate was used to investigate the formation process of hollow gold nanoparticles. Ag stripes served as working electrode for electrochemically evolution of hydrogen, and adjacent glass areas provided supporting surface for hydrogen nanobubbles nucleation and growth. Hydrogen nanobubbles served as both templates and reducing agents to trigger the autocatalytic disproportionation reaction of sodium gold sulfite. The effects of applied potential and the additives in the electrolyte have been studied. It has been found that the size and size distribution of hollow gold nanoparticle are directly relative to the applied potential, i.e. the hydrogen evolution rate. It has also been found the addition of Ni2+ ions can greatly improve the size distribution of hollow gold nanoparticles that can be contributed to that the newly electrodeposited nickel metal can enhance the hydrogen evolution efficiency. Another additive, ethylenediamine (EDA) can suppress the autocatalytic reaction of gold sulfite to increase the stability of sodium gold sulfite electrolyte. To capture such electrochemically evolved hydrogen nanobubbles, and subsequently to generate hollow gold nanoparticles in large numbers, alumina membranes were placed on the top of the working electrode. Anodic alumina membrane consists of ~200 nm pores, which provides a large surface area for the formation of hydrogen nanobubbles. By this approach, the electroless reaction can be easily separated from the electrodeposition process, and hollow gold nanoparticles can be easily collected. Synthesized hollow gold nanoparticles exhibit unique plasmonic properties; the surface plasmon resonance (SPR) lies in the near infrared region (NIR). This is very different from the solid spherical gold nanoparticles. Three-dimensional finite difference time domain (FDTD) simulation was employed to study the plasmonic properties of hollow gold nanoparticles. It has been found that the red-shifts of SPR peaks are mainly caused by their surface roughness, and the hollow nature of these particles only plays a minor role. The surface roughness of hollow gold nanoparticles can be tuned by adjusting the pH of the electrolyte (from 6.0 to 7.0) by adding sodium sulfite. Different surface roughness (from smooth to very rough) can be readily obtained, and correspondingly, surface plasmon resonance (SPR) peaks red-shift from ~600 nm to ~750 nm. Using hollow gold nanoparticles as multifunctional agents for biomedical applications have been explored. Two kinds of agents have been constructed. It has been demonstrated that pegylated Raman dye encoded hollow gold nanoparticles, terms as Raman nanotags, can serve as both diagnostic imaging agents and photothermal therapy agents. When illuminated by near infrared light, the enhanced Raman signal makes the hollow gold nanoparticles to become optically detectable for biomedical imaging, and absorbed light rapidly heat up the hollow gold nanoparticles which can be used to photothermal ablation therapy. The cytotoxicity evaluation using [3H] thymidine incorporation method has shown non-toxicity of the Raman nanotags. The photothermal effects of hollow gold nanoparticles have been examined by two methods: (1) by embedding hollow gold nanoparticles in tissue-like phantom environment; (2) by recording infrared images as temperature increase. The results show that hollow gold nanoparticles are capable to generate sufficiency heat for photothermal therapy. To fully take advantage of the unique hollow core space of hollow gold nanoparticles, a facile route has been develop to trap Fe3O4 nanoparticles into the hollow gold nanoparticles to form Fe3O4/Au core/shell nanoparticles. Fe3O4/Au core/shell nanoparticles possess the desirable magnetic and plasmonic properties that can be used as magnetic resonance contrast (MRI) agents and photothermal therapy agents.

Validation test of 125 Ah advanced design IPV nickel-hydrogen flight cells

NASA Technical Reports Server (NTRS)

Smithrick, John J.; Hall, Stephen W.

1993-01-01

An update of validation test results confirming the advanced design nickel-hydrogen cell is presented. An advanced 125 Ah individual pressure vessel Ni-H cell was designed. The primary function of the advanced cell is to store and deliver energy for long-term LEO spacecraft missions. The new features of this design are: (1) use of 26 percent rather than 31 percent KOH electrolyte; (2) use of a patented catalyzed wall wick; (3) use of serrated-edge separators to facilitate gaseous O and H flow within the cell, while maintaining physical contact with the wall wick for electrolyte management; and (4) use of a floating rather than a fixed stack to accommodate Ni electrode expansion due to charge/discharge cycling. The significant improvements resulting from these innovations are extended cycle life; enhanced thermal, electrolyte, and oxygen management; and accommodation of Ni electrode expansion. Six 125 Ah flight cells based on this design were fabricated; the catalyzed wall wick cells have been cycled for over 19,000 cycles with no cell failures in the continuing test. Two of the noncatalyzed wall wick cells failed (cycles 9588 and 13,900).

Reversible transient hydrogen storage in a fuel cell-supercapacitor hybrid device.

PubMed

Unda, Jesus E Zerpa; Roduner, Emil

2012-03-21

A new concept is investigated for hydrogen storage in a supercapacitor based on large-surface-area carbon material (Black Pearls 2000). Protons and electrons of hydrogen are separated on a fuel cell-type electrode and then stored separately in the electrical double layer, the electrons on the carbon and the protons in the aqueous electrolyte of the supercapacitor electrode. The merit of this concept is that it works spontaneously and reversibly near ambient pressure and temperature. This is in pronounced contrast to what has been known as electrochemical hydrogen storage, which does not involve hydrogen gas and where electrical work has to be spent in the loading process. With the present hybrid device, a H(2) storage capacity of 0.13 wt% was obtained, one order of magnitude more than what can be stored by conventional physisorption on large-surface-area carbons at the same pressure and temperature. Raising the pressure from 1.5 to 3.5 bar increased the capacity by less than 20%, indicating saturation. A capacitance of 11 μF cm(-2), comparable with that of a commercial double layer supercapacitor, was found using H(2)SO(4) as electrolyte. The chemical energy of the stored H(2) is almost a factor of 3 larger than the electrical energy stored in the supercapacitor. Further developments of this concept relate to a hydrogen buffer integrated inside a proton exchange membrane fuel cell to be used in case of peak power demand. This serial setup takes advantage of the suggested novel concept of hydrogen storage. It is fundamentally different from previous ways of operating a conventional supercapacitor hooked up in parallel to a fuel cell.

Alkaline regenerative fuel cell systems for energy storage

NASA Technical Reports Server (NTRS)

Schubert, F. H.; Reid, M. A.; Martin, R. E.

1981-01-01

A description is presented of the results of a preliminary design study of a regenerative fuel cell energy storage system for application to future low-earth orbit space missions. The high energy density storage system is based on state-of-the-art alkaline electrolyte cell technology and incorporates dedicated fuel cell and electrolysis cell modules. In addition to providing energy storage, the system can provide hydrogen and oxygen for attitude control of the satellite and for life support. During the daylight portion of the orbit the electrolysis module uses power provided by the solar array to generate H2 and O2 from the product water produced by the fuel cell module. The fuel cell module supplies electrical power during the dark period of the orbit.

Sulfone-based electrolytes for aluminium rechargeable batteries.

PubMed

Nakayama, Yuri; Senda, Yui; Kawasaki, Hideki; Koshitani, Naoki; Hosoi, Shizuka; Kudo, Yoshihiro; Morioka, Hiroyuki; Nagamine, Masayuki

2015-02-28

Electrolyte is a key material for success in the research and development of next-generation rechargeable batteries. Aluminium rechargeable batteries that use aluminium (Al) metals as anode materials are attractive candidates for next-generation batteries, though they have not been developed yet due to the lack of practically useful electrolytes. Here we present, for the first time, non-corrosive reversible Al electrolytes working at room temperature. The electrolytes are composed of aluminium chlorides, dialkylsulfones, and dilutants, which are realized by the identification of electrochemically active Al species, the study of sulfone dependences, the effects of aluminium chloride concentrations, dilutions and their optimizations. The characteristic feature of these materials is the lower chloride concentrations in the solutions than those in the conventional Al electrolytes, which allows us to use the Al metal anodes without corrosions. We anticipate that the sulfone-based electrolytes will open the doors for the research and development of Al rechargeable batteries.

On-line pH modification of carbonate eluents using an electrolytic potassium hydroxide generator for ion chromatography.

PubMed

Novic, Milko; Liu, Yan; Avdalovic, Nebojsa; Pihlar, Boris

2002-05-31

Classical gradient elution, based on the application of a gradient pump used for mixing two or more prepared eluent components in pre-determined concentrations, was replaced by a chromatography system equipped with an isocratic pump and an electrolytic KOH generator. The isocratic pump delivered a constant concentration eluent composed of pure hydrogencarbonate solution. Carbonate ions, the main component of carbonate/hydrogencarbonate-based eluents, were formed by titration of hydrogencarbonate with KOH formed on-line in the electrolytic KOH generator. By changing the concentration of electrolytically-generated KOH, the eluent composition could be changed from pure hydrogencarbonate to a carbonate/hydrogencarbonate buffer, and finally to a carbonate/hydroxide-based eluent. The described system was tested to achieve pH-based changes of retention behavior of phosphate under constant inflow eluent composition conditions.

Development of an operation strategy for hydrogen production using solar PV energy based on fluid dynamic aspects

NASA Astrophysics Data System (ADS)

Amores, Ernesto; Rodríguez, Jesús; Oviedo, José; de Lucas-Consuegra, Antonio

2017-06-01

Alkaline water electrolysis powered by renewable energy sources is one of the most promising strategies for environmentally friendly hydrogen production. However, wind and solar energy sources are highly dependent on weather conditions. As a result, power fluctuations affect the electrolyzer and cause several negative effects. Considering these limiting effects which reduce the water electrolysis efficiency, a novel operation strategy is proposed in this study. It is based on pumping the electrolyte according to the current density supplied by a solar PV module, in order to achieve the suitable fluid dynamics conditions in an electrolysis cell. To this aim, a mathematical model including the influence of electrode-membrane distance, temperature and electrolyte flow rate has been developed and used as optimization tool. The obtained results confirm the convenience of the selected strategy, especially when the electrolyzer is powered by renewable energies.

Electrochemical process for the preparation of nitrogen fertilizers

DOEpatents

Aulich, Ted R.; Olson, Edwin S.; Jiang, Junhua

2013-03-19

The present invention provides methods and apparatus for the preparation of nitrogen fertilizers including ammonium nitrate, urea, urea-ammonium nitrate, and/or ammonia utilizing a source of carbon, a source of nitrogen, and/or a source of hydrogen. Implementing an electrolyte serving as ionic charge carrier, (1) ammonium nitrate is produced via the reduction of a nitrogen source at the cathode and the oxidation of a nitrogen source at the anode; (2) urea or its isomers are produced via the simultaneous cathodic reduction of a carbon source and a nitrogen source; (3) ammonia is produced via the reduction of nitrogen source at the cathode and the oxidation of a hydrogen source at the anode; and (4) urea-ammonium nitrate is produced via the simultaneous cathodic reduction of a carbon source and a nitrogen source, and anodic oxidation of a nitrogen source. The electrolyte can be solid.

Electrochemical separation and concentration of hydrogen sulfide from gas mixtures

DOEpatents

Winnick, Jack; Sather, Norman F.; Huang, Hann S.

1984-10-30

A method of removing sulfur oxides of H.sub.2 S from high temperature gas mixtures (150.degree.-1000.degree. C.) is the subject of the present invention. An electrochemical cell is employed. The cell is provided with inert electrodes and an electrolyte which will provide anions compatible with the sulfur containing anions formed at the anode. The electrolyte is also selected to provide inert stable cations at the temperatures encountered. The gas mixture is passed by the cathode where the sulfur gases are converted to SO.sub.4 -- or, in the case of H.sub.2 S, to S--. The anions migrate to the anode where they are converted to a stable gaseous form at much greater concentration levels (>10X). Current flow may be effected by utilizing an external source of electrical energy or by passing a reducing gas such as hydrogen past the anode.

ELECTROCHEMICAL SEPARATION AND CONCENTRATION OF HYDROGEN SULFIDE FROM GAS MIXTURES

DOEpatents

Winnick, Jack; Sather, Norman F.; Huang, Hann S.

1984-10-30

A method of removing sulfur oxides of H.sub.2 S from high temperature gas mixtures (150.degree.-1000.degree. C.) is the subject of the present invention. An electrochemical cell is employed. The cell is provided with inert electrodes and an electrolyte which will provide anions compatible with the sulfur containing anions formed at the anode. The electrolyte is also selected to provide inert stable cations at the temperatures encountered. The gas mixture is passed by the cathode where the sulfur gases are converted to SO.sub.4 -- or, in the case of H.sub.2 S, to S--. The anions migrate to the anode where they are converted to a stable gaseous form at much greater concentration levels (>10X). Current flow may be effected by utilizing an external source of electrical energy or by passing a reducing gas such as hydrogen past the anode.

Development of a solid electrolyte carbon dioxide and water reduction system for oxygen recovery

NASA Technical Reports Server (NTRS)

Elikan, L.; Morris, J. P.; Wu, C. K.

1972-01-01

A 1/4-man solid electrolyte oxygen regeneration system, consisting of an electrolyzer, a carbon deposition reactor, and palladium membranes for separating hydrogen, was operated continuously in a 180-day test. Oxygen recovery from the carbon dioxide-water feed was 95%. One percent of the oxygen was lost to vacuum with the hydrogen off-gas. In a space cabin, the remaining 4% would have been recycled to the cabin and recovered. None of the electrolysis cells used in the 180-day test failed. Electrolysis power rose 20% during the test; the average power was 283.5 watts/man. Crew time was limited to 18 min/day of which 12 min/day was used for removing carbon. The success achieved in operating the system can be attributed to an extensive component development program, which is described. Stability of operation, ease of control, and flexibility in feed composition were demonstrated by the life test.

Pore size engineering applied to the design of separators for nickel-hydrogen cells and batteries

NASA Technical Reports Server (NTRS)

Abbey, K. M.; Britton, D. L.

1983-01-01

Pore size engineering in starved alkaline multiplate cells involves adopting techniques to widen the volume tolerance of individual cells. Separators with appropriate pore size distributions and wettability characteristics (capillary pressure considerations) to have wider volume tolerances and an ability to resist dimensional changes in the electrodes were designed. The separators studied for potential use in nickel-hydrogen cells consist of polymeric membranes as well as inorganic microporous mats. In addition to standard measurements, the resistance and distribution of electrolyte as a function of total cell electrolyte content were determined. New composite separators consisting of fibers, particles and/or binders deposited on Zircar cloth were developed in order to engineer the proper capillary pressure characteristics in the separator. These asymmetric separators were prepared from a variety of fibers, particles and binders. Previously announced in STAR as N83-24571

Ionic liquid as an electrolyte additive for high performance lead-acid batteries

NASA Astrophysics Data System (ADS)

Deyab, M. A.

2018-06-01

The performance of lead-acid battery is improved in this work by inhibiting the corrosion of negative battery electrode (lead) and hydrogen gas evolution using ionic liquid (1-ethyl-3-methylimidazolium diethyl phosphate). The results display that the addition of ionic liquid to battery electrolyte (5.0 M H2SO4 solution) suppresses the hydrogen gas evolution to very low rate 0.049 ml min-1 cm-2 at 80 ppm. Electrochemical studies show that the adsorption of ionic liquid molecules on the lead electrode surface leads to the increase in the charge transfer resistance and the decrease in the double layer capacitance. I also notice a noteworthy improvement of battery capacity from 45 mAh g-1 to 83 mAh g-1 in the presence of ionic liquid compound. Scanning electron microscopy and energy dispersive X-ray analysis confirm the adsorption of ionic liquid molecules on the battery electrode surface.

Improved cell for water-vapor electrolysis

NASA Technical Reports Server (NTRS)

Aylward, J. R.

1981-01-01

Continuous-flow electrolytic cells decompose water vapor in steam and room air into hydrogen and oxygen. Sintered iridium oxide catalytic anode coating yields dissociation rates hundredfold greater than those obtained using platinum black. Cell consists of two mirror-image cells, with dual cathode sandwiched between two anodes. Gas traverses serpentine channels within cell and is dissociated at anode. Oxygen mingles with gas stream, while hydrogen migrates through porous matrix and is liberated as gas at cathode.

Hydrogen-Oxygen PEM Regenerative Fuel Cell Energy Storage System

NASA Technical Reports Server (NTRS)

Bents, David J.; Scullin, Vincent J.; Chang, Bei-Jiann; Johnson, Donald W.; Garcia, Christopher P.

2005-01-01

An introduction to the closed cycle hydrogen-oxygen polymer electrolyte membrane (PEM) regenerative fuel cell (RFC), recently constructed at NASA Glenn Research Center, is presented. Illustrated with explanatory graphics and figures, this report outlines the engineering motivations for the RFC as a solar energy storage device, the system requirements, layout and hardware detail of the RFC unit at NASA Glenn, the construction history, and test experience accumulated to date with this unit.

ECAS Phase I fuel cell results. [Energy Conservation Alternatives Study

NASA Technical Reports Server (NTRS)

Warshay, M.

1978-01-01

This paper summarizes and discusses the fuel cell system results of Phase I of the Energy Conversion Alternatives Study (ECAS). Ten advanced electric powerplant systems for central-station baseload generation using coal were studied by NASA in ECAS. Three types of low-temperature fuel cells (solid polymer electrolyte, SPE, aqueous alkaline, and phosphoric acid) and two types of high-temperature fuel cells (molten carbonate, MC, and zirconia solid electrolyte, SE) were studied. The results indicate that (1) overall efficiency increases with fuel cell temperature, and (2) scale-up in powerplant size can produce a significant reduction in cost of electricity (COE) only when it is accompanied by utilization of waste fuel cell heat through a steam bottoming cycle and/or integration with a gasifier. For low-temperature fuel cell systems, the use of hydrogen results in the highest efficiency and lowest COE. In spite of higher efficiencies, because of higher fuel cell replacement costs integrated SE systems have higher projected COEs than do integrated MC systems. Present data indicate that life can be projected to over 30,000 hr for MC fuel cells, but data are not yet sufficient for similarly projecting SE fuel cell life expectancy.

Preparation of a self-humidifying membrane electrode assembly for fuel cell and its performance analysis

NASA Astrophysics Data System (ADS)

Wang, Cheng; Mao, Zongqiang; Xu, Jingming; Xie, Xiaofeng; Yang, Lizhai

2003-10-01

A novel nano-porous material SiO2-gel was prepared. After being purified by H2O2, then protonized by H2SO4 and desiccated in vacuum, the SiO2-gel, mixed with Nafion solution, was coated between an electrode and a solid electrolyte, which made a new type of self-humidifying membrane electrode assembly. The SiO2 powder was characterized by FTIR, BET and XRD. The surface of the electrodes was characterized by SEM and EDS. The performances of the self-humidifying membrane electrodes were analyzed by polarization discharge and AC impedance under the operation modes of external humidification and self-humidification respectively. Experimental-results indicated that the SiO2 powder held super-hydrophilicity, and the layer of SiO2 and Nafion polymer between electrode and solid electrolyte expanded three-dimension electrochemistry reac-tion area, maintained stability of catalyst layer and enhanced back-diffusion of water from cathode to anode, so the PEM Fuel cell can generate electricity at self-humidification mode. The power density of single PEM fuel cell reached 1.5 W/cm2 under 0.2 Mpa, 70°C and dry hydrogen and oxygen.

Rechargeable Metal–Air Proton‐Exchange Membrane Batteries for Renewable Energy Storage

PubMed Central

Nagao, Masahiro; Kobayashi, Kazuyo; Yamamoto, Yuta; Yamaguchi, Togo; Oogushi, Akihide

2015-01-01

Abstract Rechargeable proton‐exchange membrane batteries that employ organic chemical hydrides as hydrogen‐storage media have the potential to serve as next‐generation power sources; however, significant challenges remain regarding the improvement of the reversible hydrogen‐storage capacity. Here, we address this challenge through the use of metal‐ion redox couples as energy carriers for battery operation. Carbon, with a suitable degree of crystallinity and surface oxygenation, was used as an effective anode material for the metal redox reactions. A Sn0.9In0.1P2O7‐based electrolyte membrane allowed no crossover of vanadium ions through the membrane. The V4+/V3+, V3+/V2+, and Sn4+/Sn2+ redox reactions took place at a more positive potential than that for hydrogen reduction, so that undesired hydrogen production could be avoided. The resulting electrical capacity reached 306 and 258 mAh g−1 for VOSO4 and SnSO4, respectively, and remained at 76 and 91 % of their respective initial values after 50 cycles. PMID:27525212

Composite Ni/NiO-Cr2O3 Catalyst for Alkaline Hydrogen Evolution Reaction

PubMed Central

Bates, Michael K.; Jia, Qingying; Ramaswamy, Nagappan; Allen, Robert J.; Mukerjee, Sanjeev

2015-01-01

We report a Ni–Cr/C electrocatalyst with unprecedented mass-activity for the hydrogen evolution reaction (HER) in alkaline electrolyte. The HER kinetics of numerous binary and ternary Ni-alloys and composite Ni/metal-oxide/C samples were evaluated in aqueous 0.1 M KOH electrolyte. The highest HER mass-activity was observed for Ni–Cr materials which exhibit metallic Ni as well as NiOx and Cr2O3 phases as determined by X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) analysis. The onset of the HER is significantly improved compared to numerous binary and ternary Ni-alloys, including Ni–Mo materials. It is likely that at adjacent Ni/NiOx sites, the oxide acts as a sink for OHads, while the metallic Ni acts as a sink for the Hads intermediate of the HER, thus minimizing the high activation energy of hydrogen evolution via water reduction. This is confirmed by in situ XAS studies that show that the synergistic HER enhancement is due to NiOx content and that the Cr2O3 appears to stabilize the composite NiOx component under HER conditions (where NiOx would typically be reduced to metallic Ni0). Furthermore, in contrast to Pt, the Ni(Ox)/Cr2O3 catalyst appears resistant to poisoning by the anion exchange ionomer (AEI), a serious consideration when applied to an anionic polymer electrolyte interface. Furthermore, we report a detailed model of the double layer interface which helps explain the observed ensemble effect in the presence of AEI. PMID:26191118

Direct observation of individual hydrogen atoms at trapping sites in a ferritic steel

NASA Astrophysics Data System (ADS)

Chen, Y.-S.; Haley, D.; Gerstl, S. S. A.; London, A. J.; Sweeney, F.; Wepf, R. A.; Rainforth, W. M.; Bagot, P. A. J.; Moody, M. P.

2017-03-01

The design of atomic-scale microstructural traps to limit the diffusion of hydrogen is one key strategy in the development of hydrogen-embrittlement-resistant materials. In the case of bearing steels, an effective trapping mechanism may be the incorporation of finely dispersed V-Mo-Nb carbides in a ferrite matrix. First, we charged a ferritic steel with deuterium by means of electrolytic loading to achieve a high hydrogen concentration. We then immobilized it in the microstructure with a cryogenic transfer protocol before atom probe tomography (APT) analysis. Using APT, we show trapping of hydrogen within the core of these carbides with quantitative composition profiles. Furthermore, with this method the experiment can be feasibly replicated in any APT-equipped laboratory by using a simple cold chain.

Reactive Precipitation of Anhydrous Alkali Sulfide Nanocrystals with Concomitant Abatement of Hydrogen Sulfide and Cogeneration of Hydrogen.

PubMed

Li, Xuemin; Zhao, Yangzhi; Brennan, Alice; McCeig, Miranda; Wolden, Colin A; Yang, Yongan

2017-07-21

Anhydrous alkali sulfide (M 2 S, M=Li or Na) nanocrystals (NCs) are important materials central to the development of next generation cathodes and solid-state electrolytes for advanced batteries, but not commercially available at present. This work reports an innovative method to directly synthesize M 2 S NCs through alcohol-mediated reactions between alkali metals and hydrogen sulfide (H 2 S). In the first step, the alkali metal is complexed with alcohol in solution, forming metal alkoxide (ROM) and releasing hydrogen (H 2 ). Next, H 2 S is bubbled through the ROM solution, where both chemicals are completely consumed to produce phase-pure M 2 S NC precipitates and regenerate alcohol that can be recycled. The M 2 S NCs morphology may be tuned through the choice of the alcohol and solvent. Both synthetic steps are thermodynamically favorable (ΔG m o <-100 kJ mol -1 ), proceeding rapidly to completion at ambient temperature with almost 100 % atom efficiency. The net result, H 2 S+2 m→M 2 S+H 2 , makes good use of a hazardous chemical (H 2 S) and delivers two value-added products that naturally phase separate for easy recovery. This scalable approach provides an energy-efficient and environmentally benign solution to the production of nanostructured materials required in emerging battery technologies. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel solid oxide cells with SrCo0.8Fe0.1Ga0.1O3-δ oxygen electrode for flexible power generation and hydrogen production

NASA Astrophysics Data System (ADS)

Meng, Xiuxia; Shen, Yichi; Xie, Menghan; Yin, Yimei; Yang, Naitao; Ma, Zi-Feng; Diniz da Costa, João C.; Liu, Shaomin

2016-02-01

This work investigates the performance of solid oxide cells as fuel cells (SOFCs) for power production and also as electrolysis cells (SOECs) for hydrogen production. In order to deliver this dual mode flexible operation system, a novel perovskite oxide based on Ga3+ doped SrCo0.8Fe0.1Ga0.1O3-δ (SCFG) is synthesized via a sol-gel method. Its performance for oxygen electrode catalyst was then evaluated. Single solid oxide cell in the configuration of Ni-YSZ|YSZ|GDC|SCFG is assembled and tested in SOFC or SOEC modes from 550 to 850 °C with hydrogen as the fuel or as the product, respectively. GDC is used to avoid the reaction between the electrolyte YSZ and the cobalt-based electrode. Under SOFC mode, a maximum power density of 1044 mW cm-2 is obtained at 750 °C. Further, the cell delivers a stable power output of 650 mW cm-2 up to 125 h at 0.7 V. In the electrolysis mode, when the applied voltage is controlled at 2 V, the electrolysis current density reaches 3.33 A cm-2 at 850 °C with the hydrogen production rate up to 22.9 mL min-1 cm-2 (STP). These results reveal that SCFG is a very promising oxygen electrode material for application in both SOFC and SOEC.

Superlattice photoelectrodes for photoelectrochemical cells

DOEpatents

Nozik, A.J.

1985-07-03

The application of superlattice semiconductors as photoelectrodes in photoelectrochemical energy conversion processes is described. The invention is comprised of a multiple quantum well, or superlattice, semiconductor positioned on a plate and encapsulated in an insulation material, except the top surface, which is left exposed. An opening in insulation exposes a portion of the plate. When the photoelectrochemical cell is immersed in a liquid electrolyte and exposed to solar radiation, a redox reaction occurs, producing gases such as hydrogen and oxygen from a water electrolyte, which bubble off the cathode and anode portions of the cell. (LEW)

Combustibles sensor

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

Pebler, A.R.

1980-02-26

A gaseous mixture of oxygen and fuel (Combustibles) is supplied to first and second electrodes disposed on opposite surfaces of an oxygen ion conductive solid electrolyte member wherein the electrodes are composed of different materials each exhibiting a different catalytic action on the gaseous mixture at a given temperature. The difference in oxygen potentials established at the respective electrodes as a result of the dissimilar catalytic action produces oxygen ion conductivity in the solid electrolyte cell which produces an electrical signal the magnitude of which is indicative of the combustible present in the mixture, I.E., methane, hydrogen, carbon monoxide, etc.

Using Polymer Electrolyte Membrane Fuel Cells in a Hybrid Surface Ship Propulsion Plant to Increase Fuel Efficiency

DTIC Science & Technology

2010-06-01

cell ( PEMFC ), and the phosphoric acid fuel cell (PAFC). 2.3.1 Solid Oxide Fuel Cells (SOFC) The first type of fuel cell considered is the SOFC. This...durability issues for use within a given application. 2.3.2 Polymer Electrolyte Membrane Fuel Cells ( PEMFC ) The PEMFC operates by passing hydrogen that has...cells. Some advantages of PEMFC operating at such low temperatures is that the fuel cell doesn’t require as meticulous of a support system infrastructure

Electrochemical Characterization of InP and GaAs Based Structures for Space Solar Cell Applications.

NASA Technical Reports Server (NTRS)

Faur, Maria; Faur, Mircea; Jenkins, Philip P.; Goradia, Manju; Wilt, David M.

1994-01-01

In this paper the emphasis is on accurate majority carrier concentration EC-V profiling of structures based on Indium Phosphide and Gallium Arsenide, using a newly developed electrolyte based on Hydrogen Flouride, Acetic Acid, Phosphoric Acid, 1-phenyl-2-propanamine and Ammonia Diflouride. Some preliminary data on the use of this electrolyte for determining the energy distribution of surface and deep states of these structures, applicable to fabrication process optimization and radiation induced defects studies of solar cells, are also provided.

A Newly Designed Composite Gel Polymer Electrolyte Based on Poly(Vinylidene Fluoride-Hexafluoropropylene) (PVDF-HFP) for Enhanced Solid-State Lithium-Sulfur Batteries.

PubMed

Xia, Yan; Wang, Xiuli; Xia, Xinhui; Xu, Ruochen; Zhang, Shengzhao; Wu, Jianbo; Liang, Yanfei; Gu, Changdong; Tu, Jiangping

2017-10-26

Developing high-performance solid-state electrolytes is crucial for the innovation of next-generation lithium-sulfur batteries. Herein, a facile method for preparation of a novel gel polymer electrolyte (GPE) based on poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) is reported. Furthermore, Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 (LATP) nanoparticles as the active fillers are uniformly embedded into the GPE to form the final PVDF-HFP/LATP composite gel polymer electrolyte (CPE). Impressively, the obtained CPE demonstrates a high lithium ion transference number of 0.51 and improved electrochemical stability as compared to commercial liquid electrolyte. In addition, the assembled solid-sate Li-S battery with the composite gel polymer electrolyte membrane presents a high initial capacity of 918 mAh g -1 at 0.05 C, and better cycle performance than the counterparts with liquid electrolyte. Our designed PVDF-HFP/LATP composite can be a promising electrolyte for next-generation solid-state batteries with high cycling stability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A passive microfluidic hydrogen-air fuel cell with exceptional stability and high performance.

PubMed

Mitrovski, Svetlana M; Nuzzo, Ralph G

2006-03-01

We describe an advanced microfluidic hydrogen-air fuel cell (FC) that exhibits exceptional durability and high performance, most notably yielding stable output power (>100 days) without the use of an anode-cathode separator membrane. This FC embraces an entirely passive device architecture and, unlike conventional microfluidic designs that exploit laminar hydrodynamics, no external pumps are used to sustain or localize the reagent flow fields. The devices incorporate high surface area/porous metal and metal alloy electrodes that are embedded and fully immersed in liquid electrolyte confined in the channels of a poly(dimethylsiloxane) (PDMS)-based microfluidic network. The polymeric network also serves as a self-supporting membrane through which oxygen and hydrogen are supplied to the cathode and alloy anode, respectively, by permeation. The operational stability of the device and its performance is strongly dependent on the nature of the electrolyte used (5 M H2SO4 or 2.5 M NaOH) and composition of the anode material. The latter choice is optimized to decrease the sensitivity of the system to oxygen cross-over while still maintaining high activity towards the hydrogen oxidation reaction (HOR). Three types of high surface area anodes were tested in this work. These include: high-surface area electrodeposited Pt (Pt); high-surface area electrodeposited Pd (Pd); and thin palladium adlayers supported on a "porous" Pt electrode (Pd/Pt). The FCs display their best performance in 5 M H2SO4 using the Pd/Pt anode. This exceptional stability and performance was ascribed to several factors, namely: the high permeabilities of O2, H2, and CO2 in PDMS; the inhibition of the formation of insoluble carbonate species due to the presence of a highly acidic electrolyte; and the selectivity of the Pd/Pt anode toward the HOR. The stability of the device for long-term operation was modeled using a stack of three FCs as a power supply for a portable display that otherwise uses a 3 V battery.

A novel rechargeable zinc-air battery with molten salt electrolyte

NASA Astrophysics Data System (ADS)

Liu, Shuzhi; Han, Wei; Cui, Baochen; Liu, Xianjun; Zhao, Fulin; Stuart, Jessica; Licht, Stuart

2017-02-01

Zinc-air batteries have been proposed for EV applications and large-scale electricity storage such as wind and solar power. Although zinc-air batteries are very promising, there are numerous technological barriers to overcome. We demonstrate for the first time, a new rechargeable zinc-air battery that utilizes a molten Li0.87Na0.63K0.50CO3 eutectic electrolyte with added NaOH. Cyclic voltammetry reveals that a reversible deposition/dissolution of zinc occurs in the molten Li0.87Na0.63K0.50CO3 eutectic. At 550 °C, this zinc-air battery performs with a coulombic efficiency of 96.9% over 110 cycles, having an average charging potential of ∼1.43 V and discharge potential of ∼1.04 V. The zinc-air battery uses cost effective steel and nickel electrodes without the need for any precious metal catalysts. Moreover, the molten salt electrolyte offers advantages over aqueous electrolytes, avoiding the common aqueous alkaline electrolyte issues of hydrogen evolution, Zn dendrite formation, "drying out", and carbonate precipitation.

Influence of electrolyte composition and temperature on behaviour of AB5 hydrogen storage alloy used as negative electrode in Ni-MH batteries

NASA Astrophysics Data System (ADS)

Karwowska, Malgorzata; Jaron, Tomasz; Fijalkowski, Karol J.; Leszczynski, Piotr J.; Rogulski, Zbigniew; Czerwinski, Andrzej

2014-10-01

The AB5-type metal alloy (Mm-Ni4.1Al0.2Mn0.4Co0.45) has been investigated in different electrolytes (LiOH, NaOH, KOH, RbOH, CsOH). All of the electrochemical measurements have been performed using limited volume electrode technique (LVE). Thickness of the working electrode is nearly equal to the diameter of the grain (ca. 50 μm). Hydrogen diffusion coefficient has been determined using chronoamperometry. Hydrogen diffusion coefficient calculated for 100% state of charge reaches maximum value in KOH (DH = 4.65·10-10 cm2 s-1). We have obtained the highest value of capacity for the electrode in KOH and the lowest - in CsOH. The temperature influence on alloy capacity has been also tested. The alloy has been also characterised with SEM coupled with EDS, TGA/DSC and powder XRD. The unit cell of MmNi4.1Al0.2Mn0.4Co0.45 have been refined in the Cu5.4Yb0.8 structure type (a modified LaNi5 structure); the structure is unaffected by the electrochemical treatment.

Solid biopolymer electrolytes came from renewable biopolymer

NASA Astrophysics Data System (ADS)

Wang, Ning; Zhang, Xingxiang; Qiao, Zhijun; Liu, Haihui

2009-07-01

Solid polymer electrolytes (SPEs) have attracted many attentions as solid state ionic conductors, because of their advantages such as high energy density, electrochemical stability, and easy processing. SPEs obtained from starch have attracted many attentions in recent years because of its abundant, renewable, low price, biodegradable and biocompatible. In addition, the efficient utilization of biodegradable polymers came from renewable sources is becoming increasingly important due to diminishing resources of fossil fuels as well as white pollution caused by undegradable plastics based on petroleum. So N, N-dimethylacetamide (DMAc) with certain concentration ranges of lithium chloride (LiCl) is used as plasticizers of cornstarch. Li+ can complexes with the carbonyl atoms of DMAc molecules to produce a macro-cation and leave the Cl- free to hydrogen bond with the hydroxyl or carbonyl of starch. This competitive hydrogen bond formation serves to disrupt the intra- and intermolecular hydrogen bonding existed in starch. Therefore, melt extrusion process conditions are used to prepare conductive thermoplastic starch (TPS). The improvements of LiCl concentration increase the water absorption and conductance of TPS. The conductance of TPS containing 0.14 mol LiCl achieve to 10-0.5 S cm-1 with 18 wt% water content.

A Methodological Approach for Conducting a Business Case Analysis (BCA) of the Global Observer Joint Capability Technology Demonstration (JCTD)

DTIC Science & Technology

2007-12-01

Justthebasics.html [Accessed September 29, 2007]. [8] Smithsonian National Museum of American History . “ Proton Exchange Membrame (PEM) Fuel Cell...hydrogen-rich fuel, is fed to the anode where a catalyst separates hydrogen’s negatively charged electrons from the positively charged protons ...The protons are conducted through the electrolyte to the cathode, whereas the electrons are forced to travel in an external circuit, due to the

Effect of KOH concentration on LEO cycle life of IPV nickel-hydrogen flight cell - Update II

NASA Technical Reports Server (NTRS)

Smithrick, John J.; Hall, Stephen W.

1992-01-01

An update of validation test results confirming the breakthrough in LEO cycle life of nickel-hydrogen cells containing 26 percent KOH electrolyte is presented. A breakthrough in the LEO cycle life of individual pressure vessel (IPV) nickel-hydrogen cells has been previously reported. The cycle life of boiler plate cells containing 26 percent potassium hydroxide (KOH) electrolyte was about 40,000 LEO cycles, compared to 3500 cycles for cells containing 31 percent KOH. The cycle regime was a stressful accelerated LEO, which consisted of a 27.5 min charge followed by a 17.5 min discharge (2X normal rate). The depth-of-discharge was 80 percent. Six 48-Ah Hughes recirculation design IPV nickel-hydrogen flight battery cells are being evaluated. Three of the cells contain 26 percent KOH (test cells), and three contain 31 percent KOH (control cells). They are undergoing real time LEO cycle life testing. The cycle regime is a 90-min LEO orbit consisting of a 54-min charge followed by a 36-min discharge. The depth-of-discharge is 80 percent. The cell temperature is maintained at 10 C. The three 31 percent KOH cells failed (cycles 3729, 4165, and 11355). One of the 26 percent KOH cells failed at cycle 15314. The other two 26 percent KOH cells were cycled for over 16,000 cycles during the continuing test.

Preparation of the Pt/CNTs Catalyst and Its Application to the Fabrication of Hydrogenated Soybean Oil Containing a Low Content of Trans Fatty Acids Using the Solid Polymer Electrolyte Reactor.

PubMed

Zheng, Huanyu; Ding, Yangyue; Xu, Hui; Zhang, Lin; Cui, Yueting; Han, Jianchun; Zhu, Xiuqing; Yu, Dianyu; Jiang, Lianzhou; Liu, Lilai

2018-08-01

Pt/CNTs were synthesized with an ethylene glycol reduction method, and the effects of carboxyl functionalization, ultrasonic power and the concentration of chloroplatinic acid on the catalytic activity of Pt/CNTs were investigated. The optimal performance of the Pt/CNTs catalyst was obtained when the ultrasonic power was 300 W and the concentration of chloroplatinic acid was 40 mg/mL. The durability and stability of the Pt/CNTs catalyst were considerably better compared to Pt/C, as shown by cyclic voltammetry measurement results. The trans fatty acids content of the obtained hydrogenated soybean oil (IV: 108.4 gl2/100 g oil) using Pt/CNTs as the cathode catalyst in a solid polymer electrolyte reactor was only 1.49%. The IV of hydrogenated soybean oil obtained using CNTs as carrier with Pt loading 0.1 mg/cm2 (IV: 108.4 gl2/100 g oil) was lower than carbon with a Pt loading of 0.8 mg/cm2 (IV: 109.9 gl2/100 g oil). Thus, to achive the same IV, the usage of Pt was much less when carbon nanotubes were selected as catalyst carrier compared to traditional carbon carrier. The changes of fatty acid components and the hydrogenated selectivity of octadecenoic acid were also discussed.

Preliminary Evaluations of Polymer-based Lithium Battery Electrolytes Under Development for the Polymer Electrolyte Rechargeable Systems Program

NASA Technical Reports Server (NTRS)

Manzo, Michelle A.; Bennett, William R.

2003-01-01

A component screening facility has been established at The NASA Glenn Research Center (GRC) to evaluate candidate materials for next generation, lithium-based, polymer electrolyte batteries for aerospace applications. Procedures have been implemented to provide standardized measurements of critical electrolyte properties. These include ionic conductivity, electronic resistivity, electrochemical stability window, cation transference number, salt diffusion coefficient and lithium plating efficiency. Preliminary results for poly(ethy1ene oxide)-based polymer electrolyte and commercial liquid electrolyte are presented.

Binder Jetting: A Novel Solid Oxide Fuel-Cell Fabrication Process and Evaluation

NASA Astrophysics Data System (ADS)

Manogharan, Guha; Kioko, Meshack; Linkous, Clovis

2015-03-01

With an ever-growing concern to find a more efficient and less polluting means of producing electricity, fuel cells have constantly been of great interest. Fuel cells electrochemically convert chemical energy directly into electricity and heat without resorting to combustion/mechanical cycling. This article studies the solid oxide fuel cell (SOFC), which is a high-temperature (100°C to 1000°C) ceramic cell made from all solid-state components and can operate under a wide range of fuel sources such as hydrogen, methanol, gasoline, diesel, and gasified coal. Traditionally, SOFCs are fabricated using processes such as tape casting, calendaring, extrusion, and warm pressing for substrate support, followed by screen printing, slurry coating, spray techniques, vapor deposition, and sputter techniques, which have limited control in substrate microstructure. In this article, the feasibility of engineering the porosity and configuration of an SOFC via an additive manufacturing (AM) method known as binder jet printing was explored. The anode, cathode and oxygen ion-conducting electrolyte layers were fabricated through AM sequentially as a complete fuel cell unit. The cell performance was measured in two modes: (I) as an electrolytic oxygen pump and (II) as a galvanic electricity generator using hydrogen gas as the fuel. An analysis on influence of porosity was performed through SEM studies and permeability testing. An additional study on fuel cell material composition was conducted to verify the effects of binder jetting through SEM-EDS. Electrical discharge of the AM fabricated SOFC and nonlinearity of permeability tests show that, with additional work, the porosity of the cell can be modified for optimal performance at operating flow and temperature conditions.

Gas phase recovery of hydrogen sulfide contaminated polymer electrolyte membrane fuel cells

NASA Astrophysics Data System (ADS)

Kakati, Biraj Kumar; Kucernak, Anthony R. J.

2014-04-01

The effect of hydrogen sulfide (H2S) on the anode of a polymer electrolyte membrane fuel cell (PEMFC) and the gas phase recovery of the contaminated PEMFC using ozone (O3) were studied. Experiments were performed on fuel cell electrodes both in an aqueous electrolyte and within an operating fuel cell. The ex-situ analyses of a fresh electrode; a H2S contaminated electrode (23 μmolH2S cm-2); and the contaminated electrode cleaned with O3 shows that all sulfide can be removed within 900 s at room temperature. Online gas analysis of the recovery process confirms the recovery time required as around 720 s. Similarly, performance studies of an H2S contaminated PEMFC shows that complete rejuvenation occurs following 600-900 s O3 treatment at room temperature. The cleaning process involves both electrochemical oxidation (facilitated by the high equilibrium potential of the O3 reduction process) and direct chemical oxidation of the contaminant. The O3 cleaning process is more efficient than the external polarization of the single cell at 1.6 V. Application of O3 at room temperature limits the amount of carbon corrosion. Room temperature O3 treatment of poisoned fuel cell stacks may offer an efficient and quick remediation method to recover otherwise inoperable systems.

Replication of the Apparent Excess Heat Effect in a Light Water-Potassium Carbonate-Nickel Electrolytic Cell

NASA Technical Reports Server (NTRS)

Niedra, Janis M.; Myers, Ira T.; Fralick, Gustave C.; Baldwin, Richard S.

1996-01-01

Replication of experiments claiming to demonstrate excess heat production in light water-Ni-K2CO3 electrolytic cells was found to produce an apparent excess heat of 11 W maximum, for 60 W electrical power into the cell. Power gains range from 1.06 to 1.68. The cell was operated at four different dc current levels plus one pulsed current run at 1 Hz, 10% duty cycle. The 28 liter cell used in these verification tests was on loan from a private corporation whose own tests with similar cells are documented to produce 50 W steady excess heat for a continuous period exceeding hundreds of days. The apparent excess heat can not be readily explained either in terms of nonlinearity of the cell's thermal conductance at a low temperature differential or by thermoelectric heat pumping. However, the present data do admit efficient recombination of dissolved hydrogen-oxygen as an ordinary explanation. Calorimetry methods and heat balance calculations for the verification tests are described. Considering the large magnitude of benefit if this effect is found to be a genuine new energy source, a more thorough investigation of evolved heat in the nickel-hydrogen system in both electrolytic and gaseous loading cells remains warranted.

Highly Efficient and Robust Nickel Phosphides as Bifunctional Electrocatalysts for Overall Water-Splitting.

PubMed

Li, Jiayuan; Li, Jing; Zhou, Xuemei; Xia, Zhaoming; Gao, Wei; Ma, Yuanyuan; Qu, Yongquan

2016-05-04

To search for the efficient non-noble metal based and/or earth-abundant electrocatalysts for overall water-splitting is critical to promote the clean-energy technologies for hydrogen economy. Herein, we report nickel phosphide (NixPy) catalysts with the controllable phases as the efficient bifunctional catalysts for water electrolysis. The phases of NixPy were determined by the temperatures of the solid-phase reaction between the ultrathin Ni(OH)2 plates and NaH2PO2·H2O. The NixPy with the richest Ni5P4 phase synthesized at 325 °C (NixPy-325) delivered efficient and robust catalytic performance for hydrogen evolution reaction (HER) in the electrolytes with a wide pH range. The NixPy-325 catalysts also exhibited a remarkable performance for oxygen evolution reaction (OER) in a strong alkaline electrolyte (1.0 M KOH) due to the formation of surface NiOOH species. Furthermore, the bifunctional NixPy-325 catalysts enabled a highly performed overall water-splitting with ∼100% Faradaic efficiency in 1.0 M KOH electrolyte, in which a low applied external potential of 1.57 V led to a stabilized catalytic current density of 10 mA/cm(2) over 60 h.

Visualization of the Diffusion Pathway of Protons in (NH4)2Si0.5Ti0.5P4O13 as an Electrolyte for Intermediate-Temperature Fuel Cells.

PubMed

Sun, Chunwen; Chen, Lanli; Shi, Siqi; Reeb, Berthold; López, Carlos Alberto; Alonso, José Antonio; Stimming, Ulrich

2018-01-16

We demonstrate that (NH 4 ) 2 Si 0.5 Ti 0.5 P 4 O 13 is an excellent proton conductor. The crystallographic information concerning the hydrogen positions is unraveled from neutron-powder-diffraction (NPD) data for the first time. This study shows that all the hydrogen atoms are connected though H bonds, establishing a two-dimensional path between the [(Si 0.5 Ti 0.5 )P 4 O 13 2- ] n layers for proton diffusion across the crystal structure by breaking and reconstructing intermediate H-O═P bonds. This transient species probably reduces the potential energy of the H jump from an ammonium unit to the next neighboring NH 4 + unit. Both theoretical and experimental results support an interstitial-proton-conduction mechanism. The proton conductivities of (NH 4 ) 2 Si 0.5 Ti 0.5 P 4 O 13 reach 0.0061 and 0.024 S cm -1 in humid air at 125 and 250 °C, respectively. This finding demonstrates that (NH 4 ) 2 Si 0.5 Ti 0.5 P 4 O 13 is a promising electrolyte material operating at 150-250 °C. This work opens up a new avenue for designing and fabricating high-performance inorganic electrolytes.

On the nature of low temperature internal friction peaks in metallic glasses

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

Khonik, V.A.; Spivak, L.V.

Low temperature (30 < T < 300 K) internal friction in a metallic glass Ni{sub 60}Nb{sub 40} subjected to preliminary inhomogeneous deformation by cold rolling, homogeneous tensile deformation or electrolytic charging with hydrogen is investigated. Cold rolling or hydrogenation result in appearance of similar internal friction peaks and hysteresis damping. Homogeneous deformation has no influence on low temperature internal friction. The phenomenon of microplastic deformation during hydrogenation of weakly stressed samples is revealed. It is argued that microplastic deformation of metallic glasses during hydrogenation without external stress takes place too. Plastic flow both on cold rolling and hydrogenation occurs viamore » formation and motion of dislocation-like defects which are the reason of the observed anelastic anomalies. It is concluded that low temperature internal friction peaks described in the literature for as-cast, cold deformed and hydrogenated samples have common dislocation-like origin.« less

Improving The Efficiency Of Ammonia Electrolysis For Hydrogen Production

NASA Astrophysics Data System (ADS)

Palaniappan, Ramasamy

Given the abundance of ammonia in domestic and industrial wastes, ammonia electrolysis is a promising technology for remediation and distributed power generation in a clean and safe manner. Efficiency has been identified as one of the key issues that require improvement in order for the technology to enter the market phase. Therefore, this research was performed with the aim of improving the efficiency of hydrogen production by finding alternative materials for the cathode and electrolyte. 1. In the presence of ammonia the activity for hydrogen evolution reaction (HER) followed the trend Rh>Pt>Ru>Ni. The addition of ammonia resulted in lower rates for HER for Pt, Ru, and Ni, which have been attributed to competition from the ammonia adsorption reaction. 2. The addition of ammonia offers insight into the role of metal-hydrogen underpotential deposition (M-Hupd) on HER kinetics. In addition to offering competition via ammonia adsorption it resulted in fewer and weaker M-Hupd bonds for all metals. This finding substantiates the theory that M-Hupd bonds favor HER on Pt electrocatalyst. However, for Rh results suggest that M-Hupd bond may hinder the HER. In addition, the presence of unpaired valence shell electrons is suggested to provide higher activity for HER in the presence of ammonia. 3. Bimetals PtxM1-x (M = Ir, Ru, Rh, and Ni) offered lower overpotentials for HER compared to the unalloyed metals in the presence of ammonia. The activity of HER in the presence of ammonia follows the trend Pt-Ir>Pt-Rh>Pt-Ru>Pt-Ni. The higher activity of HER is attributed to the synergistic effect of the alloy, where ammonia adsorbs onto the more electropositive alloying metal leaving Pt available for Hupd formation and HER to take place. Additionally, this supports the theory that the presence of a higher number of unpaired electrons favors the HER in the presence of ammonia. 4. Potassium polyacrylate (PAA-K) was successfully used as a substitute for aqueous KOH for ammonia electrolysis. PAA-K allowed for a wider operating potential for the electrolytic cell while increasing the rate for HER at lower cell voltages. The conversion of ammonia improved from 16 % to 25 %, while the current efficiency for the consumption of ammonia increased from 92 +/- 1 % to 97 +/- 2 % by using PAA-K in lieu of KOH. The use of PAA-K also prevented the crossover of the hydrogen produced to the anode side, unlike aqueous KOH.

End of project report on degradation processes in hydrogen fuel cells.

DOT National Transportation Integrated Search

2008-01-01

Proton exchange membrane (PEM) fuel cells are one of the most popular types of fuel cells. They operate similarly to others with the electrolyte material inbetween the electrodes being a patented polymer called Nafion, made by DuPont. This polyelec...

Diffusion and Surface Reaction in Heterogeneous Catalysis

ERIC Educational Resources Information Center

Baiker, A.; Richarz, W.

1978-01-01

Ethylene hydrogenation on a platinum catalyst, electrolytically applied to a tube wall, is a good system for the study of the interactions between diffusion and surface reaction in heterogeneous catalysis. Theoretical background, apparatus, procedure, and student performance of this experiment are discussed. (BB)

The evaluation of layered separators for nickel-hydrogen cells

NASA Technical Reports Server (NTRS)

Gahn, Randall F.

1991-01-01

The concept of using layered separators to achieve the required electrolyte retention and bubble pressure fo nickel-hydrogen cells was evaluated in a boilerplate cell test. Zircar cloth, polyethylene paper and polypropylene felt were combined with a layer of radiation-grafted polyethylene film to achieve the required properties. Three cells of each layered separator were built and tested by characterization cycling and by low earth orbit cycling for 5000 cycles at 80 percent DOD. Three cells containing asbestos separators were used as the reference.

Investigation of the Alkaline Electrochemical Interface and Development of Composite Metal/Metal-Oxides for Hydrogen and Oxygen Electrodes

NASA Astrophysics Data System (ADS)

Bates, Michael

Understanding the fundamentals of electrochemical interfaces will undoubtedly reveal a path forward towards a society based on clean and renewable energy. In particular, it has been proposed that hydrogen can play a major role as an energy carrier of the future. To fully utilize the clean energy potential of a hydrogen economy, it is vital to produce hydrogen via water electrolysis, thus avoiding co-production of CO2 inherent to reformate hydrogen. While significant research efforts elsewhere are focused on photo-chemical hydrogen production from water, the inherent low efficiency of this method would require a massive land-use footprint to achieve sufficient hydrogen production rates to integrate hydrogen into energy markets. Thus, this research has primarily focused on the water splitting reactions on base-metal catalysts in the alkaline environment. Development of high-performance base-metal catalysts will help move alkaline water electrolysis to the forefront of hydrogen production methods, and when paired with solar and wind energy production, represents a clean and renewable energy economy. In addition to the water electrolysis reactions, research was conducted to understand the de-activation of reversible hydrogen electrodes in the corrosive environment of the hydrogen-bromine redox flow battery. Redox flow batteries represent a promising energy storage option to overcome the intermittency challenge of wind and solar energy production methods. Optimization of modular and scalable energy storage technology will allow higher penetration of renewable wind and solar energy into the grid. In Chapter 1, an overview of renewable energy production methods and energy storage options is presented. In addition, the fundamentals of electrochemical analysis and physical characterization of the catalysts are discussed. Chapter 2 reports the development of a Ni-Cr/C electrocatalyst with unprecedented mass-activity for the hydrogen evolution reaction (HER) in alkaline electrolyte. The HER kinetics of numerous binary & ternary Ni-alloys and composite Ni/metal-oxide/C samples were evaluated in aqueous 0.1 M KOH electrolyte. Furthermore a model of the double layer interface is proposed, which helps explain the observed ensemble effect in the presence of AEI. In Chapter 3, Ni-Fe and Ni-Fe-Co mixed-metal-oxide (MMO) films were investigated for oxygen evolution reaction (OER) activity in 0.1M KOH on high surface area Raney-Nickel supports. During investigations of MMO activity, aniline was identified as a useful "capping agent" for synthesis of high-surface area MMO-polyaniline (PANI) composite materials. A Ni-Fe-Co/PANI-Raney-Ni catalyst was developed which exhibits enhanced mass-activity compared to state-of-the-art Ni-Fe OER electrocatalysts reported to date. The morphology of the MMO catalyst film on PANI/Raney-Ni support provides excellent dispersion of active-sites and should maintain high active-site utilization for catalyst loading on gas-diffusion electrodes. In Chapter 4, the de-activation of reversible-hydrogen electrode catalysts was investigated and the development of a Pt-Ir-Nx/C catalyst is reported, which exhibits significantly increased stability in the HBr/Br 2 electrolyte. In contrast a Pt-Ir/C catalyst exhibited increased tolerance to high-voltage cycling and in particular showed recovery of electrocatalytic activity after reversible de-activation (presumably from bromide adsorption and subsequent oxidative bromide stripping). Under the harshest testing conditions of high-voltage cycling or exposure to Br2 the Pt-based catalyst showed a trend in stability: Pt < Pt-Ir < Pt-Ir-Nx. (Abstract shortened by UMI.).

Mechanistic Study of Electrolyte Additives to Stabilize High-Voltage Cathode-Electrolyte Interface in Lithium-Ion Batteries.

PubMed

Gao, Han; Maglia, Filippo; Lamp, Peter; Amine, Khalil; Chen, Zonghai

2017-12-27

Current developments of electrolyte additives to stabilize electrode-electrolyte interface in lithium-ion batteries highly rely on a trial-and-error search, which involves repetitive testing and intensive amount of resources. The lack of understandings on the fundamental protection mechanisms of the additives significantly increases the difficulty for the transformational development of new additives. In this study, we investigated two types of individual protection routes to build a robust cathode-electrolyte interphase at high potentials: (i) a direct reduction in the catalytic decomposition of the electrolyte solvent; and (ii) formation of a "corrosion inhibitor film" that prevents severely attack and passivation from protons that generated from the solvent oxidation, even the decomposition of solvent cannot be mitigated. Effect of two exemplary electrolyte additives, lithium difluoro(oxalato)borate (LiDFOB) and 3-hexylthiophene (3HT), on LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC 622) cathode were investigated to validate our hypothesis. It is demonstrated that understandings of both electrolyte additives and solvent are essential and careful balance between the cathode protection mechanism of additives and their side effects is critical to obtain optimum results. More importantly, this study opens up new directions of rational design of functional electrolyte additives for the next-generation high-energy-density lithium-ion chemistries.

PEM Electrolyzer Incorporating an Advanced Low-Cost Membrane

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

Hamdan, Monjid

The Department of Energy (DOE) has identified hydrogen production by electrolysis of water at forecourt stations as a critical technology for transition to the hydrogen economy; however, the cost of hydrogen produced by present commercially available electrolysis systems is considerably higher than the DOE 2015 and 2020 cost targets. Analyses of proton-exchange membrane (PEM) electrolyzer systems indicate that reductions in electricity consumption and electrolyzer stack and system capital cost are required to meet the DOE cost targets. The primary objective is to develop and demonstrate a cost-effective energy-based system for electrolytic generation of hydrogen. The goal is to increase PEMmore » electrolyzer efficiency and to reduce electrolyzer stack and system capital cost to meet the DOE cost targets for distributed electrolysis. To accomplish this objective, work was conducted by a team consisting of Giner, Inc. (Giner), Virginia Polytechnic Institute & University (VT), and domnick hunter group, a subsidiary of Parker Hannifin (Parker). The project focused on four (4) key areas: (1) development of a high-efficiency, high-strength membrane; (2) development of a long-life cell-separator; (3) scale-up of cell active area to 290 cm2 (from 160 cm²); and (4) development of a prototype commercial electrolyzer system. In each of the key stack development areas Giner and our team members conducted focused development in laboratory-scale hardware, with analytical support as necessary, followed by life-testing of the most promising candidate materials. Selected components were then scaled up and incorporated into low-cost scaled-up stack hardware. The project culminated in the fabrication and testing of a highly efficient electrolyzer system for production of 0.5 kg/hr hydrogen and validation of the stack and system in testing at the National Renewable Energy Laboratory (NREL).« less

Mechanisms for naphthalene removal during electrolytic aeration.

PubMed

Goel, Ramesh K; Flora, Joseph R V; Ferry, John

2003-02-01

Batch tests were performed to investigate chemical and physical processes that may result during electrolytic aeration of a contaminated aquifer using naphthalene as a model contaminant. Naphthalene degradation of 58-66% took place electrolytically and occurred at the same rates at a pH of 4 and 7. 1,4-naphthoquinone was identified as a product of the electrolysis. Stripping due to gases produced at the electrodes did not result in any naphthalene loss. Hydrogen peroxide (which may be produced at the cathode) did not have any effect on naphthalene, but the addition of ferrous iron (which may be present in aquifers) resulted in 67-99% disappearance of naphthalene. Chlorine (which may be produced from the anodic oxidation of chloride) can effectively degrade naphthalene at pH of 4, but not at a pH of 7. Mono-, di- and poly chloronaphthalenes were identified as oxidation products. Ferric iron coagulation (due to the oxidation of ferrous iron) did not significantly contribute to naphthalene loss. Overall, electrolytic oxidation and chemical oxidation due to the electrolytic by-products formed are significant abiotic processes that could occur and should be accounted for if bioremediation of PAH-contaminated sites via electrolytic aeration is considered. Possible undesirable products such as chlorinated compounds may be formed when significant amounts of chlorides are present.

Solid oxide fuel cell electrolytes produced via very low pressure suspension plasma spray and electrophoretic deposition

NASA Astrophysics Data System (ADS)

Fleetwood, James D.

Solid oxide fuel cells (SOFCs) are a promising element of comprehensive energy policies due to their direct mechanism for converting the oxidization of fuel, such as hydrogen, into electrical energy. Both very low pressure plasma spray and electrophoretic deposition allow working with high melting temperature SOFC suspension based feedstock on complex surfaces, such as in non-planar SOFC designs. Dense, thin electrolytes of ideal composition for SOFCs can be fabricated with each of these processes, while compositional control is achieved with dissolved dopant compounds that are incorporated into the coating during deposition. In the work reported, sub-micron 8 mole % Y2O3-ZrO2 (YSZ) and gadolinia-doped ceria (GDC), powders, including those in suspension with scandium-nitrate dopants, were deposited on NiO-YSZ anodes, via very low pressure suspension plasma spray (VLPSPS) at Sandia National Laboratories' Thermal Spray Research Laboratory and electrophoretic deposition (EPD) at Purdue University. Plasma spray was carried out in a chamber held at 320 - 1300 Pa, with the plasma composed of argon, hydrogen, and helium. EPD was characterized utilizing constant current deposition at 10 mm electrode separation, with deposits sintered from 1300 -- 1500 °C for 2 hours. The role of suspension constituents in EPD was analyzed based on a parametric study of powder loading, powder specific surface area, polyvinyl butyral (PVB) content, polyethyleneimine (PEI) content, and acetic acid content. Increasing PVB content and reduction of particle specific surface area were found to eliminate the formation of cracks when drying. PEI and acetic acid content were used to control suspension stability and the adhesion of deposits. Additionally, EPD was used to fabricate YSZ/GDC bilayer electrolyte systems. The resultant YSZ electrolytes were 2-27 microns thick and up to 97% dense. Electrolyte performance as part of a SOFC system with screen printed LSCF cathodes was evaluated with peak power densities as high as 520 mW/cm2 at 800 °C for YSZ and 350 mW/cm 2 at 800 °C for YSZ/GDC bilayer electrolytes.

Reorientation of the ‘free OH’ group in the top-most layer of air/water interface of sodium fluoride aqueous solution probed with sum-frequency generation vibrational spectroscopy

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

Feng, Ran-Ran; Guo, Yuan; Wang, Hongfei

2014-09-17

Many experimental and theoretical studies have established the specific anion, as well as cation effects on the hydrogen-bond structures at the air/water interface of electrolyte solutions. However, the ion effects on the top-most layer of the air/water interface, which is signified by the non-hydrogen-bonded so-called ‘free O-H’ group, has not been discussed or studied. In this report, we present the measurement of changes of the orientational angle of the ‘free O-H’ group at the air/water interface of the sodium fluoride (NaF) solutions at different concentrations using the interface selective sum-frequency generation vibrational spectroscopy (SFG-VS) in the ssp and ppp polarizations.more » The polarization dependent SFG-VS results show that the average tilt angle of the ‘free O-H’ changes from about 35.3 degrees ± 0.5 degrees to 43.4 degrees ± 2.1degrees as the NaF concentration increase from 0 to 0.94M (nearly saturated). Such tilt angle change is around the axis of the other O-H group of the same water molecule at the top-most layer at the air/water interface that is hydrogen-bonded to the water molecules below the top-most layer. These results provide quantitative molecular details of the ion effects of the NaF salt on the structure of the water molecules at the top-most layer of the air/water interfacial, even though both the Na+ cation and the F- anion are believed to be among the most excluded ions from the air/water interface.« less

Mathematical model of a parallel plate ammonia electrolyzer for combined wastewater remediation and hydrogen production.

PubMed

Estejab, Ali; Daramola, Damilola A; Botte, Gerardine G

2015-06-15

A mathematical model was developed for the simulation of a parallel plate ammonia electrolyzer to convert ammonia in wastewater to nitrogen and hydrogen under basic conditions. The model consists of fundamental transport equations, the ammonia oxidation kinetics at the anode, and the hydrogen evolution kinetics at the cathode of the electrochemical reactor. The model shows both qualitative and quantitative agreement with experimental measurements at ammonia concentrations found within wastewater (200-1200 mg L(-1)). The optimum electrolyzer performance is dependent on both the applied voltage and the inlet concentrations. Maximum conversion of ammonia to nitrogen at the rates of 0.569 and 0.766 mg L(-1) min(-1) are achieved at low (0.01 M NH4Cl and 0.1 M KOH) and high (0.07 M NH4Cl and 0.15 M KOH) inlet concentrations, respectively. At high and low concentrations, an initial increase in the cell voltage will cause an increase in the system response - current density generated and ammonia converted. These system responses will approach a peak value before they start to decrease due to surface blockage and/or depletion of solvated species at the electrode surface. Furthermore, the model predicts that by increasing the reactant and electrolyte concentrations at a certain voltage, the peak current density will plateau, showing an asymptotic response. Copyright © 2015 Elsevier Ltd. All rights reserved.

Improved stress corrosion cracking resistance of a novel biodegradable EW62 magnesium alloy by rapid solidification, in simulated electrolytes.

PubMed

Hakimi, O; Aghion, E; Goldman, J

2015-06-01

The high corrosion rate of magnesium (Mg) and Mg-alloys precludes their widespread acceptance as implantable biomaterials. Here, we investigated the potential for rapid solidification (RS) to increase the stress corrosion cracking (SCC) resistance of a novel Mg alloy, Mg-6%Nd-2%Y-0.5%Zr (EW62), in comparison to its conventionally cast (CC) counterpart. RS ribbons were extrusion consolidated in order to generate bioimplant-relevant geometries for testing and practical use. Microstructural characteristics were examined by SEM. Corrosion rates were calculated based upon hydrogen evolution during immersion testing. The surface layer of the tested alloys was analyzed by X-ray photoelectron spectroscopy (XPS). Stress corrosion resistance was assessed by slow strain rate testing and fractography. The results indicate that the corrosion resistance of the RS alloy is significantly improved relative to the CC alloy due to a supersaturated Nd enrichment that increases the Nd2O3 content in the external oxide layer, as well as a more homogeneous structure and reduced grain size. These improvements contributed to the reduced formation of hydrogen gas and hydrogen embrittlement, which reduced the SCC sensitivity relative to the CC alloy. Therefore, EW62 in the form of a rapidly solidified extruded structure may serve as a biodegradable implant for biomedical applications. Copyright © 2015 Elsevier B.V. All rights reserved.

A new preparation of a bifunctional crystalline heterogeneous copper electrocatalyst by electrodeposition using a Robson-type macrocyclic dinuclear copper complex for efficient hydrogen and oxygen evolution from water.

PubMed

Majumder, Samit; Abdel Haleem, Ashraf; Nagaraju, Perumandla; Naruta, Yoshinori

2017-07-18

The development of low-cost, stable bifunctional electrocatalysts, which operate in the same electrolyte with a low overpotential for water splitting, including the oxygen evolution reaction and the hydrogen evolution reaction, remains an attractive prospect and a great challenge. In this study, a water soluble Robson-type macrocyclic dicopper(ii) complex has been used for the first time as a catalyst precursor for the generation of a copper-based bifunctional heterogeneous catalyst film, which can be used for both HER and OER at a near neutral pH. In sodium borate buffer at pH 9.20, this complex decomposed to give a Cu(OH) 2 /Cu 2 O-based thin film on FTO that catalyzes both hydrogen production and water oxidation. The morphology, nature and composition of the thin film were fully characterized by scanning electron microscopy, powder X-ray diffraction, X-ray photoelectron, and energy dispersive X-ray spectroscopies. The catalyst film showed high stability during the course of electrolysis in either the cathodic or the anodic direction for more than 4 h. Faradaic efficiencies of ∼92% for HER and ∼96% for OER were achieved. The switch between the two half-reactions of catalytic water splitting was fully reversible in nature.

Utilization of aloe vera extract as electrolyte for an accumulator

NASA Astrophysics Data System (ADS)

Azmi, F.; Sispriatna, D.; Ikhsan, K.; Masrura, M.; Azzahra, S. S.; Mahidin; Supardan, M. D.

2018-03-01

Aloe vera contains acid, which has the potential to generate electric current. The objective of this research is to study the potency of aloe vera extract as electrolyte for an accumulator. Experimental results showed that aloe vera extract has no a stable value of voltage and currency. The voltage and currency of aloe vera extract were reduced more than 50% for 60 minutes. Then, aloe vera extract was mixed with accu zuur to produce electrolyte solution. The mixture composition of aloe vera extract to accu zuur of 50:50 (v/v) generated stable voltage and currency. The experimental results showed the potential use of aloe vera extract to reduce the chemicals used in a conventional electrolyte solution.

Tests of a novel sensor for α-spectrometry in drinking water matrices.

PubMed

Diener, A; Wilhelm, C

2015-09-01

The technical innovation of boron-doped diamond on top of a silicon layer as alpha nuclide measurement device offers promising advances, since the energy-resolved measurement takes place in-situ in water without matrix separation. Several experiments were performed to detect disturbance factors by investigating the yield of (241)Am in the presence of main or minor drinking water elements. The results show that an activity was detected by the sensor in any case. Generally, the yields were higher with NaNO3 as electrolyte than with Na2SO4, due to speciation and higher hydrogen formation. A reduced yield was observed for nitrate as electrolyte and maximum concentrations of Ca, Mg, PO4, and F in drinking water. The generally high standard deviation of the measurement, which is mainly due to hydrogen evolution, mass attenuation, and surface site occupation, does not allow for an exact determination of a present α-contamination. However, a significant aqueous alpha activity can be detected. Copyright © 2015 Elsevier Ltd. All rights reserved.

Catalyst supports for polymer electrolyte fuel cells.

PubMed

Subban, Chinmayee; Zhou, Qin; Leonard, Brian; Ranjan, Chinmoy; Edvenson, Heather M; Disalvo, F J; Munie, Semeret; Hunting, Janet

2010-07-28

A major challenge in obtaining long-term durability in fuel cells is to discover catalyst supports that do not corrode, or corrode much more slowly than the current carbon blacks used in today's polymer electrolyte membrane fuel cells. Such materials must be sufficiently stable at low pH (acidic conditions) and high potential, in contact with the polymer membrane and under exposure to hydrogen gas and oxygen at temperatures up to perhaps 120 degrees C. Here, we report the initial discovery of a promising class of doped oxide materials for this purpose: Ti(1-x)M(x)O(2), where M=a variety of transition metals. Specifically, we show that Ti(0.7)W(0.3)O(2) is electrochemically inert over the appropriate potential range. Although the process is not yet optimized, when Pt nanoparticles are deposited on this oxide, electrochemical experiments show that hydrogen is oxidized and oxygen reduced at rates comparable to those seen using a commercial Pt on carbon black support.

Evaluation of the effect of reactant gases mass flow rates on power density in a polymer electrolyte membrane fuel cell

NASA Astrophysics Data System (ADS)

Kahveci, E. E.; Taymaz, I.

2018-03-01

In this study it was experimentally investigated the effect of mass flow rates of reactant gases which is one of the most important operational parameters of polymer electrolyte membrane (PEM) fuel cell on power density. The channel type is serpentine and single PEM fuel cell has an active area of 25 cm2. Design-Expert 8.0 (trial version) was used with four variables to investigate the effect of variables on the response using. Cell temperature, hydrogen mass flow rate, oxygen mass flow rate and humidification temperature were selected as independent variables. In addition, the power density was used as response to determine the combined effects of these variables. It was kept constant cell and humidification temperatures while changing mass flow rates of reactant gases. From the results an increase occurred in power density with increasing the hydrogen flow rates. But oxygen flow rate does not have a significant effect on power density within determined mass flow rates.

Semiconductor-Electrocatalyst Interfaces: Theory, Experiment, and Applications in Photoelectrochemical Water Splitting.

PubMed

Nellist, Michael R; Laskowski, Forrest A L; Lin, Fuding; Mills, Thomas J; Boettcher, Shannon W

2016-04-19

Light-absorbing semiconductor electrodes coated with electrocatalysts are key components of photoelectrochemical energy conversion and storage systems. Efforts to optimize these systems have been slowed by an inadequate understanding of the semiconductor-electrocatalyst (sem|cat) interface. The sem|cat interface is important because it separates and collects photoexcited charge carriers from the semiconductor. The photovoltage generated by the interface drives "uphill" photochemical reactions, such as water splitting to form hydrogen fuel. Here we describe efforts to understand the microscopic processes and materials parameters governing interfacial electron transfer between light-absorbing semiconductors, electrocatalysts, and solution. We highlight the properties of transition-metal oxyhydroxide electrocatalysts, such as Ni(Fe)OOH, because they are the fastest oxygen-evolution catalysts known in alkaline media and are (typically) permeable to electrolyte. We describe the physics that govern the charge-transfer kinetics for different interface types, and show how numerical simulations can explain the response of composite systems. Emphasis is placed on "limiting" behavior. Electrocatalysts that are permeable to electrolyte form "adaptive" junctions where the interface energetics change during operation as charge accumulates in the catalyst, but is screened locally by electrolyte ions. Electrocatalysts that are dense, and thus impermeable to electrolyte, form buried junctions where the interface physics are unchanged during operation. Experiments to directly measure the interface behavior and test the theory/simulations are challenging because conventional photoelectrochemical techniques do not measure the electrocatalyst potential during operation. We developed dual-working-electrode (DWE) photoelectrochemistry to address this limitation. A second electrode is attached to the catalyst layer to sense or control current/voltage independent from that of the semiconductor back ohmic contact. Consistent with simulations, electrolyte-permeable, redox-active catalysts such as Ni(Fe)OOH form "adaptive" junctions where the effective barrier height for electron exchange depends on the potential of the catalyst. This is in contrast to sem|cat interfaces with dense electrolyte-impermeable catalysts, such as nanocrystalline IrOx, that behave like solid-state buried (Schottky-like) junctions. These results elucidate a design principle for catalyzed photoelectrodes. The buried heterojunctions formed by dense catalysts are often limited by Fermi-level pinning and low photovoltages. Catalysts deposited by "soft" methods, such as electrodeposition, form adaptive junctions that tend to provide larger photovoltages and efficiencies. We also preview efforts to improve theory/simulations to account for the presence of surface states and discuss the prospect of carrier-selective catalyst contacts.

Engineering rheology of electrolytes using agar for improving the performance of bioelectrochemical systems.

PubMed

Rathinam, Navanietha Krishnaraj; Tripathi, Abhilash K; Smirnova, Alevtina; Beyenal, Haluk; Sani, Rajesh K

2018-04-24

The present study is focused on enhancing the rheological properties of the electrolyte and eliminating sedimentation of microorganisms/flocs without affecting the electron transfer kinetics for improved bioelectricity generation. Agar derived from polysaccharide agarose (0.05-0.2%, w/v) was chosen as a rheology modifying agent. Electroanalytical investigations showed that electrolytes modified with 0.15% agar display a nine-fold increase in current density (1.2 mA/cm 2 ) by a thermophilic strain (Geobacillus sp. 44C, 60 °C) when compared with the control. Sodium phosphate buffer (0.1 M, pH 7) electrolyte with riboflavin (0.1 mM) was used as the control. Electrolytes modified with 0.15% agar significantly improved chemical oxygen demand removal rates. This developed electrolyte will aid in improving bioelectricity generation in Bioelectrochemical Systems (BES). The developed strategy avoids the use of peristaltic pumps and magnetic stirrers, thereby improving the energy efficiency of the process. Copyright © 2018 Elsevier Ltd. All rights reserved.

Modeling Joule Heating Effect on Lunar O2 Generation via Electrolytic Reduction.

NASA Technical Reports Server (NTRS)

Dominquez, Jesus; Poizeau, Sophie; Sibille, Laurent

2009-01-01

Kennedy Space Center is leading research work on lunar O2 generation via electrolytic reduction of regolith; the metal oxide present in the regolith is dissociated in oxygen anions and metal cations leading to the generation of gaseous oxygen at the anode and liquid metal at the cathode. Electrical resistance of molten regolith is high, leading to heating of the melt when electrical current is applied between the electrodes (Joule heating). The authors have developed a 3D model using a rigorous approach for two coupled physics (thermal and electrical potential) to not only study the effect of Joule heating on temperature distribution throughout the molten regolith but also to evaluate and optimize the design of the electrolytic cells. This paper presents the results of the thermal analysis performed on the model and used to validate the design of the electrolytic cell.

Multiphase transport in polymer electrolyte membrane fuel cells

NASA Astrophysics Data System (ADS)

Gauthier, Eric D.

Polymer electrolyte membrane fuel cells (PEMFCs) enable efficient conversion of fuels to electricity. They have enormous potential due to the high energy density of the fuels they utilize (hydrogen or alcohols). Power density is a major limitation to wide-scale introduction of PEMFCs. Power density in hydrogen fuel cells is limited by accumulation of water in what is termed fuel cell `flooding.' Flooding may occur in either the gas diffusion layer (GDL) or within the flow channels of the bipolar plate. These components comprise the electrodes of the fuel cell and balance transport of reactants/products with electrical conductivity. This thesis explores the role of electrode materials in the fuel cell and examines the fundamental connection between material properties and multiphase transport processes. Water is generated at the cathode catalyst layer. As liquid water accumulates it will utilize the largest pores in the GDL to go from the catalyst layer to the flow channels. Water collects to large pores via lateral transport at the interface between the GDL and catalyst layer. We have shown that water may be collected in these large pores from several centimeters away, suggesting that we could engineer the GDL to control flooding with careful placement and distribution of large flow-directing pores. Once liquid water is in the flow channels it forms slugs that block gas flow. The slugs are pushed along the channel by a pressure gradient that is dependent on the material wettability. The permeable nature of the GDL also plays a major role in slug growth and allowing bypass of gas between adjacent channels. Direct methanol fuel cells (DMFCs) have analogous multiphase flow issues where carbon dioxide bubbles accumulate, `blinding' regions of the fuel cell. This problem is fundamentally similar to water management in hydrogen fuel cells but with a gas/liquid phase inversion. Gas bubbles move laterally through the porous GDL and emerge to form large bubbles within the flow channel. We have compared the role of GDL materials in liquid drop and gas bubble formation and movement within fuel cells.

New Solid Polymer Electrolytes for Improved Lithium Batteries

NASA Technical Reports Server (NTRS)

Hehemann, David G.

2002-01-01

The objective of this work was to identify, synthesize and incorporate into a working prototype, next-generation solid polymer electrolytes, that allow our pre-existing solid-state lithium battery to function better under extreme conditions. We have synthesized polymer electrolytes in which emphasis was placed on the temperature-dependent performance of these candidate electrolytes. This project was designed to produce and integrate novel polymer electrolytes into a lightweight thin-film battery that could easily be scaled up for mass production and adapted to different applications.

Influence of anodizing conditions on generation of internal cracks in anodic porous tin oxide films grown in NaOH electrolyte

NASA Astrophysics Data System (ADS)

Zaraska, Leszek; Gawlak, Karolina; Gurgul, Magdalena; Dziurka, Magdalena; Nowak, Marlena; Gilek, Dominika; Sulka, Grzegorz D.

2018-05-01

Nanoporous tin oxide layers were synthesized via simple one-step anodic oxidation of a low-purity Sn foil (98.8%) in sodium hydroxide electrolyte. The process of pore formation at the early stage of anodization was discussed on the basis of concepts of oxygen bubble mould effect and viscous flow of oxide. The effect of anodizing conditions on the generation of internal cracks and fractures within the anodic film was investigated in detail. It was confirmed that crack-free tin oxide films can be obtained if the anodization is carried out at the potential of 4 V independently of the electrolyte concentration. On the other hand, the porous anodic film with a totally stacked internal morphology is obtained at the potential of 5 V in 0.1 M NaOH electrolyte. The generation of internal cracks and voids can be attributed to a much lower surface porosity and local trapping of O2 inside the pores of the oxide layer. However, increasing electrolyte concentration allows for obtaining less cracked porous films due to effective and uniform liberation of oxygen bubbles from the channels through completely open pore mouths. Furthermore, it was confirmed that uniformity of the anodic tin oxide layers can be significantly improved by vigorous electrolyte stirring. Finally, we observed that the addition of ethanol to the electrolyte can reduce anodic current density and the oxide growth rate. In consequence, less cracked anodic film can be formed even at the potential of 6 V. The generation of oxygen at the pore bottoms, together with the open pore mouths were found to be critical factors responsible for the anodic formation of crack-free porous tin oxide films.

Preparation and Characterization of Anode-Supported YSZ Thin Film Electrolyte by Co-Tape Casting and Co-Sintering Process

NASA Astrophysics Data System (ADS)

Liu, Q. L.; Fu, C. J.; Chan, S. H.; Pasciak, G.

2011-06-01

In this study, a co-tape casting and co-sintering process has been developed to prepare yttria-stabilized zirconia (YSZ) electrolyte films supported on Ni-YSZ anode substrates in order to substantially reduce the fabrication cost of solid oxide fuel cells (SOFC). Through proper control of the process, the anode/electrolyte bilayer structures with a size of 7.8cm × 7.8cm were achieved with good flatness. Scanning electron microscopy (SEM) observation indicated that the YSZ electrolyte film was about 16 μm in thickness, highly dense, crack free and well-bonded to the anode support. The electrochemical properties of the prepared anode-supported electrolyte film was evaluated in a button cell mode incorporating a (LaSr)MnO3-YSZ composite cathode. With humidified hydrogen as the fuel and stationary air as the oxidant, the cell demonstrated an open-circuit voltage of 1.081 V and a maximum power density of 1.01 W/cm2 at 800°C. The obtained results represent the important progress in the development of anode-supported intermediate temperature SOFC with reduced fabrication cost.

Synergistic effects of carboxymethyl cellulose and ZnO as alkaline electrolyte additives for aluminium anodes with a view towards Al-air batteries

NASA Astrophysics Data System (ADS)

Liu, Jie; Wang, Dapeng; Zhang, Daquan; Gao, Lixin; Lin, Tong

2016-12-01

The synergistic effects of carboxymethyl cellulose (CMC) and zinc oxide (ZnO) have been investigated as alkaline electrolyte additives for the AA5052 aluminium alloy anode in aluminium-air battery by the hydrogen evolution test, the electrochemical measurements and the surface analysis method. The combination of CMC and ZnO effectively retards the self-corrosion of AA5052 alloy in 4 M NaOH solution. A complex film is formed via the interaction between CMC and Zn2+ ions on the alloy surface. The carboxyl groups adsorbed on the surface of aluminium make the protective film more stable. The cathodic reaction process is mainly suppressed significantly. AA5052 alloy electrode has a good discharge performance in the applied electrolyte containing the composite CMC/ZnO additives.

Insulator to metal transition in WO 3 induced by electrolyte gating

DOE PAGES

Leng, X.; Pereiro, J.; Strle, J.; ...

2017-07-03

Tungsten oxide and its associated bronzes (compounds of tungsten oxide and an alkali metal) are well known for their interesting optical and electrical characteristics. We have modified the transport properties of thin WO 3 films by electrolyte gating using both ionic liquids and polymer electrolytes. We are able to tune the resistivity of the gated film by more than five orders of magnitude, and a clear insulator-to-metal transition is observed. To clarify the doping mechanism, we have performed a series of incisive operando experiments, ruling out both a purely electronic effect (charge accumulation near the interface) and oxygen-related mechanisms. Wemore » propose instead that hydrogen intercalation is responsible for doping WO 3 into a highly conductive ground state and provide evidence that it can be described as a dense polaronic gas.« less

Nanoporous palladium anode for direct ethanol solid oxide fuel cells with nanoscale proton-conducting ceramic electrolyte

NASA Astrophysics Data System (ADS)

Li, Yong; Wong, Lai Mun; Xie, Hanlin; Wang, Shijie; Su, Pei-Chen

2017-02-01

In this work, we demonstrate the operation of micro-solid oxide fuel cells (μ-SOFCs) with nanoscale proton-conducting Y-BaZrO3 (BZY) electrolyte to avoid the fuel crossover problem for direct ethanol fuel cells (DEFCs). The μ-SOFCs are operated with the direct utilisation of ethanol vapour as a fuel and Pd as anode at the temperature range of 300-400 °C. The nanoporous Pd anode is achieved by DC sputtering at high Ar pressure of 80 mTorr. The Pd-anode/BYZ-electrolyte/Pt-cathode cell show peak power densities of 72.4 mW/cm2 using hydrogen and 15.3 mW/cm2 using ethanol at 400 °C. No obvious carbon deposition is seen from XPS analysis after fuel cell test with ethanol fuel.

A self-healable and highly stretchable supercapacitor based on a dual crosslinked polyelectrolyte

NASA Astrophysics Data System (ADS)

Huang, Yan; Zhong, Ming; Huang, Yang; Zhu, Minshen; Pei, Zengxia; Wang, Zifeng; Xue, Qi; Xie, Xuming; Zhi, Chunyi

2015-12-01

Superior self-healability and stretchability are critical elements for the practical wide-scale adoption of personalized electronics such as portable and wearable energy storage devices. However, the low healing efficiency of self-healable supercapacitors and the small strain of stretchable supercapacitors are fundamentally limited by conventional polyvinyl alcohol-based acidic electrolytes, which are intrinsically neither self-healable nor highly stretchable. Here we report an electrolyte comprising polyacrylic acid dual crosslinked by hydrogen bonding and vinyl hybrid silica nanoparticles, which displays all superior functions and provides a solution to the intrinsic self-healability and high stretchability problems of a supercapacitor. Supercapacitors with this electrolyte are non-autonomic self-healable, retaining the capacitance completely even after 20 cycles of breaking/healing. These supercapacitors are stretched up to 600% strain with enhanced performance using a designed facile electrode fabrication procedure.

Hydrofluoroether electrolytes for lithium-ion batteries: Reduced gas decomposition and nonflammable

NASA Astrophysics Data System (ADS)

Nagasubramanian, Ganesan; Orendorff, Christopher J.

2011-10-01

The optimum combination of high energy density at the desired power sets lithium-ion battery technology apart from the other well known secondary battery chemistries. However, this is besieged by thermal instability of the electrolyte. This "Achilles heel" still remains a significant safety issue and unless this propensity is improved the promise of widespread adoption of Li-ion batteries for Transportation application may not be realized. With this in mind we launched a systematic study to evaluate fluoro solvents that are known to be nonflammable, for thermal and electrochemical performances. We investigated hydro-fluoro-ethers (HFE) (1) 2-trifluoromethyl-3-methoxyperfluoropentane {TMMP} and (2) 2-trifluoro-2-fluoro-3-difluoropropoxy-3-difluoro-4-fluoro-5-trifluoropentane {TPTP} in Sandia-built cells. Thermal properties under near abuse conditions that exist in thermal runaway environment and the electrochemical characteristics for these electrolytes were measured. In the thermal ramp (TR) measurement, EC:DEC:TPTP-1 M LiBETI (or TFSI or LiPF6) electrolytes exhibited no ignition/fire. Similar behavior was observed for the EC:DEC:TMMP-1 M LiBETI. Further, in ARC studies the HFE electrolytes generated less gas by 50% compared to the EC:EMC-1.2 M LiPF6 {CAR-1} electrolyte. Although in all cases the HFEs generated less gas, the onset of gas generation appears to depend on the salt. For the LiBETI and TFSI containing HFEs the onset is pushed out by ∼80 °C and for the LiPF6 the onset is comparable to that of the CAR-1. The solution ionic conductivity of these HFE electrolytes was lower (4-5 times) than that of the CAR-1 electrolyte however, the electrochemical performance was comparable. For example, full cells in 2032 type coin cells containing LiMN0.33Ni0.33Co0.33O2 cathode and carbon anode showed around 5 mA h capacity and the computed specific capacity was ∼154 mA h for all the electrolytes. In half-cells against lithium the cathode and anode gave specific capacity on the order of 170 mA h and 340 mA h respectively. These electrolytes when tested in 18,650 cells containing the above cathode and anode also showed comparable capacity. Further, the voltage stability window was not compromised by the HFEs. ARC measurements on 18,650 full cells showed less gas generation for the HFE electrolytes compared to CAR-1 electrolyte.

Density functional theory study of defect energies and space charge distribution at a solid-oxide electrolyte surface

NASA Astrophysics Data System (ADS)

Han, Chu; Bongiorno, Angelo

2014-03-01

Yttrium-doped barium zirconate (BZY) is a proton conducting electrolyte forming a class of novel materials for new generation of solid oxide fuel cells, for hydrogen separation and purification, and for electrolysis of water. Here we use density functional theory calculations to compute the energy of protons and oxygen vacancies at the surface and in the bulk of lightly Y-doped BZY materials. We found that protons are energetically more stable at the surface termination than in the bulk of BZY by about 1 eV. In contrast, doubly-positively charged oxygen vacancies are found to form iso-energetic defects at both the terminal surface layer and in the bulk of BZY, while in the sub-surface region the defect energy raises by about 1 eV with respect to the value in the bulk. The energetic behavior of protons and oxygen vacancies in the near surface region of BZY is attributed to the competition of strain and electrostatic effects. Lattice model representations of BZY surfaces are then used in combination with Monte Carlo simulations to solve the Poisson-Boltzmann equation and investigate the implication of the results above on the structure of the space charge region at the surface of BZY materials.

Effect of LEO cycling on 125 Ah advanced design IPV nickel-hydrogen battery cells

NASA Technical Reports Server (NTRS)

Smithrick, John J.; Hall, Stephen W.

1990-01-01

An advanced 125 Ah individual pressure vessel (IPV) nickel-hydrogen cell was designed. The primary function of the advanced cell, is to store and deliver energy for long term, low earth-orbit (LEO) spacecraft missions. The new features of this design are: (1) use of 26 percent rather than 31 percent potassium hydroxide (KOH) electrolyte, (2) use of a patented catalyzed wall wick, (3) use of serrated edge separators to facilitate gaseous oxygen and hydrogen flow within the cell, while still maintaining physical contact with the wall wick for electrolyte management, and (4) use of a floating rather than a fixed stack (state-of-the-art) to accommodate nickel electrode expansion. Six 125 Ah flight cells based on this design were fabricated by Eagle-Picher. Three of the cells contain all of the advanced features (test cells) and three are the same as the test cells except they don't have catalyst on the wall wick (control cells). All six cells are in the process of being evaluated in a LEO cycle life test. The cells have accumulated about 4700 LEO cycles (60 percent DOD 10 C). There have been no cell failures, the catalyzed wall wick cells however, are performing better.

Effect of LEO cycling on 125 Ah advanced design IPV nickel-hydrogen battery cells

NASA Technical Reports Server (NTRS)

Smithrick, John J.; Hall, Stephen W.

1990-01-01

An advanced 125 Ah individual pressure vessel (IPV) nickel-hydrogen cell was designed. The primary function of the advanced cell is to store and deliver energy for long-term, low earth-orbit (LEO) spacecraft missions. The new features of this design are: (1) use of 26 percent rather than 31 percent potassium hydroxide (KOH) electrolyte, (2) use of a patented catalyzed wall wick, (3) use of serrated-edge separators to facilitate gaseous oxygen and hydrogen flow within the cell, while still maintaining physical contact with the wall wick for electrolyte management, and (4) use of a floating rather than a fixed stack (state-of-the-art) to accommodate nickel electrode expansion. Six 125-Ah flight cells based on this design were fabricated by Eagle-Picher. Three of the cells contain all of the advanced features (test cells) and three are the same as the test cells except they don't have catalyst on the wall wick (control cells). All six cells are in the process of being evaluated in a LEO cycle life test. The cells have accumulated about 4700 LEO cycles (60 percent DOD 10 C). There have been no cell failures; the catalyzed wall wick cells, however, are performing better.

Toward Eco-Friendly and Highly Efficient Solar Water Splitting Using In2S3/Anatase/Rutile TiO2 Dual-Staggered-Heterojunction Nanodendrite Array Photoanode.

PubMed

Yang, Jih-Sheng; Wu, Jih-Jen

2018-01-31

The TiO 2 -based heterojunction nanodendrite (ND) array composed of anatase nanoparticles (ANPs) on the surface of the rutile ND (RND) array is selected as the model photoanode to demonstrate the strategies toward eco-friendly and efficient solar water splitting using neutral electrolyte and seawater. Compared with the performances in alkaline electrolyte, a non-negligible potential drop across the electrolyte as well as impeded charge injection and charge separation is monitored in the ANP/RND array photoanode with neutral electrolyte, which are, respectively, ascribed to the series resistance of neutral electrolyte, the fundamentally pH-dependent water oxidation mechanism on TiO 2 surface, as well as the less band bending at the interface of TiO 2 and neutral electrolyte. Accordingly, a TiO 2 -based dual-staggered heterojunction ND array photoanode is further designed in this work to overcome the issue of less band bending with the neutral electrolyte. The improvement of charge separation efficiency is realized by the deposition of a transparent In 2 S 3 layer on the ANP/RND array photoanode for constructing additional staggered heterojunction. Under illumination of AM 1.5G (100 mW cm -2 ), the improved photocurrent densities acquired both in neutral electrolyte and seawater at 1.23 V vs reversible hydrogen electrode (RHE), which approach the theoretical value for rutile TiO 2 , are demonstrated in the dual-staggered-heterojunction ND array photoanode. Faradaic efficiencies of ∼95 and ∼32% for solar water oxidation in neutral electrolyte and solar seawater oxidation for 2 h are acquired at 1.23 V vs RHE, respectively.

H2@Scale Resource and Market Analysis

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

Ruth, Mark

The 'H2@Scale' concept is based on the potential for wide-scale utilization of hydrogen as an energy intermediate where the hydrogen is produced from low cost energy resources and it is used in both the transportation and industrial sectors. H2@Scale has the potential to address grid resiliency, energy security, and cross-sectoral emissions reductions. This presentation summarizes the status of an ongoing analysis effort to quantify the benefits of H2@Scale. It includes initial results regarding market potential, resource potential, and impacts of when electrolytic hydrogen is produced with renewable electricity to meet the potential market demands. It also proposes additional analysis effortsmore » to better quantify each of the factors.« less

Combining hydrogen evolution and corrosion data - A case study on the economic viability of selected metal cathodes in microbial electrolysis cells

NASA Astrophysics Data System (ADS)

Brown, Robert Keith; Schmidt, Ulrike Christiane; Harnisch, Falk; Schröder, Uwe

2017-07-01

In this study, hydrogen evolution reaction (HER) catalytic and corrosion data is determined for selected metal cathode materials. The HER data was gathered using cyclic voltammetry (CV) in electrolytes with several pH values and varying current densities. Of the tested materials, the stainless steel alloy EN 1.4401/AISI 316 generally had the lowest HER overpotentials at the pH values 0.25, 7 and 9. At the higher pH values of 11 and 14 a custom NiMoFe alloy with a m/m% composition of 60-30-10 showed the lowest overpotentials. After each CV experiment, the electrolyte solution was analyzed to determine the corrosion of the metal cathodes. Results of corrosion measurements showed that the stainless steels EN 1.4401 had the lowest corrosion losses on average across all tested pH values. Combining HER and corrosion data revealed that: In the pH 9 electrolyte solution, EN 1.4401 was not always the best catalyst in terms of its overpotential, but it incurs the least material costs due to its lack of corrosion, this balance thereby making it the "best choice" under the given conditions. The combination of HER and corrosion data provides a more effective framework for discussing economic viability than either data set alone.

Exploration on effects of 15 nm SiO2 filler on miscibility, thermal stability and ionic conductivity of PMMA/ENR 50 electrolytes

NASA Astrophysics Data System (ADS)

Zamri, S. F. M.; Latif, F. A.; Ali, A. M. M.; Ibrahim, R.; Azuan, S. I. H. M.; Kamaluddin, N.; Hadip, F.

2017-02-01

The effects of silicon dioxide (SiO2) (15 nm) filler on miscibility, thermal stability and ionic conductivity of polymethyl methacrylate/50% epoxidized narural rubber (PMMA/ENR 50) electrolytes were successfully explored. Samples were prepared by solvent casting method with tetrahydrofuran (THF) as solvent and doped with lithium tetrafluoroborate (LiBF4). Fourier transform infrared spectroscopy (FTIR) confirmed the present of hydrogen bond between PMMA and ENR 50. However, the hydrogen bond was reduced when SiO2 was added. Differential scanning calorimeter (DSC) analysis shows that PMMA/ENR 50 blends exhibit two glass transition temperatures (Tgs) recorded at -35 and 89 °C corresponding to the Tg of ENR 50 rich phase (Tg1) and PMMA rich phase (Tg2), respectively. However, the two Tgs almost merging and reduced when SiO2 was added. Tg1 was found increases as SiO2 weight percent increased. Thermogravimetric analysis (TGA) revealed that thermal degradation temperatures (Tds) of SiO2 filled PMMA/ENR 50 was similar as PMMA/ENR 50. Interestingly, thermal degradation temperatures of the loss of impurities (Td1) and thermal degradation temperatures of PMMA side chain (Td2) were increased when SiO2 was added. Meanwhile thermal degradation temperatures of main PMMA and ENR 50 main chain (Td3) was decreased as SiO2 was added. There was no significant change in Td1, Td2 and Td3 as SiO2 weight percent was varied. Electrochemical impedence spectroscopy (EIS) analysis shows that room temperature ionic conductivity of SiO2 filled PMMA/ENR 50 electrolytes were higher compaed PMMA/ENR 50 electrolyte with two conductivity maxima.

Development status of a preprototype water electrolysis subsystem

NASA Technical Reports Server (NTRS)

Martin, R. B.; Erickson, A. C.

1981-01-01

A preprototype water electrolysis subsystem was designed and fabricated for NASA's advanced regenerative life support program. A solid polymer is used for the cell electrolyte. The electrolysis module has 12 cells that can generate 5.5 kg/day of oxygen for the metabolic requirements of three crewmembers, for cabin leakage, and for the oxygen and hydrogen required for carbon dioxide collection and reduction processes. The subsystem can be operated at a pressure between 276 and 2760 kN/sq m and in a continuous constant-current, cyclic, or standby mode. A microprocessor is used to aid in operating the subsystem. Sensors and controls provide fault detection and automatic shutdown. The results of development, demonstration, and parametric testing are presented. Modifications to enhance operation in an integrated and manned test are described. Prospective improvements for the electrolysis subsystem are discussed.

Development of compact fuel processor for 2 kW class residential PEMFCs

NASA Astrophysics Data System (ADS)

Seo, Yu Taek; Seo, Dong Joo; Jeong, Jin Hyeok; Yoon, Wang Lai

Korea Institute of Energy Research (KIER) has been developing a novel fuel processing system to provide hydrogen rich gas to residential polymer electrolyte membrane fuel cells (PEMFCs) cogeneration system. For the effective design of a compact hydrogen production system, the unit processes of steam reforming, high and low temperature water gas shift, steam generator and internal heat exchangers are thermally and physically integrated into a packaged hardware system. Several prototypes are under development and the prototype I fuel processor showed thermal efficiency of 73% as a HHV basis with methane conversion of 81%. Recently tested prototype II has been shown the improved performance of thermal efficiency of 76% with methane conversion of 83%. In both prototypes, two-stage PrOx reactors reduce CO concentration less than 10 ppm, which is the prerequisite CO limit condition of product gas for the PEMFCs stack. After confirming the initial performance of prototype I fuel processor, it is coupled with PEMFC single cell to test the durability and demonstrated that the fuel processor is operated for 3 days successfully without any failure of fuel cell voltage. Prototype II fuel processor also showed stable performance during the durability test.

Second harmonic generation study of malachite green adsorption at the interface between air and an electrolyte solution: observing the effect of excess electrical charge density at the interface.

PubMed

Song, Jinsuk; Kim, Mahn Won

2010-03-11

Understanding the differential adsorption of ions at the interface of an electrolyte solution is very important because it is closely related, not only to the fundamental aspects of biological systems, but also to many industrial applications. We have measured the excess interfacial negative charge density at air-electrolyte solution interfaces by using resonant second harmonic generation of oppositely charged probe molecules. The excess charge density increased with the square root of the bulk electrolyte concentration. A new adsorption model that includes the electrostatic interaction between adsorbed molecules is proposed to explain the measured adsorption isotherm, and it is in good agreement with the experimental results.

Thermo-electrochemical production of compressed hydrogen from methane with near-zero energy loss

NASA Astrophysics Data System (ADS)

Malerød-Fjeld, Harald; Clark, Daniel; Yuste-Tirados, Irene; Zanón, Raquel; Catalán-Martinez, David; Beeaff, Dustin; Morejudo, Selene H.; Vestre, Per K.; Norby, Truls; Haugsrud, Reidar; Serra, José M.; Kjølseth, Christian

2017-11-01

Conventional production of hydrogen requires large industrial plants to minimize energy losses and capital costs associated with steam reforming, water-gas shift, product separation and compression. Here we present a protonic membrane reformer (PMR) that produces high-purity hydrogen from steam methane reforming in a single-stage process with near-zero energy loss. We use a BaZrO3-based proton-conducting electrolyte deposited as a dense film on a porous Ni composite electrode with dual function as a reforming catalyst. At 800 °C, we achieve full methane conversion by removing 99% of the formed hydrogen, which is simultaneously compressed electrochemically up to 50 bar. A thermally balanced operation regime is achieved by coupling several thermo-chemical processes. Modelling of a small-scale (10 kg H2 day-1) hydrogen plant reveals an overall energy efficiency of >87%. The results suggest that future declining electricity prices could make PMRs a competitive alternative for industrial-scale hydrogen plants integrating CO2 capture.

Ultracapacitor having residual water removed under vacuum

DOEpatents

Wei, Chang; Jerabek, Elihu Calvin; Day, James

2002-10-15

A multilayer cell is provided that comprises two solid, nonporous current collectors, two porous electrodes separating the current collectors, a porous separator between the electrodes and an electrolyte occupying pores in the electrodes and separator. The mutilayer cell is electrolyzed to disassociate water within the cell to oxygen gas and hydrogen gas. A vacuum is applied to the cell substantially at the same time as the electrolyzing step, to remove the oxygen gas and hydrogen gas. The cell is then sealed to form a ultracapacitor substantially free from water.

Direct ethanol solid oxide fuel cell operating in gradual internal reforming

NASA Astrophysics Data System (ADS)

Nobrega, S. D.; Galesco, M. V.; Girona, K.; de Florio, D. Z.; Steil, M. C.; Georges, S.; Fonseca, F. C.

2012-09-01

An electrolyte supported solid oxide fuel cell (SOFC) using standard electrodes, doped-lanthanum manganite cathode and Ni-cermet anode, was operated with direct (anhydrous) ethanol for more than 100 h, delivering essentially the same power output as running on hydrogen. A ceria-based layer provides the catalytic activity for the gradual internal reforming, which uses the steam formed by the electrochemical oxidation of hydrogen for the decomposition of ethanol. Such a concept opens up the way for multi-fuel SOFCs using standard components and a catalytic layer.

LEED-AES-Thin Layer Electrochemical Studies of Hydrogen Adsorption on Platinum Single Crystals.

DTIC Science & Technology

1982-08-01

of the voltametry sweep and has been observed in HF but not H2SO4 as the electrolyte (1). This anomalous behavior is not easily explained by any...Fig. 3. Cyclic linear sweep voltametry curve for Pt(3ll) in 0.1 N WF. Sveep rate: 50 uV/s. Solid line: secoad cycle 0.05 to 0.5 V; dotted line: fourth...Without such cycling, the hydrogen region of the voltametry curves usually does not yield well defined peaks in either polycrystalline or single crystal

76 FR 45436 - Federal Motor Vehicle Safety Standards; Electric-Powered Vehicles; Electrolyte Spillage and...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-07-29

... electrical isolation requirements, the test specifications and requirements for electrical isolation monitoring, the state-of-charge of electric energy storage devices prior to the crash tests, a proposed protective barrier compliance option for electrical safety, the use of alternative gas to crash test hydrogen...

Strongly correlated perovskite fuel cells

NASA Astrophysics Data System (ADS)

Zhou, You; Guan, Xiaofei; Zhou, Hua; Ramadoss, Koushik; Adam, Suhare; Liu, Huajun; Lee, Sungsik; Shi, Jian; Tsuchiya, Masaru; Fong, Dillon D.; Ramanathan, Shriram

2016-06-01

Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes. Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.

Strongly correlated perovskite fuel cells

DOE PAGES

Zhou, You; Guan, Xiaofei; Zhou, Hua; ...

2016-05-16

Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes.more » Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.« less

Strongly correlated perovskite fuel cells.

PubMed

Zhou, You; Guan, Xiaofei; Zhou, Hua; Ramadoss, Koushik; Adam, Suhare; Liu, Huajun; Lee, Sungsik; Shi, Jian; Tsuchiya, Masaru; Fong, Dillon D; Ramanathan, Shriram

2016-06-09

Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes. Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.

Repeatable hydrogen generation of 3D microporous nickel membrane using chemical milling

NASA Astrophysics Data System (ADS)

Seo, Keumyoung; Lim, Taekyung; Ju, Sanghyun

2018-05-01

In this study, we investigated a novel method of hydrogen generation through a chemical milling process. In the process of generating hydrogen with a thermochemical water-splitting method using a 3D microporous nickel membrane, the nickel surface is oxidized, leading to a decreased generation of hydrogen gas with time. To regenerate hydrogen from the oxidized catalysts, the oxidized metal surface was easily removed at room temperature, re-exposing a metal surface with abundant oxygen vacancies for continuous hydrogen generation. With this method, ~110 µmol · g‑1 of hydrogen gas was continuously produced per cycle. Since this method enabled us to create a fit state for hydrogen generation without extra heat, light, or electrical energy, it can solve the biggest commercialization challenge: inefficiency because the energy required for hydrogen generation is higher than the energy of the generated hydrogen.

Hydrophobic, Porous Battery Boxes

NASA Technical Reports Server (NTRS)

Bragg, Bobby J.; Casey, John E., Jr.

1995-01-01

Boxes made of porous, hydrophobic polymers developed to contain aqueous potassium hydroxide electrolyte solutions of zinc/air batteries while allowing air to diffuse in as needed for operation. Used on other types of batteries for in-cabin use in which electrolytes aqueous and from which gases generated during operation must be vented without allowing electrolytes to leak out.

Hydrophobic interaction and charge accumulation at the diamond-electrolyte interface.

PubMed

Dankerl, M; Lippert, A; Birner, S; Stützel, E U; Stutzmann, M; Garrido, J A

2011-05-13

The hydrophobic interaction of surfaces with water is a well-known phenomenon, but experimental evidence of its influence on biosensor devices has been lacking. In this work we investigate diamond field-effect devices, reporting on Hall effect experiments and complementary simulations of the interfacial potential at the hydrogen-terminated diamond/aqueous electrolyte interface. The interfacial capacitance, derived from the gate-dependent Hall carrier concentration, can be modeled only when considering the hydrophobic nature of this surface and its influence on the structure of interfacial water. Our work demonstrates how profoundly the performance of potentiometric biosensor devices can be affected by their surfaces' hydrophobicity.

Chitosan biopolymer for fuel cell applications.

PubMed

Ma, Jia; Sahai, Yogeshwar

2013-02-15

Fuel cell is an electrochemical device which converts chemical energy stored in a fuel into electrical energy. Fuel cells have been receiving attention due to its potential applicability as a good alternative power source. Recently, cost-effective and eco-friendly biopolymer chitosan has been extensively studied as a material for membrane electrolytes and electrodes in low to intermediate temperature hydrogen polymer electrolyte fuel cell, direct methanol fuel cell, alkaline fuel cell, and biofuel cell. This paper reviews structure and property of chitosan with respect to its applications in fuel cells. Recent achievements and prospect of its applications have also been included. Copyright © 2012 Elsevier Ltd. All rights reserved.

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.

A self-healable and highly stretchable supercapacitor based on a dual crosslinked polyelectrolyte

PubMed Central

Huang, Yan; Zhong, Ming; Huang, Yang; Zhu, Minshen; Pei, Zengxia; Wang, Zifeng; Xue, Qi; Xie, Xuming; Zhi, Chunyi

2015-01-01

Superior self-healability and stretchability are critical elements for the practical wide-scale adoption of personalized electronics such as portable and wearable energy storage devices. However, the low healing efficiency of self-healable supercapacitors and the small strain of stretchable supercapacitors are fundamentally limited by conventional polyvinyl alcohol-based acidic electrolytes, which are intrinsically neither self-healable nor highly stretchable. Here we report an electrolyte comprising polyacrylic acid dual crosslinked by hydrogen bonding and vinyl hybrid silica nanoparticles, which displays all superior functions and provides a solution to the intrinsic self-healability and high stretchability problems of a supercapacitor. Supercapacitors with this electrolyte are non-autonomic self-healable, retaining the capacitance completely even after 20 cycles of breaking/healing. These supercapacitors are stretched up to 600% strain with enhanced performance using a designed facile electrode fabrication procedure. PMID:26691661

Electrochemical performance investigations on the hydrogen depolarized CO2 concentrator

NASA Technical Reports Server (NTRS)

Aylward, J. R.

1976-01-01

An extensive investigation of anode and cathode polarization in complete cells and half cells was conducted to determine the factors affecting HDC electrode polarization and the nature of this polarization. Matrix-electrolyte-electrode interactions and cell electrolyte composition were also investigated. The electrodes were found to have normal performance capabilities. The HDC anode polarization characteristics were correlated with a theoretical kinetic analysis; and, except for some quantitative details, a rather complete understanding of the causes for HDC electrode polarization was formulated. One of the important finding resulting from the kinetic analysis was that platinum appears to catalyze the decomposition of carbonic acid to carbon dioxide and water. It was concluded that the abnormal voltage performance of the One Man ARS HDC cells was caused by insufficient cell electrolyte volume under normal operating conditions due to deficiencies in the reservoir to cell interfacing.

Resource and energy management of synfuels production with hydrogen and oxygen requirements from electrolysis

NASA Astrophysics Data System (ADS)

Shannon, R. H.; Richardson, R. D.

The Resource and Energy Management System (REM), which uses electrolytic H2 and O2 to produce synthetic crude and light oils from heavy hydrocarbons is described. The heavy hydrocarbon feedstocks include heavy oils, tar sand bitumens, heavy residual oils, oil shale kerogens, liquefied coal, and pyrolytically-extracted coal liquids. The system includes mini-upgraders, which can be implemented in modular form, to pump electrolytically-derived H2 into heavy oils to upgrade their energy content. Projected costs for the production of synthetic light oils using U.S. coal reserves with the REM process after liquefaction are $30-35/bbl, with the H2 costs being a controlling factor. The modular systems could be built in a much shorter time frame than much larger projects, and would be instrumental in establishing the electrolytic H2 production infrastructure needed for eventual full conversion to an H2-based economy.

Electrolytic pretreatment unit gaseous effluent conditioning

NASA Technical Reports Server (NTRS)

Colombo, G. V.; Putnam, D. F.

1976-01-01

The electrolytic pretreatment of urine is an advanced process that eliminates the need for handling and storing the highly corrosive chemicals that are normally used in water reclamation systems. The electrolytic pretreatment process also converts the organic materials in urine to gases (N2 and O2) that can be used to replenish those lost to space by leakage, venting, and air lock operations. The electrolytic process is more than a pretreatment, since it decreases the urine solids content by approximately one third, thus reducing the load and eventual solids storage requirements of the urine processing system. The evolved gases from the pretreatment step cannot, however, be returned directly to the atmosphere of a spacecraft without first removing several impurities including hydrogen, chlorine, and certain organic compounds. A treatment concept was developed that would decrease the impurities in the gas stream that emanates from an electrolysis unit to levels sufficiently low to allow the conditioned gas stream to be safely discharged to a spacecraft atmosphere. Two methods were experimentally demonstrated that can accomplish the desired cleanup. The bases of the two methods are, repectively: (1) raw urine scrubbing and (2) silica gel sorption.

"excess Heat" during Electrolysis in Platinium /K2CO3/ Nickel Light Water System

NASA Astrophysics Data System (ADS)

Tian, J.; Jin, L. H.; Weng, Z. K.; Song, B.; Zhao, X. L.; Xiao, Z. J.; Chen, G.; Du, B. Q.

2006-02-01

The characteristic variation of heating coefficients (k = ΔT/ΔP°C/W) of Pt(H)-Ni electrolytic system with K2CO3 and Na2CO3 solutions was studied in both situations of electric and electrolytic heating, respectively. The results in equilibrium revealed that there was an obvious difference of k in electrolytic-heating (Δk ≈ 30°C/W, kK2CO3 > kNa2CO3) between these two systems, whereas there was a little difference of k in electric heating (Δk ≈ 2°C/W, kK2CO3 < kNa2CO3 between them. "Excess heat" of about 2.5 × 104 J was produced during electrolysis of K2CO3 solution over 1 day of electrolysis. The differences of K2CO3 solution after electrolysis in the potential of hydrogen value (ΔpH = 0.15) and in absorbency (ΔA = 0.108) implied that some new Ca2+ might have formed in the electrolytic system.

Palladium-directed self-assembly of multi-titanium(IV)-porphyrin arrays on the substrate surface as sensitive ultrathin films for hydrogen peroxide sensing, photocurrent generation, and photochromism of viologen

NASA Astrophysics Data System (ADS)

He, Wen-Li; Fang, Fang; Ma, Dong-Mei; Chen, Meng; Qian, Dong-Jin; Liu, Minghua

2018-01-01

Multiporphyrin arrays are large, π-conjugated chromophores with high absorption efficiency and strong chemical stability that play an important role in supramolecular and advanced material sciences. Palladium-directed self-assembly of multiporphyrin array ultrathin films was achieved on substrate surfaces using oxo[5,10,15,20-tetra(4-pyridyl)porphyrinato]titanium (IV) complex [TiO(TPyP)] as a linker and sodium tetrachloropalladate (Na2PdCl4) as a connector. The Pd-TiOTPyP films as prepared were characterized by using UV-vis absorption and X-ray photoelectron spectroscopy, as well as by atomic force and scanning electron microscopy. The Soret absorption band of TiOTPyP was observed to red shift by 6 nm when the Pd-TiOTPyP multilayer-modified quartz substrate was immersed in an aqueous solution containing hydrogen peroxide. This was attributed to the formation of a TiO2TPyP monoperoxo complex. This oxidation reaction could be accelerated in an acidic solution. Furthermore, the immobilized Pd-TiOTPyP multilayers could act as light-harvesting units for photocurrent generation and photochromism of viologens, with strong stability, reproducibility, and recyclability. The photocurrent density could be enhanced in electrolyte solutions containing electron donors such as triethanolamine, or electron acceptors such as viologens. Finally, photoinduced reduction (photochromism) of viologens was investigated using the Pd-TiOTPyP multilayers as light sensitizers and EDTA as the electron donors.

Ohm's Law, Batteries, and the Clean Energy Landscape

NASA Astrophysics Data System (ADS)

Balsara, Nitash

The need for creating safe electrolytes for lithium batteries is significant given the continued safety problems associated with current lithium-ion batteries. Nonflammable polymer electrolytes offer a possible solution but the rate of lithium ion transport is too low for practical applications. In this talk, I will discuss some of the fundamental factors that limit ion transport in polymers. Polymer electrolytes obey Ohm's Law, i.e. in the limit of small applied potentials, the current generated at steady state is proportional to the applied potential. Factors that determine the current generated will be determined using the continuum theory of Newman. Independent measurements of ion diffusion by pulsed-field gradient NMR will also be presented. The talk will end with a discussion of the possibility of commercializing all-solid batteries with polymer electrolytes.

Corrosion of Tungsten Microelectrodes used in Neural Recording Applications

PubMed Central

Patrick, Erin; Orazem, Mark E.; Sanchez, Justin C.; Nishida, Toshikazu

2011-01-01

In neuroprosthetic applications, long-term electrode viability is necessary for robust recording of the activity of neural populations used for generating communication and control signals. The corrosion of tungsten microwire electrodes used for intracortical recording applications was analyzed in a controlled bench-top study and compared to the corrosion of tungsten microwires used in an in vivo study. Two electrolytes were investigated for the benchtop electrochemical analysis: 0.9% phosphate buffered saline (PBS) and 0.9% PBS containing 30 mM of hydrogen peroxide. The oxidation and reduction reactions responsible for corrosion were found by measurement of the open circuit potential and analysis of Pourbaix diagrams. Dissolution of tungsten to form the tungstic ion was found to be the corrosion mechanism. The corrosion rate was estimated from the polarization resistance, which was extrapolated from the electrochemical impedance spectroscopy data. The results show that tungsten microwires in an electrolyte of PBS have a corrosion rate of 300–700 µm/yr. The corrosion rate for tungsten microwires in an electrolyte containing PBS and 30 mM H2O2 is accelerated to 10,000–20,000 µm/yr. The corrosion rate was found to be controlled by the concentration of the reacting species in the cathodic reaction (e.g. O2 and H2O2). The in vivo corrosion rate, averaged over the duration of implantation, was estimated to be 100 µm/yr. The reduced in vivo corrosion rate as compared to the benchtop rate is attributed to decreased rate of oxygen diffusion caused by the presence of a biological film and a reduced concentration of available oxygen in the brain. PMID:21470563

Unique Proton Transportation Pathway in a Robust Inorganic Coordination Polymer Leading to Intrinsically High and Sustainable Anhydrous Proton Conductivity.

PubMed

Gui, Daxiang; Dai, Xing; Tao, Zetian; Zheng, Tao; Wang, Xiangxiang; Silver, Mark A; Shu, Jie; Chen, Lanhua; Wang, Yanlong; Zhang, Tiantian; Xie, Jian; Zou, Lin; Xia, Yuanhua; Zhang, Jujia; Zhang, Jin; Zhao, Ling; Diwu, Juan; Zhou, Ruhong; Chai, Zhifang; Wang, Shuao

2018-05-16

Although comprehensive progress has been made in the area of coordination polymer (CP)/metal-organic framework (MOF)-based proton-conducting materials over the past decade, searching for a CP/MOF with stable, intrinsic, high anhydrous proton conductivity that can be directly used as a practical electrolyte in an intermediate-temperature proton-exchange membrane fuel cell assembly for durable power generation remains a substantial challenge. Here, we introduce a new proton-conducting CP, (NH 4 ) 3 [Zr(H 2/3 PO 4 ) 3 ] (ZrP), which consists of one-dimensional zirconium phosphate anionic chains and fully ordered charge-balancing NH 4 + cations. X-ray crystallography, neutron powder diffraction, and variable-temperature solid-state NMR spectroscopy suggest that protons are disordered within an inherent hydrogen-bonded infinite chain of acid-base pairs (N-H···O-P), leading to a stable anhydrous proton conductivity of 1.45 × 10 -3 S·cm -1 at 180 °C, one of the highest values among reported intermediate-temperature proton-conducting materials. First-principles and quantum molecular dynamics simulations were used to directly visualize the unique proton transport pathway involving very efficient proton exchange between NH 4 + and phosphate pairs, which is distinct from the common guest encapsulation/dehydration/superprotonic transition mechanisms. ZrP as the electrolyte was further assembled into a H 2 /O 2 fuel cell, which showed a record-high electrical power density of 12 mW·cm -2 at 180 °C among reported cells assembled from crystalline solid electrolytes, as well as a direct methanol fuel cell for the first time to demonstrate real applications. These cells were tested for over 15 h without notable power loss.

Corrosion of tungsten microelectrodes used in neural recording applications.

PubMed

Patrick, Erin; Orazem, Mark E; Sanchez, Justin C; Nishida, Toshikazu

2011-06-15

In neuroprosthetic applications, long-term electrode viability is necessary for robust recording of the activity of neural populations used for generating communication and control signals. The corrosion of tungsten microwire electrodes used for intracortical recording applications was analyzed in a controlled bench-top study and compared to the corrosion of tungsten microwires used in an in vivo study. Two electrolytes were investigated for the bench-top electrochemical analysis: 0.9% phosphate buffered saline (PBS) and 0.9% PBS containing 30 mM of hydrogen peroxide. The oxidation and reduction reactions responsible for corrosion were found by measurement of the open circuit potential and analysis of Pourbaix diagrams. Dissolution of tungsten to form the tungstic ion was found to be the corrosion mechanism. The corrosion rate was estimated from the polarization resistance, which was extrapolated from the electrochemical impedance spectroscopy data. The results show that tungsten microwires in an electrolyte of PBS have a corrosion rate of 300-700 μm/yr. The corrosion rate for tungsten microwires in an electrolyte containing PBS and 30 mM H₂O₂ is accelerated to 10,000-20,000 μm/yr. The corrosion rate was found to be controlled by the concentration of the reacting species in the cathodic reaction (e.g. O₂ and H₂O₂). The in vivo corrosion rate, averaged over the duration of implantation, was estimated to be 100 μm/yr. The reduced in vivo corrosion rate as compared to the bench-top rate is attributed to decreased rate of oxygen diffusion caused by the presence of a biological film and a reduced concentration of available oxygen in the brain. Copyright © 2011 Elsevier B.V. All rights reserved.

A Survey of Alternative Oxygen Production Technologies

NASA Technical Reports Server (NTRS)

Lueck, Dale E.; Parrish, Clyde F.; Buttner, William J.; Surma, Jan M.; Delgado, H. (Technical Monitor)

2001-01-01

Utilization of the Martian atmosphere for the production of fuel and oxygen has been extensively studied. The baseline fuel production process is a Sabatier reactor, which produces methane and water from carbon dioxide and hydrogen. The oxygen produced from the electrolysis of the water is only half of that needed for methane-based rocket propellant, and additional oxygen is needed for breathing air, fuel cells and other energy sources. Zirconia electrolysis cells for the direct reduction of CO2 arc being developed as an alternative means of producing oxygen, but present many challenges for a large-scale oxygen production system. The very high operating temperatures and fragile nature of the cells coupled with fairly high operating voltages leave room for improvement. This paper will survey alternative oxygen production technologies, present data on operating characteristics, materials of construction, and some preliminary laboratory results on attempts to implement each. Our goal is to significantly improve upon the characteristics of proposed zirconia cells for oxygen production. To achieve that goal we are looking at electrolytic systems that operate at significantly lower temperatures, preferably below 31C to allow the incorporation of liquid CO2 in the electrolyte. Our preliminary results indicate that such a system will have much higher current densities and have simpler cathode construction than a porous gas feed electrode system. Such a system could be achieved based on nonaqueous electrolytes or ionic liquids. We are focusing our research on the anode reaction that will produce oxygen from a product generated at the cathode using CO2 as the feed. Operation at low temperatures also will open up the full range of polymer and metal materials, allowing a more robust system design to withstand the rigors of flight, landing, and long term unattended operation on the surface of Mars.

Towards the next generation of solid oxide fuel cells operating below 600 °c with chemically stable proton-conducting electrolytes.

PubMed

Fabbri, Emiliana; Bi, Lei; Pergolesi, Daniele; Traversa, Enrico

2012-01-10

The need for reducing the solid oxide fuel cell (SOFC) operating temperature below 600 °C is imposed by cost reduction, which is essential for widespread SOFC use, but might also disclose new applications. To this aim, high-temperature proton-conducting (HTPC) oxides have gained widespread interest as electrolyte materials alternative to oxygen-ion conductors. This Progress Report describes recent developments in electrolyte, anode, and cathode materials for protonic SOFCs, addressing the issue of chemical stability, processability, and good power performance below 600 °C. Different fabrication methods are reported for anode-supported SOFCs, obtained using state-of-the-art, chemically stable proton-conducting electrolyte films. Recent findings show significant improvements in the power density output of cells based on doped barium zirconate electrolytes, pointing out towards the feasibility of the next generation of protonic SOFCs, including a good potential for the development of miniaturized SOFCs as portable power supplies. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optimizing Ionic Electrolytes for Dye-Sensitized Solar Cells

NASA Astrophysics Data System (ADS)

Fan, Xiaojuan; Hall, Sarah

2009-03-01

Dye-sensitized solar cells DSSCs provide next generation, low cost, and easy fabrication photovoltaic devices based on organic sensitizing molecules, polymer gel electrolyte, and metal oxide semiconductors. One of the key components is the solvent-free ionic liquid electrolyte that has low volatility and high stability. We report a rapid and low cost method to fabricate ionic polymer electrolyte used in DSSCs. Poly(ethylene oxide) (PEO) is blended with imidazolinium salt without any chemical solvent to form a gel electrolyte. Uniform and crack-free porous TiO2 thin films are sensitized by porphrine dye covered by the synthesized gel electrolyte. The fabricated DSSCs are more stable and potentially increase the photo-electricity conversion efficiency.

Phase-field based Multiscale Modeling of Heterogeneous Solid Electrolytes: Applications to Nanoporous Li 3 PS 4

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

Hu, Jia-Mian; Wang, Bo; Ji, Yanzhou

Modeling the effective ion conductivities of heterogeneous solid electrolytes typically involves the use of a computer-generated microstructure consisting of randomly or uniformly oriented fillers in a matrix. But, the structural features of the filler/matrix interface, which critically determine the interface ion conductivity and the microstructure morphology, have not been considered during the microstructure generation. In using nanoporous β-Li 3PS 4 electrolyte as an example, we develop a phase-field model that enables generating nanoporous microstructures of different porosities and connectivity patterns based on the depth and the energy of the surface (pore/electrolyte interface), both of which are predicted through density functionalmore » theory (DFT) calculations. Room-temperature effective ion conductivities of the generated microstructures are then calculated numerically, using DFT-estimated surface Li-ion conductivity (3.14×10 -3 S/cm) and experimentally measured bulk Li-ion conductivity (8.93×10 -7 S/cm) of β-Li 3PS 4 as the inputs. We also use the generated microstructures to inform effective medium theories to rapidly predict the effective ion conductivity via analytical calculations. Furthemore, when porosity approaches the percolation threshold, both the numerical and analytical methods predict a significantly enhanced Li-ion conductivity (1.74×10 -4 S/cm) that is in good agreement with experimental data (1.64×10 -4 S/cm). The present phase-field based multiscale model is generally applicable to predict both the microstructure patterns and the effective properties of heterogeneous solid electrolytes.« less

Phase-field based Multiscale Modeling of Heterogeneous Solid Electrolytes: Applications to Nanoporous Li 3 PS 4

DOE PAGES

Hu, Jia-Mian; Wang, Bo; Ji, Yanzhou; ...

2017-09-07

Modeling the effective ion conductivities of heterogeneous solid electrolytes typically involves the use of a computer-generated microstructure consisting of randomly or uniformly oriented fillers in a matrix. But, the structural features of the filler/matrix interface, which critically determine the interface ion conductivity and the microstructure morphology, have not been considered during the microstructure generation. In using nanoporous β-Li 3PS 4 electrolyte as an example, we develop a phase-field model that enables generating nanoporous microstructures of different porosities and connectivity patterns based on the depth and the energy of the surface (pore/electrolyte interface), both of which are predicted through density functionalmore » theory (DFT) calculations. Room-temperature effective ion conductivities of the generated microstructures are then calculated numerically, using DFT-estimated surface Li-ion conductivity (3.14×10 -3 S/cm) and experimentally measured bulk Li-ion conductivity (8.93×10 -7 S/cm) of β-Li 3PS 4 as the inputs. We also use the generated microstructures to inform effective medium theories to rapidly predict the effective ion conductivity via analytical calculations. Furthemore, when porosity approaches the percolation threshold, both the numerical and analytical methods predict a significantly enhanced Li-ion conductivity (1.74×10 -4 S/cm) that is in good agreement with experimental data (1.64×10 -4 S/cm). The present phase-field based multiscale model is generally applicable to predict both the microstructure patterns and the effective properties of heterogeneous solid electrolytes.« less

Transport dynamics of a high-power-density matrix-type hydrogen-oxygen fuel cell

NASA Technical Reports Server (NTRS)

Prokopius, P. R.; Hagedorn, N. H.

1974-01-01

Experimental transport dynamics tests were made on a space power fuel cell of current design. Various operating transients were introduced and transport-related response data were recorded with fluidic humidity sensing instruments. Also, sampled data techniques were developed for measuring the cathode-side electrolyte concentration during transient operation.

Volumetric Titrations Using Electrolytically Generated Reagents for the Determination of Ascorbic Acid and Iron in Dietary Supplement Tablets: An Undergraduate Laboratory Experiment

ERIC Educational Resources Information Center

Scanlon, Christopher; Gebeyehu, Zewdu; Griffin, Kameron; Dabke, Rajeev B.

2014-01-01

An undergraduate laboratory experiment for the volumetric quantitative analysis of ascorbic acid and iron in dietary supplement tablets is presented. Powdered samples of the dietary supplement tablets were volumetrically titrated against electrolytically generated reagents, and the mass of dietary reagent in the tablet was determined from the…

Porous media for catalytic renewable energy conversion

NASA Astrophysics Data System (ADS)

Hotz, Nico

2012-05-01

A novel flow-based method is presented to place catalytic nanoparticles into a reactor by sol-gelation of a porous ceramic consisting of copper-based nanoparticles, silica sand, ceramic binder, and a gelation agent. This method allows for the placement of a liquid precursor containing the catalyst into the final reactor geometry without the need of impregnating or coating of a substrate with the catalytic material. The so generated foam-like porous ceramic shows properties highly appropriate for use as catalytic reactor material, e.g., reasonable pressure drop due to its porosity, high thermal and catalytic stability, and excellent catalytic behavior. The catalytic activity of micro-reactors containing this foam-like ceramic is tested in terms of their ability to convert alcoholic biofuel (e.g. methanol) to a hydrogen-rich gas mixture with low concentrations of carbon monoxide (up to 75% hydrogen content and less than 0.2% CO, for the case of methanol). This gas mixture is subsequently used in a low-temperature fuel cell, converting the hydrogen directly to electricity. A low concentration of CO is crucial to avoid poisoning of the fuel cell catalyst. Since conventional Polymer Electrolyte Membrane (PEM) fuel cells require CO concentrations far below 100 ppm and since most methods to reduce the mole fraction of CO (such as Preferential Oxidation or PROX) have CO conversions of up to 99%, the alcohol fuel reformer has to achieve initial CO mole fractions significantly below 1%. The catalyst and the porous ceramic reactor of the present study can successfully fulfill this requirement.

NASA Lewis advanced IPV nickel-hydrogen technology

NASA Technical Reports Server (NTRS)

Smithrick, John J.; Britton, Doris L.

1993-01-01

Individual pressure vessel (IPV) nickel-hydrogen technology was advanced at NASA Lewis and under Lewis contracts. Some of the advancements are as follows: to use 26 percent potassium hydroxide electrolyte to improve cycle life and performance, to modify the state of the art cell design to eliminate identified failure modes and further improve cycle life, and to develop a lightweight nickel electrode to reduce battery mass, hence reduce launch and/or increase satellite payload. A breakthrough in the LEO cycle life of individual pressure vessel nickel-hydrogen battery cells was reported. The cycle life of boiler plate cells containing 26 percent KOH electrolyte was about 40,000 accelerated LEO cycles at 80 percent DOD compared to 3,500 cycles for cells containing 31 percent KOH. Results of the boiler plate cell tests have been validated at NWSC, Crane, Indiana. Forty-eight ampere-hour flight cells containing 26 and 31 percent KOH have undergone real time LEO cycle life testing at an 80 percent DOD, 10 C. The three cells containing 26 percent KOH failed on the average at cycle 19,500. The three cells containing 31 percent KOH failed on the average at cycle 6,400. Validation testing of NASA Lewis 125 Ah advanced design IPV nickel-hydrogen flight cells is also being conducted at NWSC, Crane, Indiana under a NASA Lewis contract. This consists of characterization, storage, and cycle life testing. There was no capacity degradation after 52 days of storage with the cells in the discharged state, on open circuit, 0 C, and a hydrogen pressure of 14.5 psia. The catalyzed wall wick cells have been cycled for over 22,694 cycles with no cell failures in the continuing test. All three of the non-catalyzed wall wick cells failed (cycles 9,588; 13,900; and 20,575). Cycle life test results of the Fibrex nickel electrode has demonstrated the feasibility of an improved nickel electrode giving a higher specific energy nickel-hydrogen cell. A nickel-hydrogen boiler plate cell using an 80 mil thick, 90 percent porous Fibrex nickel electrode has been cycled for 10,000 cycles at 40 percent DOD.

One-Step Facile Synthesis of Cobalt Phosphides for Hydrogen Evolution Reaction Catalysts in Acidic and Alkaline Medium.

PubMed

Sumboja, Afriyanti; An, Tao; Goh, Hai Yang; Lübke, Mechthild; Howard, Dougal Peter; Xu, Yijie; Handoko, Albertus Denny; Zong, Yun; Liu, Zhaolin

2018-05-09

Catalysts for hydrogen evolution reaction are in demand to realize the efficient conversion of hydrogen via water electrolysis. In this work, cobalt phosphides were prepared using a one-step, scalable, and direct gas-solid phosphidation of commercially available cobalt salts. It was found that the effectiveness of the phosphidation reaction was closely related to the state of cobalt precursors at the reaction temperature. For instance, a high yield of cobalt phosphides obtained from the phosphidation of cobalt(II) acetate was related to the good stability of cobalt salt at the phosphidation temperature. On the other hand, easily oxidizable salts (e.g., cobalt(II) acetylacetonate) tended to produce a low amount of cobalt phosphides and a large content of metallic cobalt. The as-synthesized cobalt phosphides were in nanostructures with large catalytic surface areas. The catalyst prepared from phosphidation of cobalt(II) acetate exhibited an improved catalytic activity as compared to its counterpart derived from phosphidation of cobalt(II) acetylacetonate, showing an overpotential of 160 and 175 mV in acidic and alkaline electrolytes, respectively. Both catalysts also displayed an enhanced long-term stability, especially in the alkaline electrolyte. This study illustrates the direct phosphidation behavior of cobalt salts, which serve as a good vantage point in realizing the large-scale synthesis of transition-metal phosphides for high-performance electrocatalysts.

SnO2, IrO2, Ta2O5, Bi2O3, and TiO2 nanoparticle anodes: electrochemical oxidation coupled with the cathodic reduction of water to yield molecular H2

NASA Astrophysics Data System (ADS)

Choi, Jina; Qu, Yan; Hoffmann, Michael R.

2012-08-01

In recent years, the search for environmentally friendly alternative energy sources with reduced carbon footprints has increased. The coupling of photovoltaic power sources with advanced electrolysis systems for hydrogen production via water splitting using organic contaminants as sacrificial electron donors has been considered to a be viable alternative. In this report, we demonstrated the feasibility of a scaled-up rooftop prototype of the proposed hybrid photovoltaic-electrolysis system, which utilizes semiconductor nanoparticles coated on to metal substrates as electrodes for the generation of hydrogen coupled with the oxidation of wastewater. Application of an anodic bias of >2.0 V to bismuth-doped TiO2 (BiO x -TiO2) on Ti metal anodes with a sequential under-coatings of nanoparticulate SnO2, IrO2, Ta2O5, and Bi2O3 results in the electrochemical degradation of a variety of organic chemical contaminants in water (i.e., rhodamine B (Rh.B), methylene blue (MB), salicylic acid, triclosan, and phenol) and actual wastewater from a chemical manufacturing plant, while at the same time, molecular hydrogen is produced at stainless steel (SS) cathodes. The kinetics of the anodic substrates oxidation is investigated as a function of the cell current ( I cell), substrate concentration, and background electrolyte composition (e.g., NaCl, Na2SO4, or seawater). Average current efficiencies were found to be in the range of 4-22 %, while the cathodic current and energy efficiencies for hydrogen production were found to be in the range of 50-70 % and 20-40 %, respectively.

Synthesis of nickel germanide (Ge12Ni19) nanoparticles for durable hydrogen evolution reaction in acid solutions.

PubMed

Chen, Jee-Yee; Jheng, Shao-Lou; Tuan, Hsing-Yu

2018-06-14

Desigining advanced materials as electrochemical catalysts for the hydrogen evolution reaction (HER) has caught great attention owing to the growing demand for clean and renewable energy. Nickel (Ni)-based compounds and alloys are promising non-noble-metal electrocatalysts due to their low cost and high activity. However, in most cases, Ni-based compounds and alloys have low durability in acid electrolyte, which limits their application in the electrolytic processes. In this study, monoclinic Ge12Ni19 nanoparticles were synthesized and exhibited high electrocatalytic activity and stability for the HER in acidic solution. Ge12Ni19 nanoparticles achieve an overpotential of 190 mV at cathodic current density of 10 mA cm-2 and a Tafel slope of 88.5 mV per decade in 0.50 M H2SO4 electrolyte. Moreover, the performance is maintained after a 10 000-cycle CV sweep (-0.3 to +0.1 V vs. RHE) or under a static overpotential of -0.7 V vs. RHE for 24 hours. The reported electrocatalytic performance of the Ge12Ni19 nanoparticles sufficiently proves the excellent endurance at lower required active overpotentials in acidic solution, enabling the broad applications of the Ni-based electrocatalysts. Finally, a large-area (5 cm2) electrocatalyst for HER was demonstrated for the first time. The great efficiency of the energy conversion performance sufficiently represented the potential of Ge12Ni19 nanoparticles as electrocatalysts in commercial fuel cells.

Electrochemical generation of useful chemical species from lunar materials

NASA Technical Reports Server (NTRS)

Sammells, Anthony F.; Semkow, Krystyna W.

1987-01-01

A high temperature electrolytic cell which simultaneously generates oxygen at the anode and liquid alkali metals at the cathode is electrochemically characterized. The electrolytic technology being investigated utilizes the oxygen vacancy conducting solid electrolyte, yttria stabilized zirconia, which effectively separates the oxygen evolving (at La0.89Sr0.10MnO3) and alkali metal (Li, Na) reducing (from a molten salt at either Pt or FeSi2) half cell reactions. In the finally engineered cell liquid alkali metal would be continuously removed from the cathode compartment and used as an effective reductant for the direct thermochemical refining of lunar ores to their metallic state with simultaneous oxidation of the alkali metal to its oxide. The alkali metal oxide would then be reintroduced into the electrolytic cell to complete the overall system cycle.

Electrochemical generation of useful chemical species from lunar materials

NASA Astrophysics Data System (ADS)

Sammells, Anthony F.; Semkow, Krystyna W.

1987-09-01

A high temperature electrolytic cell which simultaneously generates oxygen at the anode and liquid alkali metals at the cathode is electrochemically characterized. The electrolytic technology being investigated utilizes the oxygen vacancy conducting solid electrolyte, yttria stabilized zirconia, which effectively separates the oxygen evolving (at La0.89Sr0.10MnO3) and alkali metal (Li, Na) reducing (from a molten salt at either Pt or FeSi2) half cell reactions. In the finally engineered cell liquid alkali metal would be continuously removed from the cathode compartment and used as an effective reductant for the direct thermochemical refining of lunar ores to their metallic state with simultaneous oxidation of the alkali metal to its oxide. The alkali metal oxide would then be reintroduced into the electrolytic cell to complete the overall system cycle.

Amorphous Nickel-Cobalt-Borate Nanosheet Arrays for Efficient and Durable Water Oxidation Electrocatalysis under Near-Neutral Conditions.

PubMed

Chen, Lanlan; Ren, Xiang; Teng, Wanqing; Shi, Pengfei

2017-07-21

Electrolytic hydrogen generation needs earth-abundant oxygen evolution reaction electrocatalysts that perform efficiently at mild pH. Here, the development of amorphous nickel-cobalt-borate nanosheet arrays on macroporous nickel foam (NiCo-Bi/NF) as a 3D catalyst electrode for high-performance water oxidation in near-neutral media is reported. To drive a current density of 10 mA cm -2 , the resulting NiCo-Bi/NF demands an overpotential of only 430 mV in 0.1 m potassium borate (K-Bi, pH 9.2). Moreover, it also shows long-term electrochemical durability with maintenance of catalytic activity for 20 h, achieving a high turnover frequency of 0.21 s -1 at an overpotential of 550 mV. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Superprotonic solid acids: Structure, properties, and applications

NASA Astrophysics Data System (ADS)

Boysen, Dane Andrew

In this work, the structure and properties of superprotonic MH nXO4-type solid acids (where M = monovalent cation, X = S, Se, P, As, and n = 1, 2) have been investigated and, for the first time, applied in fuel cell devices. Several MH nXO4-type solid acids are known to undergo a "superprotonic" solid-state phase transition upon heating, in which the proton conductivity increases by several orders of magnitude and takes on values of ˜10 -2O-1cm-1. The presence of superprotonic conductivity in fully hydrogen bonded solid acids, such as CsH2PO4, has long been disputed. In these investigations, through the use of pressure, the unequivocal identification of superprotonic behavior in both RbH2PO4 and CsH2PO 4 has been demonstrated, whereas for chemically analogous compounds with smaller cations, such as KH2PO4 and NaH2PO 4, superprotonic conductivity was notably absent. Such observations have led to the adoption of radius ratio rules, in an attempt to identify a critical ion size effect on the presence of superprotonic conductivity in solid acids. It has been found that, while ionic size does play a prominent role in the presence of superprotonic behavior in solid acids, equally important are the effects of ionic and hydrogen bonding. Next, the properties of superprotonic phase transition have been investigated from a thermodynamic standpoint. With contributions from this work, a formulation has been developed that accounts for the entropy resulting from both the disordering of both hydrogen bonds and oxy-anion librations in the superprotonic phase of solid acids. This formulation, fundamentally derived from Linus Pauling's entropy rules for ice, accurately accounts for the change in entropy through a superprotonic phase transition. Lastly, the first proof-of-priniciple fuel cells based upon solid acid electrolytes have been demonstrated. Initial results based upon a sulfate electrolyte, CsHSO4, demonstrated the viability of solid acids, but poor chemical stability under the highly reducing H2 gas environment of the fuel cell anode. Later experiments employing a CsH2PO4 electrolyte proved quite successful. The results of these solid acid-based fuel cell measurements suggest solid acids could serve as an alternative to current state-of-the-art fuel cell electrolytes.

Nickel-hydrogen. [metal hydrides, electrochemical corrosion, and structural design

NASA Technical Reports Server (NTRS)

Mchenry, E. J.

1977-01-01

Because of the disintegration of LaNi5 as the lattice expands on absorbing hydrogen, a nickel hydrogen cell similar to a nickel cadmium cell was designed. The positive electrode is wrapped in a microporous separator and the leads are insulated. A negative conducting grid is inserted and welded to the top of the can into an open ended container which is then turned upside down and filled so that LiNa5 powder occupies all the space not used by the rest of the components. The bottom of the can is then welded on. A fill tube is located either on the bottom or on the top of the can. When welded shut, the cell is put into a pressure bomb and the lanthanum nickel is activated at about 1,000 pounds of hydrogen. Electrolytes are added to the cell as well as whatever amount of hydrogen precharge desired, and the cell is sealed. Advantages and disadvantages of the cell are discussed.

Diffusion coefficient of hydrogen in a cast gamma titanium aluminide

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

Sundaram, P.A.; Wessel, E.; Ennis, P.J.

1999-06-04

Gamma titanium aluminides have the potential for high temperature applications because of their high specific strength and specific modulus. Their oxidation resistance is good, especially at intermediate temperatures and with suitable alloying additions, good oxidation resistance can be obtained up to 800 C. One critical area of application is in combustion engines in aero-space vehicles such as hypersonic airplanes and high speed civil transport airplanes. This entails the use of hydrogen as a fuel component and hence the effect of hydrogen on the mechanical properties of gamma titanium aluminides is of significant scientific and technological utility. The purpose of thismore » short investigation is to use an electrochemical method under galvanostatic conditions to determine the diffusion coefficient of hydrogen in a cast gamma titanium aluminide, a typical technical alloy with potential application in gas turbines under creep conditions. This result will be then compared with that obtained by microhardness profiling of electrolytically hydrogen precharged material.« less

Determination of diffusion coefficients of hydrogen and deuterium in Zr-2.5%Nb pressure tube material using hot vacuum extraction-quadrupole mass spectrometry

NASA Astrophysics Data System (ADS)

Shrivastava, Komal Chandra; Kulkarni, A. S.; Ramanjaneyulu, P. S.; Sunil, Saurav; Saxena, M. K.; Singh, R. N.; Tomar, B. S.; Ramakumar, K. L.

2015-06-01

The diffusion coefficients of hydrogen and deuterium in Zr-2.5%Nb alloy were measured in the temperature range 523 to 673 K, employing hot vacuum extraction-quadrupole mass spectrometry (HVE-QMS). One end of the Zr-2.5%Nb alloy specimens was charged electrolytically with the desired hydrogen isotope. After annealing at different temperatures for a predetermined time, the specimens were cut into thin slices, which were analyzed for their H2/D2 content using the HVE-QMS technique. The depth profile data were fitted into the equation representing the solution of Fick's second law of diffusion. The activation energy of hydrogen/deuterium diffusion was obtained from the Arrhenius relation between the diffusion coefficient and temperature. The temperature dependent diffusion coefficient can be represented as DH = 1.41 × 10-7 exp(-36,000/RT) and DD = 6.16 × 10-8 exp(-35,262/RT) for hydrogen and deuterium, respectively.

Catalytic dehydrogenation of amine borane complexes

NASA Technical Reports Server (NTRS)

Mohajeri, Nahid (Inventor); Tabatabaie-Raissi, Ali (Inventor)

2007-01-01

A method of generating hydrogen includes the steps of providing an amine borane (AB) complex, at least one hydrogen generation catalyst, and a solvent, and mixing these components. Hydrogen is generated. The hydrogen produced is high purity hydrogen suitable for PEM fuel cells. A hydrolytic in-situ hydrogen generator includes a first compartment that contains an amine borane (AB) complex, a second container including at least one hydrogen generation catalyst, wherein the first or second compartment includes water or other hydroxyl group containing solvent. A connecting network permits mixing contents in the first compartment with contents in the second compartment, wherein high purity hydrogen is generated upon mixing. At least one flow controller is provided for controlling a flow rate of the catalyst or AB complex.

Catalytic dehydrogenation of amine borane complexes

NASA Technical Reports Server (NTRS)

Tabatabaie-Raissi, Ali (Inventor); Mohajeri, Nahid (Inventor); Bokerman, Gary (Inventor)

2009-01-01

A method of generating hydrogen includes the steps of providing an amine borane (AB) complex, at least one hydrogen generation catalyst, and a solvent, and mixing these components Hydrogen is generated. The hydrogen produced is high purity hydrogen suitable for PEM fuel cells. A hydrolytic in-situ hydrogen generator includes a first compartment that contains an amine borane (AB) complex, a second container including at least one hydrogen generation catalyst, wherein the first or second compartment includes water or other hydroxyl group containing solvent. A connecting network permits mixing contents in the first compartment with contents in the second compartment, wherein high purity hydrogen is generated upon mixing. At least one flow controller is provided for controlling a flow rate of the catalyst or AB complex.

Multi-Scale Ordered Cell Structure for Cost Effective Production of Hydrogen by HTWS

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

Elangovan, Elango; Rao, Ranjeet; Colella, Whitney

Production of hydrogen using an electrochemical device provides for large scale, high efficiency conversion and storage of electrical energy. When renewable electricity is used for conversion of steam to hydrogen, a low-cost and low emissions pathway to hydrogen production emerges. This project was intended to demonstrate a high efficiency High Temperature Water Splitting (HTWS) stack for the electrochemical production of low cost H2. The innovations investigated address the limitations of the state of the art through the use of a novel architecture that introduces macro-features to provide mechanical support of a thin electrolyte, and micro-features of the electrodes to lowermore » polarization losses. The approach also utilizes a combination of unique sets of fabrication options that are scalable to achieve manufacturing cost objectives. The development of HTWS process and device is guided by techno-economic and life cycle analyses.« less

Preparation and evaluation of advanced electrocatalysts for phosphoric acid fuel cells

NASA Technical Reports Server (NTRS)

Stonehart, P.; Baris, J.; Pagliaro, P.

1980-01-01

Results are presented for hydrogen oxidation and hydrogen oxidation poisoned by carbon monoxide at levels between 0 and 30%. Due to the high activities that are now being observed for our platinum based electrocatalysts, the hydrogen concentrations were reduced to 10% levels in the gas supplies. Perturbation techniques were used to determine that a mechanism for the efficient operation of our porous gas diffusion electrodes is diffusion of the carbon monoxide out of the electrode structure through the electrolyte film on the electro-catalyst. A survey of the literature on platinum group materials (PGM) was carried out so that an identification of successful electrocatalysts could be made. Two PGM electrocatalysts were prepared and performance data for hydrogen oxidation in hot phosphoric acid in the presence of high carbon monoxide concentrations showed that they matched the best platinum on carbon electrocatalysts but with an electrocatalyst cost that was half of the platinum catalyst cost.

A titania nanotube-array room-temperature sensor for selective detection of hydrogen at low concentrations.

PubMed

Varghese, Oomman K; Mor, Gopal K; Grimes, Craig A; Paulose, Maggie; Mukherjee, Niloy

2004-09-01

A tremendous variation in electrical resistance, from the semiconductor to metallic range, has been observed in titania nanotube arrays at room temperature, approximately 25 degrees C, in the presence of < or = 1000 ppm hydrogen gas. The nanotube arrays are fabricated by anodizing titanium foil in an aqueous electrolyte solution containing hydrofluoric acid and acetic acid. Subsequently, the arrays are coated with a 10 nm layer of palladium by evaporation. Electrical contacts are made by sputtering a 2 mm diameter platinum disk atop the Pd-coated nanotube array. These sensors exhibit a resistance variation of the order of 10(4) in the presence of 100 ppm hydrogen at 25 degrees C. The sensors demonstrate complete reversibility, repeatability, high selectivity, negligible drift and wide dynamic range. The nanoscale geometry of the nanotubes, in particular the points of tube-to-tube contact, is believed to be responsible for the outstanding hydrogen gas sensitivities.

Gel Electrolytes with Polyamidopyridine Dendron Modified Talc for Dye-Sensitized Solar Cells.

PubMed

Santana Andrade, Marcos A; Tiihonen, Armi; Miettunen, Kati; Lund, Peter; Nogueira, Ana F; Pastore, Heloise O

2017-06-21

Organic-inorganic hybrid layered materials are proposed as additives in a quasi-solid gel electrolyte for dye-sensitized solar cells. Talcs could provide a low-cost and environmentally friendly, as well as abundant, option as gelators. Here, talcs were prepared by functionalizing an organotalc with three polyamidopyridine dendron generations, PAMPy-talc-Gn (n = 1, 2 and 3). PAMPy dendrons grow parallel to the lamellae plane and form an organized structure by intermolecular interactions. In addition, polyiodide-dendron charge-transfer complexes were prepared onto the organotalc by adsorption of iodine. In this work, the effect of the dendron generation of PAMPy-talc and the influence of polyiodide intercalation on solar cell performance and stability were investigated. The best results were reached with the use of lowest-generation PAMPy-talc (η = 4.5 ± 0.3%, V OC = 710 ± 19 mV, J sc = 10.4 ± 0.9 mA cm -2 , and FF = 61 ± 2%): 15% higher efficiency compared to similar liquid devices. While some previously studied talcs illustrate very strong absorption of the iodide from the electrolyte, in the case of PAMPy-talc such interfering effects were absent: In a 1000 h light soaking test, the PAMPy-talc cells both with and without polyiodide intercalation demonstrated stable performances. Furthermore, the color analysis of the electrolyte indicated that the color of the electrolyte remained stable after an initial period of stabilization, which is a good indication of the compound being stable and not absorbing charge carriers from the electrolyte. The performance and stability results indicate that PAMPy-talc has potential as a gelling method for electrolytes for dye solar cells.

Theoretical performance of hydrogen-bromine rechargeable SPE fuel cell

NASA Technical Reports Server (NTRS)

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

1987-01-01

A mathematical model was formulated to describe the performance of a hydrogen-bromine fuel cell. Porous electrode theory was applied to the carbon felt flow-by electrode and was coupled to theory describing the solid polymer electrolyte (SPE) system. Parametric studies using the numerical solution to this model were performed to determine the effect of kinetic, mass transfer, and design parameters on the performance of the fuel cell. The results indicate that the cell performance is most sensitive to the transport properties of the SPE membrane. The model was also shown to be a useful tool for scale-up studies.

A mini-type hydrogen generator from aluminum for proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Wang, Er-Dong; Shi, Peng-Fei; Du, Chun-Yu; Wang, Xiao-Rui

A safe and simple hydrogen generator, which produced hydrogen by chemical reaction of aluminum and sodium hydroxide solution, was proposed for proton exchange membrane fuel cells. The effects of concentration, dropping rate and initial temperature of sodium hydroxide solution on hydrogen generation rate were investigated. The results showed that about 38 ml min -1 of hydrogen generation rate was obtained with 25 wt.% concentration and 0.01 ml s -1 dropping rate of sodium hydroxide solution. The cell fueled by hydrogen from the generator exhibited performance improvement at low current densities, which was mainly due to the humidified hydrogen reduced the protonic resistivity of the proton exchange membrane. The hydrogen generator could stably operate a single cell under 500 mA for nearly 5 h with about 77% hydrogen utilization ratio.

Preparation and Characterization of PVA Alkaline Solid Polymer Electrolyte with Addition of Bamboo Charcoal.

PubMed

Fan, Lidan; Wang, Mengyue; Zhang, Zhen; Qin, Gang; Hu, Xiaoyi; Chen, Qiang

2018-04-26

Natural bamboo charcoal (BC) powder has been developed as a novel filler in order to further improve performances of the polyvinyl alcohol (PVA)-based alkaline solid polymer electrolyte (ASPE) by solution casting method. X-ray diffraction patterns of composite polymer electrolyte with BC revealed the decrease in the degree of crystallinity with increasing content of BC. Scanning electron microscopy images showed pores on a micrometer scale (average diameter about 2 μm) distributed inside and on the surface of the membranes, indicating a three-dimension network formed in the polymer framework. The ionic conductivity was measured by the alternating-current (AC) impedance method, and the highest conductivity value of 6.63 × 10 −2 S·cm −1 was obtained with 16 wt % of BC content and m KOH : m PVA = 2:1.5 at 30 °C. The contents of BC and KOH could significantly influence the conductivity. The temperature dependence of the bulk electrical conductivity displayed a combination of Arrhenius nature, and the activation energy for the ion in polymer electrolyte has been calculated. The electrochemical stability window of the electrolyte membrane was over 1.6 V. The thermogravimetric analysis curves showed that the degradation temperatures of PVA-BC-KOH ASPE membranes shifted toward higher with adding BC. A simple nickel-hydrogen battery containing PVA-BC-KOH electrolyte membrane was assembled with a maximum discharge capacity of 193 mAh·g −1 .

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.

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

Thomas, C.E.; Kuhn, I.F. Jr.

The fuel cell electric vehicle (FCEV) is undoubtedly the only option that can meet both the California zero emission vehicle (ZEV) standard and the President`s goal of tripling automobile efficiency without sacrificing performance in a standard 5-passenger vehicle. The three major automobile companies are designing and developing FCEVs powered directly by hydrogen under cost-shared contracts with the Department of Energy. Once developed, these vehicles will need a reliable and inexpensive source of hydrogen. Steam reforming of natural gas would produce the least expensive hydrogen, but funding may not be sufficient initially to build both large steam reforming plants and themore » transportation infrastructure necessary to deliver that hydrogen to geographically scattered FCEV fleets or individual drivers. This analysis evaluates the economic feasibility of using small scale water electrolysis to provide widely dispersed but cost-effective hydrogen for early FCEV demonstrations. We estimate the cost of manufacturing a complete electrolysis system in large quantities, including compression and storage, and show that electrolytic hydrogen could be cost competitive with fully taxed gasoline, using existing residential off-peak electricity rates.« less

Elucidating Solvation Structures for Rational Design of Multivalent Electrolytes-A Review.

PubMed

Rajput, Nav Nidhi; Seguin, Trevor J; Wood, Brandon M; Qu, Xiaohui; Persson, Kristin A

2018-04-26

Fundamental molecular-level understanding of functional properties of liquid solutions provides an important basis for designing optimized electrolytes for numerous applications. In particular, exhaustive knowledge of solvation structure, stability, and transport properties is critical for developing stable electrolytes for fast-charging and high-energy-density next-generation energy storage systems. Accordingly, there is growing interest in the rational design of electrolytes for beyond lithium-ion systems by tuning the molecular-level interactions of solvate species present in the electrolytes. Here we present a review of the solvation structure of multivalent electrolytes and its impact on the electrochemical performance of these batteries. A direct correlation between solvate species present in the solution and macroscopic properties of electrolytes is sparse for multivalent electrolytes and contradictory results have been reported in the literature. This review aims to illustrate the current understanding, compare results, and highlight future needs and directions to enable the deep understanding needed for the rational design of improved multivalent electrolytes.

Electrolytic silver ion cell sterilizes water supply

NASA Technical Reports Server (NTRS)

Albright, C. F.; Gillerman, J. B.

1968-01-01

Electrolytic water sterilizer controls microbial contamination in manned spacecraft. Individual sterilizer cells are self-contained and require no external power or control. The sterilizer generates silver ions which do not impart an unpleasant taste to water.

High-Performance Flexible Solid-State Supercapacitor with an Extended Nanoregime Interface through in Situ Polymer Electrolyte Generation.

PubMed

Anothumakkool, Bihag; Torris A T, Arun; Veeliyath, Sajna; Vijayakumar, Vidyanand; Badiger, Manohar V; Kurungot, Sreekumar

2016-01-20

Here, we report an efficient strategy by which a significantly enhanced electrode-electrolyte interface in an electrode for supercapacitor application could be accomplished by allowing in situ polymer gel electrolyte generation inside the nanopores of the electrodes. This unique and highly efficient strategy could be conceived by judiciously maintaining ultraviolet-triggered polymerization of a monomer mixture in the presence of a high-surface-area porous carbon. The method is very simple and scalable, and a prototype, flexible solid-state supercapacitor could even be demonstrated in an encapsulation-free condition by using the commercial-grade electrodes (thickness = 150 μm, area = 12 cm(2), and mass loading = 7.3 mg/cm(2)). This prototype device shows a capacitance of 130 F/g at a substantially reduced internal resistance of 0.5 Ω and a high capacitance retention of 84% after 32000 cycles. The present system is found to be clearly outperforming a similar system derived by using the conventional polymer electrolyte (PVA-H3PO4 as the electrolyte), which could display a capacitance of only 95 F/g, and this value falls to nearly 50% in just 5000 cycles. The superior performance in the present case is credited primarily to the excellent interface formation of the in situ generated polymer electrolyte inside the nanopores of the electrode. Further, the interpenetrated nature of the polymer also helps the device to show a low electron spin resonance and power rate and, most importantly, excellent shelf-life in the unsealed flexible conditions. Because the nature of the electrode-electrolyte interface is the major performance-determining factor in the case of many electrochemical energy storage/conversion systems, along with the supercapacitors, the developed process can also find applications in preparing electrodes for the devices such as lithium-ion batteries, metal-air batteries, polymer electrolyte membrane fuel cells, etc.

Hydrogen sensor

DOEpatents

Duan, Yixiang; Jia, Quanxi; Cao, Wenqing

2010-11-23

A hydrogen sensor for detecting/quantitating hydrogen and hydrogen isotopes includes a sampling line and a microplasma generator that excites hydrogen from a gas sample and produces light emission from excited hydrogen. A power supply provides power to the microplasma generator, and a spectrometer generates an emission spectrum from the light emission. A programmable computer is adapted for determining whether or not the gas sample includes hydrogen, and for quantitating the amount of hydrogen and/or hydrogen isotopes are present in the gas sample.

Impact of ionization equilibrium on electrokinetic flow of weak electrolytes in nanochannels

NASA Astrophysics Data System (ADS)

Ji, Ziwei; Huang, Zhuo; Chen, Bowei; He, Yuhui; Tsutsui, Makusu; Miao, Xiangshui

2018-07-01

Weak electrolyte transport in nanochannels or nanopores has been actively explored in recent experiments. In this paper, we establish a new electrokinetic model where the ionization balance effect of weak electrolytes is outlined, and performed numerical calculations for H3PO4 concentration-biased nanochannel systems. By considering the roles of local chemical equilibrium in phosphorous acid ionization, the simulation results show quantitative agreement with experimental observations. Based on the model, we predict that enhanced energy harvesting capacity could be accomplished by utilizing weak electrolytes compared to the conventional strong electrolyte approaches in a concentration gradient-based power-generating system.

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.

Storage, generation, and use of hydrogen

DOEpatents

McClaine, Andrew W.; Rolfe, Jonathan L.; Larsen, Christopher A.; Konduri, Ravi K.

2006-05-30

A composition comprising a carrier liquid; a dispersant; and a chemical hydride. The composition can be used in a hydrogen generator to generate hydrogen for use, e.g., as a fuel. A regenerator recovers elemental metal from byproducts of the hydrogen generation process.

H2 Detection via Polarography

NASA Technical Reports Server (NTRS)

Dominquez, Jesus; Barile, Ron

2006-01-01

Polarography is the measurement of the current that flows in solution as a function of an applied voltage. The actual form of the observed polarographic current depends upon the manner in which the voltage is applied and on the characteristics of the working electrode. The new gas polarographic H2 sensor shows a current level increment with concentration of the gaseous H2 similar to those relating to metal ions in liquid electrolytes in well-known polarography. This phenomenon is caused by the fact that the diffusion of the gaseous H2 through a gas diffusion hole built in the sensor is a rate-determining step in the gaseous-hydrogen sensing mechanism. The diffusion hole artificially limits the diffusion of the gaseous H2 toward the electrode located at the sensor cavity. This gas polarographic H2 sensor is actually an electrochemical-pumping cell since the gaseous H2 is in fact pumped via the electrochemical driving force generated between the electrodes. Gaseous H2 enters the diffusion hole and reaches the first electrode (anode) located in the sensor cavity to be transformed into an H ions or protons; H ions pass through the electrolyte and reach the second electrode (cathode) to be reformed to gaseous H2. Gas polarographic O2 sensors are commercially available; a gas polarographic O2 sensor was used to prove the feasibility of building a new gas polarographic H2 sensor.

NASA Tech Briefs, November 2006

NASA Technical Reports Server (NTRS)

2006-01-01

Topics include: Simulator for Testing Spacecraft Separation Devices; Apparatus for Hot Impact Testing of Material Specimens; Instrument for Aircraft-Icing and Cloud-Physics Measurements; Advances in Measurement of Skin Friction in Airflow; Improved Apparatus for Testing Monoball Bearings; High-Speed Laser Scanner Maps a Surface in Three Dimensions; Electro-Optical Imaging Fourier-Transform Spectrometer; Infrared Instrument for Detecting Hydrogen Fires; Modified Coaxial Probe Feeds for Layered Antennas; Detecting Negative Obstacles by Use of Radar; Cryogenic Pound Circuits for Cryogenic Sapphire Oscillators; PixelLearn; New Software for Predicting Charging of Spacecraft; Conversion Between Osculating and Mean Orbital Elements; Generating a 2D Representation of a Complex Data Structure; Making Activated Carbon by Wet Pressurized Pyrolysis; Composite Solid Electrolyte Containing Li+- Conducting Fibers; Electrically Conductive Anodized Aluminum Surfaces; Rapid-Chill Cryogenic Coaxial Direct-Acting Solenoid Valve; Variable-Tension-Cord Suspension/Vibration- Isolation System; Techniques for Connecting Superconducting Thin Films; Versatile Friction Stir Welding/Friction Plug Welding System; Thermal Spore Exposure Vessels; Enumerating Spore-Forming Bacteria Airborne with Particles; Miniature Oxidizer Ionizer for a Fuel Cell; Miniature Ion-Array Spectrometer; Promoted-Combustion Chamber with Induction Heating Coil; Miniature Ion-Mobility Spectrometer; Mixed-Salt/Ester Electrolytes for Low-Temperature Li+ Cells; Miniature Free-Space Electrostatic Ion Thrusters; Miniature Bipolar Electrostatic Ion Thruster; Holographic Plossl Retroreflectors; Miniature Electrostatic Ion Thruster With Magnet; Using Apex To Construct CPM-GOMS Models; Sequence Detection for PPM Optical Communication With ISI; Algorithm for Rapid Searching Among Star-Catalog Entries; Expectation-Based Control of Noise and Chaos; Radio Heating of Lunar Soil to Release Gases; Using Electrostriction to Manipulate Ullage in Microgravity; Equations for Scoring Rules When Data Are Missing; Insulating Material for Next-Generation Spacecraft; and Pseudorandom Switching for Adding Radar to the AFF Sensor.

Ultramicroelectrode Studies of Self-Terminated Nickel Electrodeposition and Nickel Hydroxide Formation upon Water Reduction.

PubMed

Ritzert, Nicole L; Moffat, Thomas P

2016-12-08

The interaction between electrodeposition of Ni and electrolyte breakdown, namely the hydrogen evolution reaction (HER) via H 3 O + and H 2 O reduction, was investigated under well-defined mass transport conditions using ultramicroelectrodes (UME's) coupled with optical imaging, generation/collection scanning electrochemical microscopy (G/C-SECM), and preliminary microscale pH measurements. For 5 mmol/L NiCl 2 + 0.1 mol/L NaCl, pH 3.0, electrolytes, the voltammetric current at modest overpotentials, i.e. , between -0.6 V and -1.4 V vs. Ag/AgCl, was distributed between metal deposition and H 3 O + reduction, with both reactions reaching mass transport limited current values. At more negative potentials, an unusual sharp current spike appeared upon the onset of H 2 O reduction that was accompanied by a transient increase in H 2 production. The peak potential of the current spike was a function of both [Ni(H 2 O) 6 ] 2+ (aq) concentration and pH. The sharp rise in current was ascribed to the onset of autocatalytic H 2 O reduction, where electrochemically generated OH - species induce heterogeneous nucleation of Ni(OH) 2(ads) islands, the perimeter of which is reportedly active for H 2 O reduction. As the layer coalesces, further metal deposition is quenched while H 2 O reduction continues albeit at a decreased rate as fewer of the most reactive sites, e.g. , Ni/Ni(OH) 2 island edges, are available. At potentials below -1.5 V vs. Ag/AgCl, H 2 O reduction is accelerated, leading to homogeneous precipitation of bulk Ni(OH) 2 · x H 2 O within the nearly hemispherical diffusion layer of the UME.

Development and characterization of direct ethanol fuel cells using alkaline anion-exchange membranes

NASA Astrophysics Data System (ADS)

Lim, Peck Cheng

2009-08-01

Alkaline membrane fuel cell (AMFC) is a relatively new fuel cell technology that is generating considerable interests. It offers the electrocatalytic advantages of conventional alkaline fuel cells, and the manufacturing and cost advantages of solid polymer electrolyte fuel cells. This project was carried out to develop and characterize high performance membrane electrode assemblies (MEAs) for all-solid-state AMFCs. The primary fuel of interests is ethanol, but hydrogen was used in the development stages to facilitate the diagnostic and evaluation of the fuel cell performance. In the preliminary investigation, AMFC was assembled using off-the-shelf electrodes and anion-exchange membrane (AEM). It was found that the performance of AMFC operating on ethanol fuel was limited by a large high-frequency resistance (HFR) value. The advantage of using non-toxic ethanol fuel was also compromised by the need to add hydrazine and potassium hydroxide to the fuel blend. Subsequently, a high performance MEA was developed for an all-solid-state AMFC, in which liquid electrolyte or other additives were not required during the operation of the fuel cell. Ionomer was incorporated in the formulation of catalyst ink, and the catalyst ink was directly coated on the anion-exchange membrane (AEM). An ionomer content of 20 wt.% was found to be the optimum amount required in the catalyst layers. It was demonstrated that the AMFC generated a maximum power density of 365 mW/cm2 and 213 mW/cm 2 with the use of hydrogen/oxygen and hydrogen/pure air, respectively. The performance of the AMFC was also found to be influenced by exposure to carbon dioxide in the air. Hence, the CCMs were pre-treated in potassium hydroxide solution and pure oxygen was used to condition the fuel cell to maximize the power output from the AMFCs. Although satisfactory performance was demonstrated in the AMFC, its stability during cell operation remains a major issue. The poor stability was attributed to degradation of ionomer in the catalyst layers, especially at the catalyst/ionomer interfaces. Ethanol was also used as a fuel in the AMFC with newly developed MEAs. Wetproof gas diffusion layers (GDLs) was found to enhance mass transport in liquid-fed AMFC. With the use of 1M ethanol, the AMFC exhibited a maximum power density of 6.482 mW/cm2 and 3.380 mW/cm2 with pure oxygen and ambient air as oxidant, respectively. These maximum power density values are the highest reported to-date. However, significant work is still necessary in advancing the AMFC technology for direct alcohol fuel cell applications.

Effect of Vinylene Carbonate and Fluoroethylene Carbonate on SEI Formation on Graphitic Anodes in Li-Ion Batteries

DOE PAGES

Nie, Mengyun; Demeaux, Julien; Young, Benjamin T.; ...

2015-07-23

Binder free (BF) graphite electrodes were utilized to investigate the effect of electrolyte additives fluoroethylene carbonate (FEC) and vinylene carbonate (VC) on the structure of the solid electrolyte interface (SEI). The structure of the SEI has been investigated via ex-situ surface analysis including X-ray Photoelectron spectroscopy (XPS), Hard XPS (HAXPES), Infrared spectroscopy (IR) and transmission electron microscopy (TEM). The components of the SEI have been further investigated via nuclear magnetic resonance (NMR) spectroscopy of D2O extractions. The SEI generated on the BF-graphite anode with a standard electrolyte (1.2 M LiPF6 in ethylene carbonate (EC) / ethyl methyl carbonate (EMC), 3/7more » (v/v)) is composed primarily of lithium alkyl carbonates (LAC) and LiF. Incorporation of VC (3% wt) results in the generation of a thinner SEI composed of Li2CO3, poly(VC), LAC, and LiF. Incorporation of VC inhibits the generation of LAC and LiF. Incorporation of FEC (3% wt) also results in the generation of a thinner SEI composed of Li2CO3, poly(FEC), LAC, and LiF. The concentration of poly(FEC) is lower than the concentration of poly(VC) and the generation of LAC is inhibited in the presence of FEC. The SEI appears to be a homogeneous film for all electrolytes investigated.« less

Shock-activated electrochemical power supplies

DOEpatents

Benedick, William B.; Graham, Robert A.; Morosin, Bruno

1988-01-01

A shock-activated electrochemical power supply is provided which is initiated extremely rapidly and which has a long shelf life. Electrochemical power supplies of this invention are initiated much faster than conventional thermal batteries. Power supplies of this invention comprise an inactive electrolyte and means for generating a high-pressure shock wave such that the shock wave is propagated through the electrolytes rendering the electrolyte electrochemically active.

Shock-activated electrochemical power supplies

DOEpatents

Benedick, W.B.; Graham, R.A.; Morosin, B.

1988-11-08

A shock-activated electrochemical power supply is provided which is initiated extremely rapidly and which has a long shelf life. Electrochemical power supplies of this invention are initiated much faster than conventional thermal batteries. Power supplies of this invention comprise an inactive electrolyte and means for generating a high-pressure shock wave such that the shock wave is propagated through the electrolytes rendering the electrolyte electrochemically active. 2 figs.

Alkaline Ammonia Electrolysis on Electrodeposited Platinum for Controllable Hydrogen Production.

PubMed

Gwak, Jieun; Choun, Myounghoon; Lee, Jaeyoung

2016-02-19

Ammonia is beginning to attract a great deal of attention as an alternative energy source carrier, because clean hydrogen can be produced through electrolytic processes without the emission of COx . In this study, we deposited various shapes of Pt catalysts under potentiostatic mode; the electrocatalytic oxidation behavior of ammonia using these catalysts was studied in alkaline media. The electrodeposited Pt was characterized by both qualitative and quantitative analysis. To discover the optimal structure and the effect of ammonia concentration, the bulk pH value, reaction temperature, and applied current of ammonia oxidation were investigated using potential sweep and galvanostatic methods. Finally, ammonia electrolysis was conducted using a zero-gap cell, producing highly pure hydrogen with an energy efficiency over 80 %. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Design and fabrication of silver-hydrogen cells

NASA Technical Reports Server (NTRS)

Klein, M. G.

1975-01-01

The design and fabrication of silver-hydrogen secondary cells capable of delivering higher energy densities than comparable nickel-cadmium and nickel-hydrogen cells and relatively high cycle life is presented. An experimental task utilizing single electrode pairs for the optimization of the individual electrode components, the preparation of a design for lightweight 20Ahr cells, and the fabrication of four 20Ahr cells in heavy wall test housing containing electrode stacks of the lightweight design are described. The design approach is based on the use of a single cylindrical self-contained cell with a stacked disc sequence of electrodes. The electrode stack design is based on the use of NASA- Astropower Separator Material, PPF fuel cell anodes, an intercell electrolyte reservoir concept and sintered silver electrodes. Results of performance tests are given.

Increasing the operation temperature of polymer electrolyte membranes for fuel cells: From nanocomposites to hybrids

NASA Astrophysics Data System (ADS)

Licoccia, Silvia; Traversa, Enrico

Among the possible systems investigated for energy production with low environmental impact, polymeric electrolyte membrane fuel cells (PEMFCs) are very promising as electrochemical power sources for application in portable technology and electric vehicles. For practical applications, operating FCs at temperatures above 100 °C is desired, both for hydrogen and methanol fuelled cells. When hydrogen is used as fuel, an increase of the cell temperature produces enhanced CO tolerance, faster reaction kinetics, easier water management and reduced heat exchanger requirement. The use of methanol instead of hydrogen as a fuel for vehicles has several practical benefits such as easy transport and storage, but the slow oxidation kinetics of methanol needs operating direct methanol fuel cells (DMFCs) at intermediate temperatures. For this reason, new membranes are required. Our strategy to achieve the goal of operating at temperatures above 120 °C is to develop organic/inorganic hybrid membranes. The first approach was the use of nanocomposite class I hybrids where nanocrystalline ceramic oxides were added to Nafion. Nanocomposite membranes showed enhanced characteristics, hence allowing their operation up to 130 °C when the cell was fuelled with hydrogen and up to 145 °C in DMFCs, reaching power densities of 350 mW cm -2. The second approach was to prepare Class II hybrids via the formation of covalent bonds between totally aromatic polymers and inorganic clusters. The properties of such covalent hybrids can be modulated by modifying the ratio between organic and inorganic groups and the nature of the chemical components allowing to reach high and stable conductivity values up to 6.4 × 10 -2 S cm -1 at 120 °C.

A fuel-cell reactor for the direct synthesis of hydrogen peroxide alkaline solutions from H(2) and O(2).

PubMed

Yamanaka, Ichiro; Onisawa, Takeshi; Hashimoto, Toshikazu; Murayama, Toru

2011-04-18

The effects of the type of fuel-cell reactors (undivided or divided by cation- and anion-exchange membranes), alkaline electrolytes (LiOH, NaOH, KOH), vapor-grown carbon fiber (VGCF) cathode components (additives: none, activated carbon, Valcan XC72, Black Pearls 2000, Seast-6, and Ketjen Black), and the flow rates of anolyte (0, 1.5, 12 mL h(-1)) and catholyte (0, 12 mL h(-1)) on the formation of hydrogen peroxide were studied. A divided fuel-cell system, O(2) (g)|VGCF-XC72 cathode|2 M NaOH catholyte|cation-exchange membrane (Nafion-117)|Pt/XC72-VGCF anode|2 M NaOH anolyte at 12 mL h(-1) flow|H(2) (g), was effective for the selective formation of hydrogen peroxide, with 130 mA cm(-2) , a 2 M aqueous solution of H(2)O(2)/NaOH, and a current efficiency of 95 % at atmospheric pressure and 298 K. The current and formation rate gradually decreased over a long period of time. The cause of the slow decrease in electrocatalytic performance was revealed and the decrease was stopped by a flow of catholyte. Cyclic voltammetry studies at the VGCF-XC72 electrode indicated that fast diffusion of O(2) from the gas phase to the electrode, and quick desorption of hydrogen peroxide from the electrode to the electrolyte were essential for the efficient formation of solutions of H(2)O(2)/NaOH. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen generation by reaction of Si nanopowder with neutral water

NASA Astrophysics Data System (ADS)

Kobayashi, Yuki; Matsuda, Shinsuke; Imamura, Kentaro; Kobayashi, Hikaru

2017-05-01

Si and its oxide are nonpoisonous materials, and thus, it can be taken for medical effects. We have developed a method of generation of hydrogen by use of reactions of Si nanopowder with water in the neutral pH region. Si nanopowder is fabricated by the simple bead milling method. Si nanopowder reacts with water to generate hydrogen even in cases where pH is set at the neutral region between 7.0 and 8.6. The hydrogen generation rate strongly depends on pH and in the case of pH 8.0, ˜55 ml/g hydrogen which corresponds to that contained in approximately 3 L saturated hydrogen-rich water is generated in 1 h. The reaction rate for hydrogen generation greatly increases with pH, indicating that the reacting species is hydroxide ions. The change of pH after the hydrogen generation reaction is negligibly low compared with that estimated assuming that hydroxide ions are consumed by the reaction. From these results, we conclude the following reaction mechanism: Si nanopowder reacts with hydroxide ions in the rate-determining reaction to form hydrogen molecules, SiO2, and electrons in the conduction band. Then, generated electrons are accepted by water molecules, resulting in production of hydrogen molecules and hydroxide ions. The hydrogen generation rate strongly depends on the crystallite size of Si nanopowder, but not on the size of aggregates of Si nanopowder. The present study shows a possibility to use Si nanopowder for hydrogen generation in the body in order to eliminate hydroxyl radicals which cause various diseases.

Energy analysis of electric vehicles using batteries or fuel cells through well-to-wheel driving cycle simulations

NASA Astrophysics Data System (ADS)

Campanari, Stefano; Manzolini, Giampaolo; Garcia de la Iglesia, Fernando

This work presents a study of the energy and environmental balances for electric vehicles using batteries or fuel cells, through the methodology of the well to wheel (WTW) analysis, applied to ECE-EUDC driving cycle simulations. Well to wheel balances are carried out considering different scenarios for the primary energy supply. The fuel cell electric vehicles (FCEV) are based on the polymer electrolyte membrane (PEM) technology, and it is discussed the possibility to feed the fuel cell with (i) hydrogen directly stored onboard and generated separately by water hydrolysis (using renewable energy sources) or by conversion processes using coal or natural gas as primary energy source (through gasification or reforming), (ii) hydrogen generated onboard with a fuel processor fed by natural gas, ethanol, methanol or gasoline. The battery electric vehicles (BEV) are based on Li-ion batteries charged with electricity generated by central power stations, either based on renewable energy, coal, natural gas or reflecting the average EU power generation feedstock. A further alternative is considered: the integration of a small battery to FCEV, exploiting a hybrid solution that allows recovering energy during decelerations and substantially improves the system energy efficiency. After a preliminary WTW analysis carried out under nominal operating conditions, the work discusses the simulation of the vehicles energy consumption when following standardized ECE-EUDC driving cycle. The analysis is carried out considering different hypothesis about the vehicle driving range, the maximum speed requirements and the possibility to sustain more aggressive driving cycles. The analysis shows interesting conclusions, with best results achieved by BEVs only for very limited driving range requirements, while the fuel cell solutions yield best performances for more extended driving ranges where the battery weight becomes too high. Results are finally compared to those of conventional internal combustion engine vehicles, showing the potential advantages of the different solutions considered in the paper and indicating the possibility to reach the target of zero-emission vehicles (ZEV).

Influence of supporting electrolyte in electricity generation and degradation of organic pollutants in photocatalytic fuel cell.

PubMed

Khalik, Wan Fadhilah; Ong, Soon-An; Ho, Li-Ngee; Wong, Yee-Shian; Voon, Chun-Hong; Yusuf, Sara Yasina; Yusoff, Nik Athirah; Lee, Sin-Li

2016-08-01

This study investigated the effect of different supporting electrolyte (Na2SO4, MgSO4, NaCl) in degradation of Reactive Black 5 (RB5) and generation of electricity. Zinc oxide (ZnO) was immobilized onto carbon felt acted as photoanode, while Pt-coated carbon paper as photocathode was placed in a single chamber photocatalytic fuel cell, which then irradiated by UV lamp for 24 h. The degradation and mineralization of RB5 with 0.1 M NaCl rapidly decreased after 24-h irradiation time, followed by MgSO4, Na2SO4 and without electrolyte. The voltage outputs for Na2SO4, MgSO4 and NaCl were 908, 628 and 523 mV, respectively, after 24-h irradiation time; meanwhile, their short-circuit current density, J SC, was 1.3, 1.2 and 1.05 mA cm(-2), respectively. The power densities for Na2SO4, MgSO4 and NaCl were 0.335, 0.256 and 0.245 mW cm(-2), respectively. On the other hand, for without supporting electrolyte, the voltage output and short-circuit current density was 271.6 mV and 0.055 mA cm(-2), respectively. The supporting electrolyte NaCl showed greater performance in degradation of RB5 and generation of electricity due to the formation of superoxide radical anions which enhance the degradation of dye. The mineralization of RB5 with different supporting electrolyte was measured through spectrum analysis and reduction in COD concentration.

Relationship between anode material, supporting electrolyte and current density during electrochemical degradation of organic compounds in water.

PubMed

Guzmán-Duque, Fernando L; Palma-Goyes, Ricardo E; González, Ignacio; Peñuela, Gustavo; Torres-Palma, Ricardo A

2014-08-15

Taking crystal violet (CV) dye as pollutant model, the electrode, electrolyte and current density (i) relationship for electro-degrading organic molecules is discussed. Boron-doped diamond (BDD) or Iridium dioxide (IrO2) used as anode materials were tested with Na2SO4 or NaCl as electrolytes. CV degradation and generated oxidants showed that degradation pathways and efficiency are strongly linked to the current density-electrode-electrolyte interaction. With BDD, the degradation pathway depends on i: If ii(lim), generated oxidants play a major role in the CV elimination. When IrO2 was used, CV removal was not dependent on i, but on the electrolyte. Pollutant degradation in Na2SO4 on IrO2 seems to occur via IrO3; however, in the presence of NaCl, degradation was dependent on the chlorinated oxidative species generated. In terms of efficiency, the Na2SO4 electrolyte showed better results than NaCl when BDD anodes were employed. On the contrary, NaCl was superior when combined with IrO2. Thus, the IrO2/Cl(-) and BDD/SO4(2-) systems were better at removing the pollutant, being the former the most effective. On the other hand, pollutant degradation with the BDD/SO4(2-) and IrO2/Cl(-) systems is favored at low and high current densities, respectively. Copyright © 2014 Elsevier B.V. All rights reserved.

The alkaline aluminium/hydrogen peroxide power source in the Hugin II unmanned underwater vehicle

NASA Astrophysics Data System (ADS)

Hasvold, Øistein; Johansen, Kjell Håvard; Mollestad, Ole; Forseth, Sissel; Størkersen, Nils

In 1993, The Norwegian Defence Research Establishment (FFI) demonstrated AUV-Demo, an unmanned (untethered) underwater vehicle (UUV), powered by a magnesium/dissolved oxygen seawater battery (SWB). This technology showed that an underwater range of at least 1000 nautical miles at a speed of 4 knots was possible, but also that the maximum hotel load this battery system could support was very limited. Most applications for UUV technology need more power over a shorter period of time. Seabed mapping using a multibeam echo sounder mounted on an UUV was identified as a viable application and the Hugin project was started in 1995 in cooperation with Norwegian industry. For this application, an endurance of 36 h at 4 knots was required. Development of the UUV hull and electronics system resulted in the UUV Hugin I. It carries a Ni/Cd battery of 3 kW h, allowing up to 6 h under-water endurance. In parallel, we developed a battery based on a combination of alkaline Al/air and SWB technology, using a circulating alkaline electrolyte, aluminium anodes and maintaining the oxidant concentration in the electrolyte by continuously adding hydrogen peroxide (HP) to the electrolyte. This concept resulted in a safe battery, working at ambient pressure (balanced) and with sufficient power and energy density to allow the UUV Hugin II to make a number of successive dives, each of up to 36 h duration and with only 1 h deck time between dives for HP refill and electrolyte exchange. After 100 h, an exchange of anodes takes place. The power source consists of a four-cell Al/HP battery, a DC/DC converter delivering 600 W at 30 V, circulation and dosing pumps and a battery control unit. Hugin II is now in routine use by the Norwegian Underwater Intervention AS (NUI) which operates the UUV for high-precision seabed mapping down to a water depth of 600 m.

Polymer Electrolyte Membranes for Water Photo-Electrolysis

PubMed Central

Aricò, Antonino S.; Girolamo, Mariarita; Siracusano, Stefania; Sebastian, David; Baglio, Vincenzo; Schuster, Michael

2017-01-01

Water-fed photo-electrolysis cells equipped with perfluorosulfonic acid (Nafion® 115) and quaternary ammonium-based (Fumatech® FAA3) ion exchange membranes as separator for hydrogen and oxygen evolution reactions were investigated. Protonic or anionic ionomer dispersions were deposited on the electrodes to extend the interface with the electrolyte. The photo-anode consisted of a large band-gap Ti-oxide semiconductor. The effect of membrane characteristics on the photo-electrochemical conversion of solar energy was investigated for photo-voltage-driven electrolysis cells. Photo-electrolysis cells were also studied for operation under electrical bias-assisted mode. The pH of the membrane/ionomer had a paramount effect on the photo-electrolytic conversion. The anionic membrane showed enhanced performance compared to the Nafion®-based cell when just TiO2 anatase was used as photo-anode. This was associated with better oxygen evolution kinetics in alkaline conditions compared to acidic environment. However, oxygen evolution kinetics in acidic conditions were significantly enhanced by using a Ti sub-oxide as surface promoter in order to facilitate the adsorption of OH species as precursors of oxygen evolution. However, the same surface promoter appeared to inhibit oxygen evolution in an alkaline environment probably as a consequence of the strong adsorption of OH species on the surface under such conditions. These results show that a proper combination of photo-anode and polymer electrolyte membrane is essential to maximize photo-electrolytic conversion. PMID:28468242

Polymer Electrolyte Membranes for Water Photo-Electrolysis.

PubMed

Aricò, Antonino S; Girolamo, Mariarita; Siracusano, Stefania; Sebastian, David; Baglio, Vincenzo; Schuster, Michael

2017-04-29

Water-fed photo-electrolysis cells equipped with perfluorosulfonic acid (Nafion ® 115) and quaternary ammonium-based (Fumatech ® FAA3) ion exchange membranes as separator for hydrogen and oxygen evolution reactions were investigated. Protonic or anionic ionomer dispersions were deposited on the electrodes to extend the interface with the electrolyte. The photo-anode consisted of a large band-gap Ti-oxide semiconductor. The effect of membrane characteristics on the photo-electrochemical conversion of solar energy was investigated for photo-voltage-driven electrolysis cells. Photo-electrolysis cells were also studied for operation under electrical bias-assisted mode. The pH of the membrane/ionomer had a paramount effect on the photo-electrolytic conversion. The anionic membrane showed enhanced performance compared to the Nafion ® -based cell when just TiO₂ anatase was used as photo-anode. This was associated with better oxygen evolution kinetics in alkaline conditions compared to acidic environment. However, oxygen evolution kinetics in acidic conditions were significantly enhanced by using a Ti sub-oxide as surface promoter in order to facilitate the adsorption of OH species as precursors of oxygen evolution. However, the same surface promoter appeared to inhibit oxygen evolution in an alkaline environment probably as a consequence of the strong adsorption of OH species on the surface under such conditions. These results show that a proper combination of photo-anode and polymer electrolyte membrane is essential to maximize photo-electrolytic conversion.

Functionalized carbon nanotube based hybrid electrochemical capacitors using neutral bromide redox-active electrolyte for enhancing energy density

NASA Astrophysics Data System (ADS)

Tang, Xiaohui; Lui, Yu Hui; Chen, Bolin; Hu, Shan

2017-06-01

A hybrid electrochemical capacitor (EC) with enhanced energy density is realized by integrating functionalized carbon nanotube (FCNT) electrodes with redox-active electrolyte that has a neutral pH value (1 M Na2SO4 and 0.5 M KBr mixed aqueous solution). The negative electrode shows an electric double layer capacitor-type behavior. On the positive electrode, highly reversible Br-/Br3- redox reactions take place, presenting a battery-type behavior, which contributes to increase the capacitance of the hybrid cell. The voltage window of the whole cell is extended up to 1.5 V because of the high over-potentials of oxygen and hydrogen evolution reactions in the neutral electrolyte. Compared with raw CNT, the FCNT has better wettability in the aqueous electrolyte and contributes to increase the electric double layer capacitance of the cell. As a result, the maximum energy density of 28.3 Wh kg-1 is obtained from the hybrid EC at 0.5 A g-1 without sacrificing its power density, which is around 4 times larger than that of the electrical double layer capacitor constructed by FCNT electrodes and 1 M Na2SO4 electrolyte. Moreover, the discharge capacity retained 86.3% of its initial performance after 10000 cycles of galvanostatic charge and discharge test (10 A/g), suggesting its long life cycle even at high current loading.

Neutron scattering study on cathode LiMn2O4 and solid electrolyte 5(Li2O)(P2O5)

NASA Astrophysics Data System (ADS)

Kartini, E.; Putra, Teguh P.; Jahya, A. K.; Insani, A.; Adams, S.

2014-09-01

Neutron scattering is very important technique in order to investigate the energy storage materials such as lithium-ion battery. The unique advantages, neutron can see the light atoms such as Hydrogen, Lithium, and Oxygen, where those elements are negligible by other corresponding X-ray method. On the other hand, the energy storage materials, such as lithium ion battery is very important for the application in the electric vehicles, electronic devices or home appliances. The battery contains electrodes (anode and cathode), and the electrolyte materials. There are many challenging to improve the existing lithium ion battery materials, in order to increase their life time, cyclic ability and also its stability. One of the most scientific challenging is to investigate the crystal structure of both electrode and electrolyte, such as cathodes LiCoO2, LiMn2O4 and LiFePO4, and solid electrolyte Li3PO4. Since all those battery materials contain Lithium ions and Oxygen, the used of neutron scattering techniques to study their structure and related properties are very important and indispensable. This article will review some works of investigating electrodes and electrolytes, LiMn2O4 and 5(Li2O)(P2O5), by using a high resolution powder diffraction (HRPD) at the multipurpose research reactor, RSG-Sywabessy of the National Nuclear Energy Agency (BATAN), Indonesia.

Cationic Polymers Developed for Alkaline Fuel Cell Applications

DTIC Science & Technology

2015-01-20

into five categories: proton exchange membrane fuel cell ( PEMFC ), alkaline fuel cell (AFC), molten carbonate fuel cell (MCFC), solid oxide fuel...SOFC and PAFC belong to high temperature fuel cell, which can be applied in stationary power generation. PEMFC and AFC belong to low temperature fuel...function of the polymer electrolyte is to serve as electrolyte to transport ions between electrodes. PEMFC uses a polymer as electrolyte and works

Relationship between fabrication method and chemical stability of Ni-BaZr0.8Y0.2O3-δ membrane

NASA Astrophysics Data System (ADS)

Fang, Shumin; Wang, Siwei; Brinkman, Kyle S.; Su, Qing; Wang, Haiyan; Chen, Fanglin

2015-03-01

NiO effectively promotes the sintering of highly refractory Y-doped BaZrO3 (BZY) through the formation of BaY2NiO5, providing a simple and cost-effective method for the fabrication of dense BZY electrolyte and Ni-BZY hydrogen separation membrane at ∼1400 °C. Unfortunately, insulating BaCO3 and Y2O3 phases formed on the surface of BZY and Ni-BZY prepared by solid state reaction method with NiO after annealing in wet CO2. Ni-BZY membranes prepared from different methods suffered different degree of performance loss in wet H2 at 900 °C. The chemical instability of Ni-BZY is attributed to the formation of a secondary phase (BaY2O4) generated from the reduction of BaY2NiO5 in H2 during the sintering process. Both BaY2O4 and BaY2NiO5 react with H2O, and CO2 at elevated temperatures, generating insulating Ba(OH)2 and BaCO3 phases, respectively. The less BaY2O4 is formed in the fabrication process, the better chemical stability the Ni-BZY membranes possess. Therefore, a new Ni-BZY membrane is prepared through a judicial combination of BZY powders prepared from combined EDTA-citric and solid state reaction methods, and demonstrates exceptional chemical stability in H2O and CO2, enabling stable and even improved hydrogen flux in wet 50% CO2 at 900 °C.

Superior Blends Solid Polymer Electrolyte with Integrated Hierarchical Architectures for All-Solid-State Lithium-Ion Batteries.

PubMed

Zhang, Dechao; Zhang, Long; Yang, Kun; Wang, Hongqiang; Yu, Chuang; Xu, Di; Xu, Bo; Wang, Li-Min

2017-10-25

Exploration of advanced solid electrolytes with good interfacial stability toward electrodes is a highly relevant research topic for all-solid-state batteries. Here, we report PCL/SN blends integrating with PAN-skeleton as solid polymer electrolyte prepared by a facile method. This polymer electrolyte with hierarchical architectures exhibits high ionic conductivity, large electrochemical windows, high degree flexibility, good flame-retardance ability, and thermal stability (workable at 80 °C). Additionally, it demonstrates superior compatibility and electrochemical stability toward metallic Li as well as LiFePO 4 cathode. The electrolyte/electrode interfaces are very stable even subjected to 4.5 V at charging state for long time. The LiFePO 4 /Li all-solid-state cells based on this electrolyte deliver high capacity, outstanding cycling stability, and superior rate capability better than those based on liquid electrolyte. This solid polymer electrolyte is eligible for next generation high energy density all-solid-state batteries.

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

Combined soft and hard X-ray ambient pressure photoelectron spectroscopy studies of semiconductor/electrolyte interfaces

DOE PAGES

Starr, David E.; Favaro, Marco; Abdi, Fatwa F.; ...

2017-05-18

The development of solar fuel generating materials would greatly benefit from a molecular level understanding of the semiconductor/electrolyte interface and changes in the interface induced by an applied potential and illumination by solar light. Ambient pressure photoelectron spectroscopy techniques with both soft and hard X-rays, AP-XPS and AP-HAXPES respectively, have the potential to markedly contribute to this understanding. In this paper we initially provide two examples of current challenges in solar fuels material development that AP-XPS and AP-HAXPES can directly a ddress. This will be followed by a brief description of the distinguishing and complementary characteristics of soft and hardmore » X-ray AP-XPS and AP-HAXPES and best approaches to achieving monolayer sensitivity in solid/aqueous electrolyte studies. In particular we focus on the detection of surface adsorbed hydroxyl groups in the presence of aqueous hydroxide anions in the electrolyte, a common situation when investigating photoanodes for solar fuel generating applications. Finally, the article concludes by providing an example of a combined AP-XPS and AP-HAXPES study of a semiconductor/aqueous electrolyte interface currently used in water splitting devices specifically the BiVO 4/aqueous potassium phosphate electrolyte interface.« less

Production of hydrogen, liquid fuels, and chemicals from catalytic processing of bio-oils

DOEpatents

Huber, George W; Vispute, Tushar P; Routray, Kamalakanta

2014-06-03

Disclosed herein is a method of generating hydrogen from a bio-oil, comprising hydrogenating a water-soluble fraction of the bio-oil with hydrogen in the presence of a hydrogenation catalyst, and reforming the water-soluble fraction by aqueous-phase reforming in the presence of a reforming catalyst, wherein hydrogen is generated by the reforming, and the amount of hydrogen generated is greater than that consumed by the hydrogenating. The method can further comprise hydrocracking or hydrotreating a lignin fraction of the bio-oil with hydrogen in the presence of a hydrocracking catalyst wherein the lignin fraction of bio-oil is obtained as a water-insoluble fraction from aqueous extraction of bio-oil. The hydrogen used in the hydrogenating and in the hydrocracking or hydrotreating can be generated by reforming the water-soluble fraction of bio-oil.

Hydrogen purification systems for PEM fuel cells

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

Varma, Arvind; Hwang, Hyun Tae; Al-Kukhun, Ahmad

A system for generating and purifying hydrogen. To generate hydrogen, the system includes inlets configured to receive a hydrogen carrier and an inert insulator, a mixing chamber configured to combine the hydrogen carrier and the inert insulator, a heat exchanger configured to apply heat to the mixture of hydrogen carrier and the inert insulator, wherein the applied heat results in the generation of hydrogen from the hydrogen carrier, and an outlet configured to release the generated hydrogen. To purify hydrogen, the system includes a primary inlet to receive a starting material and an ammonia filtration subassembly, which may include anmore » absorption column configured to absorb the ammonia into water for providing purified hydrogen at a first purity level. The ammonia filtration subassembly may also include an adsorbent member configured to adsorb ammonia from the starting material into an adsorbent for providing purified hydrogen at a second purity level.« less

Hydrogen generation via photoelectrochemical water splitting using chemically exfoliated MoS{sub 2} layers

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

Joshi, R. K., E-mail: r.joshi@unsw.edu.au, E-mail: alwarappan@cecri.res.in; Sahajwalla, V.; Shukla, S.

2016-01-15

Study on hydrogen generation has been of huge interest due to increasing demand for new energy sources. Photoelectrochemical reaction by catalysts was proposed as a promising technique for hydrogen generation. Herein, we report the hydrogen generation via photoelectrochecmial reaction using films of exfoliated 2-dimensional (2D) MoS{sub 2}, which acts as an efficient photocatalyst. The film of chemically exfoliated MoS{sub 2} layers was employed for water splitting, leading to hydrogen generation. The amount of hydrogen was qualitatively monitored by observing overpressure of a water container. The high photo-current generated by MoS{sub 2} film resulted in hydrogen evolution. Our work shows thatmore » 2D MoS{sub 2} is one of the promising candidates as a photocatalyst for light-induced hydrogen generation. High photoelectrocatalytic efficiency of the 2D MoS{sub 2} shows a new way toward hydrogen generation, which is one of the renewable energy sources. The efficient photoelectrocatalytic property of the 2D MoS{sub 2} is possibly due to availability of catalytically active edge sites together with minimal stacking that favors the electron transfer.« less

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.

Synthesis of chemicals using solar energy with stable photoelectrochemically active heterostructures.

PubMed

Mubeen, Syed; Singh, Nirala; Lee, Joun; Stucky, Galen D; Moskovits, Martin; McFarland, Eric W

2013-05-08

Efficient and cost-effective conversion of solar energy to useful chemicals and fuels could lead to a significant reduction in fossil hydrocarbon use. Artificial systems that use solar energy to produce chemicals have been reported for more than a century. However the most efficient devices demonstrated, based on traditionally fabricated compound semiconductors, have extremely short working lifetimes due to photocorrosion by the electrolyte. Here we report a stable, scalable design and molecular level fabrication strategy to create photoelectrochemically active heterostructure (PAH) units consisting of an efficient semiconductor light absorber in contact with oxidation and reduction electrocatalysts and otherwise protected by alumina. The functional heterostructures are fabricated by layer-by-layer, template-directed, electrochemical synthesis in porous anodic aluminum oxide membranes to produce high density arrays of electronically autonomous, nanostructured, corrosion resistant, photoactive units (~10(9)-10(10) PAHs per cm(2)). Each PAH unit is isolated from its neighbor by the transparent electrically insulating oxide cellular enclosure that makes the overall assembly fault tolerant. When illuminated with visible light, the free floating devices have been demonstrated to produce hydrogen at a stable rate for over 24 h in corrosive hydroiodic acid electrolyte with light as the only input. The quantum efficiency (averaged over the solar spectrum) for absorbed photons-to-hydrogen conversion was 7.4% and solar-to-hydrogen energy efficiency of incident light was 0.9%. The fabrication approach is scalable for commercial manufacturing and readily adaptable to a variety of earth abundant semiconductors which might otherwise be unstable as photoelectrocatalysts.

Non-aqueous electrolytes for isotachophoresis of weak bases and its application to the comprehensive preconcentration of the 20 proteinogenic amino acids in column-coupling ITP/CE-MS.

PubMed

Kler, Pablo A; Huhn, Carolin

2014-11-01

Isotachophoresis (ITP) has long been used alone but also as a preconcentration technique for capillary electrophoresis (CE). Unfortunately, up to now, its application is restricted to relatively strong acids and bases as either the degree of (de)protonation is too low or the water dissociation is too high, evoking zone electrophoresis. With the comprehensive ITP analysis of all 20 proteinogenic amino acids as model analytes, we, here, show that non-aqueous ITP using dimethylsulfoxide as a solvent solves this ITP shortcoming. Dimethylsulfoxide changes the pH regime of analytes and electrolytes but, more importantly, strongly reduces the proton mobility by prohibiting hydrogen bonds and thus, the so-called Zundel-Eigen-Zundel electrical conduction mechanism of flipping hydrogen bonds. The effects are demonstrated in an electrolyte system with taurine or H(+) as terminator, and imidazole as leader together with strong acids such as oxalic and even trifluoroacetic acid as counterions, both impossible to use in aqueous solution. Mass spectrometric as well as capacitively coupled contactless conductivity detection (C(4)D) are used to follow the ITP processes. To demonstrate the preconcentration capabilities of ITP in a two-dimensional set-up, we, here, also demonstrate that our non-aqueous ITP method can be combined with capillary electrophoresis-mass spectrometry in a column-coupling system using a hybrid approach of capillaries coupled to a microfluidic interface. For this, C(4)D was optimized for on-chip detection with the electrodes aligned on top of a thin glass lid of the microfluidic chip.

Oxygen Production from Lunar Regolith using Ionic Liquids

NASA Technical Reports Server (NTRS)

Paley, Mark Steven; Karr, Laurel J.; Curreri, Peter

2009-01-01

The objective of this work and future follow-on work is to develop a safe, efficient, and recyclable method for oxygen and/or metals extraction from lunar regolith, in support of establishing a manned lunar outpost. The approach is to solubilize the oxides that comprise lunar regolith in media consisting of ionic liquids (ILs) and/or their mixtures at temperatures at or below 300 C. Once in solution, electrolysis can either be performed in-situ to generate oxygen at the anode and hydrogen and/or metals (silicon, iron, aluminum, titanium, etc.) at the cathode. Alternatively, the water that is generated during the solubilization process can be distilled out and condensed into a separate IL and then electrolysized to produce hydrogen and oxygen. In the case of lunar regolith, this method could theoretically produce 44g oxygen per 100g of regolith. The oxygen can be used for human life support and/or as an oxidizer for rocket fuels, and the metals can be used as raw materials for construction and/or device fabrication. Moreover, the hydrogen produced can be used to re-generate the acidic medium, which can then be used to process additional regolith, thereby making the materials recyclable and limiting upmass requirements. An important advantage of IL acid systems is that they are much "greener" and safer than conventional materials used for regolith processing such as sulfuric or hydrochloric acids. They have very low vapor pressures, which means that they contain virtually no toxic and/or flammable volatile content, they are relatively non-corrosive, and they can exhibit good stability in harsh environments (extreme temperatures, hard vacuum, etc.). Furthermore, regolith processing can be achieved at lower temperatures than other processes such as molten oxide electrolysis or hydrogen reduction, thereby reducing initial power requirements. Six ILs have been synthesized and tested for their capability to dissolve lunar simulant, and for electrochemical and thermal stability. The results showed that ILs can be very efficient electrolytes; in particular IL/phosphoric-acid mixtures appear extremely promising for solubilizing lunar simulant. Results from preliminary experiments for distillation of water produced from the oxygen within the metal oxides of the simulant and the hydrogen from the acid indicates that over 75% of the oxygen from the simulant can be harvested as water at a temperature of 150 C. A method for collection of oxygen from electrolysis of the water derived from solubilizing simulant was developed by using a liquid nitrogen trap to liquefy and collect the oxygen. Although precise quantification of the liquid oxygen trapped is difficult to obtain, the amount of hydrogen and oxygen collected from electrolysis of water in this system was greater than 98%. This set-up also included a portable mass spectrometer for the identification of gases released from electrolysis cells. Regeneration of ILs through re-protonation was also demonstrated. Four sequential re-generations of an IL following solubilization of simulant showed no significant differences in amounts of simulant dissolved. Follow-on work for this project should include more studies of IL/phosphoric acid systems. Also, much more work is necessary for defining methods for electrolysis and purification of metals from regolith solubilized in ILs, and for developing a system to use the produced hydrogen to regenerate the spent IL. Finally, design and development of flight breadboard and prototype hardware is required.

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

Yoo, Jongmyung; Woo, Jiyong; Song, Jeonghwan

The effect of hydrogen treatment on the threshold switching property in a Ag/amorphous Si based programmable metallization cells was investigated for selector device applications. Using the Ag filament formed during motion of Ag ions, a steep-slope (5 mV/dec.) for threshold switching with higher selectivity (∼10{sup 5}) could be achieved. Because of the faster diffusivity of Ag atoms, which are inside solid-electrolytes, the resulting Ag filament could easily be dissolved under low current regime, where the Ag filament possesses weak stability. We found that the dissolution process could be further enhanced by hydrogen treatment that facilitated the movement of the Agmore » atoms.« less

Method and system for storing and generating hydrogen

NASA Technical Reports Server (NTRS)

Kindler, Andrew (Inventor); Narayanan, Sri R. (Inventor); Huang, Yuhong (Inventor)

2011-01-01

A method and system for storing and generating hydrogen. The method comprises generating hydrogen and heat from the reaction of a metal or metal compound with water. The heat generated from this reaction may then be converted to other forms of energy such as by passing the heat through a thermal electric device to recover electrical energy for storage in a battery. In an alternative and preferred embodiment, the heat is used to drive additional reactions for generating more hydrogen and is preferably used to drive an endothermic dehydrogenation reaction resulting in increased hydrogen generation and consumption of the heat.

The effect of zinc on the aluminum anode of the aluminum-air battery

NASA Astrophysics Data System (ADS)

Tang, Yougen; Lu, Lingbin; Roesky, Herbert W.; Wang, Laiwen; Huang, Baiyun

Aluminum is an ideal material for batteries, due to its excellent electrochemical performance. Herein, the effect of zinc on the aluminum anode of the aluminum-air battery, as an additive for aluminum alloy and electrolytes, has been studied. The results show that zinc can decrease the anodic polarization, restrain the hydrogen evolution and increase the anodic utilization rate.

Emission Measurements of Ultracell XX25 Reformed Methanol Fuel Cell System

DTIC Science & Technology

2008-06-01

combination of electrochemical devices such as fuel cell and battery. Polymer electrolyte membrane fuel cells ( PEMFC ) using hydrogen or liquid...communications and computers, sensors and night vision capabilities. High temperature PEMFC offers some advantages such as enhanced electrode kinetics and better...tolerance of carbon monoxide that will poison the conventional PEMFC . Ultracell Corporation, Livermore, California has developed a first

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

Electrochemical removal of biofilms from titanium dental implant surfaces.

PubMed

Schneider, Sebastian; Rudolph, Michael; Bause, Vanessa; Terfort, Andreas

2018-06-01

The infection of dental implants may cause severe inflammation of tissue and even bone degradation if not treated. For titanium implants, a new, minimally invasive approach is the electrochemical removal of the biofilms including the disinfection of the metal surface. In this project, several parameters, such as electrode potentials and electrolyte compositions, were varied to understand the underlying mechanisms. Optimal electrolytes contained iodide as well as lactic acid. Electrochemical experiments, such as cyclic voltammetry or measurements of open circuit potentials, were performed in different cell set-ups to distinguish between different possible reactions. At the applied potentials of E < -1.4 V, the hydrogen evolution reaction dominated at the implant surface, effectively lifting off the bacterial films. In addition, several disinfecting species are formed at the anode, such as triiodide and hydrogen peroxide. Ex situ tests with model biofilms of E. coli clearly demonstrated the effectiveness of the respective anolytes in killing the bacteria, as determined by the LIVE/DEAD™ assay. Using optimized electrolysis parameters of 30 s at 7.0 V and 300 mA, a 14-day old wildtype biofilm could be completely removed from dental implants in vitro. Copyright © 2018 Elsevier B.V. All rights reserved.

Three-Man Solid Electrolyte Carbon Dioxide Electrolysis Breadboard

NASA Technical Reports Server (NTRS)

Isenberg, Arnold O.

1989-01-01

The development of the Three-Man (2.2 lb CO2/man-day) Solid Electrolyte CO2 Electrolysis Breadboard consisted of a Phase 1 and 2 effort. The Phase 1 effort constituted fabrication of three electrolysis cell types and performing parametric testing, off-design testing, and cell life testing. The Phase 2 consisted of the preliminary design, incorporation of palladium (Pd) tubes for hydrogen separation from the electrolyzer cathode feed gases, design support testing, final design, fabrication, and performance testing of the breadboard system. The results of performance tests demonstrated that CO2 electrolysis in an oxygen reclamation system for long duration space-based habitats is feasible. Closure of the oxygen system loop, therefore, can be achieved by CO2 electrolysis. In a two step process the metabolic CO2 and H2O vapor are electrolyzed into O2, H2, and CO. The CO can subsequently be disproportionated into carbon and CO2 in a carbon deposition reactor and the CO2 in turn be recycled and electrolyzed for total O2 recovery. The development effort demonstrated electrolyzer system can be designed and built to operate safely and reliably and the incorporation of Pd tubes for hydrogen diffusion can be integrated safely with predictable performance.

Dual membrane hollow fiber fuel cell and method of operating same

NASA Technical Reports Server (NTRS)

Ingham, J. D.; Lawson, D. D. (Inventor)

1978-01-01

A gaseous fuel cell is described which includes a pair of electrodes formed by open-ended, ion-exchange hollow fibers, each having a layer of metal catalyst deposited on the inner surface and large surface area current collectors such as braided metal mesh in contact with the metal catalyst layer. A fuel cell results when the electrodes are immersed in electrolytes and electrically connected. As hydrogen and oxygen flow through the bore of the fibers, oxidation and reduction reactions develop an electrical potential. Since the hollow fiber configuration provides large electrode area per unit volume and intimate contact between fuel and oxidizer at the interface, and due to the low internal resistance of the electrolyte, high power densities can be obtained.

Water dissociation in a radio-frequency electromagnetic field with ex situ electrodes—process characterization

NASA Astrophysics Data System (ADS)

Schneider, Jens; Holzer, Frank; Kraus, Markus; Kopinke, Frank-Dieter; Roland, Ulf

2013-02-01

A new type of water dissociation at ambient pressure initiated by the irradiation of aqueous electrolytes using an electromagnetic field with a frequency of 13.56 MHz is described in this study. A special reactor design allows the use of ex situ electrodes to form in situ electrical discharges in water vapour bubbles. The observed formation of molecular hydrogen (H2) and oxygen (O2) combined with the emission of light (‘burning water’ phenomenon) originates from a non-thermal plasma in water vapour bubbles. The influences of type of electrolyte, its concentration, pH value and external RF voltage on the gas formation rate as well as on the gas composition are presented.

Removal of contaminant gases from an electrolytic urine pretreatment process. [in spacecraft life support systems

NASA Technical Reports Server (NTRS)

Colombo, G. V.; Putnam, D. F.

1977-01-01

The effluent gas stream from an electrolytic urine pretreatment process was analyzed by gas chromatography-mass spectroscopy and wet chemical methods to determine its composition. The major constituents were identified as: hydrogen, carbon dioxide, oxygen, nitrogen, water vapor, and chlorine. The trace impurities were chlorinated light hydrocarbons, and a number of other organic impurities in the low ppm range. Several methods of removing all of the undesirable gases to levels acceptable for return to a space cabin atmosphere were investigated experimentally. A subsystem concept comprised of the following sequential unit processes and operations was successfully demonstrated: (1) raw urine scrubbing, (2) silica gel sorption, (3) dilution with cabin air, and (4) catalytic oxidation.

Insight into self-discharge of layered lithium-rich oxide cathode in carbonate-based electrolytes with and without additive

NASA Astrophysics Data System (ADS)

Li, Jianhui; Xing, Lidan; Zhang, Liping; Yu, Le; Fan, Weizhen; Xu, Mengqing; Li, Weishan

2016-08-01

Self-discharge behavior of layered lithium-rich oxide as cathode of lithium ion battery in a carbonated-based electrolyte is understood, and a simple boron-containing compound, trimethyl borate (TMB), is used as an electrolyte additive to suppress this self-discharge. It is found that layered lithium-rich oxide charged under 4.8 V in additive-free electrolyte suffers severe self-discharge and TMB is an effective electrolyte additive for self-discharge suppression. Physical characterizations from XRD, SEM, TEM, XPS and ICP-MS demonstrate that the crystal structure of the layered lithium-rich oxide collapses due to the chemical interaction between the charged oxide and electrolyte. When TMB is applied, the structural integrity of the oxide is maintained due to the protective cathode film generated from the preferential oxidation of TMB.

Symmetrical solid oxide fuel cells with impregnated SrFe0.75Mo0.25O3-δ electrodes

NASA Astrophysics Data System (ADS)

Meng, Xie; Liu, Xuejiao; Han, Da; Wu, Hao; Li, Junliang; Zhan, Zhongliang

2014-04-01

Here we report nominally symmetrical solid oxide fuel cells that feature thin La0.9Sr0.1Ga0.8Mg0.2O3-δ (LSGM) electrolytes and impregnated SrFe0.75Mo0.25O3-δ (SFMO)-LSGM composite electrodes. Operation on hydrogen fuels and air oxidants can produce maximum power densities of 0.39 W cm-2 at 650 °C and 0.97 W cm-2 at 800 °C. Impedance measurements indicate that the anode and the cathode polarizations are 0.22 and 0.04 Ω cm2 at 800 °C, respectively. Hydrogen partial pressure and temperature dependence of impedance data in humidified hydrogen shows that hydrogen oxidation kinetics is largely determined by hydrogen adsorption on the SFMO catalysts at high temperatures and charge transfer reactions along the SFMO|LSGM interfaces at low temperatures. Carbon tolerance of the present fuel cells is also examined in iso-octane fuels balanced by nitrogen at 800 °C that yields stable maximum power densities of 0.39 W cm-2.

Qualitative and quantitative analysis of solar hydrogen generation literature from 2001 to 2014.

PubMed

Maghami, Mohammad Reza; Asl, Shahin Navabi; Rezadad, Mohammad Esmaeil; Ale Ebrahim, Nader; Gomes, Chandima

Solar hydrogen generation is one of the new topics in the field of renewable energy. Recently, the rate of investigation about hydrogen generation is growing dramatically in many countries. Many studies have been done about hydrogen generation from natural resources such as wind, solar, coal etc. In this work we evaluated global scientific production of solar hydrogen generation papers from 2001 to 2014 in any journal of all the subject categories of the Science Citation Index compiled by Institute for Scientific Information (ISI), Philadelphia, USA. Solar hydrogen generation was used as keywords to search the parts of titles, abstracts, or keywords. The published output analysis showed that hydrogen generation from the sun research steadily increased over the past 14 years and the annual paper production in 2013 was about three times 2010-paper production. The number of papers considered in this research is 141 which have been published from 2001 to this date. There are clear distinctions among author keywords used in publications from the five most high-publishing countries such as USA, China, Australia, Germany and India in solar hydrogen studies. In order to evaluate this work quantitative and qualitative analysis methods were used to the development of global scientific production in a specific research field. The analytical results eventually provide several key findings and consider the overview hydrogen production according to the solar hydrogen generation.

Enhanced electrodes for solid state gas sensors

DOEpatents

Garzon, Fernando H.; Brosha, Eric L.

2001-01-01

A solid state gas sensor generates an electrical potential between an equilibrium electrode and a second electrode indicative of a gas to be sensed. A solid electrolyte substrate has the second electrode mounted on a first portion of the electrolyte substrate and a composite equilibrium electrode including conterminous transition metal oxide and Pt components mounted on a second portion of the electrolyte substrate. The composite equilibrium electrode and the second electrode are electrically connected to generate an electrical potential indicative of the gas that is being sensed. In a particular embodiment of the present invention, the second electrode is a reference electrode that is exposed to a reference oxygen gas mixture so that the electrical potential is indicative of the oxygen in a gas stream.

Fuel cell using a hydrogen generation system

DOEpatents

Dentinger, Paul M.; Crowell, Jeffrey A. W.

2010-10-19

A system is described for storing and generating hydrogen 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 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.

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.

High and rapid hydrogen release from thermolysis of ammonia borane near PEM fuel cell operating temperature

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

Varma, Arvind; Hwang, Hyun Tae; Al-Kukhun, Ahmad

A system for generating and purifying hydrogen. To generate hydrogen, the system includes inlets configured to receive a hydrogen carrier and an inert insulator, a mixing chamber configured to combine the hydrogen carrier and the inert insulator, a heat exchanger configured to apply heat to the mixture of hydrogen carrier and the inert insulator, wherein the applied heat results in the generation of hydrogen from the hydrogen carrier, and an outlet configured to release the generated hydrogen. To purify hydrogen, the system includes a primary inlet to receive a starting material and an ammonia filtration subassembly, which may include anmore » absorption column configured to absorb the ammonia into water for providing purified hydrogen at a first purity level. The ammonia filtration subassembly may also include an adsorbent member configured to adsorb ammonia from the starting material into an adsorbent for providing purified hydrogen at a second purity level.« less

Capacity retention in hydrogen storage alloys

NASA Technical Reports Server (NTRS)

Anani, A.; Visintin, A.; Srinivasan, S.; Appleby, A. J.; Reilly, J. J.; Johnson, J. R.

1992-01-01

Results of our examination of the properties of several candidate materials for hydrogen storage electrodes and their relation to the decrease in H-storage capacity upon open-circuit storage over time are reported. In some of the alloy samples examined to date, only about 10 percent of the hydrogen capacity was lost upon storage for 20 days, while in others, this number was as high as 30 percent for the same period of time. This loss in capacity is attributed to two separate mechanisms: (1) hydrogen desorbed from the electrode due to pressure differences between the cell and the electrode sample; and (2) chemical and/or electrochemical degradation of the alloy electrode upon exposure to the cell environment. The former process is a direct consequence of the equilibrium dissociation pressure of the hydride alloy phase and the partial pressure of hydrogen in the hydride phase in equilibrium with that in the electrolyte environment, while the latter is related to the stability of the alloy phase in the cell environment. Comparison of the equilibrium gas-phase dissociation pressures of these alloys indicate that reversible loss of hydrogen capacity is higher in alloys with P(eqm) greater than 1 atm than in those with P(eqm) less than 1 atm.

Direct solar-to-hydrogen conversion via inverted metamorphic multi-junction semiconductor architectures

DOE PAGES

Young, James L.; Steiner, Myles A.; Döscher, Henning; ...

2017-03-13

Solar water splitting via multi-junction semiconductor photoelectrochemical cells provides direct conversion of solar energy to stored chemical energy as hydrogen bonds. Economical hydrogen production demands high conversion efficiency to reduce balance-of-systems costs. For sufficient photovoltage, water-splitting efficiency is proportional to the device photocurrent, which can be tuned by judicious selection and integration of optimal semiconductor bandgaps. Here, we demonstrate highly efficient, immersed water-splitting electrodes enabled by inverted metamorphic epitaxy and a transparent graded buffer that allows the bandgap of each junction to be independently varied. Voltage losses at the electrolyte interface are reduced by 0.55 V over traditional, uniformly p-dopedmore » photocathodes by using a buried p-n junction. Lastly, advanced on-sun benchmarking, spectrally corrected and validated with incident photon-to-current efficiency, yields over 16% solar-to-hydrogen efficiency with GaInP/GaInAs tandem absorbers, representing a 60% improvement over the classical, high-efficiency tandem III-V device.« less

Direct solar-to-hydrogen conversion via inverted metamorphic multi-junction semiconductor architectures

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

Young, James L.; Steiner, Myles A.; Döscher, Henning

Solar water splitting via multi-junction semiconductor photoelectrochemical cells provides direct conversion of solar energy to stored chemical energy as hydrogen bonds. Economical hydrogen production demands high conversion efficiency to reduce balance-of-systems costs. For sufficient photovoltage, water-splitting efficiency is proportional to the device photocurrent, which can be tuned by judicious selection and integration of optimal semiconductor bandgaps. Here, we demonstrate highly efficient, immersed water-splitting electrodes enabled by inverted metamorphic epitaxy and a transparent graded buffer that allows the bandgap of each junction to be independently varied. Voltage losses at the electrolyte interface are reduced by 0.55 V over traditional, uniformly p-dopedmore » photocathodes by using a buried p-n junction. Lastly, advanced on-sun benchmarking, spectrally corrected and validated with incident photon-to-current efficiency, yields over 16% solar-to-hydrogen efficiency with GaInP/GaInAs tandem absorbers, representing a 60% improvement over the classical, high-efficiency tandem III-V device.« less

Hydrogen-enrichment-concept preliminary evaluation

NASA Technical Reports Server (NTRS)

Ecklund, E. E.

1975-01-01

A hydrogen-enriched fuels concept for automobiles is described and evaluated in terms of fuel consumption and engine exhaust emissions through multicylinder (V-8) automotive engine/hydrogen generator tests, single cylinder research engine (CFR) tests, and hydrogen-generator characterization tests. Analytical predictions are made of the fuel consumption and NO/sub x/ emissions which would result from anticipated engine improvements. The hydrogen-gas generator, which was tested to quantify its thermodynamic input-output relationships was used for integrated testing of the V-8 engine and generator.

Hydrogen Generator

NASA Technical Reports Server (NTRS)

1978-01-01

Another spinoff from spacecraft fuel cell technology is the portable hydrogen generator shown. Developed by General Electric Company, it is an aid to safer operation of systems that use hydrogen-for example, gas chromatographs, used in laboratory analysis of gases. or flame ionization detectors used as $ollution monitors. The generator eliminates the need for high-pressure hydrogen storage bottles, which can be a safety hazard, in laboratories, hospitals and industrial plants. The unit supplies high-purity hydrogen by means of an electrochemical process which separates the hydrogen and oxygen in distilled water. The oxygen is vented away and the hydrogen gas is stored within the unit for use as needed. GE's Aircraft Equipment Division is producing about 1,000 of the generators annually.

Hydrogen Fuel System Design Trades for High-Altitude Long-Endurance Remotely- Operated Aircraft

NASA Technical Reports Server (NTRS)

Millis, Marc G.; Tornabene, Robert T.; Jurns, John M.; Guynn, Mark D.; Tomsik, Thomas M.; VanOverbeke, Thomas J.

2009-01-01

Preliminary design trades are presented for liquid hydrogen fuel systems for remotely-operated, high-altitude aircraft that accommodate three different propulsion options: internal combustion engines, and electric motors powered by either polymer electrolyte membrane fuel cells or solid oxide fuel cells. Mission goal is sustained cruise at 60,000 ft altitude, with duration-aloft a key parameter. The subject aircraft specifies an engine power of 143 to 148 hp, gross liftoff weight of 9270 to 9450 lb, payload of 440 lb, and a hydrogen fuel capacity of 2650 to 2755 lb stored in two spherical tanks (8.5 ft inside diameter), each with a dry mass goal of 316 lb. Hydrogen schematics for all three propulsion options are provided. Each employs vacuum-jacketed tanks with multilayer insulation, augmented with a helium pressurant system, and using electric motor driven hydrogen pumps. The most significant schematic differences involve the heat exchangers and hydrogen reclamation equipment. Heat balances indicate that mission durations of 10 to 16 days appear achievable. The dry mass for the hydrogen system is estimated to be 1900 lb, including 645 lb for each tank. This tank mass is roughly twice that of the advanced tanks assumed in the initial conceptual vehicle. Control strategies are not addressed, nor are procedures for filling and draining the tanks.

Electrolysis cell for the manufacture of persulfates

NASA Technical Reports Server (NTRS)

Cueto, J. M.

1986-01-01

A cell for the electrolytic generation of persulfates, characterized by the fact that a housing acts as cathode, is made of metal, and consists of a lower electrolytically active section and an upper electrolytically inactive section. It is designed so that there is produced the greatest possible current density suited to produce the desired electrolysis effect. This invention, compared to the devices used until now, exhibits considerable advantages whereby it is particularly suited for the production of potassium persulfate.

MXP(M = Co/Ni)@carbon core-shell nanoparticles embedded in 3D cross-linked graphene aerogel derived from seaweed biomass for hydrogen evolution reaction.

PubMed

Zhao, Wentong; Lu, Xiaoqing; Selvaraj, Manickam; Wei, Wei; Jiang, Zhifeng; Ullah, Nabi; Liu, Jie; Xie, Jimin

2018-05-24

Low-cost electrocatalysts play an important role in the hydrogen evolution reaction (HER). Particularly, transition metal phosphides (TMPs) are widely applied in the development of HER electrocatalysts. To improve the poor electrochemical reaction kinetics of HER, we introduce a facile way to synthesize carbon core-shell materials containing cobalt phosphide nanoparticles embedded in different graphene aerogels (GAs) (CoP@C-NPs/GA-x (x = 5, 10 and 20)) using seaweed biomass as precursors. The synthesized CoP@C-NPs/GA-5 exhibits efficient catalytic activity with small overpotentials of 120 and 225 mV at current densities of 10 mA cm-2, along with the low Tafel slopes of 57 and 66 mV dec-1, for HER in acidic and alkaline electrolytes, respectively. Compared with carbon aerogel (CA) containing cobalt phosphide nanoparticles (CoP-NPs@CA), the stability of CoP@C-NPs/GA-5 coated with carbon-shells (∼0.8 nm) was significantly improved in acidic electrolytes. We also prepared carbon core-shell materials containing nickel phosphide nanoparticles embedded in GA (Ni2P@C-NPs/GA) to further expand this synthetic route. The graphene-Ni2P@C aerogel shows a similar morphology and better catalytic activity for HER in acidic and alkaline electrolytes. In this work, the robust three-dimensional (3D) GA matrix with abundant open pores and large surface area provides unblocked channels for electrolyte contact and electronic transfer and enables very close contact between the catalyst and electrolyte. The MxP@C core-shell structure prevents the inactivation of MxP NPs during HER processes, and the thin graphene oxide (GO) layers and 3D CA together build up a 3D conductive matrix, which not only adjusts the volume expansion of MxP NPs as well as preventing their aggregation, but also provides a 3D conductive pathway for rapid charge transfer processes. The present synthetic strategy for phosphides via in situ phosphorization with 3D GA can be extended to other novel high-performance catalysts. The simple synthesis and efficient catalytic activity of MXP@C-NPs/GA indicate good application prospects in HER.

Artificial solid electrolyte interphase to address the electrochemical degradation of silicon electrodes.

PubMed

Li, Juchuan; Dudney, Nancy J; Nanda, Jagjit; Liang, Chengdu

2014-07-09

Electrochemical degradation on silicon (Si) anodes prevents them from being successfully used in lithium (Li)-ion battery full cells. Unlike the case of graphite anodes, the natural solid electrolyte interphase (SEI) films generated from carbonate electrolytes do not self-passivate on Si, causing continuous electrolyte decomposition and loss of Li ions. In this work, we aim at solving the issue of electrochemical degradation by fabricating artificial SEI films using a solid electrolyte material, lithium phosphorus oxynitride (Lipon), which conducts Li ions and blocks electrons. For Si anodes coated with Lipon of 50 nm or thicker, a significant effect is observed in suppressing electrolyte decomposition, while Lipon of thinner than 40 nm has a limited effect. Ionic and electronic conductivity measurements reveal that the artificial SEI is effective when it is a pure ionic conductor, but electrolyte decomposition is only partially suppressed when the artificial SEI is a mixed electronic-ionic conductor. The critical thickness for this transition in conducting behavior is found to be 40-50 nm. This work provides guidance for designing artificial SEI films for high-capacity Li-ion battery electrodes using solid electrolyte materials.

Artificial Solid Electrolyte Interphase to Address the Electrochemical Degradation of Silicon Electrodes

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

Dudney, Nancy J; Nanda, Jagjit; Liang, Chengdu

2014-01-01

Electrochemical degradation on Si anodes prevents them from being successfully used in lithium-ion full cells. Unlike the case of graphite anodes, natural solid electrolyte interphase (SEI) films generated from carbonate electrolyte do not self-passivate on Si and causes continuous electrolyte decomposition. In this work we aim at solving the issue of electrochemical degradation by fabricating artificial SEI films using a solid electrolyte material, lithium phosphor oxynitride (Lipon), that conducts Li ions and blocks electrons. For Si anodes coated with Lipon of 50 nm or thicker, significant effect is observed in suppressing the electrolyte decomposition, while Lipon of thinner than 40more » nm has little effect. Ionic and electronic conductivity measurement reveals that the artificial SEI is effective when it is a pure ionic conductor, and the electrolyte decomposition is not suppressed when the artificial SEI is a mixed electronic-ionic conductor. The critical thickness for this transition in conducting behavior is found to be 40~50 nm. This work provides guidance for designing artificial SEI for high capacity lithium-ion battery electrodes using solid electrolyte materials.« less

An induced current method for measuring zeta potential of electrolyte solution-air interface.

PubMed

Song, Yongxin; Zhao, Kai; Wang, Junsheng; Wu, Xudong; Pan, Xinxiang; Sun, Yeqing; Li, Dongqing

2014-02-15

This paper reports a novel and very simple method for measuring the zeta potential of electrolyte solution-air interface. When a measuring electrode contacts the electrolyte solution-air interface, an electrical current will be generated due to the potential difference between the electrode-air surface and the electrolyte solution-air interface. The amplitude of the measured electric signal is linearly proportional to this potential difference; and depends only on the zeta potential at the electrolyte solution-air interface, regardless of the types and concentrations of the electrolyte. A correlation between the zeta potential and the measured voltage signal is obtained based on the experimental data. Using this equation, the zeta potential of any electrolyte solution-air interface can be evaluated quickly and easily by inserting an electrode through the electrolyte solution-air interface and measuring the electrical signal amplitude. This method was verified by comparing the obtained results of NaCl, MgCl2 and CaCl2 solutions of different pH values and concentrations with the zeta potential data reported in the published journal papers. Copyright © 2013 Elsevier Inc. All rights reserved.

Sequential reductive and oxidative biodegradation of chloroethenes stimulated in a coupled bioelectro-process.

PubMed

Lohner, Svenja T; Becker, Dirk; Mangold, Klaus-Michael; Tiehm, Andreas

2011-08-01

This article for the first time demonstrates successful application of electrochemical processes to stimulate sequential reductive/oxidative microbial degradation of perchloroethene (PCE) in mineral medium and in contaminated groundwater. In a flow-through column system, hydrogen generation at the cathode supported reductive dechlorination of PCE to cis-dichloroethene (cDCE), vinyl chloride (VC), and ethene (ETH). Electrolytically generated oxygen at the anode allowed subsequent oxidative degradation of the lower chlorinated metabolites. Aerobic cometabolic degradation of cDCE proved to be the bottleneck for complete metabolite elimination. Total removal of chloroethenes was demonstrated for a PCE load of approximately 1.5 μmol/d. In mineral medium, long-term operation with stainless steel electrodes was demonstrated for more than 300 days. In contaminated groundwater, corrosion of the stainless steel anode occurred, whereas DSA (dimensionally stable anodes) proved to be stable. Precipitation of calcareous deposits was observed at the cathode, resulting in a higher voltage demand and reduced dechlorination activity. With DSA and groundwater from a contaminated site, complete degradation of chloroethenes in groundwater was obtained for two months thus demonstrating the feasibility of the sequential bioelectro-approach for field application.

A New Miniaturized Inkjet Printed Solid State Electrolyte Sensor for Applications in Life Support Systems - First Results

NASA Astrophysics Data System (ADS)

Hill, Christine; Stefanos Fasoulas, -; Eberhart, Martin; Berndt, Felix

New generations of integrated closed loop systems will combine life support systems (incl. biological components) and energy systems such as fuel cell and electrolysis systems. Those systems and their test beds also contain complex safety sensor monitoring systems. Especially in fuel cells and electrolysis systems, the hydrogen and oxygen flows and exchange into other areas due to diffusion processes or leaks need to be monitored. Knowledge of predominant gas concentrations at all times is essential to avoid explosive gas mixtures. Solid state electrolyte sensors are promising for use as safety sensors. They have already been developed and produced at various institutes, but the power consumption for heating an existing solid state electrolyte sensor element still lies between 1 to 1.5 W and the operational readiness still takes about 20 to 30 s. This is partially due to the current manufacturing process for the solid state electrolyte sensor elements that is based on screen printing technology. However this technology has strong limitations in flexibility of the layout and re-designs. It is therefore suitable for mass production, but not for a flexible development and the production of specific individual sensors, e.g. for space applications. Moreover a disadvantage is the relatively high material consumption, especially in combination with the sensors need of expensive noble metal and ceramic pastes, which leads to a high sensor unit price. The Inkjet technology however opens up completely new possibilities in terms of dimensions, geometries, structures, morphologies and materials of sensors. This new approach is capable of printing finer high-resolution layers without the necessity of meshes or masks for patterning. Using the Inkjet technology a design change is possible at any time on the CAD screen. Moreover the ink is only deposited where it is needed. Custom made sensors, as they are currently demanded in space sensor applications, are thus realized simply, economically and ecologically. Based on the knowledge of the screen printing sensor production a complete solid state electrolyte oxygen sensor could be produced using Inkjet technology. First measurements in oxygen environment already show promising results. A defined oxygen concentration could be seen during exposition of the Inkjet sensors in an oxygen environment. The obtained results demonstrate the potential to use the technology development in other applications such as in situ respiratory gas analysis systems for human spaceflight. Further approaches at the Institute of Space Systems include the implementation of Inkjet printed solid state electrolyte sensors for the use as redundant safety sensors for the Institute's hybrid life support test beds including fuel cells and algal photo bioreactor elements.

Internal hydrogen-induced subcritical crack growth in austenitic stainless steels

NASA Astrophysics Data System (ADS)

Huang, J. H.; Altstetter, C. J.

1991-11-01

The effects of small amounts of dissolved hydrogen on crack propagation were determined for two austenitic stainless steel alloys, AISI 301 and 310S. In order to have a uniform distribution of hydrogen in the alloys, they were cathodically charged at high temperature in a molten salt electrolyte. Sustained load tests were performed on fatigue precracked specimens in air at 0 ‡C, 25 ‡C, and 50 ‡C with hydrogen contents up to 41 wt ppm. The electrical potential drop method with optical calibration was used to continuously monitor the crack position. Log crack velocity vs stress intensity curves had definite thresholds for subcritical crack growth (SCG), but stage II was not always clearly delineated. In the unstable austenitic steel, AISI 301, the threshold stress intensity decreased with increasing hydrogen content or increasing temperature, but beyond about 10 wt ppm, it became insensitive to hydrogen concentration. At higher concentrations, stage II became less distinct. In the stable stainless steel, subcritical crack growth was observed only for a specimen containing 41 wt ppm hydrogen. Fractographic features were correlated with stress intensity, hydrogen content, and temperature. The fracture mode changed with temperature and hydrogen content. For unstable austenitic steel, low temperature and high hydrogen content favored intergranular fracture while microvoid coalescence dominated at a low hydrogen content. The interpretation of these phenomena is based on the tendency for stress-induced phase transformation, the different hydrogen diffusivity and solubility in ferrite and austenite, and outgassing from the crack tip. After comparing the embrittlement due to internal hydrogen with that in external hydrogen, it is concluded that the critical hydrogen distribution for the onset of subcritical crack growth is reached at a location that is very near the crack tip.

Characterization of ceria electrolyte in solid oxide fuel cell applications

NASA Astrophysics Data System (ADS)

Milliken, Christopher Edward

The goal of this research effort is to characterize cation doped cerium dioxide for use as an electrolyte material in solid oxide fuel cell applications. A variety of analytical techniques including thermogravimetric analysis, controlled atmosphere dilatometry, and AC/DC electronic measurements on single cells and stacks have been coupled with thermodynamic calculations to evaluate the suitability of several doping schemes. The results of this analysis indicate that doping CeOsb2 with 20% SmOsb{1.5} or codoping with 19% GdOsb{1.5} + 1% PrOsb{1.83} provides the best combination of stability and performance. Under dual atmosphere fuel cell conditions, these dopants do not provide sufficient stabilization energy to prevent the reduction of ceria. A significant oxygen leakage current can be expected, particularly near open circuit conditions. Incorporation of 10% SrO provides similar short-term advantages to the lanthanide doped system but this electrolyte material undergoes an irreversible degradation mechanism that results in cell failure within 1500 hours of test. Under fuel cell conditions, the maximum efficiency of such systems in stacks will be below 40% at 200 mW/cmsp2 when operated on humidified hydrogen fuels. This compares to an expected efficiency of 45-50% at a similar power density for nonmixed conducting electrolyte (e.g., YSZ).

Systematic understanding of corrosion behavior of plasma electrolytic oxidation treated AZ31 magnesium alloy using a mouse model of subcutaneous implant.

PubMed

Jang, Yongseok; Tan, Zongqing; Jurey, Chris; Collins, Boyce; Badve, Aditya; Dong, Zhongyun; Park, Chanhee; Kim, Cheol Sang; Sankar, Jagannathan; Yun, Yeoheung

2014-12-01

This study was conducted to identify the differences between corrosion rates, corrosion types, and corrosion products in different physiological environments for AZ31 magnesium alloy and plasma electrolytic oxidation (PEO) treated AZ31 magnesium alloy. In vitro and in vivo tests were performed in Hank's Balanced Salt Solution (HBSS) and mice for 12 weeks, respectively. The corrosion rates of both AZ31 magnesium alloy and PEO treated AZ31 magnesium alloy were calculated based on DC polarization curves, volume of hydrogen evolution, and the thickness of corrosion products formed on the surface. Micro X-ray computed tomography (Micro-CT), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and X-ray diffraction (XRD) were used to analyze morphological and chemical characterizations of corrosion products. The results show that there is more severe localized corrosion after in vitro test in HBSS; however, the thicknesses of corrosion products formed on the surface for AZ31 magnesium alloy and PEO treated AZ31 magnesium alloy in vivo were about 40% thicker than the thickness of corrosion products generated in vitro. The ratio of Ca and P (Ca/P) in the corrosion products also differed. The Ca deficient region and higher content of Al in corrosion product than AZ31 magnesium alloy were identified after in vivo test in contrast with the result of in vitro test. Copyright © 2014 Elsevier B.V. All rights reserved.

Detection of pH and Enzyme-Free H2O2 Sensing Mechanism by Using GdO x Membrane in Electrolyte-Insulator-Semiconductor Structure.

PubMed

Kumar, Pankaj; Maikap, Siddheswar; Qiu, Jian-Tai; Jana, Surajit; Roy, Anisha; Singh, Kanishk; Cheng, Hsin-Ming; Chang, Mu-Tung; Mahapatra, Rajat; Chiu, Hsien-Chin; Yang, Jer-Ren

2016-12-01

A 15-nm-thick GdO x membrane in an electrolyte-insulator-semiconductor (EIS) structure shows a higher pH sensitivity of 54.2 mV/pH and enzyme-free hydrogen peroxide (H2O2) detection than those of the bare SiO2 and 3-nm-thick GdO x membranes for the first time. Polycrystalline grain and higher Gd content of the thicker GdO x films are confirmed by transmission electron microscopy (TEM) and X-ray photo-electron spectroscopy (XPS), respectively. In a thicker GdO x membrane, polycrystalline grain has lower energy gap and Gd(2+) oxidation states lead to change Gd(3+) states in the presence of H2O2, which are confirmed by electron energy loss spectroscopy (EELS). The oxidation/reduction (redox) properties of thicker GdO x membrane with higher Gd content are responsible for detecting H2O2 whereas both bare SiO2 and thinner GdO x membranes do not show sensing. A low detection limit of 1 μM is obtained due to strong catalytic activity of Gd. The reference voltage shift increases with increase of the H2O2 concentration from 1 to 200 μM owing to more generation of Gd(3+) ions, and the H2O2 sensing mechanism has been explained as well.

Superoxide (Electro)Chemistry on Well-Defined Surfaces in Organic Environments

DOE PAGES

Genorio, Bostjan; Staszak-Jirkovský, Jakub; Assary, Rajeev S.; ...

2016-02-09

Efficient chemical transformations in energy conversion and storage systems depend on understanding superoxide anion (O 2 –) electrochemistry at atomic and molecular levels. Here, in this work, a combination of experimental and theoretical techniques are used for rationalizing, and ultimately understanding, the complexity of superoxide anion (electro)chemistry in organic environments. By exploring the O 2 + e – ↔ O 2 – reaction on well-characterized metal single crystals (Au, Pt, Ir), Pt single crystal modified with a single layer of graphene (Graphene@Pt(111)), and glassy carbon (GC) in 1,2 dimethoxyethane (DME) electrolytes, we demonstrate that (i) the reaction is an outer-spheremore » process; (ii) the reaction product O 2 – can “attack” any part of the DME molecule, i.e., the C–O bond via nucleophilic reaction and the C–H bond via radical hydrogen abstraction; (iii) the adsorption of carbon-based decomposition products and the extent of formation of a “solid electrolyte interface” (“SEI”) increases in the same order as the reactivity of the substrate, i.e., Pt(hkl)/Ir(hkl) » Au(hkl)/GC > Gaphene@Pt(111); and (iv) the formation of the “SEI” layer leads to irreversible superoxide electrochemistry on Pt(hkl) and Ir(hkl) surfaces. In conclusion, we believe this fundamental insight provides a pathway for the rational design of stable organic solvents that are urgently needed for the development of a new generation of reliable and affordable battery systems.« less

Light harvesting proteins for solar fuel generation in bioengineered photoelectrochemical cells.

PubMed

Ihssen, Julian; Braun, Artur; Faccio, Greta; Gajda-Schrantz, Krisztina; Thöny-Meyer, Linda

2014-01-01

The sun is the primary energy source of our planet and potentially can supply all societies with more than just their basic energy needs. Demand of electric energy can be satisfied with photovoltaics, however the global demand for fuels is even higher. The direct way to produce the solar fuel hydrogen is by water splitting in photoelectrochemical (PEC) cells, an artificial mimic of photosynthesis. There is currently strong resurging interest for solar fuels produced by PEC cells, but some fundamental technological problems need to be solved to make PEC water splitting an economic, competitive alternative. One of the problems is to provide a low cost, high performing water oxidizing and oxygen evolving photoanode in an environmentally benign setting. Hematite, α-Fe2O3, satisfies many requirements for a good PEC photoanode, but its efficiency is insufficient in its pristine form. A promising strategy for enhancing photocurrent density takes advantage of photosynthetic proteins. In this paper we give an overview of how electrode surfaces in general and hematite photoanodes in particular can be functionalized with light harvesting proteins. Specifically, we demonstrate how low-cost biomaterials such as cyanobacterial phycocyanin and enzymatically produced melanin increase the overall performance of virtually no-cost metal oxide photoanodes in a PEC system. The implementation of biomaterials changes the overall nature of the photoanode assembly in a way that aggressive alkaline electrolytes such as concentrated KOH are not required anymore. Rather, a more environmentally benign and pH neutral electrolyte can be used.