Compact Fuel-Cell System Would Consume Neat Methanol

NASA Technical Reports Server (NTRS)

Narayanan, Sekharipuram; Kindler, Andrew; Valdez, Thomas

2007-01-01

In a proposed direct methanol fuel-cell electric-power-generating system, the fuel cells would consume neat methanol, in contradistinction to the dilute aqueous methanol solutions consumed in prior direct methanol fuel-cell systems. The design concept of the proposed fuel-cell system takes advantage of (1) electro-osmotic drag and diffusion processes to manage the flows of hydrogen and water between the anode and the cathode and (2) evaporative cooling for regulating temperature. The design concept provides for supplying enough water to the anodes to enable the use of neat methanol while ensuring conservation of water for the whole fuel-cell system.

Dual-Anode Nickel/Hydrogen Cell

NASA Technical Reports Server (NTRS)

Gahn, Randall F.; Ryan, Timothy P.

1994-01-01

Use of two hydrogen anodes in nickel/hydrogen cell reduces ohmic and concentration polarizations contributing to internal resistance, yielding cell with improved discharging performance compared to single-anode cell. Dual-anode concept incorporated into nickel/hydrogen cells of individual pressure-vessel type (for use aboard spacecraft) and common pressure-vessel type, for use on Earth to store electrical energy from photovoltaic sources, "uninterruptible" power supplies of computer and telephone systems, electric vehicles, and load leveling on power lines. Also applicable to silver/hydrogen and other metal/gas batteries.

Highly efficient lithium composite anode with hydrophobic molten salt in seawater

NASA Astrophysics Data System (ADS)

Zhang, Yancheng; Urquidi-Macdonald, Mirna

A lithium composite anode (lithium/1-butyl-3-methyl-imidazoleum hexafluorophosphate (BMI +PF 6-)/4-VLZ) for primary lithium/seawater semi-fuel-cells is proposed to reduce lithium-water parasitic reaction and, hence, increase the lithium anodic efficiency up to 100%. The lithium composite anode was activated when in contact with artificial seawater (3% NaCl solution) and the output was a stable anodic current density at 0.2 mA/cm 2, which lasted about 10 h under potentiostatic polarization at +0.5 V versus open circuit potential (OCP); the anodic efficiency was indirectly measured to be 100%. With time, a small traces of water diffused through the hydrophobic molten salt, BMI +PF 6-, reached the lithium interface and formed a double layer film (LiH/LiOH). Accordingly, the current density decreased and the anodic efficiency was estimated to be 90%. The hypothesis of small traces of water penetrating the molten salt and reaching the lithium anode—after several hours of operation—is supported by the collected experimental current density and hydrogen evolution, electrochemical impedance spectrum analysis, and non-mechanistic interface film modeling of lithium/BMI +PF 6-.

Electrochemical Hydrogen Peroxide Generator

NASA Technical Reports Server (NTRS)

Tennakoon, Charles L. K.; Singh, Waheguru; Anderson, Kelvin C.

2010-01-01

Two-electron reduction of oxygen to produce hydrogen peroxide is a much researched topic. Most of the work has been done in the production of hydrogen peroxide in basic media, in order to address the needs of the pulp and paper industry. However, peroxides under alkaline conditions show poor stabilities and are not useful in disinfection applications. There is a need to design electrocatalysts that are stable and provide good current and energy efficiencies to produce hydrogen peroxide under acidic conditions. The innovation focuses on the in situ generation of hydrogen peroxide using an electrochemical cell having a gas diffusion electrode as the cathode (electrode connected to the negative pole of the power supply) and a platinized titanium anode. The cathode and anode compartments are separated by a readily available cation-exchange membrane (Nafion 117). The anode compartment is fed with deionized water. Generation of oxygen is the anode reaction. Protons from the anode compartment are transferred across the cation-exchange membrane to the cathode compartment by electrostatic attraction towards the negatively charged electrode. The cathode compartment is fed with oxygen. Here, hydrogen peroxide is generated by the reduction of oxygen. Water may also be generated in the cathode. A small amount of water is also transported across the membrane along with hydrated protons transported across the membrane. Generally, each proton is hydrated with 3-5 molecules. The process is unique because hydrogen peroxide is formed as a high-purity aqueous solution. Since there are no hazardous chemicals or liquids used in the process, the disinfection product can be applied directly to water, before entering a water filtration unit to disinfect the incoming water and to prevent the build up of heterotrophic bacteria, for example, in carbon based filters. The competitive advantages of this process are: 1. No consumable chemicals are needed in the process. The only raw materials needed are water and oxygen or air. 2. The product is pure and can therefore be used in disinfection applications directly or after proper dilution with water. 3. Oxygen generated in the anode compartment is used in the electrochemical reduction process; in addition, external oxygen is used to establish a high flow rate in the cathode compartment to remove the desired product efficiently. Exiting oxygen can be recycled after separation of liquid hydrogen peroxide product, if so desired. 4. The process can be designed for peroxide generation under microgravity conditions. 5. High concentrations of the order of 6-7 wt% can be generated by this method. This method at the time of this reporting is superior to what other researchers have reported. 6. The cell design allows for stacking of cells to increase the hydrogen peroxide production. 7. The catalyst mix containing a diquaternary ammonium compound enabled not only higher concentration of hydrogen peroxide but also higher current efficiency, improved energy efficiency, and catalyst stability. 8. The activity of the catalyst is maintained even after repeated periods of system shutdown. 9. The catalyst system can be extended for fuel-cell cathodes with suitable modifications.

Performance of a dual anode nickel-hydrogen cell

NASA Technical Reports Server (NTRS)

Gahn, Randall F.

1991-01-01

An experimental study was conducted to characterize the voltage performance of a nickel hydrogen cell containing a hydrogen electrode on both sides of the nickel electrode. The dual anode cell was compared with a convenient single anode cell using the same nickel electrode. Higher discharge voltages and lower charge voltages were obtained with the dual anode cell during constant current discharges to 10C, pulse discharges to 8C, and polarization measurements at 50 percent of charge.

Generation mechanism of hydrogen peroxide in dc plasma with a liquid electrode

NASA Astrophysics Data System (ADS)

Takeuchi, Nozomi; Ishibashi, Naoto

2018-04-01

The production mechanism of liquid-phase H2O2 in dc driven plasma in O2 and Ar with a water electrode was investigated. When a water anode was used, the concentration of H2O2 increased linearly with the treatment time. The production rate was proportional to the discharge current, and there was no dependence on the gap distance. On the other hand, the production rate was much smaller with a water anode. We concluded that the production of gas-phase H2O2 in the cathode sheath just above a water cathode and diffusion of this H2O2 into the water constitute the key mechanism in the production of liquid-phase H2O2.

Local potential evolutions during proton exchange membrane fuel cell operation with dead-ended anode - Part II: Aging mitigation strategies based on water management and nitrogen crossover

NASA Astrophysics Data System (ADS)

Abbou, S.; Dillet, J.; Maranzana, G.; Didierjean, S.; Lottin, O.

2017-02-01

Proton exchange membrane (PEM) fuel cells operate with dead-ended anode in order to reduce system cost and complexity when compared with hydrogen re-circulation systems. In the first part of this work, we showed that localized fuel starvation events may occur, because of water and nitrogen accumulation in the anode side, which could be particularly damaging to the cell performance. To prevent these degradations, the anode compartment must be purged which may lead to an overall system efficiency decrease because of significant hydrogen waste. In the second part, we present several purge strategies in order to minimize both hydrogen waste and membrane-electrode assembly degradations during dead-ended anode operation. A linear segmented cell with reference electrodes was used to monitor simultaneously the current density distribution along the gas channel and the time evolution of local anode and cathode potentials. To asses MEA damages, Platinum ElectroChemical Surface Area (ECSA) and cell performance were periodically measured. The results showed that dead-end mode operation with an anode plate maintained at a temperature 5 °C hotter than the cathode plate limits water accumulation in the anode side, reducing significantly purge frequency (and thus hydrogen losses) as well as MEA damages. As nitrogen contribution to hydrogen starvation is predominant in this thermal configuration, we also tested a microleakage solution to discharge continuously most the nitrogen accumulating in the anode side while ensuring low hydrogen losses and minimum ECSA losses provided the right microleakage flow rate is chosen.

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.

The impact of anode acclimation strategy on microbial electrolysis cell treating hydrogen fermentation effluent.

PubMed

Li, Xiaohu; Zhang, Ruizhe; Qian, Yawei; Angelidaki, Irini; Zhang, Yifeng

2017-07-01

The impact of different anode acclimation methods for enhancing hydrogen production in microbial electrolysis cell (MEC) was investigated in this study. The anodes were first acclimated in microbial fuel cells using acetate, butyrate and corn stalk fermentation effluent (CSFE) as substrate before moving into MECs, respectively. Subsequently, CSFE was used as feedstock in all the three MECs. The maximum hydrogen yield with the anode pre-acclimated with butyrate (5.21±0.24L H 2 /L CSFE) was higher than that pre-acclimated with acetate (4.22±0.19L H 2 /L CSFE) and CSFE (4.55±0.14L H 2 /L CSFE). The current density (480±11A/m 3 ) and hydrogen production rate (4.52±0.13m 3 /m 3 /d) with the anode pre-acclimated with butyrate were also higher that another two reactors. These results demonstrated that the anode biofilm pre-acclimated with butyrate has significant advantages in CSFE treatment and could improve the performance of hydrogen production in MEC. Copyright © 2017 Elsevier Ltd. All rights reserved.

Simultaneous Extraction of Lithium and Hydrogen from Seawater

DTIC Science & Technology

2011-04-26

chromatography . Anions were analyzed by Anion Ion Chromatography (Instrument Dionex ICS-1500, Column Dionex AS9-HC; AG9-HC Guard, eluent: 9.00 mM Na2CO3, flow...rate: 1.25 mL/min, and sample loop was 25 μL). Cations were analyzed by Cation Ion Chromatography (Instrument Dionex DX-500, Cation Column Dionex ...the amount was measured volumetrically. Ion chromatography : Ions in seawater diffused from/to the anode and cathode were determined by ion

Influence of Pb 2+ ions in the H 2 oxidation on Pt catalyzed hydrogen diffusion anodes in sulfuric acid: presence of oscillatory phenomena

NASA Astrophysics Data System (ADS)

Expósito, E.; Sánchez-Sánchez, C. M.; Solla-Gullón, J.; Montiel, V.

The influence of Pb 2+ ions in sulfuric acid medium on the behavior of a platinum catalyzed hydrogen diffusion electrode (HDE) in a filter press reactor has been studied. A voltammetric study of the H 2 oxidation reaction on a polyoriented platinum electrode and a platinum rotating disk electrode (RDE) in presence of lead ions in solution has also been carried out. Potential oscillations were found in galvanostatic experiments of H 2 oxidation using a HDE catalyzed with platinum when Pb 2+ ions are present in solution. This oscillatory phenomenon was also observed when hydrogen oxidation was carried out in presence of Pb 2+ ions using a platinum RDE. The oscillatory behavior observed has been attributed to an adsorption-oxidation-desorption process of lead on the platinum surface. Due to the low solubility of Pb 2+ in sulfuric acid, at high values of coverage, lead is oxidised to insoluble lead sulfate that blocks the Pt surface. The coupling of the dissolution of lead sulfate and the Pb electrochemical adsorption-oxidation processes cause the oscillatory phenomenon.

A comparison of Fick and Maxwell-Stefan diffusion formulations in PEMFC gas diffusion layers

NASA Astrophysics Data System (ADS)

Lindstrom, Michael; Wetton, Brian

2017-01-01

This paper explores the mathematical formulations of Fick and Maxwell-Stefan diffusion in the context of polymer electrolyte membrane fuel cell cathode gas diffusion layers. The simple Fick law with a diagonal diffusion matrix is an approximation of Maxwell-Stefan. Formulations of diffusion combined with mass-averaged Darcy flow are considered for three component gases. For this application, the formulations can be compared computationally in a simple, one dimensional setting. Despite the models' seemingly different structure, it is observed that the predictions of the formulations are very similar on the cathode when air is used as oxidant. The two formulations give quite different results when the Nitrogen in the air oxidant is replaced by helium (this is often done as a diagnostic for fuel cells designs). The two formulations also give quite different results for the anode with a dilute Hydrogen stream. These results give direction to when Maxwell-Stefan diffusion, which is more complicated to implement computationally in many codes, should be used in fuel cell simulations.

Possible origin and roles of nano-porosity in ZrO2 scales for hydrogen pick-up in Zr alloys

NASA Astrophysics Data System (ADS)

Lindgren, Mikaela; Geers, Christine; Panas, Itai

2017-08-01

A mechanistic understanding of Wagnerian build-up and subsequent non-Wagnerian break-down of barrier oxide upon oxidation of zirconium alloys by water is reiterated. Hydrogen assisted build-up of nano-porosity is addressed. Growth of sub-nanometer wide stalactitic pores owing to increasing aggregation of neutral oxygen vacancies offering a means to permeate hydrogen into the alloy is explored by density functional theory. The Wagnerian channel utilizes charge separation allowing charged oxygen vacancies and electrons to move separately from nominal anode to nominal cathode. This process becomes increasingly controlled by the charging of the barrier oxide resulting in sub-parabolic rate law for oxide growth. The break-down of the barrier oxide is understood to be preceded by avalanching hydrogen pick-up in the alloy. Pore mediated diffusion allows water to effectively short circuit the barrier oxide.

In operando neutron diffraction study of LaNdMgNi9H13 as a metal hydride battery anode

NASA Astrophysics Data System (ADS)

Nazer, N. S.; Denys, R. V.; Yartys, V. A.; Hu, Wei-Kang; Latroche, M.; Cuevas, F.; Hauback, B. C.; Henry, P. F.; Arnberg, L.

2017-03-01

La2MgNi9-related alloys are superior metal hydride battery anodes as compared to the commercial AB5 alloys. Nd-substituted La2-yNdyMgNi9 intermetallics are of particular interest because of increased diffusion rate of hydrogen and thus improved performance at high discharge currents. The present work presents in operando characterization of the LaNdMgNi9 intermetallic as anode for the nickel metal hydride (Ni-MH) battery. We have studied the structural evolution of LaNdMgNi9 during its charge and discharge using in situ neutron powder diffraction. The work included experiments using deuterium gas and electrochemical charge-discharge measurements. The alloy exhibited a high electrochemical discharge capacity (373 mAh/g) which is 20% higher than the AB5 type alloys. A saturated β-deuteride synthesized by solid-gas reaction at PD2 = 1.6 MPa contained 12.9 deuterium atoms per formula unit (D/f.u.) which resulted in a volume expansion of 26.1%. During the electrochemical charging, the volume expansion (23.4%) and D-contents were found to be slightly reduced. The reversible electrochemical cycling is performed through the formation of a two-phase mixture of the α-solid solution and β-hydride phases. Nd substitution contributes to the high-rate dischargeability, while maintaining a good cyclic stability. Electrochemical Impedance Spectroscopy (EIS) was used to characterize the anode electrode on cycling. A mathematical model for the impedance response of a porous electrode was utilized. The EIS showed a decreased hydrogen transport rate during the long-term cycling, which indicated a corresponding slowing down of the electrochemical processes at the surface of the metal hydride anode.

Capacitance‐Assisted Sustainable Electrochemical Carbon Dioxide Mineralisation

PubMed Central

Lamb, Katie J.; Dowsett, Mark R.; Chatzipanagis, Konstantinos; Scullion, Zhan Wei; Kröger, Roland; Lee, James D.

2017-01-01

Abstract An electrochemical cell comprising a novel dual‐component graphite and Earth‐crust abundant metal anode, a hydrogen producing cathode and an aqueous sodium chloride electrolyte was constructed and used for carbon dioxide mineralisation. Under an atmosphere of 5 % carbon dioxide in nitrogen, the cell exhibited both capacitive and oxidative electrochemistry at the anode. The graphite acted as a supercapacitive reagent concentrator, pumping carbon dioxide into aqueous solution as hydrogen carbonate. Simultaneous oxidation of the anodic metal generated cations, which reacted with the hydrogen carbonate to give mineralised carbon dioxide. Whilst conventional electrochemical carbon dioxide reduction requires hydrogen, this cell generates hydrogen at the cathode. Carbon capture can be achieved in a highly sustainable manner using scrap metal within the anode, seawater as the electrolyte, an industrially relevant gas stream and a solar panel as an effective zero‐carbon energy source. PMID:29171724

Simultaneous Extraction of Lithium and Hydrogen from Seawater

DTIC Science & Technology

2011-08-22

to the anode and cathode were determined by ion chromatography . Anions were analyzed by Anion Ion Chromatography (Instrument Dionex ICS-1500, Column...and oxygen gases coming out of the cell were collected and the amount was measured volumetrically. Ion chromatography : Ions in seawater diffused from... Dionex AS9-HC; AG9-HC Guard, eluent: 9.00 mM Na2CO3, flow rate: 1.25 mL/min, and sample loop was 25 μL). Cations were analyzed by Cation Ion

Polymer membrane based electrolytic cell and process for the direct generation of hydrogen peroxide in liquid streams

NASA Technical Reports Server (NTRS)

White, James H. (Inventor); Schwartz, Michael (Inventor); Sammells, Anthony F. (Inventor)

1997-01-01

An electrolytic cell for generating hydrogen peroxide is provided including a cathode containing a catalyst for the reduction of oxygen, and an anode containing a catalyst for the oxidation of water. A polymer membrane, semipermeable to either protons or hydroxide ions is also included and has a first face interfacing to the cathode and a second face interfacing to the anode so that when a stream of water containing dissolved oxygen or oxygen bubbles is passed over the cathode and a stream of water is passed over the anode, and an electric current is passed between the anode and the cathode, hydrogen peroxide is generated at the cathode and oxygen is generated at the anode.

Performance of a Dual Anode Nickel-Hydrogen Cell

NASA Technical Reports Server (NTRS)

Gahn, Randall F.

1991-01-01

Nickel-hydrogen batteries are presently being used for energy storage on satellites in low Earth orbit and in geosynchronous orbit, and have also been selected for use on the proposed Space Station Freedom. Development continues on the cell technology in order to improve the specific energy and lengthen the cycle life. An experimental study was conducted to compare the voltage performance of a nickel-hydrogen cell containing a dual anode with the standard cell design which uses a single hydrogen electrode. Since the principle voltage loss in a nickel-hydrogen cell is attributed to the mass transport and resistive polarization parameters of the nickel electrode, addition of a hydrogen electrode on the other side of the nickel electrode should reduce the electrochemical polarizations by a factor of two. A 3.5 in. diameter boilerplate cell with a single 30 mils thick nickel electrode was cycled under various current conditions to evaluate its performance with a single anode and then with a double anode. A layered separator consisting of one Zircar cloth separator and one radiation-grafted polyethylene separator were used between the electrodes. The electrolyte was 26% KOH, and the tests were done at room temperature. The discharge voltage characteristics were determined as a function of current and depth-of-discharge. At the 4C discharge rate and 50% DOD, the voltage of the dual anode cell was 100 mV higher than the single anode cell. At 75% DOD the dual anode cell voltage was about 130 mV higher than the standard cell design. Resistances of the two c ell designs obtained from the slope of the mid-discharge voltages plotted against various currents indicated that the dual anode cell resistance was one-half of the state-of-the-art cell.

Capacitance-Assisted Sustainable Electrochemical Carbon Dioxide Mineralisation.

PubMed

Lamb, Katie J; Dowsett, Mark R; Chatzipanagis, Konstantinos; Scullion, Zhan Wei; Kröger, Roland; Lee, James D; Aguiar, Pedro M; North, Michael; Parkin, Alison

2018-01-10

An electrochemical cell comprising a novel dual-component graphite and Earth-crust abundant metal anode, a hydrogen producing cathode and an aqueous sodium chloride electrolyte was constructed and used for carbon dioxide mineralisation. Under an atmosphere of 5 % carbon dioxide in nitrogen, the cell exhibited both capacitive and oxidative electrochemistry at the anode. The graphite acted as a supercapacitive reagent concentrator, pumping carbon dioxide into aqueous solution as hydrogen carbonate. Simultaneous oxidation of the anodic metal generated cations, which reacted with the hydrogen carbonate to give mineralised carbon dioxide. Whilst conventional electrochemical carbon dioxide reduction requires hydrogen, this cell generates hydrogen at the cathode. Carbon capture can be achieved in a highly sustainable manner using scrap metal within the anode, seawater as the electrolyte, an industrially relevant gas stream and a solar panel as an effective zero-carbon energy source. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Effect of anodic treatment on the electrocatalytic activity of superficial Raney nickel catalyst in cathodic hydrogen

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

Korovin, N.V.; Kozlova, N.I.; Kumenko, M.V.

This work is concerned with the effect of oxidation on the activity of Raney nickel catalyst in cathodic hydrogen evolution. The superficial Raney nickel catalyst (nickel SRC) was prepared by a previously described procedure. The surface of the nickel SRC was oxidized by applying an anodic sweep over the potential range from 0.25 to 1.00 V with a potential sweep rate of 1 mV/sec. The rate of cathodic hydrogen evolution increases after pretreatment of the surface of nickel SRC by application of an anodic pulse. A significant increase in the reaction rate most probably is due to oxygen adsorption onmore » the nickel SRC surface. The largest increase in the amount of weakly bound hydrogen corresponds to the most active electrode. Oxidation of the nickel surface by an anodic pulse causes both an acceleration and a retardation of the cathodic hydrogen evolution reaction.« less

Challenge for lowering concentration polarization in solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Shimada, Hiroyuki; Suzuki, Toshio; Yamaguchi, Toshiaki; Sumi, Hirofumi; Hamamoto, Koichi; Fujishiro, Yoshinobu

2016-01-01

In the scope of electrochemical phenomena, concentration polarization at electrodes is theoretically inevitable, and lowering the concentration overpotential to improve the performance of electrochemical cells has been a continuing challenge. Electrodes with highly controlled microstructure, i.e., high porosity and uniform large pores are therefore essential to achieve high performance electrochemical cells. In this study, state-of-the-art technology for controlling the microstructure of electrodes has been developed for realizing high performance support electrodes of solid oxide fuel cells (SOFCs). The key is controlling the porosity and pore size distribution to improve gas diffusion, while maintaining the integrity of the electrolyte and the structural strength of actual sized electrode supports needed for the target application. Planar anode-supported SOFCs developed in this study realize 5 μm thick dense electrolyte (yttria-stabilized zirconia: YSZ) and the anode substrate (Ni-YSZ) of 53.6 vol.% porosity with a large median pore diameter of 0.911 μm. Electrochemical measurements reveal that the performance of the anode-supported SOFCs improves with increasing anode porosity. This Ni-YSZ anode minimizes the concentration polarization, resulting in a maximum power density of 3.09 W cm-2 at 800 °C using humidified hydrogen fuel without any electrode functional layers.

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.

Membranes for bioelectrochemical systems: challenges and research advances.

PubMed

Dhar, Bipro Ranjan; Lee, Hyung-Sool

2013-01-01

Increasing energy demand has been a big challenge for current society, as the fossil fuel sources are gradually decreasing. Hence, development of renewable and sustainable energy sources for the future is considered one of the top priorities in national strategic plans. Bioenergy can meet future energy requirements - renewability, sustainability, and even carbon-neutrality. Bioenergy production from wastes and wastewaters is especially attractive because of dual benefits of energy generation and contaminant stabilization. There are several bioenergy technologies using wastes and wastewaters as electron donor, which include anaerobic digestion, dark biohydrogen fermentation, biohydrogen production using photosynthetic microorganisms, and bioelectrochemical systems (BESs). Among them BES seems to be very promising as we can produce a variety of value-added products from wastes and wastewaters, such as electric power, hydrogen gas, hydrogen peroxide, acetate, ethanol etc. Most ofthe traditional BES uses a membrane to separate the anode and cathode chamber, which is essential for improving microbial metabolism on the anode and the recovery of value-added products on the cathode. Performance of BES lacking a membrane can be seriously deteriorated, due to oxygen diffusion or substantial loss of synthesized products. For this reason, usage of a membrane seems essential to facilitate BES performance. However, a membrane can bring several technical challenges to BES application compared to membrane-less BES. These challenges include poor proton permeability, substrate loss, oxygen back diffusion, pH gradient, internal resistance, biofouling, etc. This paper aims to review the major technical barriers associated with membranes and future research directions for their application in BESs.

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

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.

The anodic surface film and hydrogen evolution on Mg

DOE PAGES

Song, Guang -Ling; Unocic, Kinga A.

2015-06-04

This paper clarifies that the inner and outer layers of the anodic film consist of a nano/micro-porous MgO+Mg(OH) 2 mixture. The film becomes thicker and more porous with increasing potential. It can rupture when potential is too positive in a non-corrosive Mg(OH) 2 solution. Hydrogen evolution becomes more intensive as polarization potential increases, particularly when the potential at the film-covered Mg surface is close to or more positive than the hydrogen equilibrium potential, suggesting that an “anodic hydrogen evolution” (AHE) reaction occurs on the substrate Mg in film pores, and the significantly intensified AHE causes film rupture at high potential.

Sulfur tolerant molten carbonate fuel cell anode and process

DOEpatents

Remick, Robert J.

1990-01-01

Molten carbonate fuel cell anodes incorporating a sulfur tolerant carbon monoxide to hydrogen water-gas-shift catalyst provide in situ conversion of carbon monoxide to hydrogen for improved fuel cell operation using fuel gas mixtures of over about 10 volume percent carbon monoxide and up to about 10 ppm hydrogen sulfide.

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.

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.

Separating hydrogen and oxygen evolution in alkaline water electrolysis using nickel hydroxide

PubMed Central

Chen, Long; Dong, Xiaoli; Wang, Yonggang; Xia, Yongyao

2016-01-01

Low-cost alkaline water electrolysis has been considered a sustainable approach to producing hydrogen using renewable energy inputs, but preventing hydrogen/oxygen mixing and efficiently using the instable renewable energy are challenging. Here, using nickel hydroxide as a redox mediator, we decouple the hydrogen and oxygen production in alkaline water electrolysis, which overcomes the gas-mixing issue and may increase the use of renewable energy. In this architecture, the hydrogen production occurs at the cathode by water reduction, and the anodic Ni(OH)2 is simultaneously oxidized into NiOOH. The subsequent oxygen production involves a cathodic NiOOH reduction (NiOOH→Ni(OH)2) and an anodic OH− oxidization. Alternatively, the NiOOH formed during hydrogen production can be coupled with a zinc anode to form a NiOOH-Zn battery, and its discharge product (that is, Ni(OH)2) can be used to produce hydrogen again. This architecture brings a potential solution to facilitate renewables-to-hydrogen conversion. PMID:27199009

Methods and apparatus for the on-site production of hydrogen peroxide

NASA Technical Reports Server (NTRS)

Buschmann, Wayne E. (Inventor); James, Patrick I. (Inventor)

2010-01-01

Methods, apparatus, and applications for the on-site production of hydrogen peroxide are described. An embodiment of the apparatus comprises at least one anolyte chamber coupled to at least one anode, at least one catholyte chamber, wherein the at least one catholyte chamber is coupled to at least one cathode, at least one anode membrane and at least one cathode membrane, wherein the anode membrane is adjacent to the at least one anode, wherein the cathode membrane is adjacent to the at least one cathode, at least one central chamber disposed between the at least one anolyte chamber and the at least one catholyte chamber. Hydrogen peroxide is produced by reduction of an oxygen-containing gas at the cathode.

Electrochemical separation of hydrogen from reformate using PEM fuel cell technology

NASA Astrophysics Data System (ADS)

Gardner, C. L.; Ternan, M.

This article is an examination of the feasibility of electrochemically separating hydrogen obtained by steam reforming a hydrocarbon or alcohol source. A potential advantage of this process is that the carbon dioxide rich exhaust stream should be able to be captured and stored thereby reducing greenhouse gas emissions. Results are presented for the performance of the anode of proton exchange membrane (PEM) electrochemical cell for the separation of hydrogen from a H 2-CO 2 gas mixture and from a H 2-CO 2-CO gas mixture. Experiments were carried out using a single cell state-of-the-art PEM fuel cell. The anode was fed with either a H 2-CO 2 gas mixture or a H 2-CO 2-CO gas mixture and hydrogen was evolved at the cathode. All experiments were performed at room temperature and atmospheric pressure. With the H 2-CO 2 gas mixture the hydrogen extraction efficiency is quite high. When the gas mixture included CO, however, the hydrogen extraction efficiency is relatively poor. To improve the efficiency for the separation of the gas mixture containing CO, the effect of periodic pulsing on the anode potential was examined. Results show that pulsing can substantially reduce the anode potential thereby improving the overall efficiency of the separation process although the anode potential of the CO poisoned and pulsed cell still lies above that of an unpoisoned cell.

Coulometric titration of potassium hydrogen phthalate in a non-aqueous solution, with a vitreous carbon anode.

PubMed

Jennings, V J; Dodson, A; Tedds, G

1974-06-01

A vitreous carbon anode has been used as working electrode in the coulometric titration of potassium hydrogen phthalate in glacial acetic acid-acetic anhydride medium with protous generated electrochemical oxidation of quinol.

Understanding the anisotropic strain effects on lithium diffusion in graphite anodes: A first-principles study

NASA Astrophysics Data System (ADS)

Ji, Xiang; Wang, Yang; Zhang, Junqian

2018-06-01

The lithium diffusion in graphite anode, which is the most widely used commercial electrode material today, affects the charge/discharge performance of lithium-ion batteries. In this study, the anisotropic strain effects on lithium diffusion in graphite anodes are systematically investigated using first-principles calculations based on density functional theory (DFT) with van der Waals corrections. It is found that the effects of external applied strains along various directions of LixC6 (i.e., perpendicular or parallel to the basal planes of the graphite host) on lithium diffusivity are different. Along the direction perpendicular to the graphite planes, the tensile strain facilitates in-plane Li diffusion by reducing the energy barrier, and the compressive strain hinders in-plane Li diffusion by raising the energy barrier. In contrast, the in-plane biaxial tensile strain (parallel to the graphite planes) hinders in-plane Li diffusion, and the in-plane biaxial compressive strain facilitates in-plane Li diffusion. Furthermore, both in-plane and transverse shear strains slightly influence Li diffusion in graphite anodes. A discussion is presented to explain the anisotropic strain dependence of lithium diffusion. This research provides data for the continuum modelling of the electrodes in the lithium-ion batteries.

Direct methanol fuel cell and system

DOEpatents

Wilson, Mahlon S.

2004-10-26

A fuel cell having an anode and a cathode and a polymer electrolyte membrane located between anode and cathode gas diffusion backings uses a methanol vapor fuel supply. A permeable polymer electrolyte membrane having a permeability effective to sustain a carbon dioxide flux equivalent to at least 10 mA/cm.sup.2 provides for removal of carbon dioxide produced at the anode by reaction of methanol with water. Another aspect of the present invention includes a superabsorpent polymer material placed in proximity to the anode gas diffusion backing to hold liquid methanol or liquid methanol solution without wetting the anode gas diffusion backing so that methanol vapor from the liquid methanol or liquid methanol-water solution is supplied to the membrane.

Investigation of aluminosilicate as a solid oxide fuel cell refractory

NASA Astrophysics Data System (ADS)

Gentile, Paul S.; Sofie, Stephen W.

2011-05-01

Aluminosilicate represents a potential low cost alternative to alumina for solid oxide fuel cell (SOFC) refractory applications. The objectives of this investigation are to study: (1) changes of aluminosilicate chemistry and morphology under SOFC conditions, (2) deposition of aluminosilicate vapors on yttria stabilized zirconia (YSZ) and nickel, and (3) effects of aluminosilicate vapors on SOFC electrochemical performance. Thermal treatment of aluminosilicate under high temperature SOFC conditions is shown to result in increased mullite concentrations at the surface due to diffusion of silicon from the bulk. Water vapor accelerates the rate of surface diffusion resulting in a more uniform distribution of silicon. The high temperature condensation of volatile gases released from aluminosilicate preferentially deposit on YSZ rather than nickel. Silicon vapor deposited on YSZ consists primarily of aluminum rich clusters enclosed in an amorphous siliceous layer. Increased concentrations of silicon are observed in enlarged grain boundaries indicating separation of YSZ grains by insulating glassy phase. The presence of aluminosilicate powder in the hot zone of a fuel line supplying humidified hydrogen to an SOFC anode impeded peak performance and accelerated degradation. Energy dispersive X-ray spectroscopy detected concentrations of silicon at the interface between the electrolyte and anode interlayer above impurity levels.

Ohmic resistance affects microbial community and ...

EPA Pesticide Factsheets

Multi-anode microbial electrochemical cells (MXCs) are considered as one of the most promising configurations for scale-up of MXCs, but fundamental understanding of anode kinetics governing current density is limited in the MXCs. In this study we first assessed microbial community and electrochemical kinetic parameters for biofilms on individual anodes in a multi-anode MXC to better comprehend anode fundamentals. Microbial community analysis using 16S rRNA illumine sequencing showed that Geobactor genus, one of the most kinetically efficient anode-respiring bacteria (ARB), was abundant (87%) only on the biofilm anode closest to a reference electrode in which current density was the highest among four anodes. In comparison, Geobacter populations were less than 11% for other three anodes more distant from the reference electrode, generating small current density. Half-saturation anode potential (EKA) was the lowest at -0.251 to -0.242 V (vs. standard hydrogen electrode) for the closest anode, while EKA was as high as -0.134 V for the farthest anode. Our study clearly proves that ohmic resistance changes anode potential which mainly causes different biofilm communities on individual anodes and consequently influences anode kinetics. This study explored the use of multiple anodes in microelectrochemical cells and the microbial community on these anodes, as a function of the efficiency in producing hydrogen peroxide.

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.

Development of Ni-Ba(Zr,Y)O3 cermet anodes for direct ammonia-fueled solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Miyazaki, Kazunari; Okanishi, Takeou; Muroyama, Hiroki; Matsui, Toshiaki; Eguchi, Koichi

2017-10-01

In this study, the availability of Ni-Ba(Zr,Y)O3-δ (BZY) cermet for the anode of direct ammonia-fueled solid oxide fuel cells (SOFCs) is evaluated. In this device, the anodes need to be active for the catalytic ammonia decomposition as well as the electrochemical hydrogen oxidation. In the catalytic activity test, ammonia decomposes completely over Ni-BZY at ca. 600 °C, while higher temperature is required to accomplish the complete decomposition over the conventional SOFC anode of Ni-yttria-stabilized zirconia cermet. The high activity of Ni-BZY is attributed to the high basicity of BZY and the high resistance to hydrogen poisoning effect. The electrochemical property of Ni-BZY anode is also evaluated with the anode-supported cell of Ni-BZY|BZY|Pt at 600-700 °C with feeding ammonia or hydrogen as a fuel. Since the residence time of ammonia fuel in the thick Ni-BZY anode is long, the difference in the cell performance between two fuels is relatively small. Furthermore, it is proved that the steam concentration in the fuel strongly affects the cell performance. We find that this factor is important to satisfy the above mentioned requirements for the anode of direct ammonia-fueled SOFCs. Throughout this study, it is concluded that Ni-BZY cermet will be a promising anode.

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.

Fabrication of Titania Nanotubes for Gas Sensing Applications

NASA Astrophysics Data System (ADS)

Dzilal, A. A.; Muti, M. N.; John, O. D.

2010-03-01

Detection of hydrogen is needed for industrial process control and medical applications where presence of hydrogen indicates different type of health problems. Titanium dioxide nanotube structure is chosen as an active component in the gas sensor because of its highly sensitive electrical resistance to hydrogen over a wide range of concentrations. The objective of the work is to fabricate good quality titania nanotubes suitable for hydrogen sensing applications. The fabrication method used is anodizing method. The anodizing parameters namely the voltage, time duration, concentration of hydrofluoric acid in water, separation between the electrodes and the ambient temperature are varied accordingly to find the optimum anodizing conditions for production of good quality titania nanotubes. The highly ordered porous titania nanotubes produced by this method are in tabular shape and have good uniformity and alignment over large areas. From the investigation done, certain set of anodizing parameters have been found to produce good quality titania nanotubes with diameter ranges from 47 nm to 94 nm.

Ni-SDC cermet anode for medium-temperature solid oxide fuel cell with lanthanum gallate electrolyte

NASA Astrophysics Data System (ADS)

Zhang, Xinge; Ohara, Satoshi; Maric, Radenka; Mukai, Kazuo; Fukui, Takehisa; Yoshida, Hiroyuki; Nishimura, Masayoshi; Inagaki, Toru; Miura, Kazuhiro

The polarization properties and microstructure of Ni-SDC (samaria-doped ceria) cermet anodes prepared from spray pyrolysis (SP) composite powder, and element interface diffusion between the anode and a La 0.9Sr 0.1Ga 0.8Mg 0.2O 3- δ (LSGM) electrolyte are investigated as a function of anode sintering temperature. The anode sintered at 1250°C displays minimum anode polarization (with anode ohmic loss), while the anode prepared at 1300°C has the best electrochemical overpotential, viz., 27 mV at 300 mA cm -2 operating at 800°C. The anode ohmic loss gradually increases with increase in the sintering temperature at levels below 1300°C, and sharply increases at 1350°C. Electron micrographs show a clear grain growth at sintering temperatures higher than 1300°C. The anode microstructure appears to be optimized at 1300°C, in which nickel particles form a network with well-connected SDC particles finely distributed over the surfaces of the nickel particles. The anode sintered at 1350°C has severe grain growth and an apparent interface diffusion of nickel from the anode to the electrolyte. The nickel interface diffusion is assumed to be the main reason for the increment in ohmic loss, and the resulting loss in anode performance. The findings suggest that sintering Ni-SDC composite powder near 1250°C is the best method to prepare the anode on a LSGM electrolyte.

Use of low-cost aluminum in electric energy production

NASA Astrophysics Data System (ADS)

Zhuk, Andrey Z.; Sheindlin, Alexander E.; Kleymenov, Boris V.; Shkolnikov, Eugene I.; Lopatin, Marat Yu.

Suppression of the parasitic corrosion while maintaining the electrochemical activity of the anode metal is one of the serious problems that affects the energy efficiency of aluminum-air batteries. The need to use high-purity aluminum or special aluminum-based alloys results in a significant increase in the cost of the anode, and thus an increase in the total cost of energy generated by the aluminum-air battery, which narrows the range of possible applications for this type of power source. This study considers the process of parasitic corrosion as a method for hydrogen production. Hydrogen produced in an aluminum-air battery by this way may be further employed in a hydrogen-air fuel cell (Hy-air FC) or in a heat engine, or it may be burnt to generate heat. Therefore, anode materials may be provided by commercially pure aluminum, commercially produced aluminum alloys, and secondary aluminum. These materials are much cheaper and more readily available than special anode alloys of aluminum and high-purity aluminum. The aim of present study is to obtain experimental data for comparison of energy and cost parameters of some commercially produced aluminum alloys, of high-purity aluminum, and of a special Al-ln anode alloy in the context of using these materials as anodes for an Al-air battery and for combined production of electrical power and hydrogen.

Hydrogen production from switchgrass via an integrated pyrolysis-microbial electrolysis process.

PubMed

Lewis, A J; Ren, S; Ye, X; Kim, P; Labbe, N; Borole, A P

2015-11-01

A new approach to hydrogen production using an integrated pyrolysis-microbial electrolysis process is described. The aqueous stream generated during pyrolysis of switchgrass was used as a substrate for hydrogen production in a microbial electrolysis cell, achieving a maximum hydrogen production rate of 4.3 L H2/L anode-day at a loading of 10 g COD/L-anode-day. Hydrogen yields ranged from 50±3.2% to 76±0.5% while anode Coulombic efficiency ranged from 54±6.5% to 96±0.21%, respectively. Significant conversion of furfural, organic acids and phenolic molecules was observed under both batch and continuous conditions. The electrical and overall energy efficiency ranged from 149-175% and 48-63%, respectively. The results demonstrate the potential of the pyrolysis-microbial electrolysis process as a sustainable and efficient route for production of renewable hydrogen with significant implications for hydrocarbon production from biomass. Copyright © 2015 Elsevier Ltd. All rights reserved.

Inter-cusp Ion and Electron Transport in a Nstar-derivative Ion Thruster

NASA Technical Reports Server (NTRS)

Foster, John E.

2001-01-01

Diffusion of electrons and ions to anode surfaces between the magnetic cusps of a NASA Solar Electric Propulsion Technology Application Readiness ion thruster has been characterized. Ion flux measurements were made at the anode and at the screen grid electrode. The measurements indicated that the average ion current density at the anode and at the screen grid were approximately equal. Additionally, it was found that the electron flux to the anode between cusps is best described by the classical cross-field diffusion coefficient.

Ion and Electron Transport in an Nstar-derivative Ion Thruster. Revised

NASA Technical Reports Server (NTRS)

Foster, John E.

2001-01-01

Diffusion of electrons and ions to anode surfaces between the magnetic cusps of a NASA Solar Electric Propulsion Technology Application Readiness ion thruster has been characterized. Ion flux measurements were made at the anode and at the screen grid electrode. The measurements indicated that the average ion current density at the anode and at the screen grid were approximately equal. Additionally, it was found that the electron flux to the anode between cusps is best described by the classical cross-field diffusion coefficient.

Dynamics of the spatial structure of pulsed discharges in dense gases in point cathode−plane anode gaps and their erosion effect on the plane electrode surface

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

Baksht, E. Kh.; Blinova, O. M.; Erofeev, M. V., E-mail: mve@loi.hcei.tsc.ru

2016-09-15

The dynamics of the spatial structure of the plasma of pulsed discharges in air and nitrogen in a nonuniform electric field and their erosion effect on the plane anode surface were studied experimentally. It is established that, at a nanosecond front of the voltage pulse, a diffuse discharge forms in the point cathode–plane anode gap due to the ionization wave propagating from the cathode. As the gap length decreases, the diffuse discharge transforms into a spark. A bright spot on the anode appears during the diffuse discharge, while the spark channel forms in the later discharge stage. The microstructure ofmore » autographs of anode spots and spark channels in discharges with durations of several nanoseconds is revealed. The autographs consist of up to 100 and more microcraters 5–100 μm in diameter. It is shown that, due to the short duration of the voltage pulse, a diffuse discharge can be implemented, several pulses of which do not produce appreciable erosion on the plane anode or the soot coating deposited on it.« less

Electrochemical Device Comprising Composite Bipolar Plate and Method of Using the Same

NASA Technical Reports Server (NTRS)

Mittelsteadt, Cortney K. (Inventor); Braff, William A. (Inventor)

2013-01-01

An electrochemical device and methods of using the same. In one embodiment, the electrochemical device may be used as a fuel cell and/or as an electrolyzer and includes a membrane electrode assembly (MEA), an anodic gas diffusion medium in contact with the anode of the MEA, a cathodic gas diffusion medium in contact with the cathode, a first bipolar plate in contact with the anodic gas diffusion medium, and a second bipolar plate in contact with the cathodic gas diffusion medium. Each of the bipolar plates includes an electrically-conductive, chemically-inert, non-porous, liquid-permeable, substantially gas-impermeable membrane in contact with its respective gas diffusion medium, as well as a fluid chamber and a non-porous an electrically-conductive plate.

Electrochemical Device Comprising Composite Bipolar Plate and Method of Using the Same

NASA Technical Reports Server (NTRS)

Mittelsteadt, Cortney K. (Inventor); Braff, William A. (Inventor)

2017-01-01

An electrochemical device and methods of using the same. In one embodiment, the electrochemical device may be used as a fuel cell and/or as an electrolyzer and includes a membrane electrode assembly (MEA), an anodic gas diffusion medium in contact with the anode of the MEA, a cathodic gas diffusion medium in contact with the cathode, a first bipolar plate in contact with the anodic gas diffusion medium, and a second bipolar plate in contact with the cathodic gas diffusion medium. Each of the bipolar plates includes an electrically-conductive, chemically-inert, non-porous, liquid-permeable, substantially gas-impermeable membrane in contact with its respective gas diffusion medium, as well as a fluid chamber and a non-porous an electrically-conductive plate.

A biohydrogen fuel cell using a conductive polymer nanocomposite based anode.

PubMed

Hoa, Le Quynh; Sugano, Yasuhito; Yoshikawa, Hiroyuki; Saito, Masato; Tamiya, Eiichi

2010-07-15

This paper introduces a newly designed biohydrogen fuel cell by integrating a bioreactor for hydrogen production with the anode chamber in a hydrogen fuel cell. Two different composites of platinum nanoparticles decorated on functionalised multi-walled carbon nanotubes (Pt/fMWCNTs) and polyaniline (PANI) were fabricated using the electrochemical polymerisation method and used as anodes. The biohydrogen fuel cell using a thin film of PANI nanofibres deposited on Pt/fMWCNTs/carbon paper as the anode showed much higher power density than the cell using a core-shell structure PANI/Pt/fMWCNTs and Pt/fMWCNTs without PANI based anodes. The structural differences between these two composites and their effects on the interaction with hydrogen gas inside the anode chamber leading to the difference in power density of the fuel cell were also discussed. The maximum power density was 613.5 mW m(-2), which was obtained at a current density of about 2.55 A m(-2) with a cell voltage of 0.24 V using 20 mL single-chamber air-cathode, compact biohydrogen fuel cell. Copyright (c) 2010 Elsevier B.V. All rights reserved.

Partial oxidation of methane (POM) assisted solid oxide co-electrolysis

DOEpatents

Chen, Fanglin; Wang, Yao

2017-02-21

Methods for simultaneous syngas generation by opposite sides of a solid oxide co-electrolysis cell are provided. The method can comprise exposing a cathode side of the solid oxide co-electrolysis cell to a cathode-side feed stream; supplying electricity to the solid oxide co-electrolysis cell such that the cathode side produces a product stream comprising hydrogen gas and carbon monoxide gas while supplying oxygen ions to an anode side of the solid oxide co-electrolysis cell; and exposing the anode side of the solid oxide co-electrolysis cell to an anode-side feed stream. The cathode-side feed stream comprises water and carbon dioxide, and the anode-side feed stream comprises methane gas such that the methane gas reacts with the oxygen ions to produce hydrogen and carbon monoxide. The cathode-side feed stream can further comprise nitrogen, hydrogen, or a mixture thereof.

Simulation results of influence of constricted arc column on anode deformation and melting pool swirl in vacuum arcs with AMF contacts

NASA Astrophysics Data System (ADS)

Wang, Lijun; Zhang, Xiao; Huang, Xiaolong; Jia, Shenli

2017-11-01

In the process of vacuum arc breaking, the energy injected into the anode will cause anode melting, evaporation, and deformation, resulting in the formation of the anode melting pool. The anode activities have great influence on the arc behavior. When the arc current is large enough, even the influence of axial magnetic field is considered, the arc column still is in contraction state, which means the arc burns only on a part of the electrode. In this paper, the model of anode melting pool deformation and rotation is used, and the model includes anode melting and solidification module, magneto-hydro-dynamic module of the anode melting pool, the volume of fraction method, and the current continuity equation. In this paper, the diffuse arc area is selected as 100%, 75%, and 50%, respectively. The anode temperature and deformation, the anode melting layer thickness, and the rotational velocity of the anode melting pool are obtained. The results show that when the current is at 17.5 kA (rms) and the diffuse arc area is 100%, the anode's maximum temperature is 1477 K and the crater depth is 0.83 mm. But when the diffuse arc areas are 75% and 50%, the anode's maximum temperatures reach 1500 K and 1761 K, and the crater depths reach 1.2 mm and 3 mm, respectively. Arc contraction will lead to more serious anode deformation. A similar result is obtained when the simulation current is 12.5 kA. Under the similar situation, the simulation results in the crater depth, the residual melt layer thickness, the rotational speed of the melting pool, and the maximum temperature of the anode at current zero are in good agreement with the experimental results.

Studies on sulfur poisoning and development of advanced anodic materials for waste-to-energy fuel cells applications

NASA Astrophysics Data System (ADS)

Zaza, Fabio; Paoletti, Claudia; LoPresti, Roberto; Simonetti, Elisabetta; Pasquali, Mauro

Biomass is the renewable energy source with the most potential penetration in energy market for its positive environmental and socio-economic consequences: biomass live cycles for energy production is carbon neutral; energy crops promote alternative and productive utilizations of rural sites creating new economic opportunities; bioenergy productions promote local energy independence and global energy security defined as availability of energy resource supply. Different technologies are currently available for energy production from biomass, but a key role is played by fuel cells which have both low environmental impacts and high efficiencies. High temperature fuel cells, such as molten carbonate fuel cells (MCFC), are particularly suitable for bioenergy production because it can be directly fed with biogas: in fact, among its principal constituents, methane can be transformed to hydrogen by internal reforming; carbon dioxide is a safe diluent; carbon monoxide is not a poison, but both a fuel, because it can be discharged at the anode, and a hydrogen supplier, because it can produce hydrogen via the water-gas shift reaction. However, the utilization of biomass derived fuels in MCFC presents different problems not yet solved, such as the poisoning of the anode due to byproducts of biofuel chemical processing. The chemical compound with the major negative effects on cell performances is hydrogen sulfide. It reacts with nickel, the main anodic constituent, forming sulfides and blocking catalytic sites for electrode reactions. The aim of this work is to study the hydrogen sulfide effects on MCFC performances for defining the poisoning mechanisms of conventional nickel-based anode, recommending selection criteria of sulfur-tolerant materials, and selecting advanced anodes for MCFC fed with biogas.

Reprocessing of LiH in Molten Chlorides

NASA Astrophysics Data System (ADS)

Masset, Patrick J.; Gabriel, Armand; Poignet, Jean-Claude

2008-06-01

LiH was used as inactive material to stimulate the reprocessing of lithium tritiate in molten chlorides. The electrochemical properties (diffusion coefficients, apparent standard potentials) were measured by means of transient electrochemical techniques (cyclic voltammetry and chronopotentiometry). At 425 ºC the diffusion coefficient and the apparent standard potential were 2.5 · 10-5 cm2 s-1 and -1.8 V vs. Ag/AgCl, respectively. For the process design the LiH solubility was measured by means of DTA to optimize the LiH concentration in the molten phase. In addition electrolysis tests were carried out at 460 ºC with current densities up to 1 A cm-2 over 24 h. These results show that LiH may be reprocessed in molten chlorides consisting in the production of hydrogen gas at the anode and molten metallic lithium at the cathode.

Theoretical prediction of silicene as a new candidate for the anode of lithium-ion batteries.

PubMed

Seyed-Talebi, Seyedeh Mozhgan; Kazeminezhad, Iraj; Beheshtian, Javad

2015-11-28

Using density functional theory calculations, we determine the band structure and DOS of graphene and silicene supercell models. We also study the adsorption mechanism of Li metal atoms and Li-ions onto free-standing silicene (buckled, θ = 101.7°) and compare the results with those of graphene. In contrast to graphene, interactions between Li metal atoms and Li-ions with the silicene surface are quite strong due to its highly reactive buckled hexagonal structure. As a consequence of structural properties the adsorption height, the most stable adsorption site and energy barrier against Li diffusion are also discussed here to outline the prospects of using silicene in electronic devices such as Li ion batteries (LiBs), hydrogen storage and molecular machines. However, in most LiBs, graphene layers are used as anode electrodes. Here, it is shown that graphene has very limited Li storage capacity and low surface area than silicene. As our models are in good agreement with previous predictions, this finding presents a possible avenue for creating better anode materials that can replace graphene for higher capacity and better cycling performance of LiBs.

Palladium-assisted electrodehalogenation of 1,1,2-trichloro-1,2,2-trifluoroethane on lead cathodes combined with hydrogen diffusion anodes

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

Cabot, P.L.; Centelles, M.; Segarra, L.

1997-11-01

In this work, the efficiency and product formation in the electroreduction of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC 113) to obtain completely dechlorinated products has been studied using constant-current electrolysis at different current densities, gas chromatography, scanning electron microscopy, and energy dispersive x-ray. While chlorotrifluoroethene was the main product obtained from CFC 113 in MeOH-water solutions containing NH{sub 4}Cl, different and suitable conditions which lead to its complete dechlorination are described in this paper. In the presence of small amounts of Pd{sup 2+} in solution, a very thin film of Pd black was electrodeposited on the Pb cathode and the efficiency of the CFCmore » 113 electroreduction was about 98%. The efficiency was much smaller and the product composition very different in the absence of Pd{sup 2+} in solution, even in the presence of Pd black electrodeposited on the cathode. In the presence of Pd{sup 2+}, the main products in the gas were difluoroethene and trifluoroethene. Small amounts of 1,2-dichloro-1,1,2-trifluoroethane, chlorotrifluoroethene, difluoroethane, and fluoroethane were also present in the gas phase. The liquid composition was enriched in the less volatile compounds. A possible reaction pathway involving the removal of halides by successive reactions is discussed. The anode employed in these experiments was a thin Pd foil with electrodeposited Pd black, which permitted hydrogen diffusion and its further oxidation to H{sup +}. Because of this reaction, contamination of the working electrolyte by other oxidation products such as Cl{sub 2} or MeOH derivatives were avoided. This system allows new electrosynthetic processes along with CFC electrodegradation.« less

Electrochemical Generation of a Hydrogen Bubble at a Recessed Platinum Nanopore Electrode.

PubMed

Chen, Qianjin; Luo, Long; White, Henry S

2015-04-21

We report the electrochemical generation of a single hydrogen bubble within the cavity of a recessed Pt nanopore electrode. The recessed Pt electrode is a conical pore in glass that contains a micrometer-scale Pt disk (1-10 μm radius) at the nanopore base and a nanometer-scale orifice (10-100 nm radius) that restricts diffusion of electroactive molecules and dissolved gas between the nanopore cavity and bulk solution. The formation of a H2 bubble at the Pt disk electrode in voltammetric experiments results from the reduction of H(+) in a 0.25 M H2SO4 solution; the liquid-to-gas phase transformation is indicated in the voltammetric response by a precipitous decrease in the cathodic current due to rapid bubble nucleation and growth within the nanopore cavity. Finite element simulations of the concentration distribution of dissolved H2 within the nanopore cavity, as a function of the H(+) reduction current, indicate that H2 bubble nucleation at the recessed Pt electrode surface occurs at a critical supersaturation concentration of ∼0.22 M, in agreement with the value previously obtained at (nonrecessed) Pt disk electrodes (∼0.25 M). Because the nanopore orifice limits the diffusion of H2 out of the nanopore cavity, an anodic peak corresponding to the oxidation of gaseous and dissolved H2 trapped in the recessed cavity is readily observed on the reverse voltammetric scan. Integration of the charge associated with the H2 oxidation peak is found to approach that of the H(+) reduction peak at high scan rates, confirming the assignment of the anodic peak to H2 oxidation. Preliminary results for the electrochemical generation of O2 bubbles from water oxidation at a recessed nanopore electrode are consistent with the electrogeneration of H2 bubbles.

Investigation of the electrochemically active surface area and lithium diffusion in graphite anodes by a novel OsO4 staining method

NASA Astrophysics Data System (ADS)

Pfaffmann, Lukas; Birkenmaier, Claudia; Müller, Marcus; Bauer, Werner; Mitsch, Tim; Feinauer, Julian; Krämer, Yvonne; Scheiba, Frieder; Hintennach, Andreas; Schleid, Thomas; Schmidt, Volker; Ehrenberg, Helmut

2016-03-01

Negative electrodes of lithium-ion batteries generally consist of graphite-based active materials. In order to realize batteries with a high current density and therefore accelerated charging processes, the intercalation of lithium and the diffusion processes of these carbonaceous materials must be understood. In this paper, we visualized the electrochemical active surface area for three different anode materials using a novel OsO4 staining method in combination with scanning electron microscopy techniques. The diffusion behavior of these three anode materials is investigated by potentiostatic intermittent titration technique measurements. From those we determine the diffusion coefficient with and without consideration of the electrochemical active surface area.

Hydrogen production profiles using furans in microbial electrolysis cells.

PubMed

Catal, Tunc; Gover, Tansu; Yaman, Bugra; Droguetti, Jessica; Yilancioglu, Kaan

2017-06-01

Microbial electrochemical cells including microbial fuel cells (MFCs) and microbial electrolysis cells (MECs) are novel biotechnological tools that can convert organic substances in wastewater or biomass into electricity or hydrogen. Electroactive microbial biofilms used in this technology have ability to transfer electrons from organic compounds to anodes. Evaluation of biofilm formation on anode is crucial for enhancing our understanding of hydrogen generation in terms of substrate utilization by microorganisms. In this study, furfural and hydroxymethylfurfural (HMF) were analyzed for hydrogen generation using single chamber membrane-free MECs (17 mL), and anode biofilms were also examined. MECs were inoculated with mixed bacterial culture enriched using chloroethane sulphonate. Hydrogen was succesfully produced in the presence of HMF, but not furfural. MECs generated similar current densities (5.9 and 6 mA/cm 2 furfural and HMF, respectively). Biofilm samples obtained on the 24th and 40th day of cultivation using aromatic compounds were evaluated by using epi-fluorescent microscope. Our results show a correlation between biofilm density and hydrogen generation in single chamber MECs.

Homogeneous growth of TiO2-based nanotubes on nitrogen-doped reduced graphene oxide and its enhanced performance as a Li-ion battery anode.

PubMed

Mehraeen, Shayan; Taşdemir, Adnan; Gürsel, Selmiye Alkan; Yürüm, Alp

2018-06-22

The pursuit of a promising replacement candidate for graphite as a Li-ion battery anode, which can satisfy both engineering criteria and market needs has been the target of researchers for more than two decades. In this work, we have investigated the synergistic effect of nitrogen-doped reduced graphene oxide (NrGO) and nanotubular TiO 2 to achieve high rate capabilities with high discharge capacities through a simple, one-step and scalable method. First, nanotubes of hydrogen titanate were hydrothermally grown on the surface of NrGO sheets, and then converted to a mixed phase of TiO 2 -B and anatase (TB) by thermal annealing. Specific surface area, thermal gravimetric, structural and morphological characterizations were performed on the synthesized product. Electrochemical properties were investigated by cyclic voltammetry and cyclic charge/discharge tests. The prepared anode showed high discharge capacity of 150 mAh g -1 at 1 C current rate after 50 cycles. The promising capacity of synthesized NrGO-TB was attributed to the unique and novel microstructure of NrGO-TB in which long nanotubes of TiO 2 have been grown on the surface of NrGO sheets. Such architecture synergistically reduces the solid-state diffusion distance of Li + and increases the electronic conductivity of the anode.

Homogeneous growth of TiO2-based nanotubes on nitrogen-doped reduced graphene oxide and its enhanced performance as a Li-ion battery anode

NASA Astrophysics Data System (ADS)

Mehraeen, Shayan; Taşdemir, Adnan; Alkan Gürsel, Selmiye; Yürüm, Alp

2018-06-01

The pursuit of a promising replacement candidate for graphite as a Li-ion battery anode, which can satisfy both engineering criteria and market needs has been the target of researchers for more than two decades. In this work, we have investigated the synergistic effect of nitrogen-doped reduced graphene oxide (NrGO) and nanotubular TiO2 to achieve high rate capabilities with high discharge capacities through a simple, one-step and scalable method. First, nanotubes of hydrogen titanate were hydrothermally grown on the surface of NrGO sheets, and then converted to a mixed phase of TiO2-B and anatase (TB) by thermal annealing. Specific surface area, thermal gravimetric, structural and morphological characterizations were performed on the synthesized product. Electrochemical properties were investigated by cyclic voltammetry and cyclic charge/discharge tests. The prepared anode showed high discharge capacity of 150 mAh g‑1 at 1 C current rate after 50 cycles. The promising capacity of synthesized NrGO-TB was attributed to the unique and novel microstructure of NrGO-TB in which long nanotubes of TiO2 have been grown on the surface of NrGO sheets. Such architecture synergistically reduces the solid-state diffusion distance of Li+ and increases the electronic conductivity of the anode.

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.

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.

Enhanced sulfur tolerance of nickel-based anodes for oxygen-ion conducting solid oxide fuel cells by incorporating a secondary water storing phase.

PubMed

Wang, Feng; Wang, Wei; Qu, Jifa; Zhong, Yijun; Tade, Mose O; Shao, Zongping

2014-10-21

In this work, a Ni+BaZr(0.4)Ce(0.4)Y(0.2)O(3-δ) (Ni+BZCY) anode with high water storage capability is used to increase the sulfur tolerance of nickel electrocatalysts for solid oxide fuel cells (SOFCs) with an oxygen-ion conducting Sm(0.2)Ce(0.8)O(1.9) (SDC) electrolyte. Attractive power outputs are still obtained for the cell with a Ni+BZCY anode that operates on hydrogen fuels containing 100-1000 ppm of H2S, while for a similar cell with a Ni+SDC anode, it displays a much reduced performance by introducing only 100 ppm of H2S into hydrogen. Operating on a hydrogen fuel containing 100 ppm of H2S at 600 °C and a fixed current density of 200 mA cm(-2), a stable power output of 148 mW cm(-2) is well maintained for a cell with a Ni+BZCY anode within a test period of 700 min, while it was decreased from an initial value of 137 mW cm(-2) to only 81 mW cm(-2) for a similar cell with a Ni+SDC anode after a test period of only 150 min. After the stability test, a loss of the Ni percolating network and reaction between nickel and sulfur appeared over the Ni+SDC anode, but it is not observed for the Ni+BZCY anode. This result highly promises the use of water-storing BZCY as an anode component to improve sulfur tolerance for SOFCs with an oxygen-ion conducting SDC electrolyte.

Electrochemical process for the preparation of nitrogen fertilizers

DOEpatents

Jiang, Junhua; Aulich, Ted R; Ignatchenko, Alexey V

2015-04-14

Methods and apparatus for the preparation of nitrogen fertilizers including ammonium nitrate, urea, urea-ammonium nitrate, and/or ammonia are disclosed. Embodiments include (1) ammonium nitrate 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 produced via the simultaneous cathodic reduction of a carbon source and a nitrogen source: (3) ammonia 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 produced via the simultaneous cathodic reduction of a carbon source and a nitrogen source, and anodic oxidation of a nitrogen source.

The performance of 3-D graphite doped anodes in microbial electrolysis cells

NASA Astrophysics Data System (ADS)

Yasri, Nael G.; Nakhla, George

2017-02-01

This study investigated the use of granular activated carbon (GAC) as high surface area 3-dimensional (3-D) anode in MECs systems. The interfacial anodes' charge transfer resistance of the doped GAC did not impact the overall performance of MECs. Based on our finding, the 3-D anode packed with GAC-doped with nonconductive calcium sulfide (CaS) outperformed the more conductive iron (II) sulfide (FeS), magnetite (Fe3O4), or GAC without doping. The results showed higher current densities for 3-D CaS (40.1 A/m3), as compared with 3-D FeS (34.4 A/m3), 3-D Fe3O4 (29.8 A/m3), and 3-D GAC (23.1 A/m3). The higher current density in the 3-D CaS translated to higher coulombic efficiency (96.7%), hydrogen yield (3.6 mol H2/mol acetate), and attached biomass per anode mass (54.01 mg COD biomass/g GAC). Although the 3-D MEC achieved similar hydrogen yield, hydrogen recovery efficiency, and COD removal rate to a conventional sandwich type MEC, the current density, coulombic efficiency, and overall energy efficiency were higher.

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.

Preparation of Carbon-Platinum-Ceria and Carbon-Platinum-Cerium catalysts and its application in Polymer Electrolyte Fuel Cell: Hydrogen, Methanol, and Ethanol

NASA Astrophysics Data System (ADS)

Guzman Blas, Rolando Pedro

This thesis is focused on fuel cells using hydrogen, methanol and ethanol as fuel. Also, in the method of preparation of catalytic material for the anode: Supercritical Fluid Deposition (SFD) and impregnation method using ethylenediaminetetraacetic acid (EDTA) as a chelating agent. The first part of the thesis describes the general knowledge about Hydrogen Polymer Exchange Membrane Fuel Cell (HPEMFC),Direct Methanol Fuel Cell (DMFC) and Direct Ethanol Fuel Cell (DEFC), as well as the properties of Cerium and CeO2 (Ceria). The second part of the thesis describes the preparation of catalytic material by Supercritical Fluid Deposition (SFD). SFD was utilized to deposit Pt and ceria simultaneously onto gas diffusion layers. The Pt-ceria catalyst deposited by SFD exhibited higher methanol oxidation activity compared to the platinum catalyst alone. The linear sweep traces of the cathode made for the methanol cross over study indicate that Pt-Ceria/C as the anode catalyst, due to its better activity for methanol, improves the fuel utilization, minimizing the methanol permeation from anode to cathode compartment. The third and fourth parts of the thesis describe the preparation of material catalytic material Carbon-Platinum-Cerium by a simple and cheap impregnation method using EDTA as a chelating agent to form a complex with cerium (III). This preparation method allows the mass production of the material catalysts without additional significant cost. Fuel cell polarization and power curves experiments showed that the Carbon-Platinum-Cerium anode materials exhibited better catalytic activity than the only Vulcan-Pt catalysts for DMFC, DEFC and HPEMFC. In the case of Vulcan-20%Pt-5%w Cerium, this material exhibits better catalytic activity than the Vulcan-20%Pt in DMFC. In the case of Vulcan-40% Pt-doped Cerium, this material exhibits better catalytic activity than the Vulcan-40% Pt in DMFC, DEFC and HPEMFC. Finally, I propose a theory that explains the reason why the carbon-platinum-cerium has better catalytic activity than platinum-carbon. Due to the hybridization behavior of C and Ce could arise charge transfer, both carbon and cerium to the Platinum. Ce-C→Pt charge transfer could occur at the Ce-C/Pt interface. Thus, results in an increase in the catalytic activity of platinum-cerium-carbon when compared with carbon-platinum.

Hydrogen and Sulfur from Hydrogen Sulfide. 5. Anodic Oxidation of Sulfur on Activated Glassy Carbon

DTIC Science & Technology

1988-12-05

electrolyses of H S can probably be carried out at high rates with modest cell voltages in the range 1-1.5 V. The variation in anode current densities...of H2S from solutions of NaSH in aqueous NaOH was achieved using suitably ac- tivated glassy carbon anodes. Thus electrolyses of H2S can probably be...passivation by using a basic solvent at 850C. Using an H2S-saturated 6M NaOH solution, they conducted electrolyses for extended periods at current densities

Water electrolysis

NASA Technical Reports Server (NTRS)

Schubert, Franz H. (Inventor); Grigger, David J. (Inventor)

1992-01-01

This disclosure is directed to an electrolysis cell forming hydrogen and oxygen at space terminals. The anode terminal is porous and able to form oxygen within the cell and permit escape of the gaseous oxygen through the anode and out through a flow line in the presence of backpressure. Hydrogen is liberated in the cell at the opposing solid metal cathode which is permeable to hydrogen but not oxygen so that the migratory hydrogen formed in the cell is able to escape from the cell. The cell is maintained at an elevated pressure so that the oxygen liberated by the cell is delivered at elevated pressure without pumping to raise the pressure of the oxygen.

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.

Solar-microbial hybrid device based on oxygen-deficient niobium pentoxide anodes for sustainable hydrogen production.

PubMed

Li, Mingyang; He, Xinjun; Zeng, Yinxiang; Chen, Meiqiong; Zhang, Ziyang; Yang, Hao; Fang, Pingping; Lu, Xihong; Tong, Yexiang

2015-12-01

Hydrogen gas is emerging as an attractive fuel with high energy density for the direction of energy resources in the future. Designing integrated devices based on a photoelectrochemical (PEC) cell and a microbial fuel cell (MFC) represents a promising strategy to produce hydrogen fuel at a low price. In this work, we demonstrate a new solar-microbial (PEC-MFC) hybrid device based on the oxygen-deficient Nb 2 O 5 nanoporous (Nb 2 O 5- x NPs) anodes for sustainable hydrogen generation without external bias for the first time. Owing to the improved conductivity and porous structure, the as-prepared Nb 2 O 5- x NPs film yields a remarkable photocurrent density of 0.9 mA cm -2 at 0.6 V ( vs. SCE) in 1 M KOH aqueous solution under light irradiation, and can achieve a maximum power density of 1196 mW m -2 when used as an anode in a MFC device. More importantly, a solar-microbial hybrid system by combining a PEC cell with a MFC is designed, in which the Nb 2 O 5- x NPs electrodes function as both anodes. The as-fabricated PEC-MFC hybrid device can simultaneously realize electricity and hydrogen using organic matter and solar light at zero external bias. This novel design and attempt might provide guidance for other materials to convert and store energy.

Molecular Beam-Thermal Desorption Spectrometry (MB-TDS) Monitoring of Hydrogen Desorbed from Storage Fuel Cell Anodes.

PubMed

Lobo, Rui F M; Santos, Diogo M F; Sequeira, Cesar A C; Ribeiro, Jorge H F

2012-02-06

Different types of experimental studies are performed using the hydrogen storage alloy (HSA) MlNi 3.6 Co 0.85 Al 0.3 Mn 0.3 (Ml: La-rich mischmetal), chemically surface treated, as the anode active material for application in a proton exchange membrane fuel cell (PEMFC). The recently developed molecular beam-thermal desorption spectrometry (MB-TDS) technique is here reported for detecting the electrochemical hydrogen uptake and release by the treated HSA. The MB-TDS allows an accurate determination of the hydrogen mass absorbed into the hydrogen storage alloy (HSA), and has significant advantages in comparison with the conventional TDS method. Experimental data has revealed that the membrane electrode assembly (MEA) using such chemically treated alloy presents an enhanced surface capability for hydrogen adsorption.

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.

Electrochemical Device Comprising an Electrically-Conductive, Selectively-Permeable Membrane

NASA Technical Reports Server (NTRS)

Laicer, Castro S. T. (Inventor); Mittelsteadt, Cortney K. (Inventor); Harrison, Katherine E. (Inventor); McPheeters, Bryn M. (Inventor)

2017-01-01

An electrochemical device, such as a fuel cell or an electrolyzer. In one embodiment, the electrochemical device includes a membrane electrode assembly (MEA), an anodic gas diffusion medium in contact with the anode of the MEA, a cathodic gas diffusion medium in contact with the cathode, a first bipolar plate in contact with the anodic gas diffusion medium, and a second bipolar plate in contact with the cathodic gas diffusion medium. Each of the bipolar plates includes an electrically-conductive, non-porous, liquid-permeable, substantially gas-impermeable membrane in contact with its respective gas diffusion medium, the membrane including a solid polymer electrolyte and a non-particulate, electrically-conductive material, such as carbon nanotubes, carbon nanofibers, and/or metal nanowires. In addition, each bipolar plate also includes an electrically-conductive fluid chamber in contact with the electrically-conductive, selectively-permeable membrane and further includes a non-porous and electrically-conductive plate in contact with the fluid chamber.

Influence of the concentration of borohydride towards hydrogen production and escape for borohydride oxidation reaction on Pt and Au electrodes - experimental and modelling insights

NASA Astrophysics Data System (ADS)

Olu, Pierre-Yves; Bonnefont, Antoine; Braesch, Guillaume; Martin, Vincent; Savinova, Elena R.; Chatenet, Marian

2018-01-01

The Borohydride Oxidation Reaction (BOR), the anode reaction in a Direct borohydride fuel cell (DBFC), is complex and still poorly understood, which impedes the development and deployment of the DBFC technology. In particular, no practical electrocatalyst is capable to prevent gaseous hydrogen generation and escape from its anode upon operation, which lowers the fuel-efficiency of the DBFC and raises safety issues in operation. The nature of the anode electrocatalysts strongly influences the hydrogen escape characteristics of the DBFC, which demonstrates how important it is to isolate the BOR mechanism in conditions relevant to DBFC operation. In this paper, from a selected literature review and BOR experiments performed in differential electrochemical mass spectrometry (DEMS) in a wide range of NaBH4 concentration (5-500 mM), a microkinetic model of the BOR for both Pt and Au surfaces is proposed; this model takes into account the hydrogen generation and escape.

40 CFR Table F-2 to Subpart F of... - Default Data Sources for Parameters Used for CO2 Emissions

Code of Federal Regulations, 2014 CFR

2014-07-01

... metric ton Al (metric tons C/metric tons Al) Individual facility records. Sa: sulfur content in baked anode (percent weight) 2.0. Asha: ash content in baked anode (percent weight) 0.4. CO2 Emissions From... records. Hw: annual hydrogen content in green anodes (metric tons) 0.005 × GA. BA: annual baked anode...

40 CFR Table F-2 to Subpart F of... - Default Data Sources for Parameters Used for CO2 Emissions

Code of Federal Regulations, 2013 CFR

2013-07-01

... metric ton Al (metric tons C/metric tons Al) Individual facility records. Sa: sulfur content in baked anode (percent weight) 2.0. Asha: ash content in baked anode (percent weight) 0.4. CO2 Emissions From... records. Hw: annual hydrogen content in green anodes (metric tons) 0.005 × GA. BA: annual baked anode...

40 CFR Table F-2 to Subpart F of... - Default Data Sources for Parameters Used for CO2 Emissions

Code of Federal Regulations, 2012 CFR

2012-07-01

... metric ton Al (metric tons C/metric tons Al) Individual facility records. Sa: sulfur content in baked anode (percent weight) 2.0. Asha: ash content in baked anode (percent weight) 0.4. CO2 Emissions From... records. Hw: annual hydrogen content in green anodes (metric tons) 0.005 × GA. BA: annual baked anode...

40 CFR Table F-2 to Subpart F of... - Default Data Sources for Parameters Used for CO2 Emissions

Code of Federal Regulations, 2011 CFR

2011-07-01

... metric ton Al (metric tons C/metric tons Al) Individual facility records. Sa: sulfur content in baked anode (percent weight) 2.0. Asha: ash content in baked anode (percent weight) 0.4. CO2 Emissions From... records. Hw: annual hydrogen content in green anodes (metric tons) 0.005 × GA. BA: annual baked anode...

Process for forming a nickel foil with controlled and predetermined permeability to hydrogen

DOEpatents

Engelhaupt, Darell E.

1981-09-22

The present invention provides a novel process for forming a nickel foil having a controlled and predetermined hydrogen permeability. This process includes the steps of passing a nickel plating bath through a suitable cation exchange resin to provide a purified nickel plating bath free of copper and gold cations, immersing a nickel anode and a suitable cathode in the purified nickel plating bath containing a selected concentration of an organic sulfonic acid such as a napthalene-trisulfonic acid, electrodepositing a nickel layer having the thickness of a foil onto the cathode, and separating the nickel layer from the cathode to provide a nickel foil. The anode is a readily-corrodible nickel anode. The present invention also provides a novel nickel foil having a greater hydrogen permeability than palladium at room temperature.

Lithium-ion diffusion mechanisms in the battery anode material Li(1+x)V(1-x)O₂.

PubMed

Panchmatia, Pooja M; Armstrong, A Robert; Bruce, Peter G; Islam, M Saiful

2014-10-21

Layered Li(1+x)V(1-x)O2 has attracted recent interest as a potential low voltage and high energy density anode material for lithium-ion batteries. A greater understanding of the lithium-ion transport mechanisms is important in optimising such oxide anodes. Here, stoichiometric LiVO2 and Li-rich Li1.07V0.93O2 are investigated using atomistic modelling techniques. Lithium-ion migration is not found in LiVO2, which has also previously shown to be resistant to lithium intercalation. Molecular dynamics simulations of lithiated non-stoichiometric Li(1.07+y)V0.93O2 suggest cooperative interstitial Li(+) diffusion with favourable migration barriers and diffusion coefficients (D(Li)), which are facilitated by the presence of lithium in the transition metal layers; such transport behaviour is important for high rate performance as a battery anode.

Porous membrane electrochemical cell for uranium and transuranic recovery from molten salt electrolyte

DOEpatents

Willit, James L [Ratavia, IL

2007-09-11

An improved process and device for the recovery of the minor actinides and the transuranic elements (TRU's) from a molten salt electrolyte. The process involves placing the device, an electrically non-conducting barrier between an anode salt and a cathode salt. The porous barrier allows uranium to diffuse between the anode and cathode, yet slows the diffusion of uranium ions so as to cause depletion of uranium ions in the catholyte. This allows for the eventual preferential deposition of transuranics present in spent nuclear fuel such as Np, Pu, Am, Cm. The device also comprises an uranium oxidation anode. The oxidation anode is solid uranium metal in the form of spent nuclear fuel. The spent fuel is placed in a ferric metal anode basket which serves as the electrical lead or contact between the molten electrolyte and the anodic uranium metal.

Porous membrane electrochemical cell for uranium and transuranic recovery from molten salt electrolyte

DOEpatents

Willit, James L [Batavia, IL

2010-09-21

An improved process and device for the recovery of the minor actinides and the transuranic elements (TRU's) from a molten salt electrolyte. The process involves placing the device, an electrically non-conducting barrier between an anode salt and a cathode salt. The porous barrier allows uranium to diffuse between the anode and cathode, yet slows the diffusion of uranium ions so as to cause depletion of uranium ions in the catholyte. This allows for the eventual preferential deposition of transuranics present in spent nuclear fuel such as Np, Pu, Am, Cm. The device also comprises an uranium oxidation anode. The oxidation anode is solid uranium metal in the form of spent nuclear fuel. The spent fuel is placed in a ferric metal anode basket which serves as the electrical lead or contact between the molten electrolyte and the anodic uranium metal.

Performance of a passive direct ethanol fuel cell

NASA Astrophysics Data System (ADS)

Pereira, J. P.; Falcão, D. S.; Oliveira, V. B.; Pinto, A. M. F. R.

2014-06-01

Ethanol emerges as an attractive fuel since it is less toxic and has higher energy density than methanol and can be produced from biomass. Direct ethanol fuel cells (DEFCs) appear as a good choice for producing sustainable energy for portable applications. However, they are still far from attaining acceptable levels of power output, since their performance is affected by the slow electrochemical ethanol oxidation and water and ethanol crossover. In the present work, an experimental study on the performance of a passive DEFC is described. Tailored MEAs (membrane electrode assembly) with different catalyst loadings, anode diffusion layers and membranes were tested in order to select optimal working conditions at high ethanol concentrations and low ethanol crossover. The performance increased with an increase of membrane and anode diffusion layer thicknesses and anode catalyst loading. A maximum power density of 1.33 mW cm-2, was obtained using a Nafion 117 membrane, 4 mg cm-2 of Pt-Ru and 2 mg cm-2 of Pt on the anode and cathode catalyst layers, ELAT as anode diffusion layer, carbon cloth as cathode diffusion layer and an ethanol concentration of 2 M. As far as the authors are aware this is the first work reporting an experimental optimization of passive DEFCs.

Molecular Beam-Thermal Desorption Spectrometry (MB-TDS) Monitoring of Hydrogen Desorbed from Storage Fuel Cell Anodes

PubMed Central

Lobo, Rui F. M.; Santos, Diogo M. F.; Sequeira, Cesar A. C.; Ribeiro, Jorge H. F.

2012-01-01

Different types of experimental studies are performed using the hydrogen storage alloy (HSA) MlNi3.6Co0.85Al0.3Mn0.3 (Ml: La-rich mischmetal), chemically surface treated, as the anode active material for application in a proton exchange membrane fuel cell (PEMFC). The recently developed molecular beam—thermal desorption spectrometry (MB-TDS) technique is here reported for detecting the electrochemical hydrogen uptake and release by the treated HSA. The MB-TDS allows an accurate determination of the hydrogen mass absorbed into the hydrogen storage alloy (HSA), and has significant advantages in comparison with the conventional TDS method. Experimental data has revealed that the membrane electrode assembly (MEA) using such chemically treated alloy presents an enhanced surface capability for hydrogen adsorption. PMID:28817043

FINAL REPORT ON GDE GAP CELL

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

Herman, D.; Summers, W.; Danko, E.

2009-09-28

A project has been undertaken to develop an electrochemical cell and support equipment for evaluation of a gas diffusion electrode-based, narrow-electrolyte-gap anode for SO{sub 2} oxidation in the hydrogen production cycle of the hybrid sulfur (HyS) process. The project supported the HyS development program at the Savannah River National Lab (SRNL). The benefits of using a gas diffusion electrode in conjunction with the narrow anolyte gap are being determined through electrochemical polarization testing under a variety conditions, and by comparison to results produced by SRNL and others using anode technologies that have no anolyte gap. These test results indicate thatmore » the NGA cell has low resistance suitable for use in the HyS electrolyzer, exhibits good efficiency at high current densities compared to the direct feed HyS electrolyzer, and indicates robust performance in extended testing over 65 hours. Seepage episodes were mostly caused by port clogging, which can be mitigated in future designs through minor modifications to the hardware. Significant reductions in sulfur crossover have not yet been demonstrated in the NGA configuration compared to in-house direct feed testing, but corroborative sulfur layer analysis is as yet incomplete. Further testing in a single-pass anolyte configuration is recommended for complete evaluation of steady-state electrochemical efficiency and SO{sub 2} crossover in the narrow gap configuration.« less

Lithium Transport in an Amorphous Li xSi Anode Investigated by Quasi-elastic Neutron Scattering

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

Sacci, Robert L.; Lehmann, Michelle L.; Diallo, Souleymane O.

Here, we demonstrate the room temperature mechanochemical synthesis of highly defective Li xSi anode materials and characterization of the Li transport. We probed the Li + self-diffusion using quasi-elastic neutron scattering (QENS) to measure the Li self-diffusion in the alloy. Li diffusion was found to be significantly greater (3.0 × 10 –6 cm 2 s –1) than previously measured crystalline and electrochemically made Li–Si alloys; the energy of activation was determined to be 0.20 eV (19 kJ mol –1). Amorphous Li–Si structures are known to have superior Li diffusion to their crystalline counterparts; therefore, the isolation and stabilization of defectivemore » Li–Si structures may improve the utility of Si anodes for Li-ion batteries.« less

Lithium Transport in an Amorphous Li xSi Anode Investigated by Quasi-elastic Neutron Scattering

DOE PAGES

Sacci, Robert L.; Lehmann, Michelle L.; Diallo, Souleymane O.; ...

2017-04-27

Here, we demonstrate the room temperature mechanochemical synthesis of highly defective Li xSi anode materials and characterization of the Li transport. We probed the Li + self-diffusion using quasi-elastic neutron scattering (QENS) to measure the Li self-diffusion in the alloy. Li diffusion was found to be significantly greater (3.0 × 10 –6 cm 2 s –1) than previously measured crystalline and electrochemically made Li–Si alloys; the energy of activation was determined to be 0.20 eV (19 kJ mol –1). Amorphous Li–Si structures are known to have superior Li diffusion to their crystalline counterparts; therefore, the isolation and stabilization of defectivemore » Li–Si structures may improve the utility of Si anodes for Li-ion batteries.« less

Lack of electricity production by Pelobacter carbinolicus indicates that the capacity for Fe(III) oxide reduction does not necessarily confer electron transfer ability to fuel cell anodes.

PubMed

Richter, Hanno; Lanthier, Martin; Nevin, Kelly P; Lovley, Derek R

2007-08-01

The ability of Pelobacter carbinolicus to oxidize electron donors with electron transfer to the anodes of microbial fuel cells was evaluated because microorganisms closely related to Pelobacter species are generally abundant on the anodes of microbial fuel cells harvesting electricity from aquatic sediments. P. carbinolicus could not produce current in a microbial fuel cell with electron donors which support Fe(III) oxide reduction by this organism. Current was produced using a coculture of P. carbinolicus and Geobacter sulfurreducens with ethanol as the fuel. Ethanol consumption was associated with the transitory accumulation of acetate and hydrogen. G. sulfurreducens alone could not metabolize ethanol, suggesting that P. carbinolicus grew in the fuel cell by converting ethanol to hydrogen and acetate, which G. sulfurreducens oxidized with electron transfer to the anode. Up to 83% of the electrons available in ethanol were recovered as electricity and in the metabolic intermediate acetate. Hydrogen consumption by G. sulfurreducens was important for ethanol metabolism by P. carbinolicus. Confocal microscopy and analysis of 16S rRNA genes revealed that half of the cells growing on the anode surface were P. carbinolicus, but there was a nearly equal number of planktonic cells of P. carbinolicus. In contrast, G. sulfurreducens was primarily attached to the anode. P. carbinolicus represents the first Fe(III) oxide-reducing microorganism found to be unable to produce current in a microbial fuel cell, providing the first suggestion that the mechanisms for extracellular electron transfer to Fe(III) oxides and fuel cell anodes may be different.

Static feed water electrolysis subsystem development

NASA Technical Reports Server (NTRS)

Schubert, Franz H. (Inventor); Grigger, David J. (Inventor)

1991-01-01

This disclosure is directed to an electrolysis cell forming hydrogen and oxygen at spaced terminals. The anode terminal is porous and able to form oxygen within the cell and permit escape of the gaseous oxygen through the anode and out through a flow line in the presence of backpressure. Hydrogen is liberated in the cell at the opposing solid metal cathode which is permeable to hydrogen but not oxygen so that the migratory hydrogen formed in the cell is able to escape from the cell. The cell is maintained at an elevated pressure so that oxygen liberated by the cell is delivered at elevated pressure without pumping to raise the pressure of the oxygen.

Performance and microbial ecology of air-cathode microbial fuel cells with layered electrode assemblies.

PubMed

Butler, Caitlyn S; Nerenberg, Robert

2010-05-01

Microbial fuel cells (MFCs) can be built with layered electrode assemblies, where the anode, proton exchange membrane (PEM), and cathode are pressed into a single unit. We studied the performance and microbial community structure of MFCs with layered assemblies, addressing the effect of materials and oxygen crossover on the community structure. Four MFCs with layered assemblies were constructed using Nafion or Ultrex PEMs and a plain carbon cloth electrode or a cathode with an oxygen-resistant polytetrafluoroethylene diffusion layer. The MFC with Nafion PEM and cathode diffusion layer achieved the highest power density, 381 mW/m(2) (20 W/m(3)). The rates of oxygen diffusion from cathode to anode were three times higher in the MFCs with plain cathodes compared to those with diffusion-layer cathodes. Microsensor studies revealed little accumulation of oxygen within the anode cloth. However, the abundance of bacteria known to use oxygen as an electron acceptor, but not known to have exoelectrogenic activity, was greater in MFCs with plain cathodes. The MFCs with diffusion-layer cathodes had high abundance of exoelectrogenic bacteria within the genus Geobacter. This work suggests that cathode materials can significantly influence oxygen crossover and the relative abundance of exoelectrogenic bacteria on the anode, while PEM materials have little influence on anode community structure. Our results show that oxygen crossover can significantly decrease the performance of air-cathode MFCs with layered assemblies, and therefore limiting crossover may be of particular importance for these types of MFCs.

Fabrication and characterization of anode-supported micro-tubular solide oxide fuel cell by phase inversion method

NASA Astrophysics Data System (ADS)

Ren, Cong

Nowadays, the micro-tubular solid oxide fuel cells (MT-SOFCs), especially the anode supported MT-SOFCs have been extensively developed to be applied for SOFC stacks designation, which can be potentially used for portable power sources and vehicle power supply. To prepare MT-SOFCs with high electrochemical performance, one of the main strategies is to optimize the microstructure of the anode support. Recently, a novel phase inversion method has been applied to prepare the anode support with a unique asymmetrical microstructure, which can improve the electrochemical performance of the MT-SOFCs. Since several process parameters of the phase inversion method can influence the pore formation mechanism and final microstructure, it is essential and necessary to systematically investigate the relationship between phase inversion process parameters and final microstructure of the anode supports. The objective of this study is aiming at correlating the process parameters and microstructure and further preparing MT-SOFCs with enhanced electrochemical performance. Non-solvent, which is used to trigger the phase separation process, can significantly influence the microstructure of the anode support fabricated by phase inversion method. To investigate the mechanism of non-solvent affecting the microstructure, water and ethanol/water mixture were selected for the NiO-YSZ anode supports fabrication. The presence of ethanol in non-solvent can inhibit the growth of the finger-like pores in the tubes. With the increasing of the ethanol concentration in the non-solvent, a relatively dense layer can be observed both in the outside and inside of the tubes. The mechanism of pores growth and morphology obtained by using non-solvent with high concentration ethanol was explained based on the inter-diffusivity between solvent and non-solvent. Solvent and non-solvent pair with larger Dm value is benefit for the growth of finger-like pores. Three cells with different anode geometries was prepared, La0.85Sr0.15MnO 3 (LSM) was selected as the cathode. Cells were tested at 800°C using humidified H2 as fuel. Cell with anode prepared by using pure water as non-solvent shows a maximum power density up to 437mW/cm 2. By comparing the anode geometry and electrochemical performance, it indicated that microstructure with longer finger-like pores and thinner macrovoid free layer close to the inner side of the tube is benefit to cell performance. Another factor that can affect the microstructure of anode support is the ratio of solvent and polymer binder. In this research, anode-supported MT-SOFCs have been fabricated by phase inversion method. The effect of the viscosity of the casting slurry on the microstructure of YSZ-NiO anode support has been investigated. The microstructure of the YSZ-NiO support can be effectively controlled by varying the slurry composition with different solvent and polymer binder content. Gas permeation and mechanical strength of the YSZ-NiO support have been measured and four YSZ-NiO anode supports have been chosen for subsequent cell fabrication. The effective conductivity of the different anode supports has been measured at room temperature after reduced. Anode-supported single cells with YSZ electrolyte and LSM/YSZ cathode are fabricated and tested. Maximum cell power densities of 606 mWcm-2, 449 mWcm -2, 339 mWcm-2 and 253 mWcm-2 have been obtained respectively at 750 °C with humidified hydrogen as fuel and ambient air as oxidant. The correlation between the cell electrochemical performance and anode microstructures has been discussed. Adjusting the slurry composition by introducing additive is also an effective approach to tailor the microstructure of the anode support. Poly(ethylene glycol) (PEG), which is a common applied polymer additive, was selected to fabricate the YSZ-NiO anode supports. The effect of molecular weight and amount of PEG additive on the thermodynamics of the casting solutions was characterized by measuring the coagulation value. Viscosity of the casting slurries was also measured and the influence of PEG additive on viscosity was studied and discussed. The presence of PEG in the casting slurry can greatly influence the final anode support microstructure. Based on the microstructure result and the measured gas permeation value, two anode supports were selected for cell fabrication. For cell with the anode support fabricated using slurry with PEG additive, a maximum cell power density of 704 mWcm-2 is obtained at 750 oC with humidified hydrogen as fuel and ambient air as oxidant; cell fabricated without any PEG additive shows the peak cell power density of 331 mWcm-2. The relationship between anode microstructure and cell performance was discussed. Anode-supported micro-tubular solid oxide fuel cells (MT-SOFCs) based on BaZr0.1Ce0.7Y0.1Yb0.1O 3-delta (BZCYYb) proton-conducting electrolyte have been prepared using a phase inversion method. Three sulfur-free polymer binder candidates ethyl cellulose (EC), polyvinylidene fluoride (PVDF), polyetherimide (PEI) and sulfur-containing polythersulfone (PESf) were used as polymer binders to fabricate NiO-BZCYYb anode. The overall influence of polymer binder on the anode supports was evaluated. Sulfide impurity generated from PESf was revealed by XRD and X-ray photoelectron spectroscopy (XPS). The difference in the anode microstructure for samples fabricated by different polymer binders was examined by scanning electron microscope (SEM) and analyzed by measuring the gas permeation data of the reduced samples. Single cells based on different anode supports were characterized in anode-supported MT-SOFCs with the cell configuration of Ni-BZCYYb anode, BZCYYb electrolyte and La0.6Sr 0.4Co0.2Fe0.8O3-delta (LSCF)-BZCYYb cathode at 650 °C using hydrogen as fuel and ambient air as oxidant. MT-SOFCs of the anode fabricated using PEI show maximum power density of 0.45 Wcm -2 compared with 0.35 Wcm-2 for cells fabricated with PESf. The difference in cell performance was attributed to the phase purity of the anode fabricated by different polymer binders. Sulfur-free polymer binder PEI exhibits advantages over the commonly applied PESf and other sulfur-free polymer binder candidates. To eliminate the skin layer formed close to the inner side of the tubular sample when using the phase inversion method. Polyethersulfone (PESf)-polyethylenimine (PEI) blend was employed as the polymer binder to fabricate the micro-tubular solid oxide fuel cells (MT-SOFCs). The potential impurity introduced in the anode support by the polymer binder was examined by XPS and the resulting novel microstructure was analyzed based on the backscattered electron (BSE) images. Cells fabricated with blend polymer binder showed significantly enhanced power output compared with those cells only fabricated with PEI or PESf. The improved cell performance demonstrated that using blend polymer as binder is a promising and versatile approach for MT-SOFC fabrication via phase inversion method. Finally, to investigate the effect of the anode microstructure on the total cell performance, two types of anode support with different microstructure were prepared via the phase inversion method at different temperature. Cells fabricated based on these two anode supports were tested at 750 °C with hydrogen or hydrogen mixture with fuel gas. The measured current density-voltage (I-V) curves were fitted by a polarization model, and several parameters were archived through the modeling process. The influence of the anode support on the total cell performance was discussed based on the calculated result.

Conductivity dependence of lithium diffusivity and electrochemical performance for electrospun TiO2 fibers

NASA Astrophysics Data System (ADS)

Qing, Rui; Liu, Li; Bohling, Christian; Sigmund, Wolfgang

2015-01-01

TiO2 is one of the most exciting anode candidates for safe application in lithium ion batteries. However, its low intrinsic electronic conductivity limits application. In this paper, a simple sol-gel based route is presented to produce nanosize TiO2 fibers with 119 ± 27 nm diameters via electrospinning. Subsequent calcination in various atmospheres was applied to achieve anatase and anatase-rutile mixed phase crystallites with and without carbon coating. The crystallite size was 5 nm for argon calcined fibers and 13-20 nm for air calcined fibers. Argon calcined TiO2 nanofibers exhibited electronic conductivity orders of magnitude higher than those of air-calcined samples. Lithium diffusivity was increased by one time and specific capacity by 26.9% due to the enhanced conductivity. It also had a different intercalation mechanism of lithium. Hydrogen post heat-treatment was found to benefit electronic conductivity (by 3-4.5 times), lithium diffusivity (1.5-2 times) and consequently the high rate performance of the TiO2 nanofibers (over 80%). The inner mechanism and structure-property relations among these parameters were also discussed.

Electrochemical generation of oxygen. 1: The effects of anions and cations on hydrogen chemisorption and anodic oxide film formation on platinum electrode. 2: The effects of anions and cations on oxygen generation on platinum electrode

NASA Technical Reports Server (NTRS)

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

1975-01-01

The effects were studied of anions and cations on hydrogen chemisorption and anodic oxide film formation on Pt by linear sweep voltammetry, and on oxygen generation on Pt by potentiostatic overpotential measurement. The hydrogen chemisorption and anodic oxide film formation regions are greatly influenced by anion adsorption. In acids, the strongly bound hydrogen occurs at more cathodic potential when chloride and sulfate are present. Sulfate affects the initial phase of oxide film formation by produced fine structure while chloride retards the oxide-film formation. In alkaline solutions, both strongly and weakly bound hydrogen are influenced by iodide, cyanide, and barium and calcium cations. These ions also influence the oxide film formation. Factors considered to explain these effects are discussed. The Tafel slope for oxygen generation was found to be independent on the oxide thickness and the presence of cations or anions. The catalytic activity indicated by the exchange current density was observed decreasing with increasing oxide layer thickness, only a minor dependence on the addition of certain cations and anions was found.

Fully Depleted Ti-Nb-Ta-Zr-O Nanotubes: Interfacial Charge Dynamics and Solar Hydrogen Production.

PubMed

Chiu, Yi-Hsuan; Lai, Ting-Hsuan; Chen, Chun-Yi; Hsieh, Ping-Yen; Ozasa, Kazunari; Niinomi, Mitsuo; Okada, Kiyoshi; Chang, Tso-Fu Mark; Matsushita, Nobuhiro; Sone, Masato; Hsu, Yung-Jung

2018-05-01

Poor kinetics of hole transportation at the electrode/electrolyte interface is regarded as a primary cause for the mediocre performance of n-type TiO 2 photoelectrodes. By adopting nanotubes as the electrode backbone, light absorption and carrier collection can be spatially decoupled, allowing n-type TiO 2 , with its short hole diffusion length, to maximize the use of the available photoexcited charge carriers during operation in photoelectrochemical (PEC) water splitting. Here, we presented a delicate electrochemical anodization process for the preparation of quaternary Ti-Nb-Ta-Zr-O mixed-oxide (denoted as TNTZO) nanotube arrays and demonstrated their utility in PEC water splitting. The charge-transfer dynamics for the electrodes was investigated using time-resolved photoluminescence, electrochemical impedance spectroscopy, and the decay of open-circuit voltage analysis. Data reveal that the superior photoactivity of TNTZO over pristine TiO 2 originated from the introduction of Nd, Ta, and Zr elements, which enhanced the amount of accessible charge carriers, modified the electronic structure, and improved the hole injection kinetics for expediting water splitting. By modulating the water content of the electrolyte employed in the anodization process, the wall thickness of the grown TNTZO nanotubes can be reduced to a size smaller than that of the depletion layer thickness, realizing a fully depleted state for charge carriers to further advance the PEC performance. Hydrogen evolution tests demonstrate the practical efficacy of TNTZO for realizing solar hydrogen production. Furthermore, with the composition complexity and fully depleted band structure, the present TNTZO nanotube arrays may offer a feasible and universal platform for the loading of other semiconductors to construct a sophisticated heterostructure photoelectrode paradigm, in which the photoexcited charge carriers can be entirely utilized for efficient solar-to-fuel conversion.

Investigations of an Environmentally Induced Long Duration Hall Thruster Start Transient (PREPRINT)

DTIC Science & Technology

2006-02-06

Hall thruster start transient is produced by exposure of the thruster to ambient laboratory atmosphere. This behavior was first observed during operation of a cluster of four 200 W BHT-200 Hall effect thrusters where large anode discharge fluctuations, visible as increased anode current and a diffuse plume structure, occurred in an apparently random manner. During operation of a single thruster, the start transient appears as a quickly rising and later smoothly decaying elevated anode current with a diffuse plume that persists for less than 500 seconds. The start transient

Synthesis and photo-electrochemical properties of spinel-ferrite-coated hematite for solar water splitting

NASA Astrophysics Data System (ADS)

Selvaraj, Seenivasan; Moon, Hee; Kim, Do-Heyoung

2018-01-01

Photo-electrochemical water splitting with hematite photo-anodes under solar irradiation has attracted considerable attention as regards the production of renewable hydrogen energy. However, many challenges remain unresolved, as the full contribution of the catalytic over-layers has not been fully realized. Herein, we incorporate uniform spinel nickel-ferrite over-layers in hematite photo-anodes to obtain an improved understanding of the associated intrinsic changes. We achieve a 1.5-mA/cm2 photo-current density at 1.23 VRHE (RHE: reversible hydrogen electrode) under one-sun illumination conditions, along with a negative shift of 200 mV in the onset potential, for NiFe2O4-coated Sn-doped hematite photo-anodes. Fundamental electrochemical analyses clearly show that the shift in the onset potential is predominantly due to the enhanced photo-voltage development inside the hematite, rather than being purely caused by the interfacial kinetics. These insights reveal a new direction for fundamental research on photo-anodes towards fabrication of more efficient photo-anode systems.

Hydrogen production from switchgrass via a hybrid pyrolysis-microbial electrolysis process

DOE PAGES

Lewis, Alex J.; Ren, Shoujie; Ye, Philip; ...

2015-06-30

A new approach to hydrogen production using a hybrid pyrolysis-microbial electrolysis process is described. The aqueous stream generated during pyrolysis of switchgrass was used as a substrate for hydrogen production in a microbial electrolysis cell, achieving a maximum hydrogen production rate of 4.3 L H2/L-day at a loading of 10 g COD/L-anode-day. Hydrogen yields ranged from 50 3.2% to76 0.5% while anode coulombic efficiency ranged from 54 6.5% to 96 0.21%, respectively. Significant conversion of furfural, organic acids and phenolic molecules was observed under both batch and continuous conditions. The electrical and overall energy efficiency ranged from 149-175% and 48-63%,more » respectively. The results demonstrate the potential of the pyrolysis-microbial electrolysis process as a sustainable and efficient route for production of renewable hydrogen with significant implications for hydrocarbon production from biomass.« less

Steam reforming of fuel to hydrogen in fuel cells

DOEpatents

Fraioli, Anthony V.; Young, John E.

1984-01-01

A fuel cell capable of utilizing a hydrocarbon such as methane as fuel and having an internal dual catalyst system within the anode zone, the dual catalyst system including an anode catalyst supporting and in heat conducting relationship with a reforming catalyst with heat for the reforming reaction being supplied by the reaction at the anode catalyst.

Low-Energy Catalytic Electrolysis for Simultaneous Hydrogen Evolution and Lignin Depolymerization.

PubMed

Du, Xu; Liu, Wei; Zhang, Zhe; Mulyadi, Arie; Brittain, Alex; Gong, Jian; Deng, Yulin

2017-03-09

Here, a new proton-exchange-membrane electrolysis is presented, in which lignin was used as the hydrogen source at the anode for hydrogen production. Either polyoxometalate (POM) or FeCl 3 was used as the catalyst and charge-transfer agent at the anode. Over 90 % Faraday efficiency was achieved. In a thermal-insulation reactor, the heat energy could be maintained at a very low level for continuous operation. Compared to the best alkaline-water electrolysis reported in literature, the electrical-energy consumption could be 40 % lower with lignin electrolysis. At the anode, the Kraft lignin (KL) was oxidized to aromatic chemicals by POM or FeCl 3 , and reduced POM or Fe ions were regenerated during the electrolysis. Structure analysis of the residual KL indicated a reduction of the amount of hydroxyl groups and the cleavage of ether bonds. The results suggest that POM- or FeCl 3 -mediated electrolysis can significantly reduce the electrolysis energy consumption in hydrogen production and, simultaneously, depolymerize lignin to low-molecular-weight value-added aromatic chemicals. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Experimental and analytical analysis of polarization and water transport behaviors of hydrogen alkaline membrane fuel cell

NASA Astrophysics Data System (ADS)

Huo, Sen; Zhou, Jiaxun; Wang, Tianyou; Chen, Rui; Jiao, Kui

2018-04-01

Experimental test and analytical modeling are conducted to investigate the operating behavior of an alkaline electrolyte membrane (AEM) fuel cell fed by H2/air (or O2) and explore the effect of various operating pressures on the water transfer mechanism. According to the experimental test, the cell performance is greatly improved through increasing the operating pressure gradient from anode to cathode which leads to significant liquid water permeation through the membrane. The high frequency resistance of the A901 alkaline membrane is observed to be relatively stable as the operating pressure varies based on the electrochemical impedance spectroscopy (EIS) method. Correspondingly, based on the modeling prediction, the averaged water content in the membrane electrode assembly (MEA) does not change too much which leads to the weak variation of membrane ohmic resistance. This reveals that the performance enhancement should give the credit to better electro-chemical reaction kinetics for both the anode and cathode, also prone by the EIS results. The reversion of water back diffusion direction across the membrane is also observed through analytical solution.

Poisoning of Ni-Based anode for proton conducting SOFC by H2S, CO2, and H2O as fuel contaminants

NASA Astrophysics Data System (ADS)

Sun, Shichen; Awadallah, Osama; Cheng, Zhe

2018-02-01

It is well known that conventional solid oxide fuel cells (SOFCs) based on oxide ion conducting electrolyte (e.g., yttria-stabilized zirconia, YSZ) and nickel (Ni) - ceramic cermet anodes are susceptible to poisoning by trace amount of hydrogen sulfide (H2S) while not significantly impacted by the presence of carbon dioxide (CO2) and moisture (H2O) in the fuel stream unless under extreme operating conditions. In comparison, the impacts of H2S, CO2, and H2O on proton-conducting SOFCs remain largely unexplored. This study aims at revealing the poisoning behaviors caused by H2S, CO2, and H2O for proton-conducting SOFCs. Anode-supported proton-conducting SOFCs with BaZe0.1Ce0.7Y0.1Yb0.1O3 (BZCYYb) electrolyte and Ni-BZCYYb anode and La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) cathode as well as Ni-BZCYYb/BZCYYb/Ni-BZCYYb anode symmetrical cells were subjected to low ppm-level H2S or low percentage-level CO2 or H2O in the hydrogen fuel, and the responses in cell electrochemical behaviors were recorded. The results suggest that, contrary to conventional SOFCs that show sulfur poisoning and CO2 and H2O tolerance, such proton-conducting SOFCs with Ni-BZCYYb cermet anode seem to be poisoned by all three types of "contaminants". Beyond that, the implications of the experimental observations on understanding the fundamental mechanism of anode hydrogen electrochemical oxidation reaction in proton conducting SOFCs are also discussed.

Application of SR Methods for the Study of Nanocomposite Materials for Hydrogen Energy

NASA Astrophysics Data System (ADS)

Sadykov, V. A.; Pavlova, S. N.; Vinokurov, Z. S.; Shmakov, A. N.; Eremeev, N. F.; Fedorova, Yu. E.; Yakimchuk, E. P.; Kriventsov, V. V.; Bolotov, V. A.; Tanashev, Yu. Yu.; Sadovskaya, E. M.; Cherepanova, S. V.; Zolotarev, K. V.

This work summarizes results of synchrotron radiation (SR) studies of the real/defect structure of nanocrystalline/nanocomposite oxide materials, which determines their functional properties in hydrogen energy field as catalysts and mixed ionic electronic conductors (cathodes and anodes of solid oxide fuel cells, oxygen separation membranes). For nanocrystalline ceria-zirconia mixed oxide prepared via modified Pechini route using ethanol solution of reagents, a high spatial uniformity of cations distribution between domains along with the oxygen sublattice deficiency revealed by full-profile Rietveld refinement of SR diffraction data provide structure disordering enhancing oxygen mobility. For PrNi0.5Co0.5O3-δ - Ce0.9Y0.1O2-δ nanocomposite extensive transfer of Pr cations into fluorite domains generates a new path of fast oxygen diffusion along chains of Pr3+ - Pr4+ cations as directly proved by analysis of the unit cell relaxation after changing pO2 in perfect agreement with data obtained by oxygen isotope heteroexchange.

Ab initio study of novel carbon nanofoam structure as an anode material for Li secondary battery

NASA Astrophysics Data System (ADS)

Park, Hanjin; Park, Sora; Kang, Seoung-Hun; Kwon, Young-Kyun

2014-03-01

Using ab inito density functional theory, we investigate the adsorption and diffusion properties of Li atoms on a new carbon nanostructure, which may be used as an anode of Li secondary battery. We focus on a special carbon nanofoam structure consisting of Schwarzite structures with negative Gaussian curvature as core parts, which are interconnected through (4,4) CNT segments. Considering the symmetry of the nanofoam structure, we find various Li adsorption sites exhibiting relatively large binding energies (>= 2 . 00 eV). Based on these adsorption sites, we identify several diffusion paths on the outside or inside surface of the nanofoam structure and examine the diffusion barriers along the paths. Our results show that Li atom can diffuse almost freely due to its low energy barriers on both outside and inside surfaces. Finally, we also evaluate the energy gain tendency and the volume expansion as well as the average binding energy while adding Li atoms to estimate the Li-capacity and recyclability of the system, which are important characterisitics for anode materials. We conclude that the carbon nanofoam structure would be better as an anode material than graphite in Li capacity and volume expansion.

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

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

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

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

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

DOE PAGES

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

2018-03-09

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

Experimental study on the optimal purge duration of a proton exchange membrane fuel cell with a dead-ended anode

NASA Astrophysics Data System (ADS)

Lin, Yu-Fen; Chen, Yong-Song

2017-02-01

When a proton exchange membrane fuel cell (PEMFC) is operated with a dead-ended anode, impurities gradually accumulate within the anode, resulting in a performance drop. An anode purge is thereby ultimately required to remove impurities within the anode. A purge strategy comprises purge interval (valve closed) and purge duration (valve is open). A short purge interval causes frequent and unnecessary activation of the valve, whereas a long purge interval leads to excessive impurity accumulation. A short purge duration causes an incomplete performance recovery, whereas a long purge duration results in low hydrogen utilization. In this study, a series of experimental trials was conducted to simultaneously measure the hydrogen supply rate and power generation of a PEMFC at a frequency of 50 Hz for various operating current density levels and purge durations. The effect of purge duration on the cell's energy efficiency was subsequently analyzed and discussed. The results showed that the optimal purge duration for the PEMFC was approximately 0.2 s. Based on the results of this study, a methodical process for determining optimal purge durations was ultimately proposed for widespread application. Purging approximately one-fourth of anode gas can obtain optimal energy efficiency for a PEMFC with a dead-ended anode.

Novel strategy to mitigate cathode catalyst degradation during air/air startup cycling via the atmospheric resistive switching mechanism of a hydrogen anode with a platinum catalyst supported on tantalum-doped titanium dioxide

NASA Astrophysics Data System (ADS)

Shintani, Haruhiko; Kojima, Yuya; Kakinuma, Katsuyoshi; Watanabe, Masahiro; Uchida, Makoto

2015-10-01

We propose a new strategy for alleviating the reverse current phenomenon using a unique ;atmospheric resistive switching mechanism; (ARSM) of a metal oxide semiconductor support, such that the electrical resistivity changes depending on the gas atmosphere. The membrane-electrode assembly (MEA) using Ta-doped TiO2-supported platinum (Pt/Ta-TiO2) as the anode catalyst showed approximately one order of magnitude greater resistance in air than in hydrogen. The overpotential of the hydrogen oxidation reaction was negligible up to at least 1.5 A cm-2. The losses of electrochemically active surface area and carbon corrosion of the cathode catalyst during air/air startup cycling were significantly suppressed by the use of the Pt/Ta-TiO2 anode. The decrease in the degradation is attributed to a reduction of the reverse current due to a low oxygen reduction reaction rate at the anode, which showed high resistivity in air. These results demonstrate the effectiveness of the ARSM in mitigating cathode catalyst degradation during air/air startup cycling.

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.

Design and optimization of anode flow field of a large proton exchange membrane fuel cell for high hydrogen utilization

NASA Astrophysics Data System (ADS)

Yesilyurt, Serhat; Rizwandi, Omid

2016-11-01

We developed a CFD model of the anode flow field of a large proton exchange membrane fuel cell that operates under the ultra-low stoichiometric (ULS) flow conditions which intend to improve the disadvantages of the dead-ended operation such as severe voltage transient and carbon corrosion. Very small exit velocity must be high enough to remove accumulated nitrogen, and must be low enough to retain hydrogen in the active area. Stokes equations are used to model the flow distribution in the flow field, Maxwell-Stefan equations are used to model the transport of the species, and a voltage model is developed to model the reactions kinetics. Uniformity of the distribution of hydrogen concentration is quantified as the normalized area of the region in which the hydrogen mole fraction remains above a certain level, such as 0.9. Geometry of the anode flow field is modified to obtain optimal configuration; the number of baffles at the inlet, width of the gaps between baffles, width of the side gaps, and length of the central baffle are used as design variables. In the final design, the hydrogen-depleted region is less than 0.2% and the hydrogen utilization is above 99%. This work was supported by The Scientific and Technolo-gical Research Council of Turkey, TUBITAK-213M023.

Steam reforming of fuel to hydrogen in fuel cell

DOEpatents

Young, J.E.; Fraioli, A.V.

1983-07-13

A fuel cell is described capable of utilizing a hydrocarbon such as methane as fuel and having an internal dual catalyst system within the anode zone, the dual catalyst system including an anode catalyst supporting and in heat conducting relationship with a reforming catalyst with heat for the reforming reaction being supplied by the reaction at the anode catalyst.

Fabrication and electrochemical performance of nickel- and gadolinium-doped ceria-infiltrated La0·2Sr0·8TiO3 anodes for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Lee, Min-Jin; Shin, Jae-Hwa; Ji, Mi-Jung; Hwang, Hae-Jin

2018-01-01

In this work, nickel and gadolinium-doped ceria (GDC)-infiltrated lanthanum strontium titanate (LST) anodes are fabricated, and their electrode performances under a hydrogen atmosphere is investigated in terms of the Ni:GDC ratios and cell operating temperature. The Ni/GDC-infiltrated LST anode exhibits excellent electrode performance in comparison with the Ni- or GDC-infiltrated anodes, which is attributed to the synergistic effect of an extended triple-phase boundary length by GDC and good catalytic activity for hydrogen oxidation because of the Ni particles. The polarization resistances (Rp) of Ni/GDC-infiltrated LST are 0.07, 0.08, and 0.12 Ω cm2 at 800, 750, and 700 °C, respectively, which are approximately three orders of magnitude lower than that of the LST anode (68.5 Ω cm2 at 700 °C). The effect of Ni and GDC on the electrochemical performance of LST was also investigated by using electrochemical impedance spectroscopy (EIS). The anode polarization resistance (Rp) is confirmed to be dependent on the content and dispersion state (microstructure) of the Ni and GDC nanoparticles.

Corrosion behavior of austenitic alloy 690 under anodic and cathodic potentials

NASA Astrophysics Data System (ADS)

Dutta, R. S.; Dey, G. K.; Lobo, A.; Purandare, R.; Kulkarni, S. K.

2002-05-01

The corrosion behavior of austenitic alloy 690 in a solution-annealed condition has been evaluated with the application of anodic as well as cathodic potentials in an acidic chloride solution at room temperature (RT). In a 0.5M H2SO4 + 0.5M NaCl solution, the alloy displayed active-passive pitting behavior with the application of an anodic potential. Surface films, formed at the onset and later stage of the passive region, were characterized using X-ray photoelectron spectroscopy (XPS). The XPS revealed that the surface film formed at the onset of passivity (+ 100 mV SCE) consisted of Cr(OH)3, without any Fe+3/Fe+2. The presence of nickel in the film was found in a transition state of Ni+2 and Ni0. The passive film formed at the higher anodic potential (+ 700 mV SCE) consisted of Cr2O3 without any Fe+3/Fe+2 or even Ni+2/Ni0. Microscopic studies of alloy 690 after anodic polarization in an acidic chloride solution revealed pitting, which was found to be initiated at large, faceted TiN-type inclusions. The susceptibility of the alloy to hydrogen embrittlement has been investigated by conducting cathodic charging of the tensile samples in a 0.5M H2SO4 solution at RT and by subsequent tensile testing of the charged samples in air at a strain rate of 1.3 × 10-4 s-1 up to fracture. An indication toward hydrogen-induced ductility loss was noticed for the samples of the alloy, which is believed to be attributable to a hydrogen-enhanced microvoid growth process. Since the microvoid growth process occurs at the last stage of fracture, the effect of hydrogen on the ductility of the alloy is little.

Polybenzimidazole-membrane-based PEM fuel cell in the temperature range of 120-200 °C

NASA Astrophysics Data System (ADS)

Zhang, Jianlu; Tang, Yanghua; Song, Chaojie; Zhang, Jiujun

Phosphoric acid-doped polybenzimidazole-membrane-based PEM fuel cells were tested in the temperature range of 120-200 °C, with ambient backpressure and 0% RH. AC impedance spectroscopy, surface cyclic voltammetry and fuel cell performance simulation were used to obtain the exchange current densities for the cathodic oxygen reduction reaction (ORR) and anodic hydrogen oxidation reaction (HOR) on platinum-based catalysts at such high temperatures. The activation energies for ORR, HOR and membrane conductivity were also obtained separately. The results showed that temperature significantly affects the charger transfer and gas (O 2 and H 2) diffusion resistances. The effect of O 2 stoichiometry (ST air) on fuel cell performance was also investigated. Increasing ST air can effectively increase the O 2 partial pressure in the feed air, leading to improvements in both the thermodynamics and the kinetics of the fuel cell reactions. In addition, it was observed that increasing ST air could also improve the gas diffusion processes.

Anode reactive bleed and injector shift control strategy

DOEpatents

Cai, Jun [Rochester, NY; Chowdhury, Akbar [Pittsford, NY; Lerner, Seth E [Honeoye Falls, NY; Marley, William S [Rush, NY; Savage, David R [Rochester, NY; Leary, James K [Rochester, NY

2012-01-03

A system and method for correcting a large fuel cell voltage spread for a split sub-stack fuel cell system. The system includes a hydrogen source that provides hydrogen to each split sub-stack and bleed valves for bleeding the anode side of the sub-stacks. The system also includes a voltage measuring device for measuring the voltage of each cell in the split sub-stacks. The system provides two levels for correcting a large stack voltage spread problem. The first level includes sending fresh hydrogen to the weak sub-stack well before a normal reactive bleed would occur, and the second level includes sending fresh hydrogen to the weak sub-stack and opening the bleed valve of the other sub-stack when the cell voltage spread is close to stack failure.

Numerical Solution of Moving Phase Boundary and Diffusion-Induced Stress of Sn Anode in the Lithium-Ion Battery

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

Chen, Chun-Hao; Chason, Eric; Guduru, Pradeep R.

Here, we have previously observed a large transient stress in Sn film anodes at the beginning of the Sn-Li 2Sn 5 phase transformation. To understand this behavior, we use numerical modeling to simulate the kinetics of the 1-D moving boundary and Li diffusion in the Sn anodes. A mixture of diffusion-controlled and interface-controlled kinetics is found. The Li concentration in the Li 2Sn 5 phase remains near a steady-state profile as the phase boundary propagates, whereas the Li diffusion in Sn is more complicated. Li continuously diffuses into the Sn layer and produces a supersaturation; the Li can then diffusemore » toward the Sn/Li 2Sn 5 interface and contribute to further phase transformation. Finally, the evolution of Li concentration in the Sn induces strain which involves rate-dependent plasticity and elastic unloading, resulting in the complex stress evolution that is observed. In the long term, the measured stress is dominated by the stress in the growing Li 2Sn 5 phase.« less

Numerical Solution of Moving Phase Boundary and Diffusion-Induced Stress of Sn Anode in the Lithium-Ion Battery

DOE PAGES

Chen, Chun-Hao; Chason, Eric; Guduru, Pradeep R.

2017-08-02

Here, we have previously observed a large transient stress in Sn film anodes at the beginning of the Sn-Li 2Sn 5 phase transformation. To understand this behavior, we use numerical modeling to simulate the kinetics of the 1-D moving boundary and Li diffusion in the Sn anodes. A mixture of diffusion-controlled and interface-controlled kinetics is found. The Li concentration in the Li 2Sn 5 phase remains near a steady-state profile as the phase boundary propagates, whereas the Li diffusion in Sn is more complicated. Li continuously diffuses into the Sn layer and produces a supersaturation; the Li can then diffusemore » toward the Sn/Li 2Sn 5 interface and contribute to further phase transformation. Finally, the evolution of Li concentration in the Sn induces strain which involves rate-dependent plasticity and elastic unloading, resulting in the complex stress evolution that is observed. In the long term, the measured stress is dominated by the stress in the growing Li 2Sn 5 phase.« less

Final Report

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

Chidambaram, Dev; Misra, Mano; Heske, Clemens

2014-12-21

The objectives included: Develop high efficiency metal oxide nanotubular array photo-anodes for generating hydrogen by water splitting; Develop density functional theory to understand the effect of the morphology of the nanotubes on the photo-electrochemical (PEC) properties of the photo-anodes; Develop kinetics and formation mechanism of the metal oxide nanotubes under different synthesis conditions; Develop combinatorial approach to prepare hybrid photo-anodes having multiple hetero-atoms incorporation in a single photo anode; Improve the durability of the material; and Scale up the laboratory demonstration to production unit.

Method of detecting defects in ion exchange membranes of electrochemical cells by chemochromic sensors

DOEpatents

Brooker, Robert Paul; Mohajeri, Nahid

2016-01-05

A method of detecting defects in membranes such as ion exchange membranes of electrochemical cells. The electrochemical cell includes an assembly having an anode side and a cathode side with the ion exchange membrane in between. In a configuration step a chemochromic sensor is placed above the cathode and flow isolation hardware lateral to the ion exchange membrane which prevents a flow of hydrogen (H.sub.2) between the cathode and anode side. The anode side is exposed to a first reactant fluid including hydrogen. The chemochromic sensor is examined after the exposing for a color change. A color change evidences the ion exchange membrane has at least one defect that permits H.sub.2 transmission therethrough.

Penta-graphene: A Promising Anode Material as the Li/Na-Ion Battery with Both Extremely High Theoretical Capacity and Fast Charge/Discharge Rate.

PubMed

Xiao, Bo; Li, Yan-Chun; Yu, Xue-Fang; Cheng, Jian-Bo

2016-12-28

Recently, a new two-dimensional (2D) carbon allotrope named penta-graphene was theoretically proposed ( Zhang , S. ; et al. Proc. Natl. Acad. Sci. U.S.A. 2015 , 112 , 2372 ) and has been predicted to be the promising candidate for broad applications due to its intriguing properties. In this work, by using first-principles simulation, we have further extended the potential application of penta-graphene as the anode material for a Li/Na-ion battery. Our results show that the theoretical capacity of Li/Na ions on penta-graphene reaches up to 1489 mAh·g -1 , which is much higher than that of most of the previously reported 2D anode materials. Meanwhile, the calculated low open-circuit voltages (from 0.24 to 0.60 V), in combination with the low diffusion barriers (≤0.33 eV) and the high electronic conductivity during the whole Li/Na ions intercalation processes, further show the advantages of penta-graphene as the anode material. Particularly, molecular dynamics simulation (300 K) reveals that Li ion could freely diffuse on the surface of penta-graphene, and thus the ultrafast Li ion diffusivity is expected. Superior performance of penta-graphene is further confirmed by comparing with the other 2D anode materials. The light weight and unique atomic arrangement (with isotropic furrow paths on the surface) of penta-graphene are found to be mainly responsible for the high Li/Na ions storage capacity and fast diffusivity. In this regard, except penta-graphene, many other recently proposed 2D metal-free materials with pentagonal Cairo-tiled structures may be the potential candidates as the Li/Na-ion battery anodes.

Preparation and evaluation of advanced catalysts for phosphoric acid fuel cells

NASA Technical Reports Server (NTRS)

Stonehart, P.; Baris, J.; Hockmuth, J.; Pagliaro, P.

1984-01-01

The platinum electrocatalysts were characterized for their crystallite sizes and the degree of dispersion on the carbon supports. One application of these electrocatalysts was for anodic oxidation of hydrogen in hot phosphoric acid fuel cells, coupled with the influence of low concentrations of carbon monoxide in the fuel gas stream. In a similar way, these platinum on carbon electrocatalysts were evaluated for oxygen reduction in hot phosphoric acid. Binary noble metal alloys were prepared for anodic oxidation of hydrogen and noble metal-refractory metal mixtures were prepared for oxygen reduction. An exemplar alloy of platinum and palladium (50/50 atom %) was discovered for anodic oxidation of hydrogen in the presence of carbon monoxide, and patent disclosures were submitted. For the cathode, platinum-vanadium alloys were prepared showing improved performance over pure platinum. Preliminary experiments on electrocatalyst utilization in electrode structures showed low utilization of the noble metal when the electrocatalyst loading exceeded one weight percent on the carbon.

FLUORINE CELL ANODE ASSEMBLY

DOEpatents

Cable, R.E.; Goode, W.B. Jr.; Henderson, W.K.; Montillon, G.H.

1962-06-26

An improved anode assembly is deslgned for use in electrolytlc cells ln the productlon of hydrogen and fluorlne from a moIten electrolyte. The anode assembly comprises a copper post, a copper hanger supported by the post, a plurality of carbon anode members, and bolt means for clamplng half of the anode members to one slde of the hanger and for clamplng the other half of the anode members to the other slde of the hanger. The heads of the clamplng bolts are recessed withln the anode members and carbon plugs are inserted ln the recesses above the bolt heads to protect the boIts agalnst corroslon. A copper washer is provided under the head of each clamplng boIt such that the anode members can be tightly clamped to the hanger with a resultant low anode jolnt resistance. (AEC)

Solid oxide fuel cell anode degradation by the effect of hydrogen chloride in stack and single cell environments

NASA Astrophysics Data System (ADS)

Madi, Hossein; Lanzini, Andrea; Papurello, Davide; Diethelm, Stefan; Ludwig, Christian; Santarelli, Massimo; Van herle, Jan

2016-09-01

The poisoning effect by hydrogen chloride (HCl) on state-of-the-art Ni anode-supported solid oxide fuel cells (SOFCs) at 750 °C is evaluated in either hydrogen or syngas fuel. Experiments are performed on single cells and short stacks and HCl concentration in the fuel gas is increased from 1 ppm(v) up to 1000 ppm(v) at different current densities. Characterization methods such as cell voltage monitoring vs. time and electrochemical impedance response analysis (distribution of relaxation times (DRT), equivalent electrical circuit) are used to identify the prevailing degradation mechanism. Single cell experiments revealed that the poisoning is more severe when feeding with hydrogen than with syngas. Performance loss is attributed to the effects of HCl adsorption onto nickel surfaces, which lowered the catalyst activity. Interestingly, in syngas HCl does not affect stack performance even at concentrations up to 500 ppm(v), even when causing severe corrosion of the anode exhaust pipe. Furthermore, post-test analysis suggests that chlorine is present on the nickel particles in the form of adsorbed chlorine, rather than forming a secondary phase of nickel chlorine.

Anodic concentration loss and impedance characteristics in rotating disk electrode microbial fuel cells.

PubMed

Shen, Liye; Ma, Jingxing; Song, Pengfei; Lu, Zhihao; Yin, Yao; Liu, Yongdi; Cai, Lankun; Zhang, Lehua

2016-10-01

A rotating disk electrode (RDE) was used to investigate the concentration loss and impedance characteristics of anodic biofilms in microbial fuel cells (MFCs). Amperometric time-current analysis revealed that at the rotation rate of 480 rpm, a maximum current density of 168 µA cm(-2) can be achieved, which was 22.2 % higher than when there was no rotation. Linear sweep voltammetry and electrochemical impedance spectroscopy tests showed that when the anodic potential was set to -300 mV vs. Ag/AgCl reference, the power densities could increase by 59.0  %, reaching 1385 mW m(-2), the anodic resistance could reduce by 19  %, and the anodic capacitance could increase by 36 %. These results concur with a more than 85 % decrease of the diffusion layer thickness. Data indicated that concentration loss, diffusion layer thickness, and the mixing velocity play important roles in anodic resistance reduction and power output of MFCs. These findings could be helpful to the design of future industrial-scale MFCs with mixed bacteria biofilms.

The effect of current reversal on coated titanium electrodes

NASA Astrophysics Data System (ADS)

Elnathan, Francis

Coated titanium electrodes have applications in the electrochemical industry, including water treatment and swimming pool chlorination. Current/polarity reverse electrolysis is a technique used for "self-cleaning" of the coated titanium anodes employed in water disinfection and treatment. However, the literature holds very little information about the effects of polarity reversal on these anodes. The present work appears to be the first to investigate coated titanium anodes in polarity reversal in a systematic method. Two commercial titanium electrodes (RuTi and IrTa) were studied. Polarity reversal was the main electrochemical technique employing a current density of 1200 A/m 2, except when current density was studied. The effects of NO 3-, SO42-, ClO4 -, HPO42-, CO32-, Mg2+ and Ca2+ on electrode lifetime were examined. Analysis of the electrochemical results showed that plateau time (tau p), for gas evolution, is highly important to the lifetime of the coated titanium anodes. The effects of three electrolysis variables on the coated titanium anode life were examined. Current density was observed to have an inverse relationship with anode life while reversal cycle time had a direct relation with lifetime. NaCl concentration had no discernible effect. In general, the RuTi electrode exhibited longer lifetimes than IrTa except for a few specific conditions. The influence of the concentration of five anions (NO3-, SO42-, ClO 4-, HPO42-, and CO3 2-) was determined. Changing the composition and concentration of anions affected the lifetimes of the two electrodes, especially nitrate, hydrogen phosphate and carbonate. The lifetime of IrTa was highest in nitrate, and increased as a function of nitrate concentration. The service life of RuTi was highest in hydrogen phosphate, and increased with increasing hydrogen phosphate concentration. Lifetime of both anodes decreased with increasing carbonate ions. The effects of Mg2+ and Ca2+ on electrode lifetime were examined with three anions (NO3-, HPO42-, ClO4-) electrolytes. While there were numerous effects and interactions between Mg2+ or Ca2+ and anions on lifetime, these effects were found to mainly affect the amount of time the electrodes spent in the charging and discharging reactions. The times related to gas evolution (which is the plateau time, tau p) were found to be strikingly similar. The charging times (tau C) which are related to adsorption and desorption of species were not also any significantly different. Coating dissolution, substrate and/or coating passivation mechanisms were identified as being responsible for coated titanium anode failure in current reverse and hard water electrolysis. IrTa is believed to have failed predominantly by the dissolution mechanism in nitrate, hydrogen phosphate and perchlorate. RuTi failed predominantly by substrate and/or coating passivation in hydrogen phosphate, nitrate and carbonate. Anode failure is believed to be the result of plateau (taup) and charging (tauC)reactions occurring at the coating/electrolyte and/or substrate/coating interface. The tau p and tauC are useful determinants for the process of anode failure.

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.

Mathematical modeling of synthesis gas fueled electrochemistry and transport including H2/CO co-oxidation and surface diffusion in solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Bao, Cheng; Jiang, Zeyi; Zhang, Xinxin

2015-10-01

Fuel flexibility is a significant advantage of solid oxide fuel cell (SOFC). A comprehensive macroscopic framework is proposed for synthesis gas (syngas) fueled electrochemistry and transport in SOFC anode with two main novelties, i.e. analytical H2/CO electrochemical co-oxidation, and correction of gas species concentration at triple phase boundary considering competitive absorption and surface diffusion. Staring from analytical approximation of the decoupled charge and mass transfer, we present analytical solutions of two defined variables, i.e. hydrogen current fraction and enhancement factor. Giving explicit answer (rather than case-by-case numerical calculation) on how many percent of the current output contributed by H2 or CO and on how great the water gas shift reaction plays role on, this approach establishes at the first time an adaptive superposition mechanism of H2-fuel and CO-fuel electrochemistry for syngas fuel. Based on the diffusion equivalent circuit model, assuming series-connected resistances of surface diffusion and bulk diffusion, the model predicts well at high fuel utilization by keeping fixed porosity/tortuosity ratio. The model has been validated by experimental polarization behaviors in a wide range of operation on a button cell for H2-H2O-CO-CO2-N2 fuel systems. The framework could be helpful to narrow the gap between macro-scale and meso-scale SOFC modeling.

Development of the anode bipolar plate/membrane assembly unit for air breathing PEMFC stack using silicone adhesive bonding

NASA Astrophysics Data System (ADS)

Kim, Minkook; Lee, Dai Gil

2016-05-01

Polymer electrolyte membrane fuel cells (PEMFC) exhibit a wide power range, low operating temperature, high energy density and long life time. These advantages favor PEMFC for applications such as vehicle power sources, portable power, and backup power applications. With the push towards the commercialization of PEMFC, especially for portable power applications, the overall balance of plants (BOPs) of the systems should be minimized. To reduce the mass and complexity of the systems, air-breathing PEMFC stack design with open cathode channel configuration is being developed. However, the open cathode channel configuration incurs hydrogen leakage problem. In this study, the bonding strength of a silicon adhesive between the Nafion membrane and the carbon fiber/epoxy composite bipolar plate was measured. Then, an anode bipolar plate/membrane assembly unit which was bonded with the silicone adhesive was developed to solve the hydrogen leakage problem. The reliability of the anode bipolar plate/membrane assembly unit was estimated under the internal pressure of hydrogen by the FE analysis. Additionally, the gas sealability of the developed air breathing PEMFC unit cell was experimentally measured. Finally, unit cell performance of the developed anode bipolar plate/membrane assembly unit was tested and verified under operating conditions without humidity and temperature control.

Fuel cell membrane humidification

DOEpatents

Wilson, Mahlon S.

1999-01-01

A polymer electrolyte membrane fuel cell assembly has an anode side and a cathode side separated by the membrane and generating electrical current by electrochemical reactions between a fuel gas and an oxidant. The anode side comprises a hydrophobic gas diffusion backing contacting one side of the membrane and having hydrophilic areas therein for providing liquid water directly to the one side of the membrane through the hydrophilic areas of the gas diffusion backing. In a preferred embodiment, the hydrophilic areas of the gas diffusion backing are formed by sewing a hydrophilic thread through the backing. Liquid water is distributed over the gas diffusion backing in distribution channels that are separate from the fuel distribution channels.

Diffusion-driven proton exchange membrane fuel cell for converting fermenting biomass to electricity.

PubMed

Malati, P; Mehrotra, P; Minoofar, P; Mackie, D M; Sumner, J J; Ganguli, R

2015-10-01

A membrane-integrated proton exchange membrane fuel cell that enables in situ fermentation of sugar to ethanol, diffusion-driven separation of ethanol, and its catalytic oxidation in a single continuous process is reported. The fuel cell consists of a fermentation chamber coupled to a direct ethanol fuel cell. The anode and fermentation chambers are separated by a reverse osmosis (RO) membrane. Ethanol generated from fermented biomass in the fermentation chamber diffuses through the RO membrane into a glucose solution contained in the DEFC anode chamber. The glucose solution is osmotically neutral to the biomass solution in the fermentation chamber preventing the anode chamber from drying out. The fuel cell sustains >1.3 mW cm(-2) at 47°C with high discharge capacity. No separate purification or dilution is necessary, resulting in an efficient and portable system for direct conversion of fermenting biomass to electricity. Copyright © 2015 Elsevier Ltd. All rights reserved.

Hydrogen diffusion in liquid aluminum from ab initio molecular dynamics

NASA Astrophysics Data System (ADS)

Jakse, N.; Pasturel, A.

2014-05-01

Ab initio molecular dynamics simulations are used to describe the diffusion of hydrogen in liquid aluminum at different temperatures. Quasi-instantaneous jumps separating periods of localized vibrations around a mean position are found to characterize the hydrogen motion at the microscopic scale. The hydrogen motion is furthermore analyzed using the van Hove function. We highlight a non-Fickian behavior for the hydrogen diffusion due to a large spatial distribution of hydrogen jumps. We show that a generalized continuous time random walk (CTRW) model describes the experimental diffusion coefficients in a satisfactory manner. Finally, the impact of impurities and alloying elements on hydrogen diffusion in aluminum is discussed.

Diffusion of Hydrogen and Helium in Inconel 625

NASA Technical Reports Server (NTRS)

Palosz, W.; Gillies, D.; Lehoczky, S.

2006-01-01

Diffusion parameters for hydrogen and helium in Inconel 625 were investigated. The dependence of permeability of hydrogen in the temperature range 310 - 750 C is given. Solubility of hydrogen at 1 atm in the range 640 - 860 C was determined and diffusivity of the gas was calculated. Experiments with diffusion and solubility at 0.09 atm suggest a molecular mechanism of solution of hydrogen in the material. Diffusivity of helium was estimated at less than 10(exp -18) sq cm/s (at 1040 C).

The hydrogen diffusion in liquid aluminum alloys from ab initio molecular dynamics

NASA Astrophysics Data System (ADS)

Jakse, N.; Pasturel, A.

2014-09-01

We study the hydrogen diffusion in liquid aluminum alloys through extensive ab initio molecular dynamics simulations. At the microscopic scale, we show that the hydrogen motion is characterized by a broad distribution of spatial jumps that does not correspond to a Brownian motion. To determine the self-diffusion coefficient of hydrogen in liquid aluminum alloys, we use a generalized continuous time random walk model recently developed to describe the hydrogen diffusion in pure aluminum. In particular, we show that the model successfully accounts the effects of alloying elements on the hydrogen diffusion in agreement with experimental features.

Non-Faradaic electrochemical promotion of catalytic methane reforming for methanol production

DOEpatents

Fan, Qinbai

2016-11-22

A method of converting methane to methanol at low temperatures utilizes a reactor including an anode, a cathode, a membrane separator between the anode and cathode, a metal oxide catalyst at the anode and a hydrogen recovery catalyst at the cathode. The method can convert methane to methanol at as rate exceeding the theoretical Faradaic rate due to the contribution of an electrochemical reaction occurring in tandem with a Faradaic reaction.

Enzymatic fuel cells with an oxygen resistant variant of pyranose-2-oxidase as anode biocatalyst.

PubMed

Şahin, Samet; Wongnate, Thanyaporn; Chuaboon, Litavadee; Chaiyen, Pimchai; Yu, Eileen Hao

2018-06-01

In enzymatic fuel cells (EnFCs), hydrogen peroxide formation is one of the main problems when enzymes, such as, glucose oxidase (GOx) is used due to the conversion of oxygen to hydrogen peroxide in the catalytic reaction. To address this problem, we here report the first demonstration of an EnFC using a variant of pyranose-2-oxidase (P2O-T169G) which has been shown to have low activity towards oxygen. A simple and biocompatible immobilisation approach incorporating multi-walled-carbon nanotubes within ferrocene (Fc)-Nafion film was implemented to construct EnFCs. Successful immobilisation of the enzymes was demonstrated showing 3.2 and 1.7-fold higher current than when P2O-T169G and GOx were used in solution, respectively. P2O-T169G showed 25% higher power output (maximum power density value of 8.45 ± 1.6 μW cm -2 ) and better stability than GOx in aerated glucose solutions. P2O-T169G maintained > 70% of its initial current whereas GOx lost activity > 90% during the first hour of 12 h operation at 0.15 V (vs Ag/Ag + ). A different fuel cell configuration using gas-diffusion cathode and carbon paper electrodes were used to improve the power output of the fuel cell to 29.8 ± 6.1 µW cm -2 . This study suggests that P2O-T169G with low oxygen activity could be a promising anode biocatalyst for EnFC applications. Copyright © 2018. Published by Elsevier B.V.

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

Hydrogenated TiO2 Branches Coated Mn3O4 Nanorods as an Advanced Anode Material for Lithium Ion Batteries.

PubMed

Wang, Nana; Yue, Jie; Chen, Liang; Qian, Yitai; Yang, Jian

2015-05-20

Rational design and delicate control on the component, structure, and surface of electrodes in lithium ion batteries are highly important to their performances in practical applications. Compared with various components and structures for electrodes, the choices for their surface are quite limited. The most widespread surface for numerous electrodes, a carbon shell, has its own issues, which stimulates the desire to find another alternative surface. Here, hydrogenated TiO2 is exemplified as an appealing surface for advanced anodes by the growth of ultrathin hydrogenated TiO2 branches on Mn3O4 nanorods. High theoretical capacity of Mn3O4 is well matched with low volume variation (∼4%), enhanced electrical conductivity, good cycling stability, and rate capability of hydrogenated TiO2, as demonstrated in their electrochemical performances. The proof-of-concept reveals the promising potential of hydrogenated TiO2 as a next-generation material for the surface in high-performance hybrid electrodes.

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.

New electrocatalysts for hydrogen-oxygen fuel cells

NASA Technical Reports Server (NTRS)

Cattabriga, R. A.; Giner, J.; Parry, J.; Swette, L. L.

1970-01-01

Platinum-silver, palladium-gold, and platinum-gold alloys serve as oxygen reduction catalysts in high-current-density cells. Catalysts were tested on polytetrafluoroethylene-bonded cathodes and a hydrogen anode at an operating cell temperature of 80 degrees C.

Optimization studies of bio-hydrogen production in a coupled microbial electrolysis-dye sensitized solar cell system.

PubMed

Ajayi, Folusho Francis; Kim, Kyoung-Yeol; Chae, Kyu-Jung; Choi, Mi-Jin; Chang, In Seop; Kim, In S

2010-03-01

Bio-hydrogen production in light-assisted microbial electrolysis cell (MEC) with a dye sensitized solar cell (DSSC) was optimized by connecting multiple MECs to a single dye (N719) sensitized solar cell (V(OC) approx. 0.7 V). Hydrogen production occurred simultaneously in all the connected MECs when the solar cell was irradiated with light. The amount of hydrogen produced in each MEC depends on the activity of the microbial catalyst on their anode. Substrate (acetate) to hydrogen conversion efficiencies ranging from 42% to 65% were obtained from the reactors during the experiment. A moderate light intensity of 430 W m(-2) was sufficient for hydrogen production in the coupled MEC-DSSC. A higher light intensity of 915 W m(-2), as well as an increase in substrate concentration, did not show any improvement in the current density due to limitation caused by the rate of microbial oxidation on the anode. A significant reduction in the surface area of the connected DSSC only showed a slight effect on current density in the coupled MEC-DSSC system when irradiated with light.

Electrochemical and partial oxidation of methane

NASA Astrophysics Data System (ADS)

Singh, Rahul

2008-10-01

Hydrogen has been the most common fuel used for the fuel cell research but there remains challenging technological hurdles and storage issues with hydrogen fuel. The direct electrochemical oxidation of CH4 (a major component of natural gas) in a solid oxide fuel cell (SOFC) to generate electricity has a potential of commercialization in the area of auxiliary and portable power units and battery chargers. They offer significant advantages over an external reformer based SOFC, namely, (i) simplicity in the overall system architecture and balance of plant, (ii) more efficient and (iii) availability of constant concentration of fuel in the anode compartment of SOFC providing stability factor. The extreme operational temperature of a SOFC at 700-1000°C provides a thermodynamically favorable pathway to deposit carbon on the most commonly used Ni anode from CH4 according to the following reaction (CH4 = C + 2H2), thus deteriorating the cell performance, stability and durability. The coking problem on the anode has been a serious and challenging issue faced by the catalyst research community worldwide. This dissertation presents (i) a novel fabricated bi-metallic Cu-Ni anode by electroless plating of Cu on Ni anode demonstrating significantly reduced or negligible coke deposition on the anode for CH4 and natural gas fuel after long term exposure, (ii) a thorough microstructural examination of Ni and Cu-Ni anode exposed to H2, CH4 and natural gas after long term exposure at 750°C by scanning electron microscopy, energy dispersive X-ray spectroscopy and X-ray diffraction and (iii) in situ electrochemical analysis of Ni and Cu-Ni for H2, CH4 and natural gas during long term exposure at 750°C by impedance spectroscopy. A careful investigation of variation in the microstructure and performance characteristics (voltage-current curve and impedance) of Ni and Cu-Ni anode before and after a long term exposure of CH4 and natural gas would allow us to test the validation of a negligible coke formation on the novel fabricated anode by electroless plating process. Hydrogen is an environmentally cleaner source of energy. The recent increase in the demand of hydrogen as fuel for all types of fuel cells and petroleum refining process has boosted the need of production of hydrogen. Methane, a major component of natural gas is the major feedstock for production of hydrogen. The route of partial oxidation of methane to produce syngas (CO + H2) offers significant advantages over commercialized steam reforming process for higher efficiency and lower energy requirements. Partial oxidation of methane was studied by pulsing O2 into a CH4 flow over Rh/Al2O3 in a sequence of in situ infrared (IR) cell and fixed bed reactor at 773 K. The results obtained from the sequence of an IR cell followed by a fixed bed reactor show that (i) adsorbed CO produced possesses a long residence time, indicating that adsorbed oxygen leading to the formation of CO is significantly different from those leading to CO2 and (ii) CO2 is not an intermediate species for the formation of CO. In situ IR of pulse reaction coupled with alternating reactor sequence is an effective approach to study the primary and secondary reactions as well as the nature of their adsorbed species. As reported earlier, hydrogen remains to be the most effective fuel for fuel cells, the production of high purity hydrogen from naturally available resources such as coal, petroleum, and natural gas requires a number of energy-intensive steps, making fuel cell processes for stationary electric power generation prohibitively uneconomic. Direct use of coal or coal gas as the feed is a promising approach for low cost electricity generation. Coal gas solid oxide fuel cell was studied by pyrolyzing Ohio #5 coal to coal gas and transporting to a Cu anode solid oxide fuel cell to generate power. The study of coal-gas solid oxide fuel cell is divided into two sections, i.e., (i) understanding the composition of coal gas by in situ infrared spectroscopy combined with mass spectrometry and (ii) evaluating the performance of coal gas for power generation based on the composition on a Cu-SOFC. The voltage-current performance curve for coal gas suggests that hydrogen and methane rich coal gas performed better than CO2 or D2O concentrated coal gas. A slow rate of reforming reaction of D2O than CO2 with coal and coal gas was observed during pyrolysis reaction. The coal and coke (by-product of pyrolysis) were characterized by Raman spectrometer to reveal the effect of pyrolysis on the structural properties of coal.

Performance evaluation of platinum-molybdenum carbide nanocatalysts with ultralow platinum loading on anode and cathode catalyst layers of proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Saha, Shibely; Cabrera Rodas, José Andrés; Tan, Shuai; Li, Dongmei

2018-02-01

An alternative catalyst platform, consisting of a phase-pure transition carbide (TMC) support and Pt nanoparticles (NPs) in the range of subnanometer to < 2.7 nm, is established that can be used in both anode and cathode catalyst layers. While some TMCs with low Pt loadings have demonstrated similar activity as commercial Pt catalyst in idealized disk electrode screening tests, few to none have been applied in a realistic fuel cell membrane electrode assembly (MEA). We recently reported that β-Mo2C hollow nanotubes modified with Pt NPs via atomic layer deposition (ALD) possess better activity and durability than 20% Pt/C. This paper presents systematic evaluation of the Pt/Mo2C catalysts in a MEA, investigating effects of different MEA preparation techniques, gas diffusion layers (GDL) and various Pt loadings in the ultralow range (<0.04 mg/cm2) on MEA performance. Most importantly, we demonstrate, for the first time, that Pt/Mo2C catalyst on both anode and cathode, with a loading of 0.02 mg (Pt) cm-2, generated peak power density of 414 mW cm-2 that corresponds to 10.35 kWgPt-1 using hydrogen (H2) and oxygen (O2). Accelerated degradation tests (ADT) on Pt/Mo2C catalysts show 111% higher power density than commercial 20% Pt/C after the vigorous ADT.

Electrocatalytic oxidation of hydrogen peroxide on a platinum electrode in the imitation of oxidative drug metabolism of lidocaine.

PubMed

Nouri-Nigjeh, Eslam; Bruins, Andries P; Bischoff, Rainer; Permentier, Hjalmar P

2012-10-21

Electrochemistry in combination with mass spectrometry has shown promise as a versatile technique not only in the analytical assessment of oxidative drug metabolism, but also for small-scale synthesis of drug metabolites. However, electrochemistry is generally limited to reactions initiated by direct electron transfer. In the case of substituted-aromatic compounds, oxidation proceeds through a Wheland-type intermediate where resonance stabilization of the positive charge determines the regioselectivity of the anodic substitution reaction, and hence limits the extent of generating drug metabolites in comparison with in vivo oxygen insertion reactions. In this study, we show that the electrocatalytic oxidation of hydrogen peroxide on a platinum electrode generates reactive oxygen species, presumably surface-bound platinum-oxo species, which are capable of oxygen insertion reactions in analogy to oxo-ferryl radical cations in the active site of Cytochrome P450. Electrochemical oxidation of lidocaine at constant potential in the presence of hydrogen peroxide produces both 3- and 4-hydroxylidocaine, suggesting reaction via an arene oxide rather than a Wheland-type intermediate. No benzylic hydroxylation was observed, thus freely diffusing radicals do not appear to be present. The results of the present study extend the possibilities of electrochemical imitation of oxidative drug metabolism to oxygen insertion reactions.

Electrochemical and catalytic properties of Ni/BaCe0.75Y0.25O3-δ anode for direct ammonia-fueled solid oxide fuel cells.

PubMed

Yang, Jun; Molouk, Ahmed Fathi Salem; Okanishi, Takeou; Muroyama, Hiroki; Matsui, Toshiaki; Eguchi, Koichi

2015-04-08

In this study, Ni/BaCe0.75Y0.25O3-δ (Ni/BCY25) was investigated as an anode for direct ammonia-fueled solid oxide fuel cells. The catalytic activity of Ni/BCY25 for ammonia decomposition was found to be remarkably higher than Ni/8 mol % Y2O3-ZrO2 and Ni/Ce0.90Gd0.10O1.95. The poisoning effect of water and hydrogen on ammonia decomposition reaction over Ni/BCY25 was evaluated. In addition, an electrolyte-supported SOFC employing BaCe0.90Y0.10O3-δ (BCY10) electrolyte and Ni/BCY25 anode was fabricated, and its electrochemical performance was investigated at 550-650 °C with supply of ammonia and hydrogen fuel gases. The effect of water content in anode gas on the cell performance was also studied. Based on these results, it was concluded that Ni/BCY25 was a promising anode for direct ammonia-fueled SOFCs. An anode-supported single cell denoted as Ni/BCY25|BCY10|Sm0.5Sr0.5CoO3-δ was also fabricated, and maximum powder density of 216 and 165 mW cm(-2) was achieved at 650 and 600 °C, for ammonia fuel, respectively.

Auger electron spectroscopy and Rutherford backscattering studies of copper in 2024-T3 aluminum following electrochemical anodization in phosphoric acid

NASA Astrophysics Data System (ADS)

Solomon, J. S.

1981-05-01

The effects of the electrochemical anodization of dioxidized 2024-T3 aluminum on copper were characterized by Auger electron spectroscopy and Rutherford backscattering. Anodization was performed in phosphoric acid at constant potential. Data is presented which shows that constant potential anodization of 2024-T3 is more efficient than aluminum in terms of oxide growth rates for short anodization times. However the maximum anodic oxide thickness achievable on the alloy is less than the pure metal. Copper is shown to be enriched at the oxide metal interface because of its diffusion from the bulk during anodization. The presence of copper at the oxide-metal interface is shown to affect oxide morphology.

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.

Effect of the PTFE content in the gas diffusion layer on water transport in polymer electrolyte fuel cells (PEFCs)

NASA Astrophysics Data System (ADS)

Mortazavi, Mehdi; Tajiri, Kazuya

2014-01-01

The dynamic behavior of a liquid water droplet emerging and detaching from the surface of the gas diffusion layer (GDL) is investigated. The droplet growth and detachment are studied for different polytetrafluoroethylene (PTFE) contents within the GDL and for different superficial gas velocities flowing in the gas channel. To simulate the droplet behavior in the cathode and anode of an operating polymer electrolyte fuel cell, separate experiments are conducted with air and hydrogen being supplied in the gas channel, respectively. Both the superficial gas velocity and the PTFE content within the GDL are found to impact the droplet detachment diameter. Increasing the superficial gas velocity increases the drag force applied on the droplet sitting on the GDL surface. It is observed that the droplet detaches at a smaller diameter for higher superficial gas velocities. The droplets also detach at smaller diameters from GDLs with a higher amount of PTFE. Such observation is justified according to two different points of view: (1) heterogeneous through-plane PTFE distribution through the GDL and (2) reduced GDL surface roughness caused by PTFE loading.

40 CFR 98.64 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2012 CFR

2012-07-01

... effect termination routine.Facilities which operate at less than 0.2 anode effect minutes per cell day or... cell day (or anode effect overvoltage and current efficiency). (2) Monthly for aluminum production. (3... of parameters needed to complete the equations in § 98.63 (e.g., sulfur, ash, and hydrogen contents...

40 CFR 98.64 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2013 CFR

2013-07-01

... effect termination routine.Facilities which operate at less than 0.2 anode effect minutes per cell day or... cell day (or anode effect overvoltage and current efficiency). (2) Monthly for aluminum production. (3... of parameters needed to complete the equations in § 98.63 (e.g., sulfur, ash, and hydrogen contents...

40 CFR 98.64 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2014 CFR

2014-07-01

... effect termination routine.Facilities which operate at less than 0.2 anode effect minutes per cell day or... cell day (or anode effect overvoltage and current efficiency). (2) Monthly for aluminum production. (3... of parameters needed to complete the equations in § 98.63 (e.g., sulfur, ash, and hydrogen contents...

Process for forming sulfuric acid

DOEpatents

Lu, Wen-Tong P.

1981-01-01

An improved electrode is disclosed for the anode in a sulfur cycle hydrogen generation process where sulfur dioxie is oxidized to form sulfuric acid at the anode. The active compound in the electrode is palladium, palladium oxide, an alloy of palladium, or a mixture thereof. The active compound may be deposited on a porous, stable, conductive substrate.

Pd/Ni-WO3 anodic double layer gasochromic device

DOEpatents

Lee, Se-Hee; Tracy, C. Edwin; Pitts, J. Roland; Liu, Ping

2004-04-20

An anodic double layer gasochromic sensor structure for optical detection of hydrogen in improved response time and with improved optical absorption real time constants, comprising: a glass substrate; a tungsten-doped nickel oxide layer coated on the glass substrate; and a palladium layer coated on the tungsten-doped nickel oxide layer.

Leaching lithium from the anode electrode materials of spent lithium-ion batteries by hydrochloric acid (HCl).

PubMed

Guo, Yang; Li, Feng; Zhu, Haochen; Li, Guangming; Huang, Juwen; He, Wenzhi

2016-05-01

Spent lithium-ion batteries (LIBs) are considered as an important secondary resource for its high contents of valuable components, such as lithium and cobalt. Currently, studies mainly focus on the recycling of cathode electrodes. There are few studies concentrating on the recovery of anode electrodes. In this work, based on the analysis result of high amount of lithium contained in the anode electrode, the acid leaching process was applied to recycle lithium from anode electrodes of spent LIBs. Hydrochloric acid was introduced as leaching reagent, and hydrogen peroxide as reducing agent. Within the range of experiment performed, hydrogen peroxide was found to have little effect on lithium leaching process. The highest leaching recovery of 99.4wt% Li was obtained at leaching temperature of 80°C, 3M hydrochloric acid and S/L ratio of 1:50g/ml for 90min. The graphite configuration with a better crystal structure obtained after the leaching process can also be recycled. Copyright © 2015 Elsevier Ltd. All rights reserved.

In situ Van der Pauw measurements of the Ni/YSZ anode during exposure to syngas with phosphine contaminant

NASA Astrophysics Data System (ADS)

Demircan, Oktay; Xu, Chunchuan; Zondlo, John; Finklea, Harry O.

Solid oxide fuel cells (SOFCs) represent an option to provide a bridging technology for energy conversion (coal syngas) as well as a long-term technology (hydrogen from biomass). Whether the fuel is coal syngas or hydrogen from biomass, the effect of impurities on the performance of the anode is a vital question. The anode resistivity during SOFC operation with phosphine-contaminated syngas was studied using the in situ Van der Pauw method. Commercial anode-supported solid oxide fuel cells (Ni/YSZ composite anodes, YSZ electrolytes) were exposed to a synthetic coal syngas mixture (H 2, H 2O, CO, and CO 2) at a constant current and their performance evaluated periodically with electrochemical methods (cyclic voltammetry, impedance spectroscopy, and polarization curves). In one test, after 170 h of phosphine exposure, a significant degradation of cell performance (loss of cell voltage, increase of series resistance and increase of polarization resistance) was evident. The rate of voltage loss was 1.4 mV h -1. The resistivity measurements on Ni/YSZ anode by the in situ Van der Pauw method showed that there were no significant changes in anode resistivity both under clean syngas and syngas with 10 ppm PH 3. XRD analysis suggested that Ni 5P 2 and P 2O 5 are two compounds accumulated on the anode. XPS studies provided support for the presence of two phosphorus phases with different oxidation states on the external anode surface. Phosphorus, in a positive oxidation state, was observed in the anode active layer. Based on these observations, the effect of 10 ppm phosphine impurity (or its reaction products with coal syngas) is assigned to the loss of performance of the Ni/YSZ active layer next to the electrolyte, and not to any changes in the thick Ni/YSZ support layer.

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.

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.

Particle-in-cell modeling of the nanosecond field emission driven discharge in pressurized hydrogen

NASA Astrophysics Data System (ADS)

Levko, Dmitry; Yatom, Shurik; Krasik, Yakov E.

2018-02-01

The high-voltage field-emission driven nanosecond discharge in pressurized hydrogen is studied using the one-dimensional Particle-in-Cell Monte Carlo collision model. It is obtained that the main part of the field-emitted electrons becomes runaway in the thin cathode sheath. These runaway electrons propagate the entire cathode-anode gap, creating rather dense (˜1012 cm-3) seeding plasma electrons. In addition, these electrons initiate a streamer propagating through this background plasma with a speed ˜30% of the speed of light. Such a high streamer speed allows the self-acceleration mechanism of runaway electrons present between the streamer head and the anode to be realized. As a consequence, the energy of runaway electrons exceeds the cathode-anode gap voltage. In addition, the influence of the field emission switching-off time is analyzed. It is obtained that this time significantly influences the discharge dynamics.

Application of immobilized nanotubular TiO(2) electrode for photocatalytic hydrogen evolution: reduction of hexavalent chromium (Cr(VI)) in water.

PubMed

Yoon, Jaekyung; Shim, Eunjung; Bae, Sanghyun; Joo, Hyunku

2009-01-30

In this study, immobilized TiO(2) electrode is applied to reduce toxic Cr(VI) to non-toxic Cr(III) in aqueous solution under UV irradiation. To overcome the limitation of powder TiO(2), a novel technique of immobilization based on anodization was applied and investigated under various experimental conditions. The anodization was performed at 20V-5 degrees C for 45min with 0.5% hydrofluoric acid, and then the anodized samples were annealed under oxygen stream in the range 450-850 degrees C. Based on the results of the experiments, the photocatalytic Cr(VI) reduction was favorable in acidic conditions, with approximately 98% of the Cr(VI) being reduced within 2h at pH 3. Among the samples tested under same anodizing condition, the nanotubular TiO(2) annealed at 450 and 550 degrees C showed highest reduction efficiencies of Cr(VI). In addition, the surface characterizations (zeta potential, XRD, and SEM) of these samples proved that the Cr(VI) reduction efficiency was higher under acidic conditions and at a lower annealing temperature. From this research, it was concluded that the anodized TiO(2) has the potential to be a useful technology for environmental remediation as well as photocatalytic hydrogen production from water.

Y0.08Sr0.88TiO3-CeO2 composite as a diffusion barrier layer for stainless-steel supported solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Kim, Kun Joong; Kim, Sun Jae; Choi, Gyeong Man

2016-03-01

A new diffusion barrier layer (DBL) is proposed for solid oxide fuel cells (SOFCs) supported on stainless-steel where DBL prevents inter-diffusion of atoms between anode and stainless steel (STS) support during fabrication and operation of STS-supported SOFCs. Half cells consisting of dense yttria-stabilized zirconia (YSZ) electrolyte, porous Ni-YSZ anode layer, and ferritic STS support, with or without Y0.08Sr0.88TiO3-CeO2 (YST-CeO2) composite DBL, are prepared by tape casting and co-firing at 1250 and 1350 °C, respectively, in reducing (H2) atmosphere. The porous YST-CeO2 layer (t ∼ 60 μm) blocks inter-diffusion of Fe and Ni, and captures the evaporated Cr during cell fabrication (1350 °C). The cell with DBL and La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) cathode achieved a maximum power density of ∼220 mW cm-2 which is stable at 700 °C. In order to further improve the power performance, Ni coarsening in anode during co-firing must be prevented or alternative anode which is resistive to coarsening is suggested. This study demonstrates that the new YST-CeO2 layer is a promising as a DBL for stainless-steel-supported SOFCs fabricated with co-firing process.

Understanding and Enhancing the Photostability of Nanoporous Metal Oxide Thin Films for Solar Hydrogen Generation

NASA Astrophysics Data System (ADS)

Chitrada, Kalyan Chakravarthi

Solar water splitting is an environmentally benign process which has received wide attention in the recent years as an alternate method for a clean and safe production of hydrogen. This process employs a semiconductor based photocatalyst, water, and sunlight to produce hydrogen. Metal-oxide based semiconductors are considered to be ideal photocatalytic materials because of their stability against photo-corrosion combined with relatively narrow energy band-gap, appropriately placed band edge positions with reference to oxygen and hydrogen energy levels, less scattering of charges due to wider valence band, high dielectric constant, natural abundance, and non-toxicity. In this dissertation, two metal oxide based semiconductors viz., iron (III) oxide and bismuth (III) oxide were investigated to understand and enhance their photo activity as photoanodes for solar water splitting application. Iron (III) oxide has a well suited band gap to capture solar spectrum but it suffers from inappropriately positioned band edges, recombination losses due to low electron mobility, and a small minority carrier diffusion length. However, it was hypothesized that the Iron (III) oxide might show interesting photoelectrochemical properties by alloying with 4f elements and shifting the conduction band minimum of the iron oxide favorably to more negative potentials. In the present study, a nanoporous iron oxide layer incorporated with Nd3+ and B3+ was synthesized by electrochemical anodization of a FeNdB alloy. The photoelectrochemical behavior of this oxide was compared with thermally oxidized FeNdB alloy and the iron oxides obtained by anodization and thermal oxidation of pure iron foil. Incorporation of Nd3+ and B3+ in the iron oxide showed a direct bandgap of 2.05 eV, an indirect bandgap of 1.9 eV and shifted the flatband potentials to --0.8 VAg/AgCl in 1 M KOH solution. The FeNdB oxide showed marginally better catalytic activity for the oxygen evolution reaction than pure iron oxide under dark conditions. The binary bismuth (III) oxide, in spite being a good photocatalytic material, did not receive as much attention as other bismuth based ternary oxides for photoelectrochemical water splitting application. In this present study, large surface area nanoporous bismuth oxide thin films were synthesized by the electrochemical anodization. These anodic oxides exhibited a dual layered structure having a planar inner oxide and nanoporous outer oxide. Effect of the nanoscale dimensions of the oxides on the photoelectrochemical behavior was studied to understand the charge transport, charge recombination behavior, and long term stability of the material. A maximum photo current density of 0.97 mA/cm2 was observed for the sample anodized at 10 V at 1.53 VRHE. The nanoporous anodic oxides showed a charge carrier density in the range of 1.2 x 1017 -- 4.8 x 1018 cm-3 without illumination and about 60% increase in the charge carrier density upon illumination. However a decay in photo current was observed for the bismuth oxide samples was due to accumulation of holes on the electrode surface. This hole-accumulation was mitigated by the addition of hole scavengers. Addition of hydrogen peroxide as hole scavenger increased the photo current density by about 4 times in 0.5 M Na2SO 4 (pH: 5.8) electrolyte. Addition of H2O2 in 1 M KOH (pH: 13.7) showed an increase-decrease behavior and high photo current density of ~10 mA/cm2 at a bias potential of 0.65 VRHE . The high photo activity observed in this electrolyte was attributed to the in-situ formation of Bi2O4-x phase by the photo-conversion of the beta-Bi2O3 at the surface. The photo-converted Bi2O4-x has a smaller band gap (1.4 eV) and therefore harvested more light in the visible region. This in-situ formation of low band gap phases in the presence of H2O2 during solar water splitting is an interesting observation which has been reported for the first time and this will help design material with very high photo-activity.

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.

First-principles-based kinetic Monte Carlo studies of diffusion of hydrogen in Ni–Al and Ni–Fe binary alloys

DOE PAGES

Tafen, De Nyago

2015-02-14

The diffusion of dilute hydrogen in fcc Ni–Al and Ni–Fe binary alloys was examined using kinetic Monte Carlo method with input kinetic parameters obtained from first-principles density functional theory. The simulation involves the implementation of computationally efficient energy barrier model that describes the configuration dependence of the hydrogen hopping. The predicted hydrogen diffusion coefficients in Ni and Ni 89.4Fe 10.6 are compared well with the available experimental data. In Ni–Al, the model predicts lower hydrogen diffusivity compared to that in Ni. Overall, diffusion prefactors and the effective activation energies of H in Ni–Fe and Ni–Al are concentration dependent of themore » alloying element. Furthermore, the changes in their values are the results of the short-range order (nearest-neighbor) effect on the interstitial diffusion of hydrogen in fcc Ni-based alloys.« less

Double-side illuminated titania nanotubes for high volume hydrogen generation by water splitting

NASA Astrophysics Data System (ADS)

Mohapatra, Susanta K.; Mahajan, Vishal K.; Misra, Mano

2007-11-01

A sonoelectrochemical anodization method is proposed to synthesize TiO2 nanotubular arrays on both sides of a titanium foil (TiO2/Ti/TiO2). Highly ordered TiO2 nanotubular arrays of 16 cm2 area with uniform surface distribution can be obtained using this anodization procedure. These double-sided TiO2/Ti/TiO2 materials are used as both photoanode (carbon-doped titania nanotubes) and cathode (Pt nanoparticles dispersed on TiO2 nanotubes; PtTiO2/Ti/PtTiO2) in a specially designed photoelectrochemical cell to generate hydrogen by water splitting at a rate of 38 ml h-1. The nanomaterials are characterized by FESEM, HRTEM, STEM, EDS, FFT, SAED and XPS techniques. The present approach can be used for large-scale hydrogen generation using renewable energy sources.

Use of laser-induced spark for studying ignition stability and unburned hydrogen escaping from laminar diluted hydrogen diffusion jet flames

NASA Astrophysics Data System (ADS)

Phuoc, Tran X.; Chen, Ruey-Hung

2007-08-01

Ignition and unburned hydrogen escaping from hydrogen jet diffusion flames diluted with nitrogen up to 70% were experimentally studied. The successful ignition locations were about 2/3 of the flame length above the jet exit for undiluted flames and moved much closer to the exit for diluted flames. For higher levels of dilution or higher flow rates, there existed a region within which a diluted hydrogen diffusion flame can be ignited and burns with a stable liftoff height. This is contrary to previous findings that pure and diluted hydrogen jet diffusion cannot achieve a stable lifted flame configuration. With liftoff, the flame is noisy and short with significant amount of unburned hydrogen escaping into the product gases. If ignition is initiated below this region, the flame propagates upstream quickly and attaches to the burner rim. Results from measurements of unburned hydrogen in the combustion products showed that the amount of unburned hydrogen increased as the nitrogen dilution level was increased. Thus, hydrogen diffusion flame diluted with nitrogen cannot burn completely.

Fully methylated, atomically flat (111) silicon surface

NASA Astrophysics Data System (ADS)

Fidélis, A.; Ozanam, F.; Chazalviel, J.-N.

2000-01-01

The atomically flat hydrogenated (111) silicon surface has been methylated by anodization in a Grignard reagent and the surface obtained characterized by infrared spectroscopy. 100% substitution of the hydrogen atoms by methyl groups is observed. The resulting surface exhibits preserved ordering and superior chemical stability.

Hydrogen production from continuous flow, microbial reverse-electrodialysis electrolysis cells treating fermentation wastewater.

PubMed

Watson, Valerie J; Hatzell, Marta; Logan, Bruce E

2015-11-01

A microbial reverse-electrodialysis electrolysis cell (MREC) was used to produce hydrogen gas from fermentation wastewater without the need for additional electrical energy. Increasing the number of cell pairs in the reverse electrodialysis stack from 5 to 10 doubled the maximum current produced from 60 A/m(3) to 120 A/m(3) using acetate. However, more rapid COD removal required a decrease in the anolyte hydraulic retention time (HRT) from 24 to 12 h to stabilize anode potentials. Hydrogen production using a fermentation wastewater (10 cell pairs, HRT=8 h) reached 0.9±0.1 L H2/Lreactor/d (1.1±0.1 L H2/g-COD), with 58±5% COD removal and a coulombic efficiency of 74±5%. These results demonstrated that consistent rates of hydrogen gas production could be achieved using an MREC if effluent anolyte COD concentrations are sufficient to produce stable anode potentials. Copyright © 2015 Elsevier Ltd. All rights reserved.

Enhancing fermentative hydrogen production with the removal of volatile fatty acids by electrodialysis.

PubMed

Wei, Pengfei; Xia, Ao; Liao, Qiang; Sun, Chihe; Huang, Yun; Fu, Qian; Zhu, Xun; Lin, Richen

2018-05-08

A three-chamber electrodialysis bioreactor comprising fermentation, cathode and anode chambers was proposed to remove in situ volatile fatty acids during hydrogen fermentation. The electrodialysis voltage of 4 V resulted in a volumetric hydrogen productivity of 1878.0 mL/L from the fermentation chamber, which is 55.4% higher than that (1208.5 mL/L) of the control group without voltage applied. Gas production was not observed in the cathode and anode chambers throughout fermentation. By applying different voltages (0-6 V), the hydrogen content accumulated to 54.6%-84.7%, and it exhibited increases of 7.1%-66.4% compared with that of the control. Meanwhile, the maximum concentrations of acetate and butyrate in the fermentation chamber decreased to 10.3 and 13.1 mmol/L at a voltage of 4 V, respectively, which are 68.0% and 62.4% lower than that for the control. Copyright © 2018 Elsevier Ltd. All rights reserved.

High-Capacity and Long-Cycle Life Aqueous Rechargeable Lithium-Ion Battery with the FePO4 Anode.

PubMed

Wang, Yuesheng; Yang, Shi-Ze; You, Ya; Feng, Zimin; Zhu, Wen; Gariépy, Vincent; Xia, Jiexiang; Commarieu, Basile; Darwiche, Ali; Guerfi, Abdelbast; Zaghib, Karim

2018-02-28

Aqueous lithium-ion batteries are emerging as strong candidates for a great variety of energy storage applications because of their low cost, high-rate capability, and high safety. Exciting progress has been made in the search for anode materials with high capacity, low toxicity, and high conductivity; yet, most of the anode materials, because of their low equilibrium voltages, facilitate hydrogen evolution. Here, we show the application of olivine FePO 4 and amorphous FePO 4 ·2H 2 O as anode materials for aqueous lithium-ion batteries. Their capacities reached 163 and 82 mA h/g at a current rate of 0.2 C, respectively. The full cell with an amorphous FePO 4 ·2H 2 O anode maintained 92% capacity after 500 cycles at a current rate of 0.2 C. The acidic aqueous electrolyte in the full cells prevented cathodic oxygen evolution, while the higher equilibrium voltage of FePO 4 avoided hydrogen evolution as well, making them highly stable. A combination of in situ X-ray diffraction analyses and computational studies revealed that olivine FePO 4 still has the biphase reaction in the aqueous electrolyte and that the intercalation pathways in FePO 4 ·2H 2 O form a 2-D mesh. The low cost, high safety, and outstanding electrochemical performance make the full cells with olivine or amorphous hydrated FePO 4 anodes commercially viable configurations for aqueous lithium-ion batteries.

Oxygen-hydrogen fuel cell with an iodine-iodide cathode - A concept

NASA Technical Reports Server (NTRS)

Javet, P.

1970-01-01

Fuel cell uses a porous cathode through which is fed a solution of iodine in aqueous iodide solution, the anode is a hydrogen electrode. No activation polarization appears on the cathode because of the high exchange-current density of the iodine-iodide electrode.

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

Revisited reaction-diffusion model of thermal desorption spectroscopy experiments on hydrogen retention in material

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

Guterl, Jerome, E-mail: jguterl@ucsd.edu; Smirnov, R. D.; Krasheninnikov, S. I.

Desorption phase of thermal desorption spectroscopy (TDS) experiments performed on tungsten samples exposed to flux of hydrogen isotopes in fusion relevant conditions is analyzed using a reaction-diffusion model describing hydrogen retention in material bulk. Two regimes of hydrogen desorption are identified depending on whether hydrogen trapping rate is faster than hydrogen diffusion rate in material during TDS experiments. In both regimes, a majority of hydrogen released from material defects is immediately outgassed instead of diffusing deeply in material bulk when the evolution of hydrogen concentration in material is quasi-static, which is the case during TDS experiments performed with tungsten samplesmore » exposed to flux of hydrogen isotopes in fusion related conditions. In this context, analytical expressions of the hydrogen outgassing flux as a function of the material temperature are obtained with sufficient accuracy to describe main features of thermal desorption spectra (TDSP). These expressions are then used to highlight how characteristic temperatures of TDSP depend on hydrogen retention parameters, such as trap concentration or activation energy of detrapping processes. The use of Arrhenius plots to characterize retention processes is then revisited when hydrogen trapping takes place during TDS experiments. Retention processes are also characterized using the shape of desorption peaks in TDSP, and it is shown that diffusion of hydrogen in material during TDS experiment can induce long desorption tails visible aside desorption peaks at high temperature in TDSP. These desorption tails can be used to estimate activation energy of diffusion of hydrogen in material.« less

Anode sheath transition in an anodic arc for synthesis of nanomaterials

NASA Astrophysics Data System (ADS)

Nemchinsky, V. A.; Raitses, Y.

2016-06-01

The arc discharge with ablating anode or so-called anodic arc is widely used for synthesis of nanomaterials, including carbon nanotubes and fullerens, metal nanoparticles etc. We present the model of this arc, which confirms the existence of the two different modes of the arc operation with two different anode sheath regimes, namely, with negative anode sheath and with positive anode sheath. It was previously suggested that these regimes are associated with two different anode ablating modes—low ablation mode with constant ablation rate and the enhanced ablation mode (Fetterman et al 2008 Carbon 46 1322). The transition of the arc operation from low ablation mode to high ablation mode is determined by the current density at the anode. The model can be used to self-consistently determine the distribution of the electric field, electron density and electron temperature in the near-anode region of the arc discharge. Simulations of the carbon arc predict that for low arc ablating modes, the current is driven mainly by the electron diffusion to the anode. For positive anode sheath, the anode voltage is close to the ionization potential of anode material, while for negative anode sheath, the anode voltage is an order of magnitude smaller. It is also shown that the near-anode plasma, is far from the ionization equilibrium.

In situ investigation on ultrafast oxygen evolution reactions of water splitting in proton exchange membrane electrolyzer cells

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

Mo, Jingke; Kang, Zhenye; Yang, Gaoqiang

We present that the oxygen evolution reaction (OER) is a half reaction in electrochemical devices, including low-temperature water electrolysis, which is considered as one of the most promising methods to generate hydrogen/oxygen for the storage of energy. It is affected by many factors, and its mechanism is still not completely understood. A proton exchange membrane electrolyzer cell (PEMEC) with optical access to the surface of anode catalyst layer (CL) coupled with a distinguished high-speed and micro-scale visualization system (HMVS) was developed to in situ investigate OERs. It was revealed in real time that OERs only occur on the anode CLmore » adjacent to liquid/gas diffusion layer (LGDL). The CL electrical conductivity plays a crucial role in OERs on CLs. The large in-plane electrical resistance of CLs becomes a threshold of OERs over the entire CL, and causes a lot of catalyst waste in the middle of LGDL pores. Moreover, the oxygen bubble nucleation, growth, and detachment and the effect of current density on those processes were also characterized. Here, this study proposes a new approach for better understanding the mechanisms of OERs and optimizing the design and fabrication of membrane electrode assemblies.« less

In situ investigation on ultrafast oxygen evolution reactions of water splitting in proton exchange membrane electrolyzer cells

DOE PAGES

Mo, Jingke; Kang, Zhenye; Yang, Gaoqiang; ...

2017-08-25

We present that the oxygen evolution reaction (OER) is a half reaction in electrochemical devices, including low-temperature water electrolysis, which is considered as one of the most promising methods to generate hydrogen/oxygen for the storage of energy. It is affected by many factors, and its mechanism is still not completely understood. A proton exchange membrane electrolyzer cell (PEMEC) with optical access to the surface of anode catalyst layer (CL) coupled with a distinguished high-speed and micro-scale visualization system (HMVS) was developed to in situ investigate OERs. It was revealed in real time that OERs only occur on the anode CLmore » adjacent to liquid/gas diffusion layer (LGDL). The CL electrical conductivity plays a crucial role in OERs on CLs. The large in-plane electrical resistance of CLs becomes a threshold of OERs over the entire CL, and causes a lot of catalyst waste in the middle of LGDL pores. Moreover, the oxygen bubble nucleation, growth, and detachment and the effect of current density on those processes were also characterized. Here, this study proposes a new approach for better understanding the mechanisms of OERs and optimizing the design and fabrication of membrane electrode assemblies.« less

Conductive ceramic composition and method of preparation

DOEpatents

Smith, J.L.; Kucera, E.H.

1991-04-16

A ceramic anode composition is formed of a multivalent metal oxide or oxygenate such as an alkali metal, transition metal oxygenate. The anode is prepared as a non-stoichiometric crystalline structure by reaction and conditioning in a hydrogen gas cover containing minor proportions of carbon dioxide and water vapor. The structure exhibits a single phase and substantially enhanced electrical conductivity over that of the corresponding stoichiometric structure. Unexpectedly, such oxides and oxygenates are found to be stable in the reducing anode fuel gas of a molten carbonate fuel cell. 4 figures.

Conductive ceramic composition and method of preparation

DOEpatents

Smith, James L.; Kucera, Eugenia H.

1991-01-01

A ceramic anode composition is formed of a multivalent metal oxide or oxygenate such as an alkali metal, transition metal oxygenate. The anode is prepared as a non-stoichiometric crystalline structure by reaction and conditioning in a hydrogen gas cover containing minor proportions of carbon dioxide and water vapor. The structure exhibits a single phase and substantially enhanced electrical conductivity over that of the corresponding stoichiometric structure. Unexpectedly, such oxides and oxygenates are found to be stable in the reducing anode fuel gas of a molten carbonate fuel cell.

A multiscale physical model for the transient analysis of PEM water electrolyzer anodes.

PubMed

Oliveira, Luiz Fernando L; Laref, Slimane; Mayousse, Eric; Jallut, Christian; Franco, Alejandro A

2012-08-07

Polymer electrolyte membrane water electrolyzers (PEMWEs) are electrochemical devices that can be used for the production of hydrogen. In a PEMWE the anode is the most complex electrode to study due to the high overpotential of the oxygen evolution reaction (OER), not widely understood. A physical bottom-up multi-scale transient model describing the operation of a PEMWE anode is proposed here. This model includes a detailed description of the elementary OER kinetics in the anode, a description of the non-equilibrium behavior of the nanoscale catalyst-electrolyte interface, and a microstructural-resolved description of the transport of charges and O(2) at the micro and mesoscales along the whole anode. The impact of different catalyst materials on the performance of the PEMWE anode, and a study of sensitivity to the operation conditions are evaluated from numerical simulations and the results are discussed in comparison with experimental data.

Modelling the growth process of porous aluminum oxide film during anodization

NASA Astrophysics Data System (ADS)

Aryslanova, E. M.; Alfimov, A. V.; Chivilikhin, S. A.

2015-11-01

Currently it has become important for the development of metamaterials and nanotechnology to obtain regular self-assembled structures. One such structure is porous anodic alumina film that consists of hexagonally packed cylindrical pores. In this work we consider the anodization process, our model takes into account the influence of layers of aluminum and electrolyte on the rate of growth of aluminum oxide, as well as the effect of surface diffusion. In present work we consider those effects. And as a result of our model we obtain the minimum distance between centers of alumina pores in the beginning of anodizing process.

Green synthesis of boron doped graphene and its application as high performance anode material in Li ion battery

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

Sahoo, Madhumita; Sreena, K.P.; Vinayan, B.P.

2015-01-15

Graphical abstract: Boron doped graphene (B-G), synthesized by simple hydrogen induced reduction technique using boric acid as boron precursor, have more uneven surface as a result of smaller bonding distance of boron compared to carbon, showed high capacity and high rate capability compared to pristine graphene as an anode material for Li ion battery application. - Abstract: The present work demonstrates a facile route for the large-scale, catalyst free, and green synthesis approach of boron doped graphene (B-G) and its use as high performance anode material for Li ion battery (LIB) application. Boron atoms were doped into graphene framework withmore » an atomic percentage of 5.93% via hydrogen induced thermal reduction technique using graphite oxide and boric acid as precursors. Various characterization techniques were used to confirm the boron doping in graphene sheets. B-G as anode material shows a discharge capacity of 548 mAh g{sup −1} at 100 mA g{sup −1} after 30th cycles. At high current density value of 1 A g{sup −1}, B-G as anode material enhances the specific capacity by about 1.7 times compared to pristine graphene. The present study shows a simplistic way of boron doping in graphene leading to an enhanced Li ion adsorption due to the change in electronic states.« less

Enhanced methanol utilization in direct methanol fuel cell

DOEpatents

Ren, Xiaoming; Gottesfeld, Shimshon

2001-10-02

The fuel utilization of a direct methanol fuel cell is enhanced for improved cell efficiency. Distribution plates at the anode and cathode of the fuel cell are configured to distribute reactants vertically and laterally uniformly over a catalyzed membrane surface of the fuel cell. A conductive sheet between the anode distribution plate and the anodic membrane surface forms a mass transport barrier to the methanol fuel that is large relative to a mass transport barrier for a gaseous hydrogen fuel cell. In a preferred embodiment, the distribution plate is a perforated corrugated sheet. The mass transport barrier may be conveniently increased by increasing the thickness of an anode conductive sheet adjacent the membrane surface of the fuel cell.

Microbial fuel cell treatment of ethanol fermentation process water

DOEpatents

Borole, Abhijeet P [Knoxville, TN

2012-06-05

The present invention relates to a method for removing inhibitor compounds from a cellulosic biomass-to-ethanol process which includes a pretreatment step of raw cellulosic biomass material and the production of fermentation process water after production and removal of ethanol from a fermentation step, the method comprising contacting said fermentation process water with an anode of a microbial fuel cell, said anode containing microbes thereon which oxidatively degrade one or more of said inhibitor compounds while producing electrical energy or hydrogen from said oxidative degradation, and wherein said anode is in electrical communication with a cathode, and a porous material (such as a porous or cation-permeable membrane) separates said anode and cathode.

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

Abbaszadeh, D.; Wetzelaer, G. A. H.; Dutch Polymer Institute, P.O. Box 902, 5600 AX, Eindhoven

The quenching of excitons at the poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) anode in blue polyalkoxyspirobifluorene-arylamine polymer light-emitting diodes is investigated. Due to the combination of a higher electron mobility and the presence of electron traps, the recombination zone shifts from the cathode to the anode with increasing voltage. The exciton quenching at the anode at higher voltages leads to an efficiency roll-off. The voltage dependence of the luminous efficiency is reproduced by a drift-diffusion model under the condition that quenching of excitons at the PEDOT:PSS anode and metallic cathode is of equal strength. Experimentally, the efficiency roll-off at high voltages due tomore » anode quenching is eliminated by the use of an electron-blocking layer between the anode and the light-emitting polymer.« less

Increased performance of hydrogen production in microbial electrolysis cells under alkaline conditions.

PubMed

Rago, Laura; Baeza, Juan A; Guisasola, Albert

2016-06-01

This work reports the first successful enrichment and operation of alkaline bioelectrochemical systems (microbial fuel cells, MFC, and microbial electrolysis cells, MEC). Alkaline (pH=9.3) bioelectrochemical hydrogen production presented better performance (+117%) compared to conventional neutral conditions (2.6 vs 1.2 litres of hydrogen gas per litre of reactor per day, LH2·L(-1)REACTOR·d(-1)). Pyrosequencing results of the anodic biofilm showed that while Geobacter was mainly detected under conventional neutral conditions, Geoalkalibacter sp. was highly detected in the alkaline MFC (21%) and MEC (48%). This is the first report of a high enrichment of Geoalkalibacter from an anaerobic mixed culture using alkaline conditions in an MEC. Moreover, Alkalibacter sp. was highly present in the anodic biofilm of the alkaline MFC (37%), which would indicate its potentiality as a new exoelectrogen. Copyright © 2016 Elsevier B.V. All rights reserved.

Simulation of the Impact of Si Shell Thickness on the Performance of Si-Coated Vertically Aligned Carbon Nanofiber as Li-Ion Battery Anode

PubMed Central

Das, Susobhan; Li, Jun; Hui, Rongqing

2015-01-01

Micro- and nano-structured electrodes have the potential to improve the performance of Li-ion batteries by increasing the surface area of the electrode and reducing the diffusion distance required by the charged carriers. We report the numerical simulation of Lithium-ion batteries with the anode made of core-shell heterostructures of silicon-coated carbon nanofibers. We show that the energy capacity can be significantly improved by reducing the thickness of the silicon anode to the dimension comparable or less than the Li-ion diffusion length inside silicon. The results of simulation indicate that the contraction of the silicon electrode thickness during the battery discharge process commonly found in experiments also plays a major role in the increase of the energy capacity. PMID:28347120

World Hydrogen Energy Conference, 5th, Toronto, Canada, July 15-19, 1984, Proceedings

NASA Astrophysics Data System (ADS)

Veziroglu, T. N.; Taylor, J. B.

Among the topics discussed are thermochemical and hybrid processes for hydrogen production, pyrite-assisted water electrolysis, a hydrogen distribution network for industrial use in Western Europe, the combustion of alternative fuels in spark-ignition engines, the use of fuel cells in locomotive propulsion, hydrogen storage by glass microencapsulation, and FeTi compounds' hydriding. Also covered are plasmachemical methods of energy carrier production, synthetic fuels' production in small scale plants, products found in the anodic oxidation of coal, hydrogen embrittlement, and the regulating step in LaNi5 hydride formation.

Fermi level dependence of hydrogen diffusivity in GaN

NASA Astrophysics Data System (ADS)

Polyakov, A. Y.; Smirnov, N. B.; Pearton, S. J.; Ren, F.; Theys, B.; Jomard, F.; Teukam, Z.; Dmitriev, V. A.; Nikolaev, A. E.; Usikov, A. S.; Nikitina, I. P.

2001-09-01

Hydrogen diffusion studies were performed in GaN samples with different Fermi level positions. It is shown that, at 350 °C, hydrogen diffusion is quite fast in heavily Mg doped p-type material with the Fermi level close to Ev+0.15 eV, considerably slower in high-resistivity p-GaN(Zn) with the Fermi level Ev+0.9 eV, while for conducting and semi-insulating n-GaN samples with the Fermi level in the upper half of the band gap no measurable hydrogen diffusion could be detected. For these latter samples it is shown that higher diffusion temperature of 500 °C and longer times (50 h) are necessary to incorporate hydrogen to appreciable depth. These findings are in line with previously published theoretical predictions of the dependence of hydrogen interstitials formation in GaN on the Fermi level position.

Direct current H- source for the medicine accelerator (invited)

NASA Astrophysics Data System (ADS)

Belchenko, Yu.; Savkin, V.

2004-05-01

A compact cw hydrogen negative ion source having reliable operation and a simplified maintenance is developed at Budker Institute of Nuclear Physics for a tandem accelerator of boron capture neutron therapy installation. The source uses a Penning discharge with a hydrogen and cesium feed through the hollows in the cathodes. Discharge voltage is about 60-80 V, current 9 A, hydrogen pressure 4-5 Pa, magnetic field 0.05-0.1 T, and cesium seed <1 mg/h. Negative ions are mainly produced on the cesiated anode surface due to conversion of hydrogen atoms. An optimal anode temperature is 250-350 °C. Negative ion beam current is directly proportional to the discharge current and to the emission hole area. A triode system for the beam extraction and acceleration system is used. The flux of accompanying extracted electrons was decreased by filtering in the transverse magnetic field. This electron flux was intercepted to the special electrode, biased at 4 kV potential with respect to the anode. Source stable cw operation for several hour runs was multiply tested. A H- ion beam with current up to 8 mA, beam energy 23 keV was produced regularly. Negative ion current of heavy impurities had a value of about 3% of the total beam current. Beam normalized emittance is about 0.3 π mm mrad and emission current density -0.1 A/cm2. A built-in cathode heater provides the operation quick start.

High-velocity DC-VPS for diffusion and protecting barrier layers in solid oxide fuel cells (SOFCs)

NASA Astrophysics Data System (ADS)

Henne, R. H.; Franco, T.; Ruckdäschel, R.

2006-12-01

High-temperature fuel cells of the solid oxide fuel cell (SOFC) type as direct converter of chemical into electrical energy show a high potential for reducing considerably the specific energy consumption in different application fields. Of particular interest are advanced lightweight planar cells for electricity supply units in cars and other mobile systems. Such cells, in one new design, consist mainly of metallic parts, for example, of ferrite steels. These cells shall operate in the temperature range of 700 to 800 °C where oxidation and diffusion processes can be of detrimental effect on cell performance for long-term operation. Problems arise in particular by diffusion of chromium species from the interconnect or the cell containment into the electrolyte/cathode interface forming insulating phases and by the mutual diffusion of substrate and anode material, for example, iron and chromium from the ferrite into the anode and nickel from the anode into the ferrite, which in both cases reduces performance and system lifetime. Additional intermediate layers of perovskite-type material, (e.g., doped LaCrO3) applied with high-velocity direct-current vacuum plasma spraying (DC-VPS) can reduce such effects considerably if they are stable and of high electronic conductivity.

Hydrogen loss and its improved retention in hydrogen plasma treated a-SiNx:H films: ERDA study with 100 MeV Ag7+ ions

NASA Astrophysics Data System (ADS)

Bommali, R. K.; Ghosh, S.; Khan, S. A.; Srivastava, P.

2018-05-01

Hydrogen loss from a-SiNx:H films under irradiation with 100 MeV Ag7+ ions using elastic recoil detection analysis (ERDA) experiment is reported. The results are explained under the basic assumptions of the molecular recombination model. The ERDA hydrogen concentration profiles are composed of two distinct hydrogen desorption processes, limited by rapid molecular diffusion in the initial stages of irradiation, and as the fluence progresses a slow process limited by diffusion of atomic hydrogen takes over. Which of the aforesaid processes dominates, is determined by the continuously evolving Hydrogen concentration within the films. The first process dominates when the H content is high, and as the H concentration falls below a certain threshold (Hcritical) the irradiation generated H radicals have to diffuse through larger distances before recombining to form H2, thereby significantly bringing down the hydrogen evolution rate. The ERDA measurements were also carried out for films treated with low temperature (300 °C) hydrogen plasma annealing (HPA). The HPA treated films show a clear increase in Hcritical value, thus indicating an improved diffusion of atomic hydrogen, resulting from healing of weak bonds and passivation of dangling bonds. Further, upon HPA films show a significantly higher H concentration relative to the as-deposited films, at advanced fluences. These results indicate the potential of HPA towards improved H retention in a-SiNx:H films. The study distinguishes clearly the presence of two diffusion processes in a-SiNx:H whose diffusion rates differ by an order of magnitude, with atomic hydrogen not being able to diffuse further beyond ∼ 1 nm from the point of its creation.

Energy & mass-charge distribution peculiarities of ion emitted from penning source

NASA Astrophysics Data System (ADS)

Mamedov, N. V.; Kolodko, D. V.; Sorokin, I. A.; Kanshin, I. A.; Sinelnikov, D. N.

2017-05-01

The optimization of hydrogen Penning sources used, in particular, in plasma chemical processing of materials and DLC deposition, is still very important. Investigations of mass-charge composition of these ion source emitted beams are particular relevant for miniature linear accelerators (neutron flux generators) nowadays. The Penning ion source energy and mass-charge ion distributions are presented. The relation between the discharge current abrupt jumps with increasing plasma density in the discharge center and increasing potential whipping (up to 50% of the anode voltage) is shown. Also the energy spectra in the discharge different modes as the pressure and anode potential functions are presented. It has been revealed that the atomic hydrogen ion concentration is about 5-10%, and it weakly depends on the pressure and the discharge current (in the investigated range from 1 to 10 mTorr and from 50 to 1000 μA) and increases with the anode voltage (up 1 to 3,5 kV).

Enhanced activity of Au-Fe/C anodic electrocatalyst for direct borohydride-hydrogen peroxide fuel cell

NASA Astrophysics Data System (ADS)

Yi, Lanhua; Wei, Wei; Zhao, Caixian; Tian, Li; Liu, Jing; Wang, Xianyou

2015-07-01

Carbon supported Au-Fe bimetallic nanocatalysts (Au-Fe/C) are facilely prepared via a modified NaBH4 reduction method in aqueous solution at room temperature, and used as the anode electrocatalyst of direct borohydride-hydrogen peroxide fuel cell (DBHFC). The physical and electrochemical properties of the Au-Fe/C electrocatalysts are characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), cyclic voltammetry (CV), rotating disc electrode (RDE) voltammetry, chronoamperometry (CA), chronopotentiometry (CP), and fuel cell test. The results show that Au-Fe/C catalysts display higher catalytic activity for the direct electrooxidation of BH4- than carbon supported pure Au nanocatalyst (Au/C), especially Au50Fe50/C catalyst presents the highest catalytic activity among all as-prepared catalysts. Besides, the single DBHFC with Au50Fe50/C anode and Au/C cathode obtains the maximum power density as high as 34.9 mW cm-2 at 25 °C.

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

Sodium Borohydride/Hydrogen Peroxide Fuel Cells For Space Application

NASA Technical Reports Server (NTRS)

Valdez, T. I.; Deelo, M. E.; Narayanan, S. R.

2006-01-01

This viewgraph presentation examines Sodium Borohydride and Hydrogen Peroxide Fuel Cells as they are applied to space applications. The topics include: 1) Motivation; 2) The Sodium Borohydride Fuel Cell; 3) Sodium Borohydride Fuel Cell Test Stands; 4) Fuel Cell Comparisons; 5) MEA Performance; 6) Anode Polarization; and 7) Electrode Analysis. The benefits of hydrogen peroxide as an oxidant and benefits of sodium borohydride as a fuel are also addressed.

Hydrogen production in single chamber microbial electrolysis cells with different complex substrates.

PubMed

Montpart, Nuria; Rago, Laura; Baeza, Juan A; Guisasola, Albert

2015-01-01

The use of synthetic wastewater containing carbon sources of different complexity (glycerol, milk and starch) was evaluated in single chamber microbial electrolysis cell (MEC) for hydrogen production. The growth of an anodic syntrophic consortium between fermentative and anode respiring bacteria was operationally enhanced and increased the opportunities of these complex substrates to be treated with this technology. During inoculation, current intensities achieved in single chamber microbial fuel cells were 50, 62.5, and 9 A m⁻³ for glycerol, milk and starch respectively. Both current intensities and coulombic efficiencies were higher than other values reported in previous works. The simultaneous degradation of the three complex substrates favored power production and COD removal. After three months in MEC operation, hydrogen production was only sustained with milk as a single substrate and with the simultaneous degradation of the three substrates. The later had the best results in terms of current intensity (150 A m⁻³), hydrogen production (0.94 m³ m⁻³ d⁻¹) and cathodic gas recovery (91%) at an applied voltage of 0.8 V. Glycerol and starch as substrates in MEC could not avoid the complete proliferation of hydrogen scavengers, even under low hydrogen retention time conditions induced by continuous nitrogen sparging.

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.

Diffusion of hydrogen in a hydrogen-saturated tungsten

NASA Astrophysics Data System (ADS)

Krstic, Predrag; Kaganovich, Igor

2015-11-01

Hydrogen diffusion in monoscrystalline tungsten is studied by molecular dynamics with BOP potential in function of hydrogen concentration and temperature. Tungsten surface is prepared by cumulative irradiation of the 25 eV deuterium atoms at various fluences. The diffusion coefficients for T>500K and various D concentrations were calculated from the average slope of the mean square displacements of deuterium as functions of time. The accumulation of deuterium suppresses its diffusion at all temperatures. The results are in a reasonable agreement with the existing experiments. Supported by the LDRD of PPPL.

Borophane as a Benchmate of Graphene: A Potential 2D Material for Anode of Li and Na-Ion Batteries.

PubMed

Jena, Naresh K; Araujo, Rafael B; Shukla, Vivekanand; Ahuja, Rajeev

2017-05-17

Borophene, single atomic-layer sheet of boron ( Science 2015 , 350 , 1513 ), is a rather new entrant into the burgeoning class of 2D materials. Borophene exhibits anisotropic metallic properties whereas its hydrogenated counterpart borophane is reported to be a gapless Dirac material lying on the same bench with the celebrated graphene. Interestingly, this transition of borophane also rendered stability to it considering the fact that borophene was synthesized under ultrahigh vacuum conditions on a metallic (Ag) substrate. On the basis of first-principles density functional theory computations, we have investigated the possibilities of borophane as a potential Li/Na-ion battery anode material. We obtained a binding energy of -2.58 (-1.08 eV) eV for Li (Na)-adatom on borophane and Bader charge analysis revealed that Li(Na) atom exists in Li + (Na + ) state. Further, on binding with Li/Na, borophane exhibited metallic properties as evidenced by the electronic band structure. We found that diffusion pathways for Li/Na on the borophane surface are anisotropic with x direction being the favorable one with a barrier of 0.27 and 0.09 eV, respectively. While assessing the Li-ion anode performance, we estimated that the maximum Li content is Li 0.445 B 2 H 2 , which gives rises to a material with a maximum theoretical specific capacity of 504 mAh/g together with an average voltage of 0.43 V versus Li/Li + . Likewise, for Na-ion the maximum theoretical capacity and average voltage were estimated to be 504 mAh/g and 0.03 V versus Na/Na + , respectively. These findings unambiguously suggest that borophane can be a potential addition to the map of Li and Na-ion anode materials and can rival some of the recently reported 2D materials including graphene.

Electrochemical properties of electrodes with different shapes and diffusion kinetic analysis of microbial fuel cells on ocean floor

NASA Astrophysics Data System (ADS)

Fu, Yubin; Liu, Jia; Su, Jia; Zhao, Zhongkai; Liu, Yang; Xu, Qian

2012-03-01

Microbial fuel cell (MFC) on the ocean floor is a kind of novel energy- harvesting device that can be developed to drive small instruments to work continuously. The shape of electrode has a great effect on the performance of the MFC. In this paper, several shapes of electrode and cell structure were designed, and their performance in MFC were compared in pairs: Mesh (cell-1) vs. flat plate (cell-2), branch (cell-3) vs. cylinder (cell-4), and forest (cell-5) vs. disk (cell-6) FC. Our results showed that the maximum power densities were 16.50, 14.20, 19.30, 15.00, 14.64, and 9.95 mWm-2 for cell-1, 2, 3, 4, 5 and 6 respectively. And the corresponding diffusion-limited currents were 7.16, 2.80, 18.86, 10.50, 18.00, and 6.900 mA. The mesh and branch anodes showed higher power densities and much higher diffusion-limited currents than the flat plate and the cylinder anodes respectively due to the low diffusion hindrance with the former anodes. The forest cathode improved by 47% of the power density and by 161% of diffusion-limited current than the disk cathode due to the former's extended solid/liquid/gas three-phase boundary. These results indicated that the shape of electrode is a major parameter that determining the diffusion-limited current of an MFC, and the differences in the electrode shape lead to the differences in cell performance. These results would be useful for MFC structure design in practical applications.

Systems and methods for preparation and separation of products

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

Gilliam, Ryan J.; Boggs, Bryan; Self, Kyle

There are provided methods and systems for an electrochemical cell including an anode and a cathode where the anode is contacted with a metal ion that converts the metal ion from a lower oxidation state to a higher oxidation state. The metal ion in the higher oxidation state is reacted with hydrogen gas, an unsaturated hydrocarbon, and/or a saturated hydrocarbon to form products.

Single-ring magnetic cusp low gas pressure ion source

DOEpatents

Bacon, Frank M.; Brainard, John P.; O'Hagan, James B.; Walko, Robert J.

1985-01-01

A single-ring magnetic cusp low gas pressure ion source designed for use in a sealed, nonpumped neutron generator utilizes a cathode and an anode, three electrically floating electrodes (a reflector behind the cathode, a heat shield around the anode, and an aperture plate), together with a single ring-cusp magnetic field, to establish and energy-filtering mechanism for producing atomic-hydrogen ions.

Systems and methods for preparation and separation of products

DOEpatents

Gilliam, Ryan J.; Boggs, Bryan; Self, Kyle; Leclerc, Margarete K.; Gorer, Alexander; Weiss, Michael J.; Miller, John H.; Mohanta, Samaresh

2015-12-01

There are provided methods and systems for an electrochemical cell including an anode and a cathode where the anode is contacted with a metal ion that converts the metal ion from a lower oxidation state to a higher oxidation state. The metal ion in the higher oxidation state is reacted with hydrogen gas, an unsaturated hydrocarbon, and/or a saturated hydrocarbon to form products.

Incorporation of heterostructured Sn/SnO nanoparticles in crumpled nitrogen-doped graphene nanosheets for application as anodes in lithium-ion batteries.

PubMed

Du, Fei-Hu; Liu, Yu-Si; Long, Jie; Zhu, Qian-Cheng; Wang, Kai-Xue; Wei, Xiao; Chen, Jie-Sheng

2014-09-07

Sn/SnO nanoparticles are incorporated in crumpled nitrogen-doped graphene nanosheets by a simple melting diffusion method. The resulting composite exhibits large specific capacity, excellent cycling stability and high rate capability as an anode for lithium-ion batteries.

Electrolytic production of metals using a resistant anode

DOEpatents

Tarcy, Gary P.; Gavasto, Thomas M.; Ray, Siba P.

1986-01-01

An electrolytic process comprising evolving oxygen on an anode in a molten salt, the anode comprising an alloy comprising a first metal and a second metal, both metals forming oxides, the oxide of the first metal being more resistant than the second metal to attack by the molten salt, the oxide of the second metal being more resistant than the first metal to the diffusion of oxygen. The electrode may also be formed of CuAlO.sub.2 and/or Cu.sub.2 O.

Efficient Flexible Organic/Inorganic Hybrid Perovskite Light-Emitting Diodes Based on Graphene Anode.

PubMed

Seo, Hong-Kyu; Kim, Hobeom; Lee, Jaeho; Park, Min-Ho; Jeong, Su-Hun; Kim, Young-Hoon; Kwon, Sung-Joo; Han, Tae-Hee; Yoo, Seunghyup; Lee, Tae-Woo

2017-03-01

Highly efficient organic/inorganic hybrid perovskite light-emitting diodes (PeLEDs) based on graphene anode are developed for the first time. Chemically inert graphene avoids quenching of excitons by diffused metal atom species from indium tin oxide. The flexible PeLEDs with graphene anode on plastic substrate show good bending stability; they provide an alternative and reliable flexible electrode for highly efficient flexible PeLEDs. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Theory of ion transport with fast acid-base equilibrations in bioelectrochemical systems.

PubMed

Dykstra, J E; Biesheuvel, P M; Bruning, H; Ter Heijne, A

2014-07-01

Bioelectrochemical systems recover valuable components and energy in the form of hydrogen or electricity from aqueous organic streams. We derive a one-dimensional steady-state model for ion transport in a bioelectrochemical system, with the ions subject to diffusional and electrical forces. Since most of the ionic species can undergo acid-base reactions, ion transport is combined in our model with infinitely fast ion acid-base equilibrations. The model describes the current-induced ammonia evaporation and recovery at the cathode side of a bioelectrochemical system that runs on an organic stream containing ammonium ions. We identify that the rate of ammonia evaporation depends not only on the current but also on the flow rate of gas in the cathode chamber, the diffusion of ammonia from the cathode back into the anode chamber, through the ion exchange membrane placed in between, and the membrane charge density.

Anisotropic hydrogen diffusion in α-Zr and Zircaloy predicted by accelerated kinetic Monte Carlo simulations

NASA Astrophysics Data System (ADS)

Zhang, Yongfeng; Jiang, Chao; Bai, Xianming

2017-01-01

This report presents an accelerated kinetic Monte Carlo (KMC) method to compute the diffusivity of hydrogen in hcp metals and alloys, considering both thermally activated hopping and quantum tunneling. The acceleration is achieved by replacing regular KMC jumps in trapping energy basins formed by neighboring tetrahedral interstitial sites, with analytical solutions for basin exiting time and probability. Parameterized by density functional theory (DFT) calculations, the accelerated KMC method is shown to be capable of efficiently calculating hydrogen diffusivity in α-Zr and Zircaloy, without altering the kinetics of long-range diffusion. Above room temperature, hydrogen diffusion in α-Zr and Zircaloy is dominated by thermal hopping, with negligible contribution from quantum tunneling. The diffusivity predicted by this DFT + KMC approach agrees well with that from previous independent experiments and theories, without using any data fitting. The diffusivity along is found to be slightly higher than that along , with the anisotropy saturated at about 1.20 at high temperatures, resolving contradictory results in previous experiments. Demonstrated using hydrogen diffusion in α-Zr, the same method can be extended for on-lattice diffusion in hcp metals, or systems with similar trapping basins.

Anisotropic hydrogen diffusion in α-Zr and Zircaloy predicted by accelerated kinetic Monte Carlo simulations

PubMed Central

Zhang, Yongfeng; Jiang, Chao; Bai, Xianming

2017-01-01

This report presents an accelerated kinetic Monte Carlo (KMC) method to compute the diffusivity of hydrogen in hcp metals and alloys, considering both thermally activated hopping and quantum tunneling. The acceleration is achieved by replacing regular KMC jumps in trapping energy basins formed by neighboring tetrahedral interstitial sites, with analytical solutions for basin exiting time and probability. Parameterized by density functional theory (DFT) calculations, the accelerated KMC method is shown to be capable of efficiently calculating hydrogen diffusivity in α-Zr and Zircaloy, without altering the kinetics of long-range diffusion. Above room temperature, hydrogen diffusion in α-Zr and Zircaloy is dominated by thermal hopping, with negligible contribution from quantum tunneling. The diffusivity predicted by this DFT + KMC approach agrees well with that from previous independent experiments and theories, without using any data fitting. The diffusivity along is found to be slightly higher than that along , with the anisotropy saturated at about 1.20 at high temperatures, resolving contradictory results in previous experiments. Demonstrated using hydrogen diffusion in α-Zr, the same method can be extended for on-lattice diffusion in hcp metals, or systems with similar trapping basins. PMID:28106154

Anisotropic hydrogen diffusion in α-Zr and Zircaloy predicted by accelerated kinetic Monte Carlo simulations

DOE PAGES

Zhang, Yongfeng; Jiang, Chao; Bai, Xianming

2017-01-20

Here, this report presents an accelerated kinetic Monte Carlo (KMC) method to compute the diffusivity of hydrogen in hcp metals and alloys, considering both thermally activated hopping and quantum tunneling. The acceleration is achieved by replacing regular KMC jumps in trapping energy basins formed by neighboring tetrahedral interstitial sites, with analytical solutions for basin exiting time and probability. Parameterized by density functional theory (DFT) calculations, the accelerated KMC method is shown to be capable of efficiently calculating hydrogen diffusivity in α-Zr and Zircaloy, without altering the kinetics of long-range diffusion. Above room temperature, hydrogen diffusion in α-Zr and Zircaloy ismore » dominated by thermal hopping, with negligible contribution from quantum tunneling. The diffusivity predicted by this DFT + KMC approach agrees well with that from previous independent experiments and theories, without using any data fitting. The diffusivity along < c > is found to be slightly higher than that along < a >, with the anisotropy saturated at about 1.20 at high temperatures, resolving contradictory results in previous experiments. Demonstrated using hydrogen diffusion in α-Zr, the same method can be extended for on-lattice diffusion in hcp metals, or systems with similar trapping basins.« less

Hydrogen generation by electrolysis of aqueous organic solutions

NASA Technical Reports Server (NTRS)

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

2006-01-01

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

Hydrogen generation by electrolysis of aqueous organic solutions

NASA Technical Reports Server (NTRS)

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

2002-01-01

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

The charge-discharge characteristics and diffusion mechanism of Ti-Si-Al thin film anode using an electrically induced crystallization process

NASA Astrophysics Data System (ADS)

Chen, Yen-Ting; Hung, Fei-Yi; Lui, Truan-Sheng

2018-04-01

In this study, an Al-Si-Ti multilayer thin film structure is designed as the anode of a lithium ion battery. The novel structure restricts the expansion of Si during charge-discharge, and its battery capacity can reach 1112 mA h g-1 after a 100-cycle charge-charging test under a 0.2 C charge-discharge rate without annealing. Notably, after a 200 °C vacuum annealing process, the cyclic capacity of the anode rises to 1208 mA h g-1 through crystallization of the Al and Ti buffer layer. However, its thermal diffusion behavior in the Al/Si or Ti/Si interfaces seriously reduces the performance and restricts the expansion of Si. The electrically induced crystallization (EIC) process not only performs crystallization but also controls the interfacial stability, after which its capacity can obviously improve to 1602 mA h g-1 after 100 cycles. Using EIC, the electron flow drives the Cu and Al atoms to endow the Si matrix with doping properties and further increases the electron conductivity of the anode. This result demonstrates that the EIC process is a suitable post-treatment process for multilayer anodes and provides a reference for future battery designs.

Natural gas-assisted steam electrolyzer

DOEpatents

Pham, Ai-Quoc; Wallman, P. Henrik; Glass, Robert S.

2000-01-01

An efficient method of producing hydrogen by high temperature steam electrolysis that will lower the electricity consumption to an estimated 65 percent lower than has been achievable with previous steam electrolyzer systems. This is accomplished with a natural gas-assisted steam electrolyzer, which significantly reduces the electricity consumption. Since this natural gas-assisted steam electrolyzer replaces one unit of electrical energy by one unit of energy content in natural gas at one-quarter the cost, the hydrogen production cost will be significantly reduced. Also, it is possible to vary the ratio between the electricity and the natural gas supplied to the system in response to fluctuations in relative prices for these two energy sources. In one approach an appropriate catalyst on the anode side of the electrolyzer will promote the partial oxidation of natural gas to CO and hydrogen, called Syn-Gas, and the CO can also be shifted to CO.sub.2 to give additional hydrogen. In another approach the natural gas is used in the anode side of the electrolyzer to burn out the oxygen resulting from electrolysis, thus reducing or eliminating the potential difference across the electrolyzer membrane.

Three-Dimensional Transport Modeling for Proton Exchange Membrane(PEM) Fuel Cell with Micro Parallel Flow Field

PubMed Central

Lee, Pil Hyong; Han, Sang Seok; Hwang, Sang Soon

2008-01-01

Modeling and simulation for heat and mass transport in micro channel are being used extensively in researches and industrial applications to gain better understanding of the fundamental processes and to optimize fuel cell designs before building a prototype for engineering application. In this study, we used a single-phase, fully three dimensional simulation model for PEMFC that can deal with both anode and cathode flow field for examining the micro flow channel with electrochemical reaction. The results show that hydrogen and oxygen were solely supplied to the membrane by diffusion mechanism rather than convection transport, and the higher pressure drop at cathode side is thought to be caused by higher flow rate of oxygen at cathode. And it is found that the amount of water in cathode channel was determined by water formation due to electrochemical reaction plus electro-osmotic mass flux directing toward the cathode side. And it is very important to model the back diffusion and electro-osmotic mass flux accurately since the two flux was closely correlated each other and greatly influenced for determination of ionic conductivity of the membrane which directly affects the performance of fuel cell. PMID:27879774

Hydrogen sulfide-powered solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Liu, Man

2004-12-01

The potential utilization of hydrogen sulfide as fuel in solid oxide fuel cells has been investigated using an oxide-ion conducting YSZ electrolyte and different kinds of anode catalysts at operating temperatures in the range of 700--900°C and at atmospheric pressure. This technology offers an economically attractive alternative to present methods for removing toxic and corrosive H2S gas from sour gas streams and a promising approach for cogenerating electrical energy and useful chemicals. The primary objective of the present research was to find active and stable anode materials. Fuel cell experimental results showed that platinum was a good electrocatalyst for the conversion of H2S, but the Pt/YSZ interface was physically unstable due to the reversible formation and decomposition of PtS in H 2S streams at elevated temperatures. Moreover, instability of the Pt/YSZ interface was accelerated significantly by electrochemical reactions, and ultimately led to the detachment of the Pt anode from the electrolyte. It has been shown that an interlayer of TiO2 stabilized the Pt anode on YSZ electrolyte, thereby prolonging cell lifetime. However, the current output for a fuel cell using Pt/TiO2 as anode was not improved compared to using Pt alone. It was therefore necessary to investigate novel anode systems for H 2S-air SOFCs. New anode catalysts comprising composite metal sulfides were developed. These catalysts exhibited good electrical conductivity and better catalytic activity than Pt. In contrast to MoS2 alone, composite catalysts (M-Mo-S, M = Fe, Co, Ni) were not volatile and had superior stability. However, when used for extended periods of time, detachment of Pt current collecting film from anodes comprising metal sulfides alone resulted in a large increase in contact resistance and reduction in cell performance. Consequently, a systematic investigation was conducted to identify alternative electronic conductors for use with M-Mo-S catalysts. Anode catalysts comprising Co-Mo-S admixed with up to 10% Ag powder were found to have excellent performance and longevity, as well as improved electrical contact when compared with Pt/M-Mo-S anode systems. The highest current density of 450 mA/cm2 and power density of 115 mW/cm2 were achieved with an anode that consisted of 95% (Co-Mo-S) and 5% Ag.

Unsteady planar diffusion flames: Ignition, travel, burnout

NASA Technical Reports Server (NTRS)

Fendell, F.; Wu, F.

1995-01-01

In microgravity, a thin planar diffusion flame is created and thenceforth travels so that the flame is situated at all times at an interface at which the hydrogen and oxygen meet in stoichiometric proportion. If the initial amount of hydrogen is deficient relative to the initial amount of oxygen, then the planar flame will travel further and further into the half volume initially containing hydrogen, until the hydrogen is (virtually) fully depleted. Of course, when the amount of residual hydrogen becomes small, the diffusion flame is neither vigorous nor thin; in practice, the flame is extinguished before the hydrogen is fully depleted, owing to the finite rate of the actual chemical-kinetic mechanism. The rate of travel of the hydrogen-air diffusion flame is much slower than the rate of laminar flame propagation through a hydrogen-air mixture. This slow travel facilitates diagnostic detection of the flame position as a function of time, but the slow travel also means that the time to burnout (extinction) probably far exceeds the testing time (typically, a few seconds) available in earth-sited facilities for microgravity-environment experiments. We undertake an analysis to predict (1) the position and temperature of the diffusion flame as a function of time, (2) the time at which extinction of the diffusion flame occurs, and (3) the thickness of quench layers formed on side walls (i.e., on lateral boundaries, with normal vectors parallel to the diffusion-flame plane), and whether, prior to extinction, water vapor formed by burning will condense on these cold walls.

Towards Stable Lithium-Sulfur Batteries with a Low Self-Discharge Rate: Ion Diffusion Modulation and Anode Protection.

PubMed

Xu, Wen-Tao; Peng, Hong-Jie; Huang, Jia-Qi; Zhao, Chen-Zi; Cheng, Xin-Bing; Zhang, Qiang

2015-09-07

The self-discharge of a lithium-sulfur cell decreases the shelf-life of the battery and is one of the bottlenecks that hinders its practical applications. New insights into both the internal chemical reactions in a lithium-sulfur system and effective routes to retard self-discharge for highly stable batteries are crucial for the design of lithium-sulfur cells. Herein, a lithium-sulfur cell with a carbon nanotube/sulfur cathode and lithium-metal anode in lithium bis(trifluoromethanesulfonyl)imide/1,3-dioxolane/dimethyl ether electrolyte was selected as the model system to investigate the self-discharge behavior. Both lithium anode passivation and polysulfide anion diffusion suppression strategies are applied to reduce self-discharge of the lithium-sulfur cell. When the lithium-metal anode is protected by a high density passivation layer induced by LiNO3 , a very low shuttle constant of 0.017 h(-1) is achieved. The diffusion of the polysulfides is retarded by an ion-selective separator, and the shuttle constants decreased. The cell with LiNO3 additive maintained a discharge capacity of 97 % (961 mAh g(-1) ) of the initial capacity after 120 days at open circuit, which was around three times higher than the routine cell (32 % of initial capacity, corresponding to 320 mAh g(-1) ). It is expected that lithium-sulfur batteries with ultralow self-discharge rates may be fabricated through a combination of anode passivation and polysulfide shuttle control, as well as optimization of the lithium-sulfur cell configuration. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Computational modeling of transport and electrochemical reactions in proton-exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Um, Sukkee

A comprehensive, multi-physics computational fuel cell dynamics (CFCD) model integrating electrochemical kinetics, charge transport, mass transport (particularly water transport), and flow dynamics is developed in this thesis. The numerical model is validated against published experimental data and utilized to generate results that reveal the internal operation of a PEM fuel cell. A number of model applications are demonstrated in the present work. First, the CFCD model is applied to explore hydrogen dilution effects in the anode feed. Detailed two-dimensional electrochemical and flow/transport simulations are provided to examine substantial anode concentration polarization due to hydrogen depletion at the reaction sites. A transient simulation of the cell current response to a step change in cell voltage is also attempted to elucidate characteristics of the dynamic response of a fuel cell for the first time. After the two-dimensional computational study, the CFCD model is applied to illustrate three-dimensional interactions between mass transfer and electrochemical kinetics. Emphasis is placed on obtaining a fundamental understanding of fully three-dimensional flow in the air cathode with interdigitated flowfield design and how it impacts the transport and electrochemical reaction processes. The innovative design concept for enhanced oxygen transport to, and effective water removal from the cathode, is explored numerically. Next, an analytical study of water transport is performed to investigate various water transport regimes of practical interest. The axial locations characteristic of anode water loss and cathode flooding are predicted theoretically and compared with numerical results. A continuous stirred fuel cell reactor (CSFCR) model is also proposed for the limiting situation where the anode and cathode sides reach equilibrium in water concentration with a thin ionomer membrane in between. In addition to the analytical solutions, a detailed water transport model extending the CFCD framework is developed in which a unified water equation is arrived at using the equilibrium water uptake curve between the gas and membrane phases. Various modes of water transport, i.e. diffusion, convection, and electro-osmotic drag, are incorporated in the unified water transport equation. This water transport model is then applied to elucidate water management in three-dimensional fuel cells with dry to low humidified inlet gases after its validation against available experimental data with dry oxidant and fuel streams. An internal circulation of water with the aid of counter-flow design is found to be essential for low-humidity operation, for example, in portable application of a PEM fuel cell without external humidifier. Finally, to handle the most important issue associated with PEM fuel cells using reformate gas, namely the CO poisoning anode Pt catalysts, a major modification of the present CFCD model is made to include CO oxidation processes. A four-step CO poisoning mechanism is implemented here and anode species equation for CO is added to model the electro- and chemical-oxidation processes on the anode. Numerical results of CO poisoning effects using a commercial package, STAR-CD, are presented. Basic features of CO poisoning are delineated and discussed. Future research areas of the fuel cell modeling are also indicated. As an example, preliminary results of extending the CFCD model to include heat transfer using a commercial package, FLUENTRTM, are given to demonstrate the need for careful thermal management in a multi-cell stack design.

Measurements of the Activation Energies for Atomic Hydrogen Diffusion on Pure Solid CO

NASA Astrophysics Data System (ADS)

Kimura, Y.; Tsuge, M.; Pirronello, V.; Kouchi, A.; Watanabe, N.

2018-05-01

The diffusion of hydrogen atoms on dust grains is a key process in the formation of interstellar H2 and some hydrogenated molecules such as formaldehyde and methanol. We investigate the adsorption and diffusion of H atoms on pure solid CO as an analog of dust surfaces observed toward some cold interstellar regions. Using a combination of photostimulated desorption and resonance-enhanced multiphoton ionization methods to detect H atoms directly, the relative adsorption probabilities and diffusion coefficients of the H atoms are measured on pure solid CO at 8, 12, and 15 K. There is little difference between the diffusion coefficients of the hydrogen and deuterium atoms, indicating that the diffusion is limited by thermal hopping. The activation energies controlling the H-atom diffusion depend on the surface temperature, and values of 22, 30, and ∼37 meV were obtained for 8, 12, and 15 K, respectively.

High-pressure-assisted design of porous topological semimetal carbon for Li-ion battery anode with high-rate performance

NASA Astrophysics Data System (ADS)

Liu, Junyi; Wang, Shuo; Qie, Yu; Zhang, Cunzhi; Sun, Qiang

2018-02-01

It has been a great challenge to develop a high-rate anode material with high-capacity, fast Li-ions diffusion and long cycling life going beyond the commercially used graphite in Li-ion battery. Here for the first time we propose a strategy combined high-pressure synthesis method with the global structure search to find a topological semimetal porous carbon as the desired anode. Our crystal-structure searching shows that we can obtain the ground state of an orthorhombic phase Li C6 with regular pores at 30 GPa, and when the Li atoms are removed, the resulting carbon structure is the recently predicted interlocked graphene network (IGN) that is a topological semimetal with an intrinsic high electronic conductivity. Based on the state-of-the-art first-principles calculations, we further find that the Li-ion migration energy barrier in the IGN is extremely low and the estimated diffusion coefficient can reach a magnitude of 10-4c m2/s at both low and high Li concentrations, which is three orders of magnitude larger than that of graphite anode. Moreover, the volume changes during the Li insertion and deinsertion are smaller than 3.2 % , while the theoretical specific capacity is the same as that of graphite anode. Our studies not only suggest a practical way of synthesizing the topological semimetal carbon but also propose a new anode material for Li-ion battery.

Electrochemical performance and interfacial investigation on Si composite anode for lithium ion batteries in full cell

NASA Astrophysics Data System (ADS)

Shobukawa, Hitoshi; Alvarado, Judith; Yang, Yangyuchen; Meng, Ying Shirley

2017-08-01

Lithium ion batteries (LIBs) containing silicon (Si) as a negative electrode have gained much attention recently because they deliver high energy density. However, the commercialization of LIBs with Si anode is limited due to the unstable electrochemical performance associated with expansion and contraction during electrochemical cycling. This study investigates the electrochemical performance and degradation mechanism of a full cell containing Si composite anode and LiFePO4 (lithium iron phosphate (LFP)) cathode. Enhanced electrochemical cycling performance is observed when the full cell is cycled with fluoroethylene carbonate (FEC) additive compared to the standard electrolyte. To understand the improvement in the electrochemical performance, x-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and scanning electron microscopy (SEM) are used. Based on the electrochemical behavior, FEC improves the reversibility of lithium ion diffusion into the solid electrolyte interphase (SEI) on the Si composite anode. Moreover, XPS analysis demonstrates that the SEI composition generated from the addition of FEC consists of a large amount of LiF and less carbonate species, which leads to better capacity retention over 40 cycles. The effective SEI successively yields more stable capacity retention and enhances the reversibility of lithium ion diffusion through the interphase of the Si anode, even at higher discharge rate. This study contributes to a basic comprehension of electrochemical performance and SEI formation of LIB full cells with a high loading Si composite anode.

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.

Effects of wastewater constituents and operational conditions on the composition and dynamics of anodic microbial communities in bioelectrochemical systems.

PubMed

Kokko, Marika; Epple, Stefanie; Gescher, Johannes; Kerzenmacher, Sven

2018-06-01

Over the last decade, there has been an ever-growing interest in bioelectrochemical systems (BES) as a sustainable technology enabling simultaneous wastewater treatment and biological production of, e.g. electricity, hydrogen, and further commodities. A key component of any BES degrading organic matter is the anode where electric current is biologically generated from the oxidation of organic compounds. The performance of BES depends on the interactions of the anodic microbial communities. To optimize the operational parameters and process design of BES a better comprehension of the microbial community dynamics and interactions at the anode is required. This paper reviews the abundance of different microorganisms in anodic biofilms and discusses their roles and possible side reactions with respect to their implications on the performance of BES utilizing wastewaters. The most important operational parameters affecting anodic microbial communities grown with wastewaters are highlighted and guidelines for controlling the composition of microbial communities are given. Copyright © 2018 Elsevier Ltd. All rights reserved.

High Voltage, Low Inductance Hydrogen Thyratron Study Program.

DTIC Science & Technology

1981-01-01

E-E Electrode Spacing Ef Cathode Heater Voltage egy Peak Forward Grid Voltage epy Peak Forward Anode Voltage epx Peak Inverse Anode Voltage Eres... electrodes . ........... 68 30 Marx generator used for sample testing. ........... 68 31 Waveforms showing sample holdoff and sample breakdown 73 32...capability (a function of gas pressure and electrode spacing) could be related to its current rise time capability (a function of gas pressure and inductance

Relativistic electron beam device

DOEpatents

Freeman, J.R.; Poukey, J.W.; Shope, S.L.; Yonas, G.

1975-07-01

A design is given for an electron beam device for irradiating spherical hydrogen isotope bearing targets. The accelerator, which includes hollow cathodes facing each other, injects an anode plasma between the cathodes and produces an approximately 10 nanosecond, megajoule pulse between the anode plasma and the cathodes. Targets may be repetitively positioned within the plasma between the cathodes, and accelerator diode arrangement permits materials to survive operation in a fusion power source. (auth)

Hydration and dehydration cycles in polymer electrolyte fuel cells operated with wet anode and dry cathode feed: A neutron imaging and modeling study

NASA Astrophysics Data System (ADS)

García-Salaberri, P. A.; Sánchez, D. G.; Boillat, P.; Vera, M.; Friedrich, K. A.

2017-08-01

Proper water management plays an essential role in the performance and durability of Polymer Electrolyte Fuel Cells (PEFCs), but it is challenged by the variety of water transport phenomena that take place in these devices. Previous experimental work has shown the existence of fluctuations between low and high current density levels in PEFCs operated with wet hydrogen and dry air feed. The alternation between both performance states is accompanied by strong changes in the high frequency resistance, suggesting a cyclic hydration and dehydration of the membrane. This peculiar scenario is examined here considering liquid water distributions from neutron imaging and predictions from a 3D two-phase non-isothermal model. The results show that the hydration-dehydration cycles are triggered by the periodic condensation and shedding of liquid water at the anode inlet. The input of liquid water humidifies the anode channel and offsets the membrane dry-out induced by the dry air stream, thus leading to the high-performance state. When liquid water is flushed out of the anode channel, the dehydration process takes over, and the cell comes back to the low-performance state. The predicted amplitude of the current oscillations grows with decreasing hydrogen and increasing air flow rates, in agreement with previous experimental data.

Effects of anode material on arcjet performance

NASA Technical Reports Server (NTRS)

Sankovic, John M.; Curran, Frank M.; Larson, C. A.

1992-01-01

Anodes fabricated from four different materials were tested in a modular arcjet thruster at 1 kW power level on nitrogen/hydrogen mixtures. A two-percent thoriated tungsten anode served as the control. Graphite was chosen for its ease in fabrication, but experienced severe erosion in the constrictor and diverging side. Hafnium carbide and lanthanum hexaboride were chosen for their low work functions but failed due to thermal stress and reacted with the propellant. When compared to the thoriated tungsten nozzle, thruster performance was significantly lower for the lanthanum hexaboride insert and the graphite nozzle, but was slightly higher for the hafnium carbide nozzle. Both the lanthanum hexaboride and hafnium carbide nozzle operated at higher voltages. An attempt was made to duplicate higher performance hafnium carbide results, but repeated attempts at machining a second anode insert were unsuccessful. Graphite, hafnium carbide, and lanthanum hexaboride do not appear viable anode materials for low power arcjet thrusters.

Anode protection system for shutdown of solid oxide fuel cell system

DOEpatents

Li, Bob X; Grieves, Malcolm J; Kelly, Sean M

2014-12-30

An Anode Protection Systems for a SOFC system, having a Reductant Supply and safety subsystem, a SOFC anode protection subsystem, and a Post Combustion and slip stream control subsystem. The Reductant Supply and safety subsystem includes means for generating a reducing gas or vapor to prevent re-oxidation of the Ni in the anode layer during the course of shut down of the SOFC stack. The underlying ammonia or hydrogen based material used to generate a reducing gas or vapor to prevent the re-oxidation of the Ni can be in either a solid or liquid stored inside a portable container. The SOFC anode protection subsystem provides an internal pressure of 0.2 to 10 kPa to prevent air from entering into the SOFC system. The Post Combustion and slip stream control subsystem provides a catalyst converter configured to treat any residual reducing gas in the slip stream gas exiting from SOFC stack.

Investigation of the degradation of different nickel anode types for alkaline fuel cells (AFCs)

NASA Astrophysics Data System (ADS)

Gülzow, E.; Schulze, M.; Steinhilber, G.

Alkaline fuel cells (AFCs) have the opportunity of becoming important for mobile energy systems as, in contrast to other low temperature fuel cells, the alkaline type requires neither noble metal catalysts nor an expensive polymer electrolyte. In AFCs, nickel is used as anode catalyst in gas diffusion electrodes. The metal catalyst was mixed with polytetraflourethylene (PTFE) as organic binder in a knife mile and rolled onto a metal web in a calendar to prepare the electrode. After an activation process with hydrogen evolution at 5 mA/cm 2 for 18 h, the electrodes were stressed at constant loading in a half cell equipment. During the fuel cell operation, the electrochemical performance decreased due to changes of the polymer (PTFE) and of the metal particles in the electrode, which is described in detail in another paper. In this study, three types of electrodes were investigated. The first type of electrode is composed of pure Raney-nickel and PTFE powder, the nickel particles in the second electrode type were selected according to particle size and in the third electrode copper powder was added to the nickel powder not selected by size. The size selected nickel particles show a better electrochemical performance related to the non-selected catalyst, but due to the electrochemically induced disintegration of the nickel particles the electrochemical performance decreases stronger. The copper powder in the third electrode is added to improve the electronic conductivity of the nickel catalyst, but the copper is not stable under the electrochemical conditions in fuel cell operation. With all three anode types long-term experiments have been performed. The electrodes have been characterized after the electrochemical stressing to investigate the degradation processes.

Using light transmission to watch hydrogen diffuse

PubMed Central

Pálsson, Gunnar K.; Bliersbach, Andreas; Wolff, Max; Zamani, Atieh; Hjörvarsson, Björgvin

2012-01-01

Because of its light weight and small size, hydrogen exhibits one of the fastest diffusion rates in solid materials, comparable to the diffusion rate of liquid water molecules at room temperature. The diffusion rate is determined by an intricate combination of quantum effects and dynamic interplay with the displacement of host atoms that is still only partially understood. Here we present direct observations of the spatial and temporal changes in the diffusion-induced concentration profiles in a vanadium single crystal and we show that the results represent the experimental counterpart of the full time and spatial solution of Fick's diffusion equation. We validate the approach by determining the diffusion rate of hydrogen in a single crystal vanadium (001) film, with net diffusion in the [110] direction. PMID:22692535

Using light transmission to watch hydrogen diffuse

NASA Astrophysics Data System (ADS)

Pálsson, Gunnar K.; Bliersbach, Andreas; Wolff, Max; Zamani, Atieh; Hjörvarsson, Björgvin

2012-06-01

Because of its light weight and small size, hydrogen exhibits one of the fastest diffusion rates in solid materials, comparable to the diffusion rate of liquid water molecules at room temperature. The diffusion rate is determined by an intricate combination of quantum effects and dynamic interplay with the displacement of host atoms that is still only partially understood. Here we present direct observations of the spatial and temporal changes in the diffusion-induced concentration profiles in a vanadium single crystal and we show that the results represent the experimental counterpart of the full time and spatial solution of Fick's diffusion equation. We validate the approach by determining the diffusion rate of hydrogen in a single crystal vanadium (001) film, with net diffusion in the [110] direction.

Turning Cellulose Waste Into Electricity: Hydrogen Conversion by a Hydrogenase Electrode

PubMed Central

Abramov, Sergey M.; Sadraddinova, Elmira R.; Shestakov, Andrey I.; Voronin, Oleg G.; Karyakin, Arkadiy A.; Zorin, Nikolay A.; Netrusov, Alexander I.

2013-01-01

Hydrogen-producing thermophilic cellulolytic microorganisms were isolated from cow faeces. Rates of cellulose hydrolysis and hydrogen formation were 0.2 mM L-1 h-1 and 1 mM L-1 h-1, respectively. An enzymatic fuel cell (EFC) with a hydrogenase anode was used to oxidise hydrogen produced in a microbial bioreactor. The hydrogenase electrode was exposed for 38 days (912 h) to a thermophilic fermentation medium. The hydrogenase activity remaining after continuous operation under load was 73% of the initial value. PMID:24312437

Applications of Carbon Nanotubes for Lithium Ion Battery Anodes

PubMed Central

Xiong, Zhili; Yun, Young Soo; Jin, Hyoung-Joon

2013-01-01

Carbon nanotubes (CNTs) have displayed great potential as anode materials for lithium ion batteries (LIBs) due to their unique structural, mechanical, and electrical properties. The measured reversible lithium ion capacities of CNT-based anodes are considerably improved compared to the conventional graphite-based anodes. Additionally, the opened structure and enriched chirality of CNTs can help to improve the capacity and electrical transport in CNT-based LIBs. Therefore, the modification of CNTs and design of CNT structure provide strategies for improving the performance of CNT-based anodes. CNTs could also be assembled into free-standing electrodes without any binder or current collector, which will lead to increased specific energy density for the overall battery design. In this review, we discuss the mechanism of lithium ion intercalation and diffusion in CNTs, and the influence of different structures and morphologies on their performance as anode materials for LIBs. PMID:28809361

Effects of various applied voltages on physical properties of TiO2 nanotubes by anodization method

NASA Astrophysics Data System (ADS)

Hoseinzadeh, T.; Ghorannevis, Z.; Ghoranneviss, M.; Sari, A. H.; Salem, M. K.

2017-09-01

Three steps anodization process is used to synthesize highly ordered and uniform multilayered titanium oxide (TiO2) nanotubes and effect of different anodization voltages are studied on their physical properties such as structural, morphological and optical. The crystalized structure of the synthesized tubes is investigated by X-ray diffractometer analysis. To study the morphology of the tubes, field emission scanning electron microscopy is used, which showed that the wall thicknesses and the diameters of the tubes are affected by the different anodization voltages. Moreover, optical studies performed by diffuse reflection spectra suggested that band gap of the TiO2 nanotubes are also changed by applying different anodization voltages. In this study using physical investigations, an optimum anodization voltage is obtained to synthesize the uniform crystalized TiO2 nanotubes with suitable diameter, wall thickness and optical properties.

Thin film integrated capacitors with sputtered-anodized niobium pentoxide dielectric for decoupling applications

NASA Astrophysics Data System (ADS)

Jacob, Susan

Electronics system miniaturization is a major driver for high-k materials. High-k materials in capacitors allow for high capacitance, enabling system miniaturization. Ta2O5 (k˜24) has been the dominant high-k material in the electronic industry for decoupling capacitors, filter capacitors, etc. In order to facilitate further system miniaturization, this project has investigated thin film integrated capacitors with Nb2O5 dielectric. Nb2O 5 has k˜41 and is a potential candidate for replacing Ta2O5. But, the presence of suboxides (NbO2 and NbO) in the dielectric deteriorates the electrical properties (leakage current, thermal instability of capacitance, etc.). Also, the high oxygen solubility of niobium results in oxygen diffusion from the dielectric to niobium metal, if any is present. The major purpose of this project was to check the ability of NbN as a diffusion barrier and fabricate thermally stable niobium capacitors. As a first step to produce niobium capacitors, the material characterizations of reactively sputtered Nb2O5 and NbN were done. Thickness and film composition, and crystal structures of the sputtered films were obtained and the deposition parameters for the desired stoichiometry were found. Also, anodized Nb2O5 was characterized for its stoichiometry and thickness. To study the effect of nitrides on capacitance and thermal stability, Ta2O5 capacitors were initially fabricated with and without TaN. The results showed that the nitride does not affect the capacitance, and that capacitors with TaN are stable up to 150°C. In the next step, niobium capacitors were first fabricated with anodized dielectric and the oxygen diffusion issues associated with capacitor processing were studied. Reactively sputtered Nb2O5 was anodized to form complete Nb2O5 (with few oxygen vacancies) and NbN was used to sandwich the dielectric. The capacitor fabrication was not successful due to the difficulties in anodizing the sputtered dielectric. Another method, anodizing reactively sputtered Nb2O5 and a thin layer of sputtered niobium metal yielded high yield (99%) capacitors. Capacitors were fabricated with and without NbN and the results showed 93% decrease in leakage for a capacitor with ˜2000 A dielectric when NbN was present in the structure. These capacitors could withstand 20 V and showed 2.7 muA leakage current at 5 V. These results were obtained after thermal storage at 100°C and 150°C in air for 168 hours at each temperature. Two set of experiments were performed using Ta2O5 dielectric: one to determine the effect of anodization end point on the thickness (capacitance) and the second to determine the effect of boiling the dielectric on functional yield. The anodization end point experiment showed that the final current of anodization along with the anodizing voltage determines the anodic oxide thickness. The lower the current, the thicker the films produced by anodization. Therefore, it was important to specify the final current along with the anodization voltage for oxide growth rate. The capacitors formed with boiled wafers showed better functional yield 3 out of 5 times compared with the unboiled wafer. Niobium anodization was studied for the Nb--->Nb 2O5 conversion ratio and the effect of anodization bath temperature on the oxide film; a color chart was prepared for thicknesses ranging from 1900 A - 5000 A. The niobium metal to oxide conversion ratio was found to change with temperature.

Moderate temperature detector development

NASA Technical Reports Server (NTRS)

Marciniec, J. W.; Briggs, R. J.; Sood, A. K.

1981-01-01

P-side backside reflecting constant, photodiode characterization, and photodiode diffusion and G-R currents were investigated in an effort to develop an 8 m to 12 m infrared quantum detector using mercury cadmium telluride. Anodization, phosphorus implantation, and the graded band gap concept were approaches considered for backside formation. Variable thickness diodes were fabricated with a back surface anodic oxide to investigate the effect of this surface preparation on the diffusion limited zero bias impedance. A modeling technique was refined to thoroughly model diode characteristics. Values for the surface recombination velocity in the depletion region were obtained. These values were improved by implementing better surface damage removal techniques.

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.

Large Scale PEM Electrolysis to Enable Renewable Hydrogen Fuel Production

DTIC Science & Technology

2010-02-10

PEM Fuel Cell Anode + -Cathode e- e- e- e- Electric load...BOP system. • Enables new product launch (C- Series) Proton PEM cell stack for UK Vanguard subs 18UNCLASSIFIED: Dist A. Approved for public release...UNCLASSIFIED: Dist A. Approved for public release “Large Scale PEM Electrolysis to Enable Renewable Hydrogen Fuel Production” Alternative Energy

Pseudocapacitance of TiO2-x /CNT Anodes for High-Performance Quasi-Solid-State Li-Ion and Na-Ion Capacitors.

PubMed

Que, Lan-Fang; Yu, Fu-Da; Wang, Zhen-Bo; Gu, Da-Ming

2018-04-01

It is challenging for flexible solid-state hybrid capacitors to achieve high-energy-high-power densities in both Li-ion and Na-ion systems, and the kinetics discrepancy between the sluggish faradaic anode and the rapid capacitive cathode is the most critical issue needs to be addressed. To improve Li-ion/Na-ion diffusion kinetics, flexible oxygen-deficient TiO 2- x /CNT composite film with ultrafast electron/ion transport network is constructed as self-supported and light-weight anode for a quasi-solid-state hybrid capacitor. It is found that the designed porous yolk-shell structure endows large surface area and provides short diffusion length, the oxygen-deficient composite film can improve electrical conductivity, and enhance ion diffusion kinetic by introducing intercalation pseudocapacitance, therefore resulting in advance electrochemical properties. It exhibits high capacity, excellent rate performance, and long cycle life when utilized as self-supported anodes for Li-ion and Na-ion batteries. When assembled with activated carbon/carbon nanotube (AC/CNT) flexible cathode, using ion conducting gel polymer as the electrolyte, high energy densities of 104 and 109 Wh kg -1 are achieved at 250 W kg -1 in quasi-solid-state Li-ion and Na-ion capacitors (LICs and SICs), respectively. Still, energy densities of 32 and 36 Wh kg -1 can be maintained at high power densities of 5000 W kg -1 in LICs and SICs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-consistent modeling of self-organized patterns of spots on anodes of DC glow discharges

NASA Astrophysics Data System (ADS)

Bieniek, M. S.; Almeida, P. G. C.; Benilov, M. S.

2018-05-01

Self-organized patterns of spots on a flat metallic anode in a cylindrical glow discharge tube are simulated. A standard model of glow discharges is used, comprising conservation and transport equations for a single species of ion and electrons, written with the use of the drift-diffusion and local-field approximations, and the Poisson equation. Only processes in the near-anode region are considered and the computation domain is the region between the anode and the discharge column. Multiple solutions, existing in the same range of discharge current and describing modes with and without anode spots, are computed for the first time. A reversal of the local anode current density in the spots was found, i.e. mini-cathodes are formed inside the spots or, as one could say, anode spots operate as a unipolar glow discharge. The solutions do not fit into the conventional pattern of self-organization in bistable nonlinear dissipative systems; In particular, the modes are not joined by bifurcations.

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 mitigation in submerged arc welding

NASA Astrophysics Data System (ADS)

Klimowicz, Steven

With the role of hydrogen in weld metal well understood in its relation to cold cracking, there has been a push to produce welds with lower and lower diffusible hydrogen contents. The push for lower diffusible hydrogen contents has placed pressure on consumables manufactures to create consumables that can achieve the requirements for lower diffusible hydrogen content. Currently EM12K flux is produced so that it can achieve below 4 ml of diffusible hydrogen for every 100g of weld metal deposited (ml/100g) for submerged arc welding (SAW). The recent trend for industry is to preferentially achieve diffusible hydrogen contents below 3 ml/100g. Making it necessary to find a way to modify the flux to achieve a lower diffusible hydrogen content for the welds it produces. To achieve this goal a two phase plan was developed. The first phase was to characterize the entire welding system for hydrogen. Since the goal of the project is hydrogen mitigation, any amount of hydrogen that could be reduced is helpful and therefore must first be discovered. Sources of hydrogen may be found by analyzing the welding wire and base metal, as well as breaking the flux down into its components and production steps. The wire was analyzed for total hydrogen content as was the base metal. The flux and its components were analyzed using differential thermal analysis-simultaneous thermal analysis (DTA-STA) and later vacuum degassing for moisture content. The analysis of the wire showed that the copper coating on the wire was the largest contributor of hydrogen. There was lubricant present on the wire surface as well, but it did not contribute as much as the copper coating. It was found that a simple low temperature baking of the wire was enough to remove the lubricant and coating moisture. The base metal was found to have a similar total hydrogen content to that of the wire. The breakdown of the flux and production process for moisture content analysis revealed that the production process removes the moisture that is added by the water based binder. The second phase of the project was to modify the flux with fluoride additions to remove hydrogen from the arc while welding. The introduction of fluorine into the arc would lower the amount of hydrogen that may be absorbed as diffusible hydrogen by the weld metal. To select the fluorides a series of thermodynamic calculations were performed as well as simple tests to determine the fluorides behavior in a welding arc and flux. From these tests the following fluorides were selected to be used to be added to EM12K flux as oneweight percent additions: SrF 2, K2TiF6, K2SiF6, and LiF. Welds were then run with the experimental fluxes according to AWS A4.3 standard for diffusible hydrogen testing. From these tests it was found that none experimental fluxes were able to achieve a diffusible hydrogen content lower than the original EM12K flux. It was also found that fluoride reduction in a simple flux is a better predictor of fluoride effectiveness than decomposition temperature.

Symmetry and diffusivity of the interstitial hydrogen shallow-donor center in In 2O 3

DOE PAGES

Weiser, Philip; Qin, Ying; Yin, Weikai; ...

2016-11-16

Uniaxial stress experiments performed for the 3306 cm -1 vibrational line assigned to the interstitial-hydrogen, shallow-donor center in In 2O 3 reveal its symmetry and transition- moment direction. The defect alignment that can be produced by a [001] stress applied at 165 K is due to a process that is also a hydrogen- diffusion jump, providing a microscopic determination of the diffusion constant for H in In 2O 3 and its mechanism. Lastly, our experimental results strongly complement theoretical predictions for the structure and diffusion of the interstitial hydrogen donor center in In 2O 3.

Electrolytic production of metals using a resistant anode

DOEpatents

Tarcy, G.P.; Gavasto, T.M.; Ray, S.P.

1986-11-04

An electrolytic process is described comprising evolving oxygen on an anode in a molten salt, the anode comprising an alloy comprising a first metal and a second metal, both metals forming oxides, the oxide of the first metal being more resistant than the second metal to attack by the molten salt, the oxide of the second metal being more resistant than the first metal to the diffusion of oxygen. The electrode may also be formed of CuAlO[sub 2] and/or Cu[sub 2]O. 2 figs.

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

Junhua Jiang; Ted Aulich

An electrolytic renewable nitrogen fertilizer process that utilizes wind-generated electricity, N{sub 2} extracted from air, and syngas produced via the gasification of biomass to produce nitrogen fertilizer ammonia was developed at the University of North Dakota Energy & Environmental Research Center. This novel process provides an important way to directly utilize biosyngas generated mainly via the biomass gasification in place of the high-purity hydrogen which is required for Haber Bosch-based production of the fertilizer for the production of the widely used nitrogen fertilizers. Our preliminary economic projection shows that the economic competitiveness of the electrochemical nitrogen fertilizer process strongly dependsmore » upon the cost of hydrogen gas and the cost of electricity. It is therefore expected the cost of nitrogen fertilizer production could be considerably decreased owing to the direct use of cost-effective 'hydrogen-equivalent' biosyngas compared to the high-purity hydrogen. The technical feasibility of the electrolytic process has been proven via studying ammonia production using humidified carbon monoxide as the hydrogen-equivalent vs. the high-purity hydrogen. Process optimization efforts have been focused on the development of catalysts for ammonia formation, electrolytic membrane systems, and membrane-electrode assemblies. The status of the electrochemical ammonia process is characterized by a current efficiency of 43% using humidified carbon monoxide as a feedstock to the anode chamber and a current efficiency of 56% using high-purity hydrogen as the anode gas feedstock. Further optimization of the electrolytic process for higher current efficiency and decreased energy consumption is ongoing at the EERC.« less

Enhanced electrochemical etching of ion irradiated silicon by localized amorphization

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

Dang, Z. Y.; Breese, M. B. H.; Lin, Y.

2014-05-12

A tailored distribution of ion induced defects in p-type silicon allows subsequent electrochemical anodization to be modified in various ways. Here we describe how a low level of lattice amorphization induced by ion irradiation influences anodization. First, it superposes a chemical etching effect, which is observable at high fluences as a reduced height of a micromachined component. Second, at lower fluences, it greatly enhances electrochemical anodization by allowing a hole diffusion current to flow to the exposed surface. We present an anodization model, which explains all observed effects produced by light ions such as helium and heavy ions such asmore » cesium over a wide range of fluences and irradiation geometries.« less

Hydrogen bonds and heat diffusion in α-helices: a computational study.

PubMed

Miño, German; Barriga, Raul; Gutierrez, Gonzalo

2014-08-28

Recent evidence has shown a correlation between the heat diffusion pathways and the known allosteric communication pathways in proteins. Allosteric communication in proteins is a central, yet unsolved, problem in biochemistry, and the study and characterization of the structural determinants that mediate energy transfer among different parts of proteins is of major importance. In this work, we characterized the role of hydrogen bonds in diffusivity of thermal energy for two sets of α-helices with different abilities to form hydrogen bonds. These hydrogen bonds can be a constitutive part of the α-helices or can arise from the lateral chains. In our in vacuo simulations, it was observed that α-helices with a higher possibility of forming hydrogen bonds also had higher rates of thermalization. Our simulations also revealed that heat readily flowed through atoms involved in hydrogen bonds. As a general conclusion, according to our simulations, hydrogen bonds fulfilled an important role in heat diffusion in structural patters of proteins.

Technique for determining the amount of hydrogen diffusing through a steel membrane

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

Kardash, N.V.; Batrakov, V.V.

1995-07-01

Hydrogen diffusion through steel membranes still attracts much attention from scientists, and during recent years new results have been reported. Hydrogen diffusion is usually studied in the cell designed by M.A. Devanathan, but there are also other techniques for determining hydrogen permeability, namely: from the change in the solution volume in a horizontal or gas microburette; from the hydrogen ionization current; from the penetration current; and from the buckling of the cathode. The authors developed an analytical method using autocatalytic titration for determining the amount of hydrogen passed through a steel membrane. The method is based on permanganatometry which ismore » widely used in analytical chemistry.« less

Hydrogen consentration meter utilizing a diffusion tube composed of 2 1/4 C r

DOEpatents

Roy, Prodyot; Sandusky, David W.; Hartle, Robert T.

1979-01-01

A diffusion tube hydrogen meter for improving the sensitivity and response time for the measurement of hydrogen in liquid sodium. The improved hydrogen meter has a composite membrane composed of pure nickel sleeve fitted, for example, over a 2 1/4 Cr-1 Mo steel or niobium diffusion tube. Since the hydrogen permeation rate through 2 1/4 Cr-1 Mo steels is a factor of four higher than pure nickel, and the permeation rate of hydrogen through niobium is two orders of magnitude greater than the 2 1/4 Cr-1 Mo steel, this results in a decrease in response time and an increase in the sensitivity.

Quantum fluctuations increase the self-diffusive motion of para-hydrogen in narrow carbon nanotubes.

PubMed

Kowalczyk, Piotr; Gauden, Piotr A; Terzyk, Artur P; Furmaniak, Sylwester

2011-05-28

Quantum fluctuations significantly increase the self-diffusive motion of para-hydrogen adsorbed in narrow carbon nanotubes at 30 K comparing to its classical counterpart. Rigorous Feynman's path integral calculations reveal that self-diffusive motion of para-hydrogen in a narrow (6,6) carbon nanotube at 30 K and pore densities below ∼29 mmol cm(-3) is one order of magnitude faster than the classical counterpart. We find that the zero-point energy and tunneling significantly smoothed out the free energy landscape of para-hydrogen molecules adsorbed in a narrow (6,6) carbon nanotube. This promotes a delocalization of the confined para-hydrogen at 30 K (i.e., population of unclassical paths due to quantum effects). Contrary the self-diffusive motion of classical para-hydrogen molecules in a narrow (6,6) carbon nanotube at 30 K is very slow. This is because classical para-hydrogen molecules undergo highly correlated movement when their collision diameter approached the carbon nanotube size (i.e., anomalous diffusion in quasi-one dimensional pores). On the basis of current results we predict that narrow single-walled carbon nanotubes are promising nanoporous molecular sieves being able to separate para-hydrogen molecules from mixtures of classical particles at cryogenic temperatures. This journal is © the Owner Societies 2011

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.

Electrochemical behavior of zinc particles with silica based coatings as anode material for zinc air batteries with improved discharge capacity

NASA Astrophysics Data System (ADS)

Schmid, M.; Willert-Porada, M.

2017-05-01

Silica coatings on zinc particles as anode material for alkaline zinc air batteries are expected to reduce early formation of irreversible ZnO passivation layers during discharge by controlling zinc dissolution and precipitation of supersaturated zincates, Zn(OH)42-. Zinc particles were coated with SiO2 (thickness: 15 nm) by chemical solution deposition and with Zn2SiO4 (thickness: 20 nm) by chemical vapor deposition. These coatings formed a Si(OH)4 gel in aqueous KOH and retarded hydrogen evolution by 40%. By treatment in aqueous KOH and drying afterwards, the silica coatings were changed into ZnO-K2O·SiO2 layers. In this work, the electrochemical performance of such coated zinc particles is investigated by different electrochemical methods in order to gain a deeper understanding of the mechanisms of the coatings, which reduce zinc passivation. In particular, zinc utilization and changes in internal resistance are investigated. Moreover, methods for determination of diffusion coefficients, charge carrier numbers and activation energies for electrochemical oxidation are determined. SiO2-coated zinc particles show improved discharge capacity (CVD-coated zinc: 69% zinc utilization, CSD-coated zinc: 62% zinc utilization) as compared to as-received zinc (57% zinc utilization) at C/20 rate, by reducing supersaturation of zincates. Additionally, KOH-modified SiO2-coated zinc particles enhance rechargeability after 100% depth-of-discharge.

Characteristics of the high-rate discharge capability of a nickel/metal hydride battery electrode

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

Geng, M.; Han, J.; Feng, F.

1999-10-01

The high rate discharge capability of the negative electrode in a Ni/MH battery is mainly determined by the charge transfer process at the interface between the metal hydride (MH) alloy powder and the electrolyte, and the mass transfer process in the bulk MH alloy powder. In this study, the anodic polarization curves of a MH electrode were measured and analyzed. An alloy of nominal composition Mm{sub 0.95}Ti{sub 0.05}Ni{sub 3.85}Co{sub 0.45}Mn{sub 0.35}Al{sub 0.35} was used as the negative electrode material. With increasing number of charge/discharge cycles, the MH alloy powders microcrack into particles several micrometers in diameter. The decrease in themore » MH alloy particle size results in an increase in both the activation surface area and the exchange current density of the MH alloy electrode. The electrode overpotentials of the MH electrode decreases with increasing number of cycles at a large value of anodic polarization current. The decrease in electrode overpotential leads to an increase in the high rate discharge capability of the MH electrode. By using the limiting current, the hydrogen diffusion coefficient in the MH alloy was estimated to be 1.2 x 10{sup {minus}11}cm{sup 2}s{sup {minus}1} assuming an average particle radius of 5 {micro}m.« less

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.

New Designs of Biofuel Cells and Their Work Testing

NASA Astrophysics Data System (ADS)

Stom, D. I.; Zhdanova, G. O.; Kashevskii, A. V.

2017-11-01

The developed designs and modifications of biofuel elements (BFC) are presented. The approbation of their work using strains and consortia of microorganisms is given. The proposed designs made it possible to solve a number of problems that arise when working with BFC: 1) gain access to the contents of the anode BFC space without disturbing its sterility and anaerobic environment; 2) take samples from the anode space for chemical and microbiological analysis without interrupting the BFC operation; 3) conduct continuous monitoring of electrochemical processes directly in the anode space (Ox-Red media, electrode charge, concentration of hydrogen and other ions by means of potentiometry).

Diffusion Analysis Of Hydrogen-Desorption Measurements

NASA Technical Reports Server (NTRS)

Danford, Merlin D.

1988-01-01

Distribution of hydrogen in metal explains observed desorption rate. Report describes application of diffusion theory to anaylsis of experimental data on uptake and elimination of hydrogen in high-strength alloys of 25 degree C. Study part of program aimed at understanding embrittlement of metals by hydrogen. Two nickel-base alloys, Rene 41 and Waspaloy, and one ferrous alloy, 4340 steel, studied. Desorption of hydrogen explained by distribution of hydrogen in metal. "Fast" hydrogen apparently not due to formation of hydrides on and below surface as proposed.

Innovative self-powered submersible microbial electrolysis cell (SMEC) for biohydrogen production from anaerobic reactors.

PubMed

Zhang, Yifeng; Angelidaki, Irini

2012-05-15

A self-powered submersible microbial electrolysis cell (SMEC), in which a specially designed anode chamber and external electricity supply were not needed, was developed for in situ biohydrogen production from anaerobic reactors. In batch experiments, the hydrogen production rate reached 17.8 mL/L/d at the initial acetate concentration of 410 mg/L (5 mM), while the cathodic hydrogen recovery ( [Formula: see text] ) and overall systemic coulombic efficiency (CE(os)) were 93% and 28%, respectively, and the systemic hydrogen yield ( [Formula: see text] ) peaked at 1.27 mol-H(2)/mol-acetate. The hydrogen production increased along with acetate and buffer concentration. The highest hydrogen production rate of 32.2 mL/L/d and [Formula: see text] of 1.43 mol-H(2)/mol-acetate were achieved at 1640 mg/L (20 mM) acetate and 100 mM phosphate buffer. Further evaluation of the reactor under single electricity-generating or hydrogen-producing mode indicated that further improvement of voltage output and reduction of electron losses were essential for efficient hydrogen generation. In addition, alternate exchanging the electricity-assisting and hydrogen-producing function between the two cell units of the SMEC was found to be an effective approach to inhibit methanogens. Furthermore, 16S rRNA genes analysis showed that this special operation strategy resulted same microbial community structures in the anodic biofilms of the two cell units. The simple, compact and in situ applicable SMEC offers new opportunities for reactor design for a microbial electricity-assisted biohydrogen production system. Copyright © 2012 Elsevier Ltd. All rights reserved.

A multiphase interfacial model for the dissolution of spent nuclear fuel

NASA Astrophysics Data System (ADS)

Jerden, James L.; Frey, Kurt; Ebert, William

2015-07-01

The Fuel Matrix Dissolution Model (FMDM) is an electrochemical reaction/diffusion model for the dissolution of spent uranium oxide fuel. The model was developed to provide radionuclide source terms for use in performance assessment calculations for various types of geologic repositories. It is based on mixed potential theory and consists of a two-phase fuel surface made up of UO2 and a noble metal bearing fission product phase in contact with groundwater. The corrosion potential at the surface of the dissolving fuel is calculated by balancing cathodic and anodic reactions occurring at the solution interfaces with UO2 and NMP surfaces. Dissolved oxygen and hydrogen peroxide generated by radiolysis of the groundwater are the major oxidizing agents that promote fuel dissolution. Several reactions occurring on noble metal alloy surfaces are electrically coupled to the UO2 and can catalyze or inhibit oxidative dissolution of the fuel. The most important of these is the oxidation of hydrogen, which counteracts the effects of oxidants (primarily H2O2 and O2). Inclusion of this reaction greatly decreases the oxidation of U(IV) and slows fuel dissolution significantly. In addition to radiolytic hydrogen, large quantities of hydrogen can be produced by the anoxic corrosion of steel structures within and near the fuel waste package. The model accurately predicts key experimental trends seen in literature data, the most important being the dramatic depression of the fuel dissolution rate by the presence of dissolved hydrogen at even relatively low concentrations (e.g., less than 1 mM). This hydrogen effect counteracts oxidation reactions and can limit fuel degradation to chemical dissolution, which results in radionuclide source term values that are four or five orders of magnitude lower than when oxidative dissolution processes are operative. This paper presents the scientific basis of the model, the approach for modeling used fuel in a disposal system, and preliminary calculations to demonstrate the application and value of the model.

Nitrogen diffusion in hafnia and the impact of nitridation on oxygen and hydrogen diffusion: A first-principles study

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

Sathiyanarayanan, Rajesh, E-mail: rajessat@in.ibm.com, E-mail: rajesh.sathiyanarayanan@gmail.com; Pandey, R. K.; Murali, K. V. R. M.

2015-01-21

Using first-principles simulations, we have computed incorporation energies and diffusion barriers of ammonia, the nitrogen molecule and atomic nitrogen in monoclinic hafnia (m-HfO{sub 2}). Our calculations show that ammonia is likely to dissociate into an NH{sub 2} molecular unit, whereas the nitrogen molecule remains as a molecule either in the interstitial space or at an oxygen lattice site. The lowest energy pathway for the diffusion of atomic nitrogen interstitials consists of the hopping of the nitrogen interstitial between neighboring three-coordinated lattice oxygen atoms that share a single Hf atom, and the barrier for such hops is determined by a switchingmore » mechanism. The substitutional nitrogen atom shows a preference for diffusion through the doubly positive oxygen vacancy-mediated mechanism. Furthermore, we have investigated the impact of nitrogen atoms on the diffusion barriers of oxygen and hydrogen interstitials in m-HfO{sub 2}. Our results show that nitrogen incorporation has a significant impact on the barriers for oxygen and hydrogen diffusion: nitrogen atoms attract oxygen and hydrogen interstitials diffusing in the vicinity, thereby slowing down (reducing) their diffusion (diffusion length)« less

Pulse-reverse electrodeposition for mesoporous metal films: combination of hydrogen evolution assisted deposition and electrochemical dealloying.

PubMed

Cherevko, Serhiy; Kulyk, Nadiia; Chung, Chan-Hwa

2012-01-21

Hydrogen evolution assisted electrodeposition is a new bottom-up technique allowing the fast and simple synthesis of nanometals. Electrochemical dealloying is a top-down approach with the same purpose. In this work, we show that a combination of these two methods in sequence by pulse-reverse electrodeposition can be used to prepare high-surface-area nanostructured metals. Highly porous adherent platinum is obtained by the deposition of CuPt alloy during the cathodic cycles and the selective dissolution of copper during the anodic cycles. The convection created by the movement of the hydrogen bubbles increases the deposition rate and removes the dissolved copper ions from the diffusion layer, which ensures the deposition of a film with the same stoichiometry throughout the whole process. Due to the relatively high ratio of copper atoms on the surface in the as-deposited layer, it is proposed that the dealloying kinetics is significantly higher than that usually observed during the dealloying process in a model system. The proposed approach has several advantages over other methods, such as a very high growth rate and needlessness of any post-treatment processes. A detailed analysis of the effect of pulse-reverse waveform parameters on the properties of the films is presented. Mesoporous platinum with pores and ligaments having characteristic sizes of less than 10 nm, an equivalent surface area of up to ca. 220 m(2) cm(-3), and a roughness factor of more than 1000 is fabricated.

Model anodes and anode models for understanding the mechanism of hydrogen oxidation in solid oxide fuel cells.

PubMed

Bessler, Wolfgang G; Vogler, Marcel; Störmer, Heike; Gerthsen, Dagmar; Utz, Annika; Weber, André; Ivers-Tiffée, Ellen

2010-11-14

This article presents a literature review and new results on experimental and theoretical investigations of the electrochemistry of solid oxide fuel cell (SOFC) model anodes, focusing on the nickel/yttria-stabilized zirconia (Ni/YSZ) materials system with operation under H(2)/H(2)O atmospheres. Micropatterned model anodes were used for electrochemical characterization under well-defined operating conditions. Structural and chemical integrity was confirmed by ex situ pre-test and post-test microstructural and chemical analysis. Elementary kinetic models of reaction and transport processes were used to assess reaction pathways and rate-determining steps. The comparison of experimental and simulated electrochemical behaviors of pattern anodes shows quantitative agreement over a wide range of operating conditions (p(H(2)) = 8×10(2) - 9×10(4) Pa, p(H(2)O) = 2×10(1) - 6×10(4) Pa, T = 400-800 °C). Previously published experimental data on model anodes show a strong scatter in electrochemical performance. Furthermore, model anodes exhibit a pronounced dynamics on multiple time scales which is not reproduced in state-of-the-art models and which is also not observed in technical cermet anodes. Potential origin of these effects as well as consequences for further steps in model anode and anode model studies are discussed.

Hydrogen adsorption and diffusion, and subcritical-crack growth in high strength steels and nickel base alloys

NASA Technical Reports Server (NTRS)

Wei, R. P.; Klier, K.; Simmons, G. W.; Chornet, E.

1973-01-01

Embrittlement, or the enhancement of crack growth by gaseous hydrogen in high strength alloys, is of primary interest in selecting alloys for various components in the space shuttle. Embrittlement is known to occur at hydrogen gas pressures ranging from fractions to several hundred atmospheres, and is most severe in the case of martensitic high strength steels. Kinetic information on subcritical crack growth in gaseous hydrogen is sparse at this time. Corroborative information on hydrogen adsorption and diffusion is inadequate to permit a clear determination of the rate controlling process and possible mechanism in hydrogen enhanced crack growth, and for estimating behavior over a range of temperatures and pressures. Therefore, coordinated studies of the kinetics of crack growth, and adsorption and diffusion of hydrogen, using identical materials, have been initiated. Comparable conditions of temperature and pressure will be used in the chemical and mechanical experiments. Inconel 718 alloy and 18Ni(200) maraging steel have been selected for these studies. Results from these studies are expected to provide not only a better understanding of the gaseous hydrogen embrittlement phenomenon itself, but also fundamental information on hydrogen adsorption and diffusion, and crack growth information that can be used directly for design.

Meso-scale anisotropic hydrogen segregation near grain-boundaries in polycrystalline nickel characterized by EBSD/SIMS

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

Oudriss, A.; Le Guernic, Solenne; Wang, Zhaoying

2016-02-15

To study anisotropic hydrogen segregation and diffusion in nickel polycrystalline, Secondary Ion Mass Spectrometry (SIMS) and Electron Back Scattered Diffraction (EBSD) are integrated to investigate hydrogen distribution around grain boundaries. Hydrogen distribution in pre-charged samples were correlated with grain boundary character by integrating high-resolution grain microstructure from EBSD inverse pole figure map and low-resolution hydrogen concentration profile map from SIMS. This multimodal imaging instrumentation shows that grain boundaries in nickel can be categorized into two families based on behavior of hydrogen distribution crossing grain boundary: the first one includes random grain boundaries with fast hydrogen diffusivity, showing a sharp gapmore » for hydrogen concentration profile cross the grain boundaries. The second family are special Σ3n grain boundaries with low hydrogen diffusivity, showing a smooth gradient of hydrogen concentration cross the grain boundary. Heterogeneous hydrogen distributions due to grain boundary family revealed by SIMS/EBSD on mesoscale further validate the recent hydrogen permeation data and anisotropic ab-initio calculations in nanoscale. The results highlight the fact that grain boundaries character impacts hydrogen distribution significantly.« less

Cathodic electrocatalyst layer for electrochemical generation of hydrogen peroxide

NASA Technical Reports Server (NTRS)

Tennakoon, Charles L. K. (Inventor); Singh, Waheguru Pal (Inventor); Rhodes, Christopher P. (Inventor); Anderson, Kelvin C. (Inventor)

2011-01-01

A cathodic gas diffusion electrode for the electrochemical production of aqueous hydrogen peroxide solutions. The cathodic gas diffusion electrode comprises an electrically conductive gas diffusion substrate and a cathodic electrocatalyst layer supported on the gas diffusion substrate. A novel cathodic electrocatalyst layer comprises a cathodic electrocatalyst, a substantially water-insoluble quaternary ammonium compound, a fluorocarbon polymer hydrophobic agent and binder, and a perfluoronated sulphonic acid polymer. An electrochemical cell using the novel cathodic electrocatalyst layer has been shown to produce an aqueous solution having between 8 and 14 weight percent hydrogen peroxide. Furthermore, such electrochemical cells have shown stable production of hydrogen peroxide solutions over 1000 hours of operation including numerous system shutdowns.

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.

Bipolar electrochemical mechanism for the propulsion of catalytic nanomotors in hydrogen peroxide solutions.

PubMed

Wang, Yang; Hernandez, Rose M; Bartlett, David J; Bingham, Julia M; Kline, Timothy R; Sen, Ayusman; Mallouk, Thomas E

2006-12-05

Bimetallic nanorods are propelled in aqueous solutions by the catalytic decomposition of hydrogen peroxide to oxygen and water. Several mechanisms (interfacial tension gradients, bubble recoil, viscous Brownian ratchet, self-electrophoresis) have been proposed for the transduction of chemical to mechanical energy in this system. From Tafel plots of anodic and cathodic hydrogen peroxide reactions at various metal (Au, Pt, Rh, Ni, Ru, and Pd) ultramicroelectrodes, we determine the potential at which the anodic and cathodic reaction rates are equal for each metal. These measurements allow one to predict the direction of motion of all possible bimetallic combinations according to the bipolar electrochemical (or self-electrophoretic) mechanism. These predictions are consistent with the observed direction of motion in all cases studied, providing strong support for the mechanism. We also find that segmented nanorods with one Au end and one poly(pyrrole) end containing catalase, an enzyme that decomposes hydrogen peroxide nonelectrochemically, perform the overall catalytic reaction at a rate similar to that of nanorods containing Au and Pt segments. However, in this case there is no observed axial movement, again supporting the bipolar electrochemical propulsion mechanism for bimetallic nanorods.

Effect of Low-Temperature Environment on Stress Corrosion Cracking Behavior of X80 Pipeline Steel in Simulated Alkaline Soil Solution

NASA Astrophysics Data System (ADS)

Xie, Fei; Wang, Dan; Wu, Ming; Yu, Chengxiang; Sun, Dongxu; Yang, Xu; Xu, Changhao

2018-04-01

The stress corrosion cracking (SCC) of X80 pipeline steel in simulated alkaline soil solution under different temperatures was investigated by slow-strain-rate testing, scanning electron microscopy and energy-dispersive spectroscopy. Results showed that the fracture was transgranular and brittle at 273 K to 278 K (0 °C to 5 °C), and the metal surface was dissolved by a large number of chloride ions. Furthermore, hydrogen embrittlement was caused by the hydrogen atom extended to the high-stress region. The fracture process was controlled by hydrogen-induced cracking, and SCC was highly sensitive at this stage. At 288 K to 298 K (15 °C to 25 °C), the fracture morphology was attributed to the mixed mode of ductile and brittle fractures, the fracture process was controlled by the mechanism of hydrogen-induced cracking and anodic dissolution, and the susceptibility to SCC decreased. When the temperature reached 308 K to 318 K (35 °C to 45 °C), the fracture was mainly intergranular and ductile, the fracture process was controlled by anodic dissolution, and SCC sensitivity was the smallest in this temperature range.

Diffusivity of hydrogen in iron-bearing olivine at 3 GPa

NASA Astrophysics Data System (ADS)

Demouchy, Sylvie; Thoraval, Catherine; Bolfan-Casanova, Nathalie; Manthilake, Geeth

2016-11-01

The kinetics of hydrogenation of dry iron-bearing olivine single crystals was determined by performing hydration experiments under hydrothermal conditions at high pressure. The experiments were performed in a multi-anvil press at 3 GPa, for a temperature range between 900 and 1200 °C and for various durations. The oxygen fugacity was buffered along Ni-NiO joint. Polarized Fourier transform infrared spectroscopy and recent empirical calibration were used to quantify the hydroxyl distributions in the samples along crystallographic axes after the experiments. The chemical diffusion coefficients are similar (barely slower) than in olivine hydrated at lower pressure (0.2 and 0.3 GPa) for the same diffusion mechanism. Under the given experimental conditions, the anisotropy of diffusion is the same as for proton-vacancy mechanism, with diffusion along the [0 0 1] axis faster than along the [1 0 0]. However, the anisotropy at 3 GPa is weaker compared to measurements at lower pressures and the analysis of concentration profiles using 3D models shows that an isotropic solution could also be relevant. Fits of the diffusion data to an Arrhenius law yield activation energies for the slightly faster [0 0 1] axis of the crystallographic axes around 198 ± 5 kJ mol-1, a value only slightly lower than the results from previous experimental studies for natural iron-bearing olivine hydrogenated at lower confining pressure. At 3 GPa, hydrogenation can be well approximated by a single mechanism controlled by coupled diffusion of protons and octahedral vacancies (di- and tri-valent ions). The diffusion rates are fast enough to alter hydrogen concentration within olivine in xenoliths ascending from the mantle or experiencing hydrogen-rich metasomatism events, but too slow to permit complete homogenization of hydrogen in olivine-rich rocks at kilometer scale in less than one My.

Determination of the diffusion coefficient of hydrogen ion in hydrogels.

PubMed

Schuszter, Gábor; Gehér-Herczegh, Tünde; Szűcs, Árpád; Tóth, Ágota; Horváth, Dezső

2017-05-17

The role of diffusion in chemical pattern formation has been widely studied due to the great diversity of patterns emerging in reaction-diffusion systems, particularly in H + -autocatalytic reactions where hydrogels are applied to avoid convection. A custom-made conductometric cell is designed to measure the effective diffusion coefficient of a pair of strong electrolytes containing sodium ions or hydrogen ions with a common anion. This together with the individual diffusion coefficient for sodium ions, obtained from PFGSE-NMR spectroscopy, allows the determination of the diffusion coefficient of hydrogen ions in hydrogels. Numerical calculations are also performed to study the behavior of a diffusion-migration model describing ionic diffusion in our system. The method we present for one particular case may be extended for various hydrogels and diffusing ions (such as hydroxide) which are relevant e.g. for the development of pH-regulated self-healing mechanisms and hydrogels used for drug delivery.

Intraparticle diffusion limitations in the hydrogenation of monounsaturated edible oils and their fatty acid methyl esters

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

Jonker, G.H.; Veldsink, J.W.; Beenackers, A.A.C.M.

1998-12-01

Intraparticle diffusion limitation in the hydrogenation and isomerization of fatty acid methyl esters (FAMEs) and edible oils (triacylglycerol, TAG) in porous nickel catalyst was investigated both under reactive and under inert conditions. Under reactive conditions, the diffusion coefficients were determined from the best fits of the model simulations applying the intrinsic reacting kinetics of monounsaturated FAME hydrogenation to experiments under diffusion limited conditions. Due to the absence of reaction (hydrogenation of double bonds), the obtained effective H{sub z} diffusion coefficient (D{sub e}) with the HPLC technique is volume averaged and thereby determined by the larger intercrystalline pores (<30% of themore » total pore volume) only. Moreover, D{sub e} measured under reaction conditions reflected the influence of the micropores, resulting in a 10-fold lower value.« less

A Novel Unitized Regenerative Proton Exchange Membrane Fuel Cell

NASA Technical Reports Server (NTRS)

Murphy, O. J.; Cisar, A. J.; Gonzalez-Martin, A.; Salinas, C. E.; Simpson, S. F.

1996-01-01

A difficulty encountered in designing a unitized regenerative proton exchange membrane (PEM) fuel cell lies in the incompatibility of electrode structures and electrocatalyst materials optimized for either of the two functions (fuel cell or electrolyzer) with the needs of the other function. This difficulty is compounded in previous regenerative fuel cell designs by the fact that water, which is needed for proton conduction in the PEM during both modes of operation, is the reactant supplied to the anode in the electrolyzer mode of operation and the product formed at the cathode in the fuel cell mode. Drawbacks associated with existing regenerative fuel cells have been addressed. In a first innovation, electrodes function either as oxidation electrodes (hydrogen ionization or oxygen evolution) or as reduction electrodes (oxygen reduction or hydrogen evolution) in the fuel cell and electrolyzer modes, respectively. Control of liquid water within the regenerative fuel cell has been brought about by a second innovation. A novel PEM has been developed with internal channels that permit the direct access of water along the length of the membrane. Lateral diffusion of water along the polymer chains of the PEM provides the water needed at electrode/PEM interfaces. Fabrication of the novel single cell unitized regenerative fuel cell and results obtained on testing it are presented.

A novel unitized regenerative proton exchange membrane fuel cell

NASA Technical Reports Server (NTRS)

Murphy, O. J.; Cisar, A. J.; Gonzalez-Martin, A.; Salinas, C. E.; Simpson, S. F.

1995-01-01

A difficulty encountered in designing a unitized regenerative proton exchange membrane (PEM) fuel cell lies in the incompatibility of electrode structures and electrocatalyst materials optimized for either of the two functions (fuel cell or electrolyzer) with the needs of the other function. This difficulty is compounded in previous regenerative fuel cell designs by the fact that water, which is needed for proton conduction in the PEM during both modes of operation, is the reactant supplied to the anode in the electrolyzer mode of operation and the product formed at the cathode in the fuel cell mode. Drawbacks associated with existing regenerative fuel cells have been addressed in work performed at Lynntech. In a first innovation, electrodes function either as oxidation electrodes (hydrogen ionization or oxygen evolution) or as reduction electrodes (oxygen reduction or hydrogen evolution) in the fuel cell and electrolyzer modes, respectively. Control of liquid water within the regenerative fuel cell has been brought about by a second innovation. A novel PEM has been developed with internal channels that permit the direct access of water along the length of the membrane. Lateral diffusion of water along the polymer chains of the PEM provides the water needed at electrode/PEM interfaces. Fabrication of the novel unitized regenerative fuel cell and results obtained on testing it will be presented.

The Synthesis and Characterization of Cerium Carbonate Hydroxide Nanorods as an Anode for Lithium-Ion Batteries

NASA Astrophysics Data System (ADS)

Zhou, Yining; Liu, Hefen; Liu, Jianqiang; Liu, Haowen

2018-03-01

Nanorods cerium carbonate hydroxide, CeCO3OH, was synthesized through a low-temperature reaction route. The data of x-ray diffraction and scanning electron microscopy revealed that the as-prepared samples were CeCO3OH nanorods. The diameters of the nanorods were in the range of 50-100 nm, and the lengths were around 300-500 nm. As an anode of a lithium ion battery, the charge-discharge capacity, cyclability and lithium-ion diffusion kinetics of CeCO3OH nanorods were investigated. The calculated lithium ion diffusion coefficient was 1.36 × 10-19 cm2 s-1. The initial discharge capacity was about 621.6 mA h g-1 at 0.2 mA cm-2 in 0.05-2.5 V. After 100 cycles, the discharge capacity stabilized at about 362 mA h g-1 and the Coulombic efficiency was nearly 98%, indicating the potential application in anodes of lithium-ion batteries.

Silver plating ensures reliable diffusion bonding of dissimilar metals

NASA Technical Reports Server (NTRS)

1967-01-01

Dissimilar metals are reliably joined by diffusion bonding when the surfaces are electroplated with silver. The process involves cleaning and etching, anodization, silver striking, and silver plating with a conventional plating bath. It minimizes the formation of detrimental intermetallic phases and provides greater tolerance of processing parameters.

Air plasma spray processing and electrochemical characterization of Cu-SDC coatings for use in solid oxide fuel cell anodes

NASA Astrophysics Data System (ADS)

Benoved, Nir; Kesler, O.

Air plasma spraying has been used to produce porous composite anodes based on Ce 0.8Sm 0.2O 1.9 (SDC) and Cu for use in solid oxide fuel cells (SOFCs). Preliminarily, a range of plasma conditions has been examined for the production of composite coatings from pre-mixed SDC and CuO powders. Plasma gas compositions were varied to obtain a range of plasma temperatures. After reduction in H 2, coatings were characterized for composition and microstructure using EDX and SEM. As a result of these tests, symmetrical sintered electrolyte-supported anode-anode cells were fabricated by air plasma spraying of the anodes, followed by in situ reduction of the CuO to Cu. Full cells deposited on SS430 porous substrates were then produced in one integrated process. Fine CuO and SDC powders have been used to produce homogeneously mixed anode coatings with higher surface area microstructures, resulting in area-specific polarization resistances of 4.8 Ω cm 2 in impedance tests in hydrogen at 712 °C.

Single-Wall Carbon Nanotube Production by the Arc Process: A Parametric Study

NASA Technical Reports Server (NTRS)

Scott, Carl D.; Gorelik, Olga; Proft, William J.

2000-01-01

Single wall carbon nanotubes are produced using the arc discharge process. Graphite anodes are filled with a mixture of nickel and yttrium metallic powders, then vaporized by creating a high current arc. By varying the current, gap distance, and ambient pressure it is shown that the best yield of single wall carbon nanotubes is obtained within a narrow range of conditions. The relative yield and purity of the product are indicated semi-quantitatively from scanning electric microscopy (SEM) and thermogravimetric analysis (TGA). Two types of anodes have been investigated. The first is hollow and filled with a powder mixture of graphite, nickel and yttrium. The second is filled with a paste made of a mixture of metal nitrates, graphite powder and carbon adhesive, then reduced in an argon atmosphere at high temperature. Product purity and yield will be compared for the two types of anodes. The graphite in the anodes may have hydrogen attached in the pores. To remove this impurity anodes have been baked up to 1400 - 1500 C. The effect of baking the anodes on impurities in the product will be given.

Influence of anode thickness on the power output of solid oxide fuel cells with (La,Sr)(Co,Fe)-type cathode

NASA Astrophysics Data System (ADS)

Menzler, Norbert H.; Haanappel, Vincent A. C.

The influence of the thickness of the anode (functional layer) on the power output of anode-supported solid oxide fuel cells with a lanthanum-strontium-cobalt-ferrite cathode was investigated. The anode was applied by vacuum slip casting and the thickness varied between 1 and 22 μm. All other material and microstructural parameters were kept constant. Single cells with dimensions of 50 mm × 50 mm and with an active cathode area of 40 mm × 40 mm were manufactured and tested in an alumina housing with air as oxidant and hydrogen with 3% water vapour as the fuel gas. Results have shown that SOFCs with anodes between 1 and 13 μm have slightly better performance than those with thicker anodes (∼1.7 A cm -2 versus 1.5 A cm -2 at 800 °C and 0.7 V). The current densities were discussed with respect to cell area specific resistance, helium leak rate of the half-cell, and microstructure.

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.

Modelling the growth of porous alumina matrix for creating hyperbolic media

NASA Astrophysics Data System (ADS)

Aryslanova, E. M.; Alfimov, A. V.; Chivilikhin, S. A.

2016-08-01

Porous aluminum oxide is a regular self-assembled structure. During anodization it is possible to control nano-parameters of the structure using macroscopic parameters of anodization. Porous alumina films can be used as a template for the creation of hyperbolic media. In this work we consider the anodization process, our model takes into account the influence of layers of aluminum and electrolyte on the rate of growth of aluminum oxide, as well as the effect of surface diffusion. As a result of our model we obtain the minimum distance between centers of alumina pores in the beginning of anodizing process. We also present the results obtained by numerical modelling of hyperbolic media based on porous alumina film.

Model of porous aluminium oxide growth during initial stage of anodization

NASA Astrophysics Data System (ADS)

Aryslanova, E. M.; Alfimov, A. V.; Chivilikhin, S. A.

2014-10-01

Currently, the development of nanotechnology and metamaterials requires the ability to obtain regular self-assembled structures with different parameters. One such structure is porous alumina in which the pores grow perpendicular to the substrate and are hexagonally packed. Pore size and the distance between them can be varied depending on the anodization voltage, the electrolyte and the anodization time (pore diameter - from 2 to 350 nm, the distance between the pores - from 5 to 50 nm). At the moment, there are different models describing the process of anodizing aluminum, in this paper we propose a model that takes into account the effect of layers of aluminum, aluminum oxide, and the electrolyte, as well as the influence of the effect of surface diffusion.

Comparative study on the structure and electrochemical hydriding properties of MgTi, Mg 0.5Ni 0.5Ti and MgTi 0.5Ni 0.5 alloys prepared by high energy ball milling

NASA Astrophysics Data System (ADS)

Rousselot, Steeve; Guay, Daniel; Roué, Lionel

MgTi, Mg 0.5Ni 0.5Ti and MgTi 0.5Ni 0.5 alloys doped with 10 wt.% Pd were prepared by high energy ball milling and evaluated as hydrogen storage electrodes for Ni-MH batteries. X-ray diffraction analyses indicated that the Mg 0.5Ni 0.5Ti and MgTi 0.5Ni 0.5 alloys could be monophased or composed of a nanoscale mixture of MgTi + NiTi and MgTi + MgNi phases, respectively. Their hydrogen storage characteristics were investigated electrochemically in KOH electrolyte. No activation step was observed during the cycling of the Mg-Ti-Ni electrodes in contrast to that observed with the MgTi electrode. The highest hydrogen discharge capacity was obtained with the MgTi 0.5Ni 0.5 electrode (536 mAh g -1) compared to 401 and 475 mAh g -1 for the Mg 0.5Ni 0.5Ti and MgTi electrodes, respectively. The ternary Mg-Ti-Ni alloys showed a better cycle life with an average capacity decay rate per cycle lower than 1.5% compared to ∼7% for the binary MgTi electrode. The Mg-Ni-Ti electrodes also displayed a much higher discharge rate capability than the binary MgTi electrode, especially with the Mg 0.5Ni 0.5Ti electrode. The origin of this was established on the basis of the anodic polarization curves, where a substantial decrease of the concentration overpotential (reflecting a higher hydrogen diffusivity) was observed for the Mg 0.5Ni 0.5Ti electrode.

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.

Modular Advanced Oxidation Process Enabled by Cathodic Hydrogen Peroxide Production

PubMed Central

2015-01-01

Hydrogen peroxide (H2O2) is frequently used in combination with ultraviolet (UV) light to treat trace organic contaminants in advanced oxidation processes (AOPs). In small-scale applications, such as wellhead and point-of-entry water treatment systems, the need to maintain a stock solution of concentrated H2O2 increases the operational cost and complicates the operation of AOPs. To avoid the need for replenishing a stock solution of H2O2, a gas diffusion electrode was used to generate low concentrations of H2O2 directly in the water prior to its exposure to UV light. Following the AOP, the solution was passed through an anodic chamber to lower the solution pH and remove the residual H2O2. The effectiveness of the technology was evaluated using a suite of trace contaminants that spanned a range of reactivity with UV light and hydroxyl radical (HO•) in three different types of source waters (i.e., simulated groundwater, simulated surface water, and municipal wastewater effluent) as well as a sodium chloride solution. Irrespective of the source water, the system produced enough H2O2 to treat up to 120 L water d–1. The extent of transformation of trace organic contaminants was affected by the current density and the concentrations of HO• scavengers in the source water. The electrical energy per order (EEO) ranged from 1 to 3 kWh m–3, with the UV lamp accounting for most of the energy consumption. The gas diffusion electrode exhibited high efficiency for H2O2 production over extended periods and did not show a diminution in performance in any of the matrices. PMID:26039560

Diffusive Gas Loss from Silica Glass Ampoules at Elevated Temperatures

NASA Technical Reports Server (NTRS)

Palosz, W.

1998-01-01

Changes in the pressure of hydrogen, helium and neon due to diffusion through the wall of silica crystal growth ampoules at elevated temperatures were determined experimentally. We show that, while both He- and Ne-losses closely follow conventional model of diffusive gas permeation through the wall, hydrogen losses, in particular at low fill pressures, can be much larger. This is interpreted in terms of the high solubility of hydrogen in silica glasses.

Free-standing hierarchically sandwich-type tungsten disulfide nanotubes/graphene anode for lithium-ion batteries.

PubMed

Chen, Renjie; Zhao, Teng; Wu, Weiping; Wu, Feng; Li, Li; Qian, Ji; Xu, Rui; Wu, Huiming; Albishri, Hassan M; Al-Bogami, A S; El-Hady, Deia Abd; Lu, Jun; Amine, Khalil

2014-10-08

Transition metal dichalcogenides (TMD), analogue of graphene, could form various dimensionalities. Similar to carbon, one-dimensional (1D) nanotube of TMD materials has wide application in hydrogen storage, Li-ion batteries, and supercapacitors due to their unique structure and properties. Here we demonstrate the feasibility of tungsten disulfide nanotubes (WS2-NTs)/graphene (GS) sandwich-type architecture as anode for lithium-ion batteries for the first time. The graphene-based hierarchical architecture plays vital roles in achieving fast electron/ion transfer, thus leading to good electrochemical performance. When evaluated as anode, WS2-NTs/GS hybrid could maintain a capacity of 318.6 mA/g over 500 cycles at a current density of 1A/g. Besides, the hybrid anode does not require any additional polymetric binder, conductive additives, or a separate metal current-collector. The relatively high density of this hybrid is beneficial for high capacity per unit volume. Those characteristics make it a potential anode material for light and high-performance lithium-ion batteries.

Diffusion of hydrogen in olivine: Implications for water in the mantle

NASA Astrophysics Data System (ADS)

Mackwell, Stephen J.; Kohlstedt, David L.

1990-04-01

To investigate the kinetics of diffusion of hydrogen in olivine, single crystals from San Carlos in Arizona have been annealed at temperatures between 800° and 1000°C under hydrothermal conditions at a confining pressure of 300 MPa. The hydrogen diffusivities were determined for the [100], [010], and [001] directions from concentration profiles for hydroxyl in the samples. These profiles were obtained from infrared spectra taken at 100-μm intervals across a thin slice which was cut from the central portion of each annealed crystal. The rate of diffusion is anisotropic, with fastest transport along the [100] axis and slowest along the [010] axis. The fit of the data to an Arrhenius law for diffusion parallel to [100] yields an activation enthalpy of 130±30 kJ/mol with a preexponential term of (6±3)×10-5 m2 s-1. For diffusion parallel to [001], as there are insufficient data to calculate the activation enthalpy for diffusion, we used the same value as that for diffusion parallel to [100] and determined a preexponential term of (5±4)×10-6 m2 s-1. The diffusion rate parallel to [010] is about 1 order of magnitude slower than along [001]. The measured diffusivities are large enough that the hydrogen content of olivine grains which are millimeters in diameter will adjust to changing environmental conditions in time scales of hours at temperatures as low as 800°C. As xenoliths ascending from the mantle remain at high temperatures (i.e., >1000°C) but experience a rapid decrease in pressure, and hence hydrogen fugacity, olivine grains may dehydrate during ascent. By comparison, slow rates of carbon diffusion (Tingle et al., 1988) suggest that carbon will not be lost from olivine during ascent. Thus, low hydrogen contents within olivine and within fluid inclusions in olivine cannot be taken as support for low water contents in the mantle.

Kinetic Monte Carlo simulation on influence of vacancy on hydrogen diffusivity in tungsten

NASA Astrophysics Data System (ADS)

Oda, Takuji; Zhu, Deqiong; Watanabe, Yoshiyuki

2015-12-01

Kinetic Mote Carlo (KMC) simulations are performed to quantify the influence of trap in hydrogen diffusivity in tungsten. As a typical trap, mono-vacancy is considered in the simulation. Experimental results reported by Frauenfelder are nicely reproduced when hydrogen concentration and trap concentration expected in the experiment are employed in the simulation. The effective diffusivity of hydrogen is evidently decreased by traps even at high temperatures like 1300 K. These results suggest that only high-temperature experimental data, which are not significantly affected by traps, should be fitted to, in order to derive the true hydrogen diffusivity from experiments. Therefore, we recommend D = 1.58 ×10-7exp(- 0.25 eV / kT) m2 s-1 as the equation for hydrogen diffusion coefficient in tungsten, which was obtained by fitting only to experimental data at 1500-2400 K by Heinola and Ahlgren, rather than the most cited equation D = 4.1 ×10-7exp(- 0.39 eV / kT) m2 s-1, which was obtained by fitting to all experimental data at 1100-2400 K including some data that should be affected by traps.

Recent Progress in Synthesis and Application of Low-Dimensional Silicon Based Anode Material for Lithium Ion Battery

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

Sun, Yuandong; Liu, Kewei; Zhu, Yu

Silicon is regarded as the next generation anode material for LIBs with its ultra-high theoretical capacity and abundance. Nevertheless, the severe capacity degradation resulting from the huge volume change and accumulative solid-electrolyte interphase (SEI) formation hinders the silicon based anode material for further practical applications. Hence, a variety of methods have been applied to enhance electrochemical performances in terms of the electrochemical stability and rate performance of the silicon anodes such as designing nanostructured Si, combining with carbonaceous material, exploring multifunctional polymer binders, and developing artificial SEI layers. Silicon anodes with low-dimensional structures (0D, 1D, and 2D), compared with bulkymore » silicon anodes, are strongly believed to have several advanced characteristics including larger surface area, fast electron transfer, and shortened lithium diffusion pathway as well as better accommodation with volume changes, which leads to improved electrochemical behaviors. Finally, in this review, recent progress of silicon anode synthesis methodologies generating low-dimensional structures for lithium ion batteries (LIBs) applications is listed and discussed.« less

Recent Progress in Synthesis and Application of Low-Dimensional Silicon Based Anode Material for Lithium Ion Battery

DOE PAGES

Sun, Yuandong; Liu, Kewei; Zhu, Yu

2017-07-31

Silicon is regarded as the next generation anode material for LIBs with its ultra-high theoretical capacity and abundance. Nevertheless, the severe capacity degradation resulting from the huge volume change and accumulative solid-electrolyte interphase (SEI) formation hinders the silicon based anode material for further practical applications. Hence, a variety of methods have been applied to enhance electrochemical performances in terms of the electrochemical stability and rate performance of the silicon anodes such as designing nanostructured Si, combining with carbonaceous material, exploring multifunctional polymer binders, and developing artificial SEI layers. Silicon anodes with low-dimensional structures (0D, 1D, and 2D), compared with bulkymore » silicon anodes, are strongly believed to have several advanced characteristics including larger surface area, fast electron transfer, and shortened lithium diffusion pathway as well as better accommodation with volume changes, which leads to improved electrochemical behaviors. Finally, in this review, recent progress of silicon anode synthesis methodologies generating low-dimensional structures for lithium ion batteries (LIBs) applications is listed and discussed.« less

Electrosorption of organic acids from aqueous bio-oil and conversion into hydrogen via microbial electrolysis cells

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

Park, Lydia Kyoung-Eun; Satinover, Scott J.; Yiacoumi, Sotira

Neutralization of the bio-oil pH has been shown to generate a neutralized bio-oil aqueous phase (NBOAP) that includes most of the acidic components and a neutralized bio-oil organic phase (NBOOP) that includes hydrophobic organics, such as phenols. NBOOP can be used for fuel production, while NBOAP can be fed to microbial electrolysis cells (MECs) for hydrogen production. After pH neutralization, some organic acidic components remain in NBOOP. This work is focused on capturing acidic compounds from NBOOP through water extraction and electrosorption, and demonstrating hydrogen production via MECs. Capacitive deionization (CDI) is proven effective in capturing ions from NBOOP-contacted watermore » and NBOAP via electrosorption. Captured acidic compounds enable the MEC application to effectively produce renewable hydrogen. Chemical oxygen demand (COD) removal of 49.2%, 61.5%, and 60.8% for 2, 4, and 10 g/L-anode/day loading were observed, corresponding to a total COD degradation of 0.19 g/L, 0.79 g/L, and 1.3 g/L, respectively. A maximum hydrogen productivity of 4.3 L-H 2/L-anode/day was obtained. Major compounds in the water phase such as fatty acids, sugar derivatives, furanic and phenolic compounds were converted to hydrogen with an efficiency of 80–90%. Lastly, this approach may lead the entire biomass pyrolysis process to be an overall carbon-neutral process.« less

Electrosorption of organic acids from aqueous bio-oil and conversion into hydrogen via microbial electrolysis cells

DOE PAGES

Park, Lydia Kyoung-Eun; Satinover, Scott J.; Yiacoumi, Sotira; ...

2018-02-17

Neutralization of the bio-oil pH has been shown to generate a neutralized bio-oil aqueous phase (NBOAP) that includes most of the acidic components and a neutralized bio-oil organic phase (NBOOP) that includes hydrophobic organics, such as phenols. NBOOP can be used for fuel production, while NBOAP can be fed to microbial electrolysis cells (MECs) for hydrogen production. After pH neutralization, some organic acidic components remain in NBOOP. This work is focused on capturing acidic compounds from NBOOP through water extraction and electrosorption, and demonstrating hydrogen production via MECs. Capacitive deionization (CDI) is proven effective in capturing ions from NBOOP-contacted watermore » and NBOAP via electrosorption. Captured acidic compounds enable the MEC application to effectively produce renewable hydrogen. Chemical oxygen demand (COD) removal of 49.2%, 61.5%, and 60.8% for 2, 4, and 10 g/L-anode/day loading were observed, corresponding to a total COD degradation of 0.19 g/L, 0.79 g/L, and 1.3 g/L, respectively. A maximum hydrogen productivity of 4.3 L-H 2/L-anode/day was obtained. Major compounds in the water phase such as fatty acids, sugar derivatives, furanic and phenolic compounds were converted to hydrogen with an efficiency of 80–90%. Lastly, this approach may lead the entire biomass pyrolysis process to be an overall carbon-neutral process.« less

Solution and diffusion of hydrogen isotopes in tungsten-rhenium alloy

NASA Astrophysics Data System (ADS)

Ren, Fei; Yin, Wen; Yu, Quanzhi; Jia, Xuejun; Zhao, Zongfang; Wang, Baotian

2017-08-01

Rhenium is one of the main transmutation elements forming in tungsten under neutron irradiation. Therefore, it is essential to understand the influence of rhenium impurity on hydrogen isotopes retention in tungsten. First-principle calculations were used to study the properties of hydrogen solution and diffusion in perfect tungsten-rhenium lattice. The interstitial hydrogen still prefers the tetrahedral site in presence of rhenium, and rhenium atom cannot act directly as a trapping site of hydrogen. The presence of rhenium in tungsten raises the solution energy and the real normal modes of vibration on the ground state and the transition state, compared to hydrogen in pure tungsten. Without zero point energy corrections, the presence of rhenium decreases slightly the migration barrier. It is found that although the solution energy would tend to increase slightly with the rising of the concentration of rhenium, but which does not influence noticeably the solution energy of hydrogen in tungsten-rhenium alloy. The solubility and diffusion coefficient of hydrogen in perfect tungsten and tungsten-rhenium alloy have been estimated, according to Sievert's law and harmonic transition state theory. The results show the solubility of hydrogen in tungsten agrees well the experimental data, and the presence of Re would decrease the solubility and increase the diffusivity for the perfect crystals.

Investigation of anodic and chemical oxides grown on p-type InP with applications to surface passivation for n(+)-p solar cell fabrication

NASA Technical Reports Server (NTRS)

Faur, Maria; Faur, Mircea; Goradia, Manju; Goradia, Chandra; Jenkins, Phillip; Jayne, Douglas; Weinberg, Irving

1991-01-01

Most of the previously reported InP anodic oxides were grown on a n-type InP with applications to fabrication of MISFET structures and were described as a mixture of In2O3 and P2O5 stoichiometric compounds or nonstoichiometric phases which have properties similar to crystalline compounds In(OH)3, InPO4, and In(PO3)3. Details of the compositional change of the anodic oxides grown under different anodization conditions were previously reported. The use of P-rich oxides grown either by anodic or chemical oxidation are investigated for surface passivation of p-type InP and as a protective cap during junction formation by closed-ampoule sulfur diffusion. The investigation is based on but not limited to correlations between PL intensity and X-ray photoelectron spectroscopy (XPS) chemical composition data.

Ultrahigh Storage and Fast Diffusion of Na and K in Blue Phosphorene Anodes.

PubMed

Mukherjee, Sankha; Kavalsky, Lance; Singh, Chandra Veer

2018-03-14

In the wake of blue phosphorene's (BP) computational discovery and experimental realization, it has emerged as a versatile material with interesting optical, electrical, and mechanical properties. In this study, using first principles density functional theory calculations, we have investigated the adsorption and diffusion of Na and K over monolayer BP to assess its suitability as Na-ion and K-ion battery anodes. The optimized adsorption energies were found to be -0.96 eV for Na and -1.54 eV for K, which are sufficiently large to ensure stability and safety during operation. In addition, BP could adsorb Na and K atoms up to a stoichiometric ratio of 1:1 which yields a high storage capacity of 865 mA h/g for both adatom species. Through examination of the electronic structure and projected density of states of BP as a function of Na/K concentration, we predict that the band gap of the system increasingly shrinks, and in the case of maximum K adsorption, the band gap diminishes completely. Additionally, the diffusion of Na and K over BP is observed to be ultrafast, especially for K, and anisotropic with modest energy barriers of 0.11 and 0.093 eV for Na and K, respectively. Building upon these findings, we employed vibrational analysis techniques with transition state theory to incorporate kinetic effects and predicted a diffusivity of 7.2 × 10 -5 cm 2 /s for Na and 8.58 × 10 -5 cm 2 /s for K on BP. Given these advantages, that is, ultrahigh capacity, electrical conductivity, and high Na/K diffusivity, we conclude that BP can be considered as an excellent candidate for anodes in Na- and K-ion batteries.

Improved bio-hydrogen production from glucose by adding a specific methane inhibitor to microbial electrolysis cells with a double anode arrangement.

PubMed

Zhang, Jingnan; Bai, Yanxia; Fan, Yaoting; Hou, Hongwei

2016-10-01

Improved hydrogen production from glucose was achieved by adding a specific methane inhibitor (such as chloroform) to repress the activity of methanogens in a single-chamber microbial electrolysis cells (MECs) with a double anode arrangement. A maximum hydrogen production of 8.4±0.2 mol H2/mol-G (G represents glucose), a hydrogen production rate of 2.39±0.3 m(3) H2/m3/d and a high energy efficiency (relative to the electrical input) of ηE=165±5% had been recorded from 1 g/L glucose at a low dosage of chloroform (5‰, v:v) and an applied voltage of 0.8 V. Almost all of the glucose was removed within 4 h, with 66% of the electrons in intermediates (mainly including acetate and ethanol), and methane gas was not detected in the MECs through 11 batch cycles. The experimental results confirmed that chloroform was an effective methane inhibitor that improved hydrogen production from glucose in the MECs. In addition, the cyclic voltammetry tests demonstrated that the electron transfer in the MECs was mainly due to the biofilm-bound redox compounds rather than soluble electron shuttles. Copyright © 2016 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

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.

Caramel popcorn shaped silicon particle with carbon coating as a high performance anode material for Li-ion batteries.

PubMed

He, Meinan; Sa, Qina; Liu, Gao; Wang, Yan

2013-11-13

Silicon is a very promising anode material for lithium ion batteries. It has a 4200 mAh/g theoretical capacity, which is ten times higher than that of commercial graphite anodes. However, when lithium ions diffuse to Si anodes, the volume of Si will expand to almost 400% of its initial size and lead to the crack of Si. Such a huge volume change and crack cause significant capacity loss. Meanwhile, with the crack of Si particles, the conductivity between the electrode and the current collector drops. Moreover, the solid electrolyte interphase (SEI), which is generated during the cycling, reduces the discharge capacity. These issues must be addressed for widespread application of this material. In this work, caramel popcorn shaped porous silicon particles with carbon coating are fabricated by a set of simple chemical methods as active anode material. Si particles are etched to form a porous structure. The pores in Si provide space for the volume expansion and liquid electrolyte diffusion. A layer of amorphous carbon is formed inside the pores, which gives an excellent isolation between the Si particle and electrolyte, so that the formation of the SEI layer is stabilized. Meanwhile, this novel structure enhances the mechanical properties of the Si particles, and the crack phenomenon caused by the volume change is significantly restrained. Therefore, an excellent cycle life under a high rate for the novel Si electrode is achieved.

Natural dye sensitizer from cassava (Manihot utilissima) leaves extract and its adsorption onto TiO2 photo-anode

NASA Astrophysics Data System (ADS)

Nurlela; Wibowo, R.; Gunlazuardi, J.

2017-04-01

Interaction between TiO2 and dyes sensitizer have been studied. The chlorophyll presents in the crude leave extract (CLE-dye) from cassava (Manihot utilissima) was immobilized on to the photo-anode, consists of TiO2 supported by fluor doped Tin oxide (SnO2-F) Glass. The TiO2 was prepared by Rapid Breakdown Anodization (RBA) method then immobilized on to glass coated by SnO2-F using doctor blade technique, to give CLE-dye/TiO2/SnO2-F/Glass photo-anode. The prepared photo-anode was characterized by UV-Vis-DRS, FTIR, XRD, SEM, electrochemical and spectro-electrochemical systems. In this study, the HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) energy level of the CLE-dye were empirically determined by cyclic voltammetry method, while spectro-electro-chemistry method was used to determine the coefficient of degradation and formation of the dyes, and diffusion coefficient of the hole recombination as well. Good anchoring between TiO2 with dye extracts (CLE-dye) can be seen from value of dye LUMO energy level (-4.26 eV), which is approaching the conduction band of TiO2 (-4.3 eV). The coefficient of degradation and formation of the CLE-dye showed a quasi reversible and diffusion coefficient hole recombination values were small, indicated that it is quite suitable as a sensitizer in a dyes sensitized solar cell.

Experimental study of mass diffusion coefficients of hydrogen in dimethyl phosphate and n-heptane

NASA Astrophysics Data System (ADS)

Guo, Y.; Zhu, L. K.; Zhang, Y. P.; Liu, J.; Guo, J. S.

2017-11-01

In this study, a laser holographic interferometer experimental system was developed for studying the gas-liquid mass diffusion coefficient. Then the experimental system’s uncertainty was analyzed to be at most ±0.2% therefore, this system was reliable. The mass diffusion coefficient of hydrogen in dimethyl phosphate and n-heptane was measured at atmospheric pressure in the temperature range of 273.15-338.15 K. Then, the experimental data were used to fit the correlations of the mass diffusion coefficient of hydrogen in dimethyl phosphate and n-heptane with temperature.

Hydrogen production from a rectangular horizontal filter press Divergent Electrode-Flow-Through (DEFT™) alkaline electrolysis stack

NASA Astrophysics Data System (ADS)

Gillespie, M. I.; Kriek, R. J.

2017-12-01

A membraneless Divergent Electrode-Flow-Through (DEFT™) alkaline electrolyser, for unlocking profitable hydrogen production by combining a simplistic, inexpensive, modular and durable design, capable of overcoming existing technology current density thresholds, is ideal for decentralised renewable hydrogen production, with the only requirement of electrolytic flow to facilitate high purity product gas separation. Scale-up of the technology was performed, representing a deviation from the original tested stack design, incorporating elongated electrodes housed in a filter press assembly. The pilot plant operating parameters were limited to a low flow velocity range (0.03 m s-1 -0.04 m s-1) with an electrode gap of 2.5 mm. Performance of this pilot plant demonstrated repeatability to results previously obtained. Mesh electrodes with geometric area of 344.32 cm2 were used for plant performance testing. A NiO anode and Ni cathode combination developed optimal performance yielding 508 mA cm-2 at 2 VDC in contrast to a Ni anode and cathode combination providing 467 mA cm-2 at 2.26 VDC at 0.04 m s-1, 30% KOH and 80 °C. An IrO2/RuO2/TiO2 anode and Pt cathode combination underwent catalyst deactivation. Owing to the nature of the gas/liquid separation system, gas qualities were inadequate compared to results achieved previously. Future improvements will provide qualities similar to results achieved before.

Moisture contamination and welding parameter effects on flux cored arc welding diffusible hydrogen

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

Kiefer, J.J.

1994-12-31

Gas metal arc (GMAW) and flux cored arc (FCAW) welding are gas shielded semiautomatic processes widely used for achieving high productivity in steel fabrication. Contamination of the shielding has can occur due to poorly maintained gas distribution systems. Moisture entering as a gas contaminant is a source of hydrogen that can cause delayed cold cracking in welds. Limiting heat-affected zone hardness is one method of controlling cracking. Even this is based on some assumptions about the hydrogen levels in the weld. A study was conducted to investigate the effect of shielding gas moisture contamination and welding parameters on the diffusiblemore » hydrogen content of gas shielded flux cored arc welding. The total wire hydrogen of various electrodes was also tested and compared to the diffusible weld hydrogen. An empirical equation has been developed that estimates the diffusible hydrogen in weld metal for gas shielded flux cored arc welding. The equation is suitable for small diameter electrodes and welding parameter ranges commonly used for out-of-position welding. by combining this with the results from the total wire hydrogen tests, it is possible to estimate diffusible hydrogen directly from measured welding parameters, shielding gas dew point, and total hydrogen of the consumable. These equations are also useful for evaluating the effect of welding procedure variations from known baseline conditions.« less

Ternary CNTs@TiO2/CoO Nanotube Composites: Improved Anode Materials for High Performance Lithium Ion Batteries

PubMed Central

Madian, Mahmoud; Ummethala, Raghunandan; Abo El Naga, Ahmed Osama; Ismail, Nahla; Rümmeli, Mark Hermann; Eychmüller, Alexander; Giebeler, Lars

2017-01-01

TiO2 nanotubes (NTs) synthesized by electrochemical anodization are discussed as very promising anodes for lithium ion batteries, owing to their high structural stability, high surface area, safety, and low production cost. However, their poor electronic conductivity and low Li+ ion diffusivity are the main drawbacks that prevent them from achieving high electrochemical performance. Herein, we report the fabrication of a novel ternary carbon nanotubes (CNTs)@TiO2/CoO nanotubes composite by a two-step synthesis method. The preparation includes an initial anodic fabrication of well-ordered TiO2/CoO NTs from a Ti-Co alloy, followed by growing of CNTs horizontally on the top of the oxide films using a simple spray pyrolysis technique. The unique 1D structure of such a hybrid nanostructure with the inclusion of CNTs demonstrates significantly enhanced areal capacity and rate performances compared to pure TiO2 and TiO2/CoO NTs, without CNTs tested under identical conditions. The findings reveal that CNTs provide a highly conductive network that improves Li+ ion diffusivity, promoting a strongly favored lithium insertion into the TiO2/CoO NT framework, and hence resulting in high capacity and an extremely reproducible high rate capability. PMID:28773032

Ternary CNTs@TiO₂/CoO Nanotube Composites: Improved Anode Materials for High Performance Lithium Ion Batteries.

PubMed

Madian, Mahmoud; Ummethala, Raghunandan; Naga, Ahmed Osama Abo El; Ismail, Nahla; Rümmeli, Mark Hermann; Eychmüller, Alexander; Giebeler, Lars

2017-06-20

TiO₂ nanotubes (NTs) synthesized by electrochemical anodization are discussed as very promising anodes for lithium ion batteries, owing to their high structural stability, high surface area, safety, and low production cost. However, their poor electronic conductivity and low Li⁺ ion diffusivity are the main drawbacks that prevent them from achieving high electrochemical performance. Herein, we report the fabrication of a novel ternary carbon nanotubes (CNTs)@TiO₂/CoO nanotubes composite by a two-step synthesis method. The preparation includes an initial anodic fabrication of well-ordered TiO₂/CoO NTs from a Ti-Co alloy, followed by growing of CNTs horizontally on the top of the oxide films using a simple spray pyrolysis technique. The unique 1D structure of such a hybrid nanostructure with the inclusion of CNTs demonstrates significantly enhanced areal capacity and rate performances compared to pure TiO₂ and TiO₂/CoO NTs, without CNTs tested under identical conditions. The findings reveal that CNTs provide a highly conductive network that improves Li⁺ ion diffusivity, promoting a strongly favored lithium insertion into the TiO₂/CoO NT framework, and hence resulting in high capacity and an extremely reproducible high rate capability.

The effects of temperature and aeration on the corrosion of A508III low alloy steel in boric acid solutions at 25-95 °C

NASA Astrophysics Data System (ADS)

Xiao, Qian; Lu, Zhanpeng; Chen, Junjie; Yao, Meiyi; Chen, Zhen; Ejaz, Ahsan

2016-11-01

The effects of temperature, solution composition and dissolved oxygen on the corrosion rate and electrochemical behavior of an A508III low alloy steel in boric acid solution with lithium hydroxide at 25-95 °C are investigated. In aerated solutions, increasing the boric acid concentration increases the corrosion rate and the anodic current density. The corrosion rate in deaerated solutions increases with increasing temperature. A corrosion rate peak value is found at approximately 75 °C in aerated solutions. Increasing temperature increases the oxygen diffusion coefficient, decreases the dissolved oxygen concentration, accelerates the hydrogen evolution reaction, and accelerates both the active dissolution and the film forming reactions. Increasing dissolved oxygen concentration does not significantly affect the corrosion rate at 50 and 60 °C, increases the corrosion rate at 70 and 80 °C, and decreases the corrosion rate at 87.5 and 95 °C in a high concentration boric acid solution with lithium hydroxide.

The effect of tensile stress on hydrogen diffusion in metal alloys

NASA Technical Reports Server (NTRS)

Danford, M. D.

1992-01-01

The effect of tensile stress on hydrogen diffusion has been determined for Type 303 stainless steel, A286 CRES, and Waspaloy and IN100 nickel-base alloys. It was found that hydrogen diffusion coefficients are not significantly affected by stress, while the hydrogen permeabilities are greatly affected in Type 303 stainless steel and A286 CRES (iron-based alloys), but are affected little in Waspaloy (nickel-base) and not affected in all in IN100 (nickel base). These observations might be taken as an indication that hydrogen permeabilities are affected by stress in iron-based alloys, but only slightly affected in nickel-based alloys. However, it is too early to make such a generalization based on the study of only these four alloys.

Molecular dynamics simulations of hydrogen diffusion in aluminum

DOE PAGES

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

2016-03-23

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

Isotope effects on desorption kinetics of hydrogen isotopes implanted into stainless steel by glow discharge

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

Matsuyama, M.; Kondo, M.; Noda, N.

2015-03-15

In a fusion device the control of fuel particles implies to know the desorption rate of hydrogen isotopes by the plasma-facing materials. In this paper desorption kinetics of hydrogen isotopes implanted into type 316L stainless steel by glow discharge have been studied by experiment and numerical calculation. The temperature of a maximum desorption rate depends on glow discharge time and heating rate. Desorption spectra observed under various experimental conditions have been successfully reproduced by numerical simulations that are based on a diffusion-limited process. It is suggested, therefore, that desorption rate of a hydrogen isotope implanted into the stainless steel ismore » limited by a diffusion process of hydrogen isotope atoms in bulk. Furthermore, small isotope effects were observed for the diffusion process of hydrogen isotope atoms. (authors)« less

Investigation on Sr0.2Na0.8Nb1-xVxO3 (x=0.1, 0.2, 0.3) as new ceramic anode materials for low-temperature solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Pan, Ke-Ji; Hussain, A. Mohammed; Wachsman, Eric D.

2017-04-01

Variants of SNNV (Sr0.2Na0.8Nb1-xVxO3, X = 0.1-0.3) ceramic oxides were synthesized via wet chemical method. SNNVs show high electronic conductivity of >100 S/cm when reduced in hydrogen at a relatively low temperature of 650 °C. In particular, 30% V-doped SNNV exhibited the highest conductivity of 300 S/cm at 450 °C. In order to investigate the fuel cell performance, Gd0.1Ce0.9O2-δ (GDC) based electrolyte-supported fuel cells were prepared to study the anode characteristics. Sr0.2Na0.8Nb0.9V0.1O3 (SNNV10)-GDC composite was used as an anode and La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF)-GDC as a cathode. Both electrodes were porous and sintered at 1050 °C for 2 h in air. The anode side of the fuel cell was infiltrated with 10 wt% GDC/Ni-GDC precursor to activate the anode for fuel oxidation. I-V characteristics were determined in gas conditions such as dry/humidified hydrogen and methane at 650 °C. With the infiltration Ni-GDC, peak power density (PPD) of 280 mW/cm2 and 220 mW/cm2 in dry H2 and CH4, respectively, were obtained at 650 °C, which is higher than GDC alone as infiltrate. The high resistances in the humidified conditions are attributed to the lower conductivity of SNNV10 in high PO2 atmospheres.

Characteristic properties of the frame-antenna-produced RF discharge evolution in the Uragan-3M torsatron

NASA Astrophysics Data System (ADS)

Chechkin, V. V.; Grigor'eva, L. I.; Pavlichenko, R. O.; Kulaga, A. Ye.; Zamanov, N. V.; Moiseenko, V. E.; Burchenko, P. Ya.; Lozin, A. V.; Tsybenko, S. A.; Tarasov, I. K.; Pankratov, I. M.; Grekov, D. L.; Beletskii, A. A.; Kasilov, A. A.; Voitsenya, V. S.; Pashnev, V. K.; Konovalov, V. G.; Shapoval, A. N.; Mironov, Yu. K.; Romanov, V. S.

2014-08-01

In the ℓ = 3 Uragan-3M torsatron, hydrogen plasma is produced and heated by RF fields in the Alfvén range of frequencies (ω ≲ ω ci ). To this end, a frame antenna with a broad spectrum of generated parallel wavenumbers is used. The RF discharge evolution is studied experimentally at different values of the RF power fed to the antenna (the anode voltage of the oscillator and the antenna current) and the initial pressure of the fueling gas. It is shown that, depending on the antenna current and hydrogen pressure, the discharge can operate in two regimes differing in the plasma density, temperature, and particle loss. The change in the discharge regime with increasing anode voltage is steplike in character. The particular values of the anode voltage and pressure at which the change occurs are affected by RF preionization or breakdown stabilization by a microwave discharge. The obtained results will be used in future experiments to choose the optimal regimes of the frame-antenna-produced RF discharge as a target for the production and heating of a denser plasma by another, shorter wavelength three-half-turn antenna.

In situ fabrication of electrochemically grown mesoporous metallic thin films by anodic dissolution in deep eutectic solvents.

PubMed

Renjith, Anu; Roy, Arun; Lakshminarayanan, V

2014-07-15

We describe here a simple electrodeposition process of forming thin films of noble metallic nanoparticles such as Au, Ag and Pd in deep eutectic solvents (DES). The method consists of anodic dissolution of the corresponding metal in DES followed by the deposition on the cathodic surface. The anodic dissolution process in DES overcomes the problems associated with copious hydrogen and oxygen evolution on the electrode surface when carried out in aqueous medium. The proposed method utilizes the inherent abilities of DES to act as a reducing medium while simultaneously stabilizing the nanoparticles that are formed. The mesoporous metal films were characterized by SEM, XRD and electrochemical techniques. Potential applications of these substrates in surface enhanced Raman spectroscopy and electrocatalysis have been investigated. A large enhancement of Raman signal of analyte was achieved on the mesoporous silver substrate after removing all the stabilizer molecules from the surface by calcination. The highly porous texture of the electrodeposited film provides superior electro catalytic performance for hydrogen evolution reaction (HER). The mechanisms of HER on the fabricated substrates were studied by Tafel analysis and electrochemical impedance spectroscopy (EIS). Copyright © 2014 Elsevier Inc. All rights reserved.

Applied-field MPD thruster geometry effects

NASA Technical Reports Server (NTRS)

Myers, Roger M.

1991-01-01

Eight MPD thruster configurations were used to study the effects of applied field strength, propellant, and facility pressure on thruster performance. Vacuum facility background pressures higher than approx. 0.12 Pa were found to greatly influence thruster performance and electrode power deposition. Thrust efficiency and specific impulse increased monotonically with increasing applied field strength. Both cathode and anode radii fundamentally influenced the efficiency specific impulse relationship, while their lengths influence only the magnitude of the applied magnetic field required to reach a given performance level. At a given specific impulse, large electrode radii result in lower efficiencies for the operating conditions studied. For all test conditions, anode power deposition was the largest efficiency loss, and represented between 50 and 80 pct. of the input power. The fraction of the input power deposited into the anode decreased with increasing applied field and anode radii. The highest performance measured, 20 pct. efficiency at 3700 seconds specific impulse, was obtained using hydrogen propellant.

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.

Titanium-containing Raney nickel catalyst for hydrogen electrodes in alkaline fuel cell systems

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

Mund, K.; Richter, G.; von Sturm, F.

In alkaline hydrogen-oxygen fuel cells Raney nickel is employed as catalyst for hydrogen electrodes. The rate of anodic hydrogen conversion has been increased significantly by using a titanium-containing Raney nickel. The properties of the catalyst powder, the influence of particle diameter, and the behavior of electrodes under load are described. Impedance measurements have been used to characterize the electrodes. In fuel cell systems the supported electrodes are normally operated at current densities up to 0.4 A . cm/sup -2/; the overload current density of 1 A . cm/sup -2/ can be maintained for several hours. (15 fig.)

Modeling of hydrogen-air diffusion flame

NASA Technical Reports Server (NTRS)

Isaac, Kakkattukuzhy

1988-01-01

The present research objective is to determine the effects of contaminants on extinction limits of simple, well defined, counterflow Hydrogen 2-air diffusion flames, with combustion at 1 atmosphere. Results of extinction studies and other flame characterizations, with appropriate mechanistic modeling (presently underway), will be used to rationalize the observed effects of contamination over a reasonably wide range of diffusion flame conditions. The knowledge gained should help efforts to anticipate the effects of contaminants on combustion processes in Hydrogen 2-fueled scramjets.

Photoelectrolytic production of hydrogen using semiconductor electrodes

NASA Technical Reports Server (NTRS)

Byvik, C. E.; Walker, G. H.

1976-01-01

Experimental data for the photoelectrolytic production of hydrogen using GaAs photoanodes was presented. Four types of GaAs anodes were investigated: polished GaAs, GaAs coated with gold, GaAs coated with silver, and GaAs coated with tin. The maximum measured efficiency using a tungsten light source was 8.9 percent for polished GaAs electrodes and 6.3 percent for tin coated GaAs electrodes.

Hydrogen mobility in transition zone silicates

NASA Astrophysics Data System (ADS)

Caracas, Razvan; Panero, Wendy R.

2017-12-01

We study the hydrogen mobility in ringwoodite and wadsleyite considering multiple charge-balanced defects, including Mg < = > 2H, Si < = > Mg + 2H, and the hydrogarnet defect, Si < = > 4H, using molecular dynamics simulations based on the density functional theory at transition zone pressures and temperatures between 1500 and 2500 K. We determine the diffusion coefficients and study in detail the mechanism of hydrogen mobility during lengthy simulations. Our results show that temperature, water concentration, and defect mechanism have a significant effect on mobility. We find that the fastest diffusion is for the Mg < = > 2H defect, while H is more mobile when incorporated as Si < = > Mg + 2H than as hydrogarnet defects. The computed diffusivities for ringwoodite are larger than for wadsleyite: at 2000 K, diffusivity is 1.13 × 10-09 m2/s for ringwoodite compared to 0.93 × 10-09 m2/s for wadsleyite. In general, the hydrogen atoms spend on the order of tens of picoseconds or more trapped in or around the vacancy sites with net migration between sites over timescales of tens of femtoseconds. At 2500 K, some of these hydrogen excursions take place over several angstroms, while at 2000 K, they do not always result in net diffusion. At 1500 K, most of the defects fail to make excursions from their defect sites resulting in diffusion.

Diffusion Study on Dissolved Hydrogen toward Effective Bioremediation of Chlorinated Ethenes in Aquitards

NASA Astrophysics Data System (ADS)

Yoshikawa, M.; Zhang, M.; Takeuchi, M.; Komai, T.

2010-12-01

In Japan, the demand for in-situ remediation of contaminated sediments is expected to increase in the future due to the recent amendment of Soil Contamination Countermeasures Act. The Japanese law requires remediating not only contaminated groundwater but also contaminated sediments including those in aquitards. In-situ remediation of contaminated aquitards has been a challenging issue and bioremediation is considered to be one of the effective techniques. In microbial degradation of chrolinated ethenes such as tetrachloroethene and trichloroethene under anaerobic environments, dissolved hydrogen plays an important role. The dechlorinating microbes utilize hydrogen and chlorinated ethenes as an electron donor and an electron accepter, respectively. The size of hydrogen molecule is extremely small and the diffusion rate of dissolved hydrogen in an aquitard would be the key factor that controls the process of microbial dechlorination. However, the diffusion behavior of dissolved hydrogen in subsurface sediments remains unclear. The purposes of this study are to develop a practically utilizable test apparatus, carry out a series of dissolved hydrogen diffusion tests on representative samples, and illustrate the applicability of bioremediation in aquitards. A completely leak-free apparatus was developed by using aluminum alloy and gas tight rubber. This apparatus is capable of testing specimens with a diameter as large as 100 mm by a length from 5 mm to 10 mm, depending on the maximum grain size within a test specimen. Preliminary tests have been performed with glass beads as an ideal material, commercially available kaolin clay, and core samples taken from a polluted site containing clay minerals. The effective diffusion coefficients of these samples were all on the order of 10E-10 m2/s, though their coefficients of permeability varied between the orders of 10E-2 and 10E-7 cm/s. These results showed that there was no obvious relationship between the effective diffusion coefficient of hydrogen and coefficient of permeability. This observation indicates that dissolved hydrogen also diffuses through hydraulically-tight soil particles and bioremediation of chlorinated ethenes in aquitards would be possible from the aspect of electron donor supply.

Use of La 0.75Sr 0.25Cr 0.5Mn 0.5O 3 materials in composite anodes for direct ethanol solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Ye, Xiao-Feng; Wang, S. R.; Wang, Z. R.; Hu, Q.; Sun, X. F.; Wen, T. L.; Wen, Z. Y.

The perovskite system La 1- xSr xCr 1- yM yO 3- δ (M, Mn, Fe and V) has recently attracted much attention as a candidate material for the fabrication of solid oxide fuel cells (SOFCs) due to its stability in both H 2 and CH 4 atmospheres at temperatures up to 1000 °C. In this paper, we report the synthesis of La 0.75Sr 0.25Cr 0.5Mn 0.5O 3 (LSCM) by solid-state reaction and its employment as an alternative anode material for anode-supported SOFCs. Because LSCM shows a greatly decreased electronic conductivity in a reducing atmosphere compared to that in air, we have fabricated Cu-LSCM-ScSZ (scandia-stabilized zirconia) composite anodes by tape-casting and a wet-impregnation method. Additionally, a composite structure (support anode, functional anode and electrolyte) structure with a layer of Cu-LSCM-YSZ (yttria-stabilized zirconia) on the supported anode surface has been manufactured by tape-casting and screen-printing. Single cells with these two kinds of anodes have been fabricated, and their performance characteristics using hydrogen and ethanol have been measured. In the operation period, no obvious carbon deposition was observed when these cells were operated on ethanol. These results demonstrate the stability of LSCM in an ethanol atmosphere and its potential utilization in anode-supported SOFCs.

Hydrogen-facilitated corrosion and stress corrosion cracking of austenitic stainless steel of type 310

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

Qiao Lijie; Chu Wuyang; Miao Huijun

1993-04-01

The effects of hydrogen precharge and stress on anodic dissolution for Type 310 austenitic stainless steel (ASS) have been investigated. An experiment determining the effect of hydrogen on stress corrosion cracking (SCC) was carried out in a boiling 42% MgCl[sub 2] solution and in a 2.5 mol/l H[sub 2]SO[sub 4] + 1 mol/l HCl solution. The results showed that both hydrogen and stress would increase the dissolution rate, and the effects of hydrogen and stress on the dissolution rate were synergistic rather than simply additive. Hydrogen lowered the threshold stress and the shortened fracture time of SCC in a boilingmore » MgCl[sub 2] solution by a factor of 1/5 and 10, respectively.« less

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.

Diffusion of hydrogen into and through γ-iron by density functional theory

NASA Astrophysics Data System (ADS)

Chohan, Urslaan K.; Koehler, Sven P. K.; Jimenez-Melero, Enrique

2018-06-01

This study is concerned with the early stages of hydrogen embrittlement on an atomistic scale. We employed density functional theory to investigate hydrogen diffusion through the (100), (110) and (111) surfaces of γ-Fe. The preferred adsorption sites and respective energies for hydrogen adsorption were established for each plane, as well as a minimum energy pathway for diffusion. The H atoms adsorb on the (100), (110) and (111) surfaces with energies of ∼4.06 eV, ∼3.92 eV and ∼4.05 eV, respectively. The barriers for bulk-like diffusion for the (100), (110) and (111) surfaces are ∼0.6 eV, ∼0.5 eV and ∼0.7 eV, respectively. We compared these calculated barriers with previously obtained experimental data in an Arrhenius plot, which indicates good agreement between experimentally measured and theoretically predicted activation energies. Texturing austenitic steels such that the (111) surfaces of grains are preferentially exposed at the cleavage planes may be a possibility to reduce hydrogen embrittlement.

Composition and method for polymer moderated catalytic water formation

DOEpatents

Shepodd, Timothy Jon

1999-01-01

A composition suitable for safely removing hydrogen from gaseous mixtures containing hydrogen and oxygen, particularly those mixtures wherein the hydrogen concentration is within the explosive range. The composition comprises a hydrogenation catalyst, preferably Pd dispersed on carbon, wherein the concentration of Pd is from about 1-10 wt %, dispersed in a polymeric material matrix. As well as serving as a matrix to contain the hydrogenation catalyst, the polymeric material, which is substantially unreactive to hydrogen, provides both a diffusion restriction to hydrogen and oxygen, thereby limiting the rate at which the reactants (hydrogen and oxygen) can diffuse to the catalyst surface and thus, the production of heat from the recombination reaction and as a heat sink.

Hydration dynamics of a lipid membrane: Hydrogen bond networks and lipid-lipid associations

NASA Astrophysics Data System (ADS)

Srivastava, Abhinav; Debnath, Ananya

2018-03-01

Dynamics of hydration layers of a dimyristoylphosphatidylcholine (DMPC) bilayer are investigated using an all atom molecular dynamics simulation. Based upon the geometric criteria, continuously residing interface water molecules which form hydrogen bonds solely among themselves and then concertedly hydrogen bonded to carbonyl, phosphate, and glycerol head groups of DMPC are identified. The interface water hydrogen bonded to lipids shows slower relaxation rates for translational and rotational dynamics compared to that of the bulk water and is found to follow sub-diffusive and non-diffusive behaviors, respectively. The mean square displacements and the reorientational auto-correlation functions are slowest for the interfacial waters hydrogen bonded to the carbonyl oxygen since these are buried deep in the hydrophobic core among all interfacial water studied. The intermittent hydrogen bond auto-correlation functions are calculated, which allows breaking and reformations of the hydrogen bonds. The auto-correlation functions for interfacial hydrogen bonded networks develop humps during a transition from cage-like motion to eventual power law behavior of t-3/2. The asymptotic t-3/2 behavior indicates translational diffusion dictated dynamics during hydrogen bond breaking and formation irrespective of the nature of the chemical confinement. Employing reactive flux correlation analysis, the forward rate constant of hydrogen bond breaking and formation is calculated which is used to obtain Gibbs energy of activation of the hydrogen bond breaking. The relaxation rates of the networks buried in the hydrophobic core are slower than the networks near the lipid-water interface which is again slower than bulk due to the higher Gibbs energy of activation. Since hydrogen bond breakage follows a translational diffusion dictated mechanism, chemically confined hydrogen bond networks need an activation energy to diffuse through water depleted hydrophobic environments. Our calculations reveal that the slow relaxation rates of interfacial waters in the vicinity of lipids are originated from the chemical confinement of concerted hydrogen bond networks. The analysis suggests that the networks in the hydration layer of membranes dynamically facilitate the water mediated lipid-lipid associations which can provide insights on the thermodynamic stability of soft interfaces relevant to biological systems in the future.

Hydrogen diffusion in Zircon

NASA Astrophysics Data System (ADS)

Ingrin, Jannick; Zhang, Peipei

2016-04-01

Hydrogen mobility in gem quality zircon single crystals from Madagascar was investigated through H-D exchange experiments. Thin slices were annealed in a horizontal furnace flushed with a gas mixture of Ar/D2(10%) under ambient pressure between 900 ° C to 1150 ° C. FTIR analyses were performed on oriented slices before and after each annealing run. H diffusion along [100] and [010] follow the same diffusion law D = D0exp[-E /RT], with log D0 = 2.24 ± 1.57 (in m2/s) and E = 374 ± 39 kJ/mol. H diffusion along [001] follows a slightly more rapid diffusion law, with log D0 = 1.11 ± 0.22 (in m2/s) and E = 334 ± 49 kJ/mol. H diffusion in zircon has much higher activation energy and slower diffusivity than other NAMs below 1150 ° C even iron-poor garnets which are known to be among the slowest (Blanchard and Ingrin, 2004; Kurka et al. 2005). During H-D exchange zircon incorporates also deuterium. This hydration reaction involves uranium reduction as it is shown from the exchange of U5+ and U4+ characteristic bands in the near infrared region during annealing. It is the first time that a hydration reaction U5+ + OH- = U4+ + O2- + 1/2H2, is experimentally reported. The kinetics of deuterium incorporation is slightly slower than hydrogen diffusion, suggesting that the reaction is limited by hydrogen mobility. Hydrogen isotopic memory of zircon is higher than other NAMs. Zircons will be moderately retentive of H signatures at mid-crustal metamorphic temperatures. At 500 ° C, a zircon with a radius of 300 μm would retain its H isotopic signature over more than a million years. However, a zircon is unable to retain this information for geologically significant times under high-grade metamorphism unless the grain size is large enough. Refrences Blanchard, M. and Ingrin, J. (2004) Hydrogen diffusion in Dora Maira pyrope. Physics and Chemistry of Minerals, 31, 593-605. Kurka, A., Blanchard, M. and Ingrin, J. (2005) Kinetics of hydrogen extraction and deuteration in grossular. Mineralogical Magazine, 69, 359-371.

Study on the fabrication of back surface reflectors in nano-crystalline silicon thin-film solar cells by using random texturing aluminum anodization

NASA Astrophysics Data System (ADS)

Shin, Kang Sik; Jang, Eunseok; Cho, Jun-Sik; Yoo, Jinsu; Park, Joo Hyung; Byungsung, O.

2015-09-01

In recent decades, researchers have improved the efficiency of amorphous silicon solar cells in many ways. One of the easiest and most practical methods to improve solar-cell efficiency is adopting a back surface reflector (BSR) as the bottom layer or as the substrate. The BSR reflects the incident light back to the absorber layer in a solar cell, thus elongating the light path and causing the so-called "light trapping effect". The elongation of the light path in certain wavelength ranges can be enhanced with the proper scale of BSR surface structure or morphology. An aluminum substrate with a surface modified by aluminum anodizing is used to improve the optical properties for applications in amorphous silicon solar cells as a BSR in this research due to the high reflectivity and the low material cost. The solar cells with a BSR were formed and analyzed by using the following procedures: First, the surface of the aluminum substrate was degreased by using acetone, ethanol and distilled water, and it was chemically polished in a dilute alkali solution. After the cleaning process, the aluminum surface's morphology was modified by using a controlled anodization in a dilute acid solution to form oxide on the surface. The oxidized film was etched off by using an alkali solution to leave an aluminum surface with randomly-ordered dimple-patterns of approximately one micrometer in size. The anodizing conditions and the anodized aluminum surfaces after the oxide layer had been removed were systematically investigated according to the applied voltage. Finally, amorphous silicon solar cells were deposited on a modified aluminum plate by using dc magnetron sputtering. The surfaces of the anodized aluminum were observed by using field-emission scanning electron microscopy. The total and the diffuse reflectances of the surface-modified aluminum sheets were measured by using UV spectroscopy. We observed that the diffuse reflectances increased with increasing anodizing voltage. The properties of the solar cells on anodized aluminum substrates were analyzed by using a solar simulator.

Self-diffusion of protons in H{sub 2}O ice VII at high pressures: Anomaly around 10 GPa

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

Noguchi, Naoki, E-mail: noguchi-n@okayama-u.ac.jp; Okuchi, Takuo

2016-06-21

The self-diffusion of ice VII in the pressure range of 5.5–17 GPa and temperature range of 400–425 K was studied using micro Raman spectroscopy and a diamond anvil cell. The diffusion was monitored by observing the distribution of isotope tracers: D{sub 2}O and H{sub 2}{sup 18}O. The diffusion coefficient of hydrogen reached a maximum value around 10 GPa. It was two orders of magnitude greater at 10 GPa than at 6 GPa. Hydrogen diffusion was much faster than oxygen diffusion, which indicates that protonic diffusion is the dominant mechanism for the diffusion of hydrogen in ice VII. This mechanism ismore » in remarkable contrast to the self-diffusion in ice I{sub h} that is dominated by an interstitial mechanism for the whole water molecule. An anomaly around 10 GPa in ice VII indicates that the rate-determining process for the proton diffusion changes from the diffusion of ionic defects to the diffusion of rotational defects, which was suggested by proton conductivity measurements and molecular dynamics simulations.« less

A fractal process of hydrogen diffusion in a-Si:H with exponential energy distribution

NASA Astrophysics Data System (ADS)

Hikita, Harumi; Ishikawa, Hirohisa; Morigaki, Kazuo

2017-04-01

Hydrogen diffusion in a-Si:H with exponential distribution of the states in energy exhibits the fractal structure. It is shown that a probability P(t) of the pausing time t has a form of tα (α: fractal dimension). It is shown that the fractal dimension α = Tr/T0 (Tr: hydrogen temperature, T0: a temperature corresponding to the width of exponential distribution of the states in energy) is in agreement with the Hausdorff dimension. A fractal graph for the case of α ≤ 1 is like the Cantor set. A fractal graph for the case of α > 1 is like the Koch curves. At α = ∞, hydrogen migration exhibits Brownian motion. Hydrogen diffusion in a-Si:H should be the fractal process.

Hydrogen species motion in piezoelectrics: A quasi-elastic neutron scattering study

NASA Astrophysics Data System (ADS)

Alvine, K. J.; Tyagi, M.; Brown, C. M.; Udovic, T. J.; Jenkins, T.; Pitman, S. G.

2012-03-01

Hydrogen is known to damage or degrade piezoelectric materials, at low pressure for ferroelectric random access memory applications, and at high pressure for hydrogen-powered vehicle applications. The piezoelectric degradation is in part governed by the motion of hydrogen species within the piezoelectric materials. We present here quasi-elastic neutron scattering (QENS) measurements of the local hydrogen species motion within lead zirconate titanate (PZT) and barium titanate (BTO) on samples charged by exposure to high-pressure gaseous hydrogen (≈17 MPa). Neutron vibrational spectroscopy (NVS) studies of the hydrogen-enhanced vibrational modes are presented as well. Results are discussed in the context of theoretically predicted interstitial hydrogen lattice sites and compared to comparable bulk diffusion studies of hydrogen diffusion in lead zirconate titanate.

Hydrogen generation from natural gas for the fuel cell systems of tomorrow

NASA Astrophysics Data System (ADS)

Dicks, Andrew L.

In most cases hydrogen is the preferred fuel for use in the present generation of fuel cells being developed for commercial applications. Of all the potential sources of hydrogen, natural gas offers many advantages. It is widely available, clean, and can be converted to hydrogen relatively easily. When catalytic steam reforming is used to generate hydrogen from natural gas, it is essential that sulfur compounds in the natural gas are removed upstream of the reformer and various types of desulfurisation processes are available. In addition, the quality of fuel required for each type of fuel cell varies according to the anode material used, and the cell temperature. Low temperature cells will not tolerate high concentrations of carbon monoxide, whereas the molten fuel cell (MCFC) and solid oxide fuel cell (SOFC) anodes contain nickel on which it is possible to electrochemically oxidise carbon monoxide directly. The ability to internally reform fuel gas is a feature of the MCFC and SOFC. Internal reforming can give benefits in terms of increased electrical efficiency owing to the reduction in the required cell cooling and therefore parasitic system losses. Direct electrocatalysis of hydrocarbon oxidation has been the elusive goal of fuel cell developers over many years and recent laboratory results are encouraging. This paper reviews the principal methods of converting natural gas into hydrogen, namely catalytic steam reforming, autothermic reforming, pyrolysis and partial oxidation; it reviews currently available purification techniques and discusses some recent advances in internal reforming and the direct use of natural gas in fuel cells.

RF plasma probe diagnostics: a method for eliminating measurement errors for Langmuir probes with bare protective shields

NASA Astrophysics Data System (ADS)

Riaby, V. A.; Masherov, P. E.; Savinov, V. P.; Yakunin, V. G.

2018-02-01

The new DC arc T-plasmatron of long service life [1] is studied. The well known method of the electric field strength measurements in a stabilized arc channel [2] was applied in a modified form as a consequence of the specific form of the presumably diffuse anode spot attached to a gas vortex on the external surface of the anode unit. The electrical field strength was determined assuming that the potential drop across the diffuse anode spot in the new plasmatron was small. This gave the mean argon plasma conductivity: σ≤118 Ohm-1cm-1 for arc currents I ≤ 180 A which agreed with the independent experiment [2] affirming the correctness of the above assumption. Analysis of the known experimental and theoretic data on atmospheric argon plasma conductivity resulted in the selection of R.S.Devoto’s theoretic dependence σ(T) [3] as the most reliable one for T=8000…20000 K at P = 1 atm that allowed the evaluation of the mean argon plasma temperature at the exit of the plasmatron: T ≤ 19500 K.

Quantification of ionic transport within thermally-activated batteries using electron probe micro-analysis

DOE PAGES

Humplik, Thomas; Stirrup, Emily K.; Grillet, Anne M.; ...

2016-04-30

The transient transport of electrolytes in thermally-activated batteries is studied in this paper using electron probe micro-analysis (EPMA), demonstrating the robust capability of EPMA as a useful tool for studying and quantifying mass transport within porous materials, particularly in difficult environments where classical flow measurements are challenging. By tracking the mobility of bromine and potassium ions from the electrolyte stored within the separator into the lithium silicon anode and iron disulfide cathode, we are able to quantify the transport mechanisms and physical properties of the electrodes including permeability and tortuosity. Due to the micron to submicron scale porous structure ofmore » the initially dry anode, a fast capillary pressure driven flow is observed into the anode from which we are able to set a lower bound on the permeability of 10 -1 mDarcy. The transport into the cathode is diffusion-limited because the cathode originally contained some electrolyte before activation. Finally, using a transient one-dimensional diffusion model, we estimate the tortuosity of the cathode electrode to be 2.8 ± 0.8.« less

Progress in Metal-Supported Axial-Injection Plasma Sprayed Solid Oxide Fuel Cells Using Nanostructured NiO-Y0.15Zr0.85O1.925 Dry Powder Anode Feedstock

NASA Astrophysics Data System (ADS)

Metcalfe, C.; Harris, J.; Kuhn, J.; Marr, M.; Kesler, O.

2013-06-01

A composite NiO-Y0.15Zr0.85O1.925 (YSZ) agglomerated feedstock having nanoscale NiO and YSZ primary particles was used to fabricate anodes having sub-micrometer structure. These anodes were incorporated into two different metal-supported SOFC architectures, which differ in the order of electrode deposition. The composition of the composite Ni-YSZ anodes is controllable by selection of the agglomerate size fraction and standoff distance, while the porosity is controllable by selection of agglomerate size fraction and addition of a sacrificial pore-forming material. A bi-layer anode was fabricated having a total porosity of 33% for the diffusion layer and 23% porosity for the functional layer. A power density of 630 mW/cm2 was obtained at 750 °C in humidified H2 with cells having the bi-layer anode deposited on the metal support. Cells having the cathode deposited on the metal support showed poor performance due to a significant number of vertical cracks through the electrolyte, allowing excessive gas cross-over between the anode and the cathode compartments.

Electrodeposition of Amorphous Molybdenum Chalcogenides from Ionic Liquids and Their Activity for the Hydrogen Evolution Reaction.

PubMed

Redman, Daniel W; Rose, Michael J; Stevenson, Keith J

2017-09-19

This work reports on the general electrodeposition mechanism of tetrachalcogenmetallates from 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. Both tetrathio- and tetraselenomolybdate underwent anodic electrodeposition and cathodic corrosion reactions as determined by UV-vis spectroelectrochemistry. Electrodeposition was carried out by cycling the potential between the anodic and cathodic regimes. This resulted in a film of densely packed nanoparticles of amorphous MoS x or MoSe x as determined by SEM, Raman, and XPS. The films were shown to have high activity for the hydrogen evolution reaction. The onset potential (J = 1 mA/cm 2 ) of the MoS x film was E = -0.208 V vs RHE, and that of MoSe x was E = -0.230 V vs RHE. The Tafel slope of MoS x was 42 mV/decade, and that of MoSe x was 59 mV/decade.

Study of the highly ordered TiO2 nanotubes physical properties prepared with two-step anodization

NASA Astrophysics Data System (ADS)

Pishkar, Negin; Ghoranneviss, Mahmood; Ghorannevis, Zohreh; Akbari, Hossein

2018-06-01

Highly ordered hexagonal closely packed titanium dioxide nanotubes (TiO2 NTs) were successfully grown by a two-step anodization process. The TiO2 NTs were synthesized by electrochemical anodization of titanium foils in an ethylene glycol based electrolyte solution containing 0.3 wt% NH4F and 2 vol% deionized (DI) water at constant potential (50 V) for 1 h at room temperature. Physical properties of the TiO2 NTs, which were prepared via one and two-step anodization, were investigated. Atomic Force Microscopy (AFM) analysis revealed that anodization and subsequently peeled off the TiO2 NTs caused to the periodic pattern on the Ti surface. In order To study the nanotubes morphology, Field Emission Scanning Electron Microscopy (FESEM) was used, which was revealed that the two-step anodization resulted highly ordered hexagonal TiO2 NTs. Crystal structures of the TiO2 NTs were mainly anatase, determined by X-ray diffraction analysis. Optical studies were performed by Diffuse Reflection Spectra (DRS) and Photoluminescence (PL) analysis showed that the band gap of TiO2 NTs prepared via two-step anodization was lower than the band gap of samples prepared by one-step anodization process.

Anodizing of High Electrically Stressed Components

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

Flores, P.; Henderson, D. J.; Good, D. E.

2013-06-01

Anodizing creates an aluminum oxide coating that penetrates into the surface as well as builds above the surface of aluminum creating a very hard ceramic-type coating with good dielectric properties. Over time and use, the electrical carrying components (or spools in this case) experience electrical breakdown, yielding undesirable x-ray dosages or failure. The spool is located in the high vacuum region of a rod pinch diode section of an x-ray producing machine. Machine operators have recorded decreases in x-ray dosages over numerous shots using the reusable spool component, and re-anodizing the interior surface of the spool does not provide themore » expected improvement. A machine operation subject matter expert coated the anodized surface with diffusion pump oil to eliminate electrical breakdown as a temporary fix. It is known that an anodized surface is very porous, and it is because of this porosity that the surface may trap air that becomes a catalyst for electrical breakdown. In this paper we present a solution of mitigating electrical breakdown by oiling. We will also present results of surface anodizing improvements achieved by surface finish preparation and surface sealing. We conclude that oiling the anodized surface and using anodized hot dip sealing processes will have similar results.« less

Modeling of the anode of a liquid-feed DMFC: Inhomogeneous compression effects and two-phase transport phenomena

NASA Astrophysics Data System (ADS)

García-Salaberri, Pablo A.; Vera, Marcos; Iglesias, Immaculada

2014-01-01

An isothermal two-phase 2D/1D across-the-channel model for the anode of a liquid-feed Direct Methanol Fuel Cell (DMFC) is presented. The model takes into account the effects of the inhomogeneous assembly compression of the Gas Diffusion Layer (GDL), including the spatial variations of porosity, diffusivity, permeability, capillary pressure, and electrical conductivity. The effective anisotropic properties of the GDL are evaluated from empirical data reported in the literature corresponding to Toray carbon paper TGP-H series. Multiphase transport is modeled according to the classical theory of porous media (two-fluid model), considering the effect of non-equilibrium evaporation and condensation of methanol and water. The numerical results evidence that the hydrophobic Leverett J-function approach is physically inconsistent to describe capillary transport in the anode of a DMFC when assembly compression effects are considered. In contrast, more realistic results are obtained when GDL-specific capillary pressure curves reflecting the mixed-wettability characteristics of GDLs are taken into account. The gas coverage factor at the GDL/channel interface also exhibits a strong influence on the gas-void fraction distribution in the GDL, which in turn depends on the relative importance between the capillary resistance induced by the inhomogeneous compression, Rc(∝ ∂pc / ∂ ε) , and the capillary diffusivity, Dbarc(∝ ∂pc / ∂ s) .

Experimental advances and preliminary mathematical modeling of the Swiss-roll mixed-reactant direct borohydride fuel cell

NASA Astrophysics Data System (ADS)

Aziznia, Amin; Oloman, Colin W.; Gyenge, Előd L.

2014-11-01

The Swiss-roll single-cell mixed reactant (SR-MRFC) borohydride - oxygen fuel cell equipped with Pt/carbon cloth 3D anode and either MnO2 or Ag gas-diffusion cathodes is investigated by a combination of experimental studies and preliminary mathematical modeling of the polarization curve. We investigate the effects of four variables: cathode side metallic mesh fluid distributor, separator type (Nafion 112® vs. Viledon®), cathode catalyst (MnO2 vs. Ag), and the hydrophilic pore volume fraction of the gas-diffusion cathode. Using a two-phase feed of alkaline borohydride solution (1 M NaBH4 - 2 M NaOH) and O2 gas in an SR-MRFC equipped with Pt/C 3D anode, MnO2 gas diffusion cathode, Viledon® porous diaphragm, expanded mesh cathode-side fluid distributor, the maximum superficial power density is 2230 W m-2 at 323 K and 105 kPa(abs). The latter superficial power density is almost 3.5 times higher than our previously reported superficial power density for the same catalyst combinations. Furthermore, with a Pt anode and Ag cathode catalyst combination, a superficial power density of 2500 W m-2 is achieved with superior performance durability compared to the MnO2 cathode. The fuel cell results are substantiated by impedance spectroscopy analysis and preliminary mathematical model predictions based on mixed potential theory.

Amorphous mesoporous GeO x anode for Na-ion batteries with high capacity and long lifespan.

PubMed

Shen, Kangze; Lin, Ning; Xu, Tianjun; Han, Ying; Qian, Yitai

2018-01-01

It is recently demonstrated that amorphous Ge anode shows higher reversible Na-ion storage capacity (590 mA h g -1 ) than crystallized Ge anode (369 mA h g -1 ). Here, amorphous GeO x anode is prepared by a simple wet-chemistry reduction route at room temperature. The obtained amorphous GeO x shows a porous hierarchical architecture, accompanied with a Brunauer-Emmett-Teller surface area of 159 m 2  g -1 and an average pore diameter of 14 nm. This unique structure enables the GeO x anode to enhance the Na-ion/electron diffusion rate, and buffer the volume change. As anode for Na-ion battery, high reversible capacity over 400 mA h g -1 , fine rate capability with a capacity of 200 mA h g -1 maintained at 3.0 A g -1 and long-term cycling stability with 270 mA h g -1 even over 1000 cycles at 1.0 A g -1 are obtained.

Transformation of sludge Si to nano-Si/SiOx structure by oxygen inward diffusion as precursor for high performance anodes in lithium ion batteries

NASA Astrophysics Data System (ADS)

Hua, Qiqi; Dai, Dongyang; Zhang, Chengzhi; Han, Fei; Lv, Tiezheng; Li, Xiaoshan; Wang, Shijie; Zhu, Rui; Liao, Haojie; Zhang, Shiguo

2018-05-01

Although several Si/C composite structures have been proposed for high-performance lithium-ion batteries (LIBs), they have still suffered from expensive and complex processes of nano-Si production. Herein, a simple, controllable oxygen inward diffusion was utilized to transform Si sludge obtained from the photovoltaic (PV) industry into the nano-Si/SiOx structure as a result of the high diffusion efficiency of O inside Si and high surface area of the sludge. After further process, a yolk/shell Si/C structure was obtained as an anode material for LIBs. This composite demonstrated an excellent cycling stability, with a high reversible capacity (˜ 1250 mAh/g for 500 cycles), by void space originally left by the SiOx accommodate inner Si expansion. We believe this is a rather simple way to convert the waste Si into a valuable nano-Si for LIB applications.

Rechargeable Zinc Alkaline Anodes for Long-Cycle Energy Storage

DOE PAGES

Turney, Damon E.; Gallaway, Joshua W.; Yadav, Gautam G.; ...

2017-05-03

Zinc alkaline anodes command significant share of consumer battery markets and are a key technology for the emerging grid-scale battery market. Improved understanding of this electrode is required for long-cycle deployments at kWh and MWh scale due to strict requirements on performance, cost, and safety. For this article, we give a modern literature survey of zinc alkaline anodes with levelized performance metrics and also present an experimental assessment of leading formulations. Long-cycle materials characterization, performance metrics, and failure analysis are reported for over 25 unique anode formulations with up to 1500 cycles and ~1.5 years of shelf life per test.more » Statistical repeatability of these measurements is made for a baseline design (fewest additives) via 15 duplicates. Baseline design capacity density is 38 mAh per mL of anode volume, and lifetime throughput is 72 Ah per mL of anode volume. We then report identical measurements for anodes with improved material properties via additives and other perturbations, some of which achieve capacity density over 192 mAh per mL of anode volume and lifetime throughput of 190 Ah per mL of anode volume. Novel in operando X-ray microscopy of a cycling zinc paste anode reveals the formation of a nanoscale zinc material that cycles electrochemically and replaces the original anode structure over long-cycle life. Ex situ elemental mapping and other materials characterization suggest that the key physical processes are hydrogen evolution reaction (HER), growth of zinc oxide nanoscale material, concentration deficits of OH – and ZnOH 4 2–, and electrodeposition of Zn growths outside and through separator membranes.« less

Rechargeable Zinc Alkaline Anodes for Long-Cycle Energy Storage

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

Turney, Damon E.; Gallaway, Joshua W.; Yadav, Gautam G.

Zinc alkaline anodes command significant share of consumer battery markets and are a key technology for the emerging grid-scale battery market. Improved understanding of this electrode is required for long-cycle deployments at kWh and MWh scale due to strict requirements on performance, cost, and safety. For this article, we give a modern literature survey of zinc alkaline anodes with levelized performance metrics and also present an experimental assessment of leading formulations. Long-cycle materials characterization, performance metrics, and failure analysis are reported for over 25 unique anode formulations with up to 1500 cycles and ~1.5 years of shelf life per test.more » Statistical repeatability of these measurements is made for a baseline design (fewest additives) via 15 duplicates. Baseline design capacity density is 38 mAh per mL of anode volume, and lifetime throughput is 72 Ah per mL of anode volume. We then report identical measurements for anodes with improved material properties via additives and other perturbations, some of which achieve capacity density over 192 mAh per mL of anode volume and lifetime throughput of 190 Ah per mL of anode volume. Novel in operando X-ray microscopy of a cycling zinc paste anode reveals the formation of a nanoscale zinc material that cycles electrochemically and replaces the original anode structure over long-cycle life. Ex situ elemental mapping and other materials characterization suggest that the key physical processes are hydrogen evolution reaction (HER), growth of zinc oxide nanoscale material, concentration deficits of OH – and ZnOH 4 2–, and electrodeposition of Zn growths outside and through separator membranes.« less

Performance of Solid Oxide Fuel Cell With La and Cr Co-doped SrTiO3 as Anode.

PubMed

Yi, Fenyun; Chen, Hongyu; Li, He

2014-06-01

The La 0.3 Sr 0.55 Ti 0.9 Cr 0.1 O 3-δ (LSTC10) anode material was synthesized by citric acid-nitrate process. The yttria-stabilized zirconia (YSZ) electrolyte-supported cell was fabricated by screen printing method using LSTC10 as anode and (La 0.75 Sr 0.25 ) 0.95 MnO 3-δ (LSM) as cathode. The electrochemical performance of cell was tested by using dry hydrogen as fuel and air as oxidant in the temperature range of 800-900 °C. At 900 °C, the open circuit voltage (OCV) and the maximum power density of cell are 1.08 V and 13.0 mW·cm -2 , respectively. The microstructures of cell after performance testing were investigated by scanning electron microscope (SEM). The results show that the anode and cathode films are porous and closely attached to the YSZ electrolyte. LSTC10 is believed to be a kind of potential solid oxide fuel cell (SOFC) anode material.

The influence of coating solution and calcination condition on the durability of Ir1-xSnxO2/Ti anodes for oxygen evolution

NASA Astrophysics Data System (ADS)

Kato, Zenta; Kashima, Ryo; Tatsumi, Kohei; Fukuyama, Shinnosuke; Izumiya, Koichi; Kumagai, Naokazu; Hashimoto, Koji

2016-12-01

For oxygen formation without forming chlorine in seawater electrolysis for hydrogen production we have been using the anode consisting of three layers of MnO2-type multiple oxide catalyst, intermediate layer and titanium substrate. The intermediate layer was used for prevention of oxidation of the titanium substrate during anodic polarization for oxygen evolution and was prepared by calcination of butanol solutions of H2IrCl6 and SnCl4 coated on titanium. The protectiveness of Ir1-xSnxO2 layer formed was directly examined using Ir1-xSnxO2/Ti anodes in H2SO4 solution changing the preparation conditions of the layer. When the sum of Ir4+ and Sn4+ was 0.1 M, the highest protectiveness was observed at 0.06 M Sn4+. Although an increase in calcination temperature led to the formation of Ir1-x-ySnxTiyO2 triple oxide with a slightly lower catalytic activity for oxygen evolution, the anode calcined at 450 °C showed the highest protectiveness.

°Enhancing High Temperature Anode Performance with 2° Anchoring Phases

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

Walker, Robert A.; Sofie, Stephen W.; Amendola, Roberta

2015-10-01

Project accomplishments included developing and optimizing strength testing of aluminum titanate (ALT)-doped Ni-YSZ materials and identified the dopant levels that optimized mechanical strength and enhanced electrochemical performance. We also optimized our ability to fabricate electrolyte supported button cells with anodes consisting of powders provided by Fuel Cell Energy. In several instances, those anodes were infiltrated with ALT and tested with hydrogen for 30 hours at 800°C at an applied potential of 0.4 V. Our research activities were focused in three areas: 1) mechanical strength testing on as prepared and reducced nickel-YSZ structures that were either free of a dopant ormore » prepared by mechanically mixing in ALT at various weight percents (up to 10 wt%); 2) 24-hour electrochemical testing of electroylte supported cells having anodes made from Ni/YSZ and Ni/YSZ/ALT anodes with specific attention focused on modeling degradation rates; and 3) operando EIS and optical testing of both in-house fabricated devices as well as membrane electrode assemblies that were acquired from commercial vendors.« less

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

Weiser, Philip; Qin, Ying; Yin, Weikai

Uniaxial stress experiments performed for the 3306 cm -1 vibrational line assigned to the interstitial-hydrogen, shallow-donor center in In 2O 3 reveal its symmetry and transition- moment direction. The defect alignment that can be produced by a [001] stress applied at 165 K is due to a process that is also a hydrogen- diffusion jump, providing a microscopic determination of the diffusion constant for H in In 2O 3 and its mechanism. Lastly, our experimental results strongly complement theoretical predictions for the structure and diffusion of the interstitial hydrogen donor center in In 2O 3.

Effect of a microstructure and surface hydrogen alloying of a VT6 alloy on diffusion welding

NASA Astrophysics Data System (ADS)

Senkevich, K. S.; Skvortsova, S. V.; Kudelina, I. M.; Knyazev, M. I.; Zasypkin, V. V.

2014-01-01

The effect of a structural type (lamellar, fine, gradient) and additional surface alloying with hydrogen on the diffusion bonding of titanium alloy VT6 samples is studied. It is shown that the surface alloying of VT6 alloy parts with hydrogen allows one to decrease the diffusion welding temperature by 50-100°C, to obtain high-quality pore-free bonding, and to remove the "structural" boundary between materials to be welded that usually forms during welding of titanium alloys with a lamellar structure.

Electrochemical Separation, Pumping, and Storage of Hydrogen or Oxygen into Nanocapillaries Via High Pressure MEA Seals

DTIC Science & Technology

2015-10-13

Fabrication (3) Integrate Membrane & (4) Fill with Hydrogen Shaped Al Aluminum Oxide Nanocapillary Array CNT Coated Pore Wall Complete Gas Storage...nanocapillary arrays are produced through aluminum anodization . The nanocapillary arrays are capped with either a PEM or an alkaline (anion) exchange...24,600 psi)  Circumferential Stress  Proportional to  Pore radius  Wall thickness Aluminum AAO AAO /CNT Nanocapillary Array (Not to scale

First-Principles Approach to Model Electrochemical Reactions: Understanding the Fundamental Mechanisms behind Mg Corrosion

NASA Astrophysics Data System (ADS)

Surendralal, Sudarsan; Todorova, Mira; Finnis, Michael W.; Neugebauer, Jörg

2018-06-01

Combining concepts of semiconductor physics and corrosion science, we develop a novel approach that allows us to perform ab initio calculations under controlled potentiostat conditions for electrochemical systems. The proposed approach can be straightforwardly applied in standard density functional theory codes. To demonstrate the performance and the opportunities opened by this approach, we study the chemical reactions that take place during initial corrosion at the water-Mg interface under anodic polarization. Based on this insight, we derive an atomistic model that explains the origin of the anodic hydrogen evolution.

Self-organized and uniform TiO2 nanotube arrays with optimized NH4F concentration in electrolyte by high voltage electrochemical anodization

NASA Astrophysics Data System (ADS)

Chamanzadeh, Z.; Noormohammadi, M.; Zahedifar, M.

2018-05-01

Large diameter and ordered TiO2 nanotubes (NTs) were fast fabricated in an electrolyte containing lactic acid and ethylene glycol with different amount of NH4F at various high anodization voltages up to 220 V. In this work, we could optimize F‑ ionic concentration in the electrolyte at each anodization voltage and the uniform films without any oxide breakdown were successfully achieved. The optimum NH4F concentration at which NTs can be formed homogeneously, decreases with the increment of anodization voltage. As a result, the fastest mean growth rate of 2.45 μm min‑1 was attained in 0.075 M NH4F at 150 V. Growth rate of TiO2 nanotubes is explained taking into account the role of F‑ ions and their limited diffusion through TiO2 nanotubes from bulk electrolyte. The interpore distance of the nanotubes is increased with enhanced anodization voltage.

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

Han, Sang -Don; Rajput, Nav Nidhi; Qu, Xiaohui

Through coupled experimental analysis and computational techniques, we uncover the origin of anodic stability for a range of nonaqueous zinc electrolytes. By examination of electrochemical, structural, and transport properties of nonaqueous zinc electrolytes with varying concentrations, it is demonstrated that the acetonitrile Zn(TFSI) 2, acetonitrile Zn(CF 3SO 3) 2, and propylene carbonate Zn(TFSI) 2 electrolytes can not only support highly reversible Zn deposition behavior on a Zn metal anode (≥99% of Coulombic efficiency), but also provide high anodic stability (up to ~3.8 V). The predicted anodic stability from DFT calculations is well in accordance with experimental results, and elucidates thatmore » the solvents play an important role in anodic stability of most electrolytes. Molecular dynamics (MD) simulations were used to understand the solvation structure (e.g., ion solvation and ionic association) and its effect on dynamics and transport properties (e.g., diffusion coefficient and ionic conductivity) of the electrolytes. Lastly, the combination of these techniques provides unprecedented insight into the origin of the electrochemical, structural, and transport properties in nonaqueous zinc electrolytes« less

Methanol Fuel Cell

NASA Technical Reports Server (NTRS)

Voecks, G. E.

1985-01-01

In proposed fuel-cell system, methanol converted to hydrogen in two places. External fuel processor converts only part of methanol. Remaining methanol converted in fuel cell itself, in reaction at anode. As result, size of fuel processor reduced, system efficiency increased, and cost lowered.

Facile Synthesis of Robust Free-Standing TiO2 Nanotubular Membranes for Biofiltration Applications

PubMed Central

Schweicher, Julien; Desai, Tejal A.

2014-01-01

Robust monodisperse nanoporous membranes have a wide range of biotechnological applications, but are often difficult or costly to fabricate. Here, a simple technique is reported to produce free-standing TiO2 nanotubular membranes with through-hole morphology. It consists in a 3-step anodization procedure carried out at room temperature on a Ti foil. The first anodization (1 h at 80 V) is used to pattern the surface of the metallic foil. Then, the second anodization (24 h at 80 V) produces the array of TiO2 nanotubes that will constitute the final membrane. A higher voltage anodization (3-5 minutes at 180 V) is finally applied to detach the TiO2 nanotubular layer from the underlying Ti foil. In order to completely remove the barrier layer that obstructs some pores of the membrane, the latter is etched 2 minutes in a buffered oxide etch solution. The overall process produces 60 μm-thick TiO2 nanotubular membranes with tube openings of 110 nm on one side and 73 nm on the other side. The through-hole morphology of these membranes has been verified by performing diffusion experiments with glucose, insulin and immunoglobulin G where in differences in diffusion rate are observed based on molecular weight. Such biocompatible TiO2 nanotubular membranes, with controlled pore size and morphology, have broad biotechnological and biomedical applications. PMID:24634542

Facile Synthesis of Robust Free-Standing TiO2 Nanotubular Membranes for Biofiltration Applications.

PubMed

Schweicher, Julien; Desai, Tejal A

2014-03-01

Robust monodisperse nanoporous membranes have a wide range of biotechnological applications, but are often difficult or costly to fabricate. Here, a simple technique is reported to produce free-standing TiO 2 nanotubular membranes with through-hole morphology. It consists in a 3-step anodization procedure carried out at room temperature on a Ti foil. The first anodization (1 h at 80 V) is used to pattern the surface of the metallic foil. Then, the second anodization (24 h at 80 V) produces the array of TiO 2 nanotubes that will constitute the final membrane. A higher voltage anodization (3-5 minutes at 180 V) is finally applied to detach the TiO 2 nanotubular layer from the underlying Ti foil. In order to completely remove the barrier layer that obstructs some pores of the membrane, the latter is etched 2 minutes in a buffered oxide etch solution. The overall process produces 60 μm-thick TiO 2 nanotubular membranes with tube openings of 110 nm on one side and 73 nm on the other side. The through-hole morphology of these membranes has been verified by performing diffusion experiments with glucose, insulin and immunoglobulin G where in differences in diffusion rate are observed based on molecular weight. Such biocompatible TiO 2 nanotubular membranes, with controlled pore size and morphology, have broad biotechnological and biomedical applications.

Metal hydrides: an innovative and challenging conversion reaction anode for lithium-ion batteries

PubMed Central

Oumellal, Yassine; Bonnet, Jean-Pierre

2015-01-01

Summary The state of the art of conversion reactions of metal hydrides (MH) with lithium is presented and discussed in this review with regard to the use of these hydrides as anode materials for lithium-ion batteries. A focus on the gravimetric and volumetric storage capacities for different examples from binary, ternary and complex hydrides is presented, with a comparison between thermodynamic prediction and experimental results. MgH2 constitutes one of the most attractive metal hydrides with a reversible capacity of 1480 mA·h·g−1 at a suitable potential (0.5 V vs Li+/Li0) and the lowest electrode polarization (<0.2 V) for conversion materials. Conversion process reaction mechanisms with lithium are subsequently detailed for MgH2, TiH2, complex hydrides Mg2MHx and other Mg-based hydrides. The reversible conversion reaction mechanism of MgH2, which is lithium-controlled, can be extended to others hydrides as: MHx + xLi+ + xe− in equilibrium with M + xLiH. Other reaction paths—involving solid solutions, metastable distorted phases, and phases with low hydrogen content—were recently reported for TiH2 and Mg2FeH6, Mg2CoH5 and Mg2NiH4. The importance of fundamental aspects to overcome technological difficulties is discussed with a focus on conversion reaction limitations in the case of MgH2. The influence of MgH2 particle size, mechanical grinding, hydrogen sorption cycles, grinding with carbon, reactive milling under hydrogen, and metal and catalyst addition to the MgH2/carbon composite on kinetics improvement and reversibility is presented. Drastic technological improvement in order to the enhance conversion process efficiencies is needed for practical applications. The main goals are minimizing the impact of electrode volume variation during lithium extraction and overcoming the poor electronic conductivity of LiH. To use polymer binders to improve the cycle life of the hydride-based electrode and to synthesize nanoscale composite hydride can be helpful to address these drawbacks. The development of high-capacity hydride anodes should be inspired by the emergent nano-research prospects which share the knowledge of both hydrogen-storage and lithium-anode communities. PMID:26425434

Influence of Hydrogen Bonding on the Surface Diffusion of Molecular Glasses: Comparison of Three Triazines

DOE PAGES

Chen, Yinshan; Zhu, Men; Laventure, Audrey; ...

2017-06-26

Surface grating decay measurements have been performed on three closely related molecular glasses to study the effect of intermolecular hydrogen bonds on surface diffusion. The three molecules are derivatives of bis(3,5-dimethyl-phenylamino)-1,3,5-triazine and differ only in the functional group R at the 2-position, with R being C 2H 5, OCH 3, and NHCH 3, and referred to as “Et”, “OMe”, and “NHMe”, respectively. Of the three molecules, NHMe forms more extensive intermolecular hydrogen bonds than Et and OMe and was found to have slower surface diffusion. For Et and OMe, surface diffusion is so fast that it replaces viscous flow asmore » the mechanism of surface grating decay as temperature is lowered. In contrast, no such transition was observed for NHMe under the same conditions, indicating significantly slower surface diffusion. This result is consistent with the previous finding that extensive intermolecular hydrogen bonds slow down surface diffusion in molecular glasses and is attributed to the persistence of hydrogen bonds even in the surface environment. Here, this result is also consistent with the lower stability of the vapor-deposited glass of NHMe relative to those of Et and OMe and supports the view that surface mobility controls the stability of vapor-deposited glasses.« less

Methane-free biogas for direct feeding of solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Leone, P.; Lanzini, A.; Santarelli, M.; Calì, M.; Sagnelli, F.; Boulanger, A.; Scaletta, A.; Zitella, P.

This paper deals with the experimental analysis of the performance and degradation issues of a Ni-based anode-supported solid oxide fuel cell fed by a methane-free biogas from dark-anaerobic digestion of wastes by pastry and fruit shops. The biogas is produced by means of an innovative process where the biomass is fermented with a pre-treated bacteria inoculum (Clostridia) able to completely inhibit the methanization step during the fermentation process and to produce a H 2/CO 2 mixture instead of conventional CH 4/CO 2 anaerobic digested gas (bio-methane). The proposed biogas production route leads to a biogas composition which avoids the need of introducing a reformer agent into or before the SOFC anode in order to reformate it. In order to analyse the complete behaviour of a SOFC with the bio-hydrogen fuel, an experimental session with several H 2/CO 2 synthetic mixtures was performed on an anode-supported solid oxide fuel cell with a Ni-based anode. It was found that side reactions occur with such mixtures in the typical thermodynamic conditions of SOFCs (650-800 °C), which have an effect especially at high currents, due to the shift to a mixture consisting of hydrogen, carbon monoxide, carbon dioxide and water. However, cells operated with acceptable performance and carbon deposits (typical of a traditional hydrocarbon-containing biogas) were avoided after 50 h of cell operation even at 650 °C. Experiments were also performed with traditional bio-methane from anaerobic digestion with 60/40 vol% of composition. It was found that the cell performance dropped after few hours of operation due to the formation of carbon deposits. A short-term test with the real as-produced biogas was also successfully performed. The cell showed an acceptable power output (at 800 °C, 0.35 W cm -2 with biogas, versus 0.55 W cm -2 with H 2) although a huge quantity of sulphur was present in the feeding fuel (hydrogen sulphide at 103 ppm and mercaptans up to 10 ppm). Therefore, it was demonstrated the interest relying on a sustainable biomass processing which produces a biogas which can be directly fed to SOFC using traditional anode materials and avoiding the reformer component since the methane-free mixture is already safe for carbon deposition.

Interplay between translational diffusion and large-amplitude angular jumps of water molecules

NASA Astrophysics Data System (ADS)

Liu, Chao; Zhang, Yangyang; Zhang, Jian; Wang, Jun; Li, Wenfei; Wang, Wei

2018-05-01

Understanding the microscopic mechanism of water molecular translational diffusion is a challenging topic in both physics and chemistry. Here, we report an investigation on the interplay between the translational diffusion and the large-amplitude angular jumps of water molecules in bulk water using molecular dynamics simulations. We found that large-amplitude angular jumps are tightly coupled to the translational diffusions. Particularly, we revealed that concurrent rotational jumps of spatially neighboring water molecules induce inter-basin translational jumps, which contributes to the fast component of the water translational diffusion. Consequently, the translational diffusion shows positional heterogeneity; i.e., the neighbors of the water molecules with inter-basin translational jumps have larger probability to diffuse by inter-basin translational jumps. Our control simulations showed that a model water molecule with moderate hydrogen bond strength can diffuse much faster than a simple Lennard-Jones particle in bulk water due to the capability of disturbing the hydrogen bond network of the surrounding water molecules. Our results added to the understanding of the microscopic picture of the water translational diffusion and demonstrated the unique features of water diffusion arising from their hydrogen bond network structure compared with those of the simple liquids.

The role of grain boundaries in hydrogen diffusion in metals at 25 C

NASA Technical Reports Server (NTRS)

Danford, M. D.

1993-01-01

The effect of grain size on hydrogen diffusion at 25 C was examined for 4340 steel (body-centered cubic) and for Inconel 718 (face-centered cubic). It was found that the effect of grain size is important for body-centered cubic structures, but plays a much less important role in face centered cubic structures. Accurate measurements of hydrogen desorption coefficients during hydrogen desorption show that these are not greatly different for both types of structures.

Sodium adsorption and diffusion on monolayer black phosphorus with intrinsic defects

NASA Astrophysics Data System (ADS)

Sun, Xiaoli; Wang, Zhiguo

2018-01-01

Monolayer black phosphorus is a potential anode material for rechargeable ion batteries. In this work, the effects of intrinsic defects including mono-vacancy (MV), di-vacancy, and Stone-Wales (SW) defects on the adsorption and diffusion of sodium on monolayer black phosphorus were investigated using first-principles calculations. The adsorption energies for sodium on monolayer black phosphorus are in the range of -1.80 to -0.56 eV, which is lower than the value of -0.48 eV for sodium adsorbed on pristine monolayer phosphorus. This indicates that these defects can enhance the adsorption of sodium on monolayer black phosphorus. The diffusivity of sodium on monolayer phosphorus with SW and MV defects is 2.35 × 10-4-3.36 × 10-6 cm2/s, and 7.38 × 10-5-1.48 × 10-9 cm2/s, respectively. Although these values are smaller than that of the pristine monolayer phosphorus at 7.38 × 10-5 cm2/s, defects are inevitably introduced during these fabrication processes. These diffusivity values are reasonable for defective monolayer phosphorus used as an effective anode for sodium ion batteries.

Mechanical process for enhancing metal hydride for the anode of a Ni-MH secondary battery

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

Ikeya, T.; Kumai, K.; Iwahori, T.

1993-11-01

This study attempted to find a simpler method for modifying hydrogen storage alloys that are used as anodes in Ni-MH batteries to prolong their cycle life. The alloy was modified by mechanical grinding with cobalt metal powder. A short grinding time yielded samples with a higher discharge capacity and longer cycle life than those of the alloy which was mixed with the cobalt powder without the mechanical treatment. However, prolonged grinding caused a decrease in the discharge capacity because of amorphization of the alloy by mechanical stress. The authors believed the formation of a cobalt compound on the alloy surfacemore » plus closer contact between particle enhanced the cyclic durability and discharge capacity of metal hydride anodes.« less

The improvement of SiO2 nanotubes electrochemical behavior by hydrogen atmosphere thermal treatment

NASA Astrophysics Data System (ADS)

Spataru, Nicolae; Anastasescu, Crina; Radu, Mihai Marian; Balint, Ioan; Negrila, Catalin; Spataru, Tanta; Fujishima, Akira

2018-06-01

Highly defected SiO2 nanotubes (SiO2-NT) were obtained by a simple sol-gel procedure followed by calcination. Boron-doped diamond (BDD) polycrystalline films coated with SiO2-NT were used as working electrodes and, unexpectedly, cyclic voltammetric experiments have shown that the concentration of both positive and negative defects at the surface is high enough to enable redox processes involving positively charged Ru(bpy)32+/3+ to occur. Conversely, no electrochemical activity was put into evidence for Fe(CN)63-/4- species, most likely as a result of the strong electrostatic repulsion exerted by the negatively charged SiO2 surface. The concentration of surface defects was further increased by a subsequent thermal treatment in a hydrogen atmosphere which, as EIS measurements have shown, significantly promotes Ru(bpy)32+ anodic oxidation. Digital simulation of the voltammetric responses demonstrated that this treatment does not lead to a similar increase of the number of electron-donor sites. It was also found that methanol anodic oxidation at hydrogenated SiO2-NT-supported platinum results in Tafel slopes of 116-220 mV decade-1, comparable to those reported for both conventional PtRu and Pt-oxide catalysts.

Anodically Grown Binder-Free Nickel Hexacyanoferrate Film: Toward Efficient Water Reduction and Hexacyanoferrate Film Based Full Device for Overall Water Splitting.

PubMed

Bui, Hoa Thi; Shrestha, Nabeen K; Khadtare, Shubhangi; Bathula, Chinna D; Giebeler, Lars; Noh, Yong-Young; Han, Sung-Hwan

2017-05-31

One of the challenges in obtaining hydrogen economically by electrochemical water splitting is to identify and substitute cost-effective earth-abundant materials for the traditionally used precious-metal-based water-splitting electrocatalysts. Herein, we report the electrochemical formation of a thin film of nickel-based Prussian blue analogue hexacyanoferrate (Ni-HCF) through the anodization of a nickel substrate in ferricyanide electrolyte. As compared to the traditionally used Nafion-binder-based bulk film, the anodically obtained binder-free Ni-HCF film demonstrates superior performance in the electrochemical hydrogen evolution reaction (HER), which is highly competitive with that shown by a Pt-plate electrode. The HER onset and the benchmark cathodic current density of 10 mA cm -2 were achieved at small overpotentials of 15 mV and 0.2 V (not iR-corrected), respectively, in 1 M KOH electrolyte, together with the long-term electrochemical durability of the film. Further, a metal-HCF-electrode-based full water-splitting device consisting of the binder-free Ni-HCF film on a Ni plate and a one-dimensional Co-HCF film on carbon paper as the electrodes for the HER and the oxygen evolution reaction (OER), respectively, was designed and was found to demonstrate very promising performance for overall water splitting.

Collision cascades enhanced hydrogen redistribution in cobalt implanted hydrogenated diamond-like carbon films

NASA Astrophysics Data System (ADS)

Gupta, P.; Becker, H.-W.; Williams, G. V. M.; Hübner, R.; Heinig, K.-H.; Markwitz, A.

2017-03-01

Hydrogenated diamond-like carbon films produced by C3H6 deposition at 5 kV and implanted at room temperature with 30 keV Co atoms to 12 at.% show not only a bimodal distribution of Co atoms but also a massive redistribution of hydrogen in the films. Resonant nuclear reaction analysis was used to measure the hydrogen depth profiles (15N-method). Depletion of hydrogen near the surface was measured to be as low as 7 at.% followed by hydrogen accumulation from 27 to 35 at.%. A model is proposed considering the thermal energy deposited by collision cascade for thermal insulators. In this model, sufficient energy is provided for dissociated hydrogen to diffuse out of the sample from the surface and diffuse into the sample towards the interface which is however limited by the range of the incoming Co ions. At a hydrogen concentration of ∼35 at.%, the concentration gradient of the mobile unbounded hydrogen atoms is neutralised effectively stopping diffusion towards the interface. The results point towards new routes of controlling the composition and distribution of elements at the nanoscale within a base matrix without using any heat treatment methods. Exploring these opportunities can lead to a new horizon of materials and device engineering needed for enabling advanced technologies and applications.

Investigation of nanosecond pulsed dielectric barrier discharge using plate-to-plate electrode with asymmetric dielectric arrangement in airflow

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

Qi, Haicheng; School of Physics Science and Technology, Anshan Normal University, Anshan 114005; Fan, Zhihui

Atmospheric pressure dielectric barrier discharge plasma is produced in airflow by applying nanosecond high voltage pulses with peak voltage about 35 kV and rising time about 40 ns on a plate-to-plate electrode arrangement. The effects of airflow rate (0–50 m/s) on the discharge characteristics are investigated under different barrier conditions (the bare anode case and the bare cathode case). For both cases, the breakdown voltage and the time lag increase distinctly and the discharge intensity decreases sharply when the airflow rate increases from 0 to 30 m/s, and then keep almost constant until the airflow rate is further increased to 50 m/s. For the baremore » anode case (the cathode is covered by dielectric plate), the discharge mode transforms gradually from filamentary to diffuse discharge with the increasing airflow rate. While for the bare cathode case, some micro-discharge channels are still excited, though the discharge becomes more diffuse when the airflow rate is higher than 30 m/s. By acquiring the time-resolved images of the discharge, it is proved that it is the primary discharge which becomes diffuse when airflow is introduced and the following two discharges of the same voltage pulse occur principally at the positions where the primary discharge is more intense. And in both cases, the plasma temperatures are reduced, but the degree is different. All the phenomena can be explained mainly by the variation of the space charge distribution when the airflow is introduced into the discharge gap. And it is indicated that the bare anode case has an advantage in obtaining diffuse discharge.« less

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

An electrochemical model for hot-salt stress-corrosion of titanium alloys

NASA Technical Reports Server (NTRS)

Garfinkle, M.

1972-01-01

An electrochemical model of hot-salt stress-corrosion cracking of titanium alloys is proposed based on an oxygen-concentration cell. Hydrogen embrittlement is proposed as the direct cause of cracking, the hydrogen being generated as the results of the hydrolysis of complex halides formed at the shielded anode of the electrochemical cell. The model found to be consistent with the diverse observations made both in this study and by many investigators in this field.

Characterization of Pulse Reverses Electroforming on Hard Gold Coating.

PubMed

Byoun, Young-Min; Noh, Young-Tai; Kim, Young-Geun; Ma, Seung-Hwan; Kim, Gwan-Hoon

2018-03-01

Effect of pulse reverse current (PRC) method on brass coatings electroplated from gold solution was investigated by various plating parameters such as plating duration, the anodic duty cycle, the anodic current density and the cathodic current density. The reversed current results in a significant change in the morphology of electrodeposits, improvement of the overall current efficiency and reduction of deposit porosity. With longer pulses, hemispherical surface features are generated, while larger grains result from shorter pulse widths. The porosity of the plated samples is found to decrease compared with results at the same time-average plating rate obtained from DC or Pulse plating. A major impediment to reducing gold later thickness is the corrosion of the underlying substrate, which is affected by the porosity of the gold layer. Both the morphology and the hydrogen evolution reaction have significant impact on porosity. PRC plating affect hydrogen gold and may oxidize hydrogen produced during the cathodic portion of the waveform. Whether the dissolution of gold and oxidation of hydrogen occur depends on the type of plating bath and the plating conditions adapted. In reversed pulse plating, the amount of excess near-surface cyanide is changed after the cathodic current is applied, and the oxidation of gold under these conditions has not been fully addressed. The effects of the current density, pulse-reverse ratio and brightener concentration of the electroplating process were investigated and optimized for suitable performance.

Control of malodorous hydrogen sulfide compounds using microbial fuel cell.

PubMed

Eaktasang, Numfon; Min, Hyeong-Sik; Kang, Christina; Kim, Han S

2013-10-01

In this study, a microbial fuel cell (MFC) was used to control malodorous hydrogen sulfide compounds generated from domestic wastewaters. The electricity production demonstrated a distinct pattern of a two-step increase during 170 h of system run: the first maximum current density was 118.6 ± 7.2 mA m⁻² followed by a rebound of current density increase, reaching the second maximum of 176.8 ± 9.4 mA m⁻². The behaviors of the redox potential and the sulfate level in the anode compartment indicated that the microbial production of hydrogen sulfide compounds was suppressed in the first stage, and the hydrogen sulfide compounds generated from the system were removed effectively as a result of their electrochemical oxidation, which contributed to the additional electricity production in the second stage. This was also directly supported by sulfur deposits formed on the anode surface, which was confirmed by analyses on those solids using a scanning electron microscope equipped with energy dispersive X-ray spectroscopy as well as an elemental analyzer. To this end, the overall reduction efficiencies for HS⁻ and H₂S(g) were as high as 67.5 and 96.4 %, respectively. The correlations among current density, redox potential, and sulfate level supported the idea that the electricity signal generated in the MFC can be utilized as a potential indicator of malodor control for the domestic wastewater system.

Effect of anode-cathode geometry on performance of the HIP-1 hot ion plasma. [magnetic mirrors

NASA Technical Reports Server (NTRS)

Lauver, M. R.

1978-01-01

Hot-ion hydrogen plasma experiments were conducted in the NASA Lewis HIP-1 magnetic mirror facility to determine how the ion temperature was influenced by the axial position of the cathode tips relative to the anodes. A steady-state EXB plasma was formed by applying a strong radially inward dc electric field near the throats of the magnetic mirrors. The dc electric field was created between hollow cathode rods inside hollow anode cylinders, both concentric with the magnetic axis. The highest ion temperatures, 900 eV, were attained when the tip of each cathode was in the same plane as the end of its anode. These temperatures were reached with 22 kV applied to the electrodes in a field of 1.1 tesla. Scaling relations were empirically determined for ion temperature and the product of ion density and neutral particle density as a function of cathode voltage, discharge current, and electrode positions. Plasma discharge current vs voltage (I-V) characteristics were determined.

Electrode design for direct-methane micro-tubular solid oxide fuel cell (MT-SOFC)

NASA Astrophysics Data System (ADS)

Rabuni, Mohamad Fairus; Li, Tao; Punmeechao, Puvich; Li, Kang

2018-04-01

Herein, a micro-structured electrode design has been developed via a modified phase-inversion method. A thin electrolyte integrated with a highly porous anode scaffold has been fabricated in a single-step process and developed into a complete fuel cell for direct methane (CH4) utilisation. A continuous and well-dispersed layer of copper-ceria (Cu-CeO2) was incorporated inside the micro-channels of the anode scaffold. A complete cell was investigated for direct CH4 utilisation. The well-organised micro-channels and nano-structured Cu-CeO2 anode contributed to an increase in electrochemical reaction sites that promoted charge-transfer as well as facilitating gaseous fuel distribution, resulting in outstanding performances. Excellent electrochemical performances have been achieved in both hydrogen (H2) and CH4 operation. The power density of 0.16 Wcm-2 at 750 °C with dry CH4 as fuel is one of the highest ever reported values for similar anode materials.

Enhancement of Combustion and Flame Stabilization Using Transient Non-Equilibrium Plasma

DTIC Science & Technology

2007-03-31

cathode spot D = diameter of MGA device D= diffusivity of i’h species d = diameter of arc dcoected= diametrically corrected diameter of arc d.rwwd... cathode and anode, stabilization (4) respectively (Fig. 1). A wire was attached to the cathode , which was separated from the outer anode by 2 mm at the...smallest gap (point (1) in Fig. 1). The wire spiraled progressively closer to the cathode , where it was attached at the largest gap between the two

Electrochemical formation of hydroxide for enhancing carbon dioxide and acid gas uptake by a solution

DOEpatents

Rau, Gregory Hudson [Castro Valley, CA

2012-05-15

A system is described for forming metal hydroxide from a metal carbonate utilizing a water electrolysis cell having an acid-producing anode and a hydroxyl-producing cathode immersed in a water solution of sufficient ionic content to allow an electric current to pass between the hydroxyl-producing cathode and the acid-producing anode. A metal carbonate, in particular water-insoluble calcium carbonate or magnesium carbonate, is placed in close proximity to the acid-producing anode. A direct current electrical voltage is provided across the acid-producing anode and the hydroxyl-producing cathode sufficient to generate acid at the acid-producing anode and hydroxyl ions at the hydroxyl-producing cathode. The acid dissolves at least part of the metal carbonate into metal and carbonate ions allowing the metal ions to travel toward the hydroxyl-producing cathode and to combine with the hydroxyl ions to form the metal hydroxide. The carbonate ions travel toward the acid-producing anode and form carbonic acid and/or water and carbon dioxide. Among other uses, the metal hydroxide formed can be employed to absorb acid gases such as carbon dioxide from a gas mixture. The invention can also generate hydrogen and oxidative gases such as oxygen or chlorine.

Evaluation of anode (electro)catalytic materials for the direct borohydride fuel cell: Methods and benchmarks

NASA Astrophysics Data System (ADS)

Olu, Pierre-Yves; Job, Nathalie; Chatenet, Marian

2016-09-01

In this paper, different methods are discussed for the evaluation of the potential of a given catalyst, in view of an application as a direct borohydride fuel cell DBFC anode material. Characterizations results in DBFC configuration are notably analyzed at the light of important experimental variables which influence the performances of the DBFC. However, in many practical DBFC-oriented studies, these various experimental variables prevent one to isolate the influence of the anode catalyst on the cell performances. Thus, the electrochemical three-electrode cell is a widely-employed and useful tool to isolate the DBFC anode catalyst and to investigate its electrocatalytic activity towards the borohydride oxidation reaction (BOR) in the absence of other limitations. This article reviews selected results for different types of catalysts in electrochemical cell containing a sodium borohydride alkaline electrolyte. In particular, propositions of common experimental conditions and benchmarks are given for practical evaluation of the electrocatalytic activity towards the BOR in three-electrode cell configuration. The major issue of gaseous hydrogen generation and escape upon DBFC operation is also addressed through a comprehensive review of various results depending on the anode composition. At last, preliminary concerns are raised about the stability of potential anode catalysts upon DBFC operation.

Controlling Morphological Parameters of Anodized Titania Nanotubes for Optimized Solar Energy Applications

PubMed Central

Haring, Andrew; Morris, Amanda; Hu, Michael

2012-01-01

Anodized TiO2 nanotubes have received much attention for their use in solar energy applications including water oxidation cells and hybrid solar cells [dye-sensitized solar cells (DSSCs) and bulk heterojuntion solar cells (BHJs)]. High surface area allows for increased dye-adsorption and photon absorption. Titania nanotubes grown by anodization of titanium in fluoride-containing electrolytes are aligned perpendicular to the substrate surface, reducing the electron diffusion path to the external circuit in solar cells. The nanotube morphology can be optimized for the various applications by adjusting the anodization parameters but the optimum crystallinity of the nanotube arrays remains to be realized. In addition to morphology and crystallinity, the method of device fabrication significantly affects photon and electron dynamics and its energy conversion efficiency. This paper provides the state-of-the-art knowledge to achieve experimental tailoring of morphological parameters including nanotube diameter, length, wall thickness, array surface smoothness, and annealing of nanotube arrays.

Commercial expanded graphite as a low-cost, long-cycling life anode for potassium-ion batteries with conventional carbonate electrolyte

NASA Astrophysics Data System (ADS)

An, Yongling; Fei, Huifang; Zeng, Guifang; Ci, Lijie; Xi, Baojuan; Xiong, Shenglin; Feng, Jinkui

2018-02-01

Design and synthesis of capable anode materials that can store the large size K+ is the key of development for potassium-ion batteries. The low-cost and commercial expanded graphite with large particles is a graphite-derived material with good conductivity and enlarged interlayer spaces to boost the potassium ion diffusion coefficient during charge/discharge process. Thus, we achieve excellent anode performance for potassium-ion batteries based on an expanded graphite. It can deliver a capacity of 263 mAh g-1 at the rate of 10 mA g-1 and the reversible capacity remains almost unchanged after 500 cycles at a high rate of 200 mA g-1 with a coulombic efficiency of around 100%. The potassium storage mechanism is investigated by the ex situ XRD technique. This excellent potassium storage performance will make the expanded graphite promising anode candidate for potassium ion batteries.

Effect of nanostructured titanium on anodization growth of self-organized TiO2 nanotubes

NASA Astrophysics Data System (ADS)

Zhang, Lan; Han, Yong

2010-02-01

To understand the effect of substrate microstructure on the formation of TiO2 nanotubes, anodic oxidizations of commercially pure titanium subjected to surface mechanical attrition treatment (SMATed-Ti) and unSMATed-Ti in a glycol solution containing NH4F and small amounts of water were investigated. The SMATed-Ti exhibit a nanocrystallized surface layer containing a high density of grain boundaries compared with unSMATed-Ti. The anodization results show that the formed TiO2 nanotube layer on the SMATed-Ti is much thicker than that on the unSMATed-Ti. It is indicated that nanocrystallized Ti is propitious to the growth of TiO2 nanotubes; grain boundaries and dislocations play the leading role in accelerating the reaction rate and ion diffusion coefficient during anodization. In addition, nanocrystallization of Ti does not change surface morphologies and phase components of the TiO2 nanotubes.

Modification of the Near Surface Region Metastable Phases and Ion Induced Reactions

DTIC Science & Technology

1984-02-03

cell Si Dave Lilienfeld - amorphous Si layer thickness Au diffusion in metallic glasses Dave Lilienfeld & - low temperature Cu diffusion in Si Tim...Sullivan Fritz Stafford - defect characterization in implanted & annealed silicon-on-sapphire Peter Zielinski - Composition of CuZr metallic glass...ribbons 5. Prof. Johnson Dave Kuhn - measurement of Pd layer thickness Alexandra Elve - hydrogen profiles in metals Lauren Heitner - hydrogen diffusion in

Modeling Issues and Results for Hydrogen Isotopes in NIF Materials

NASA Astrophysics Data System (ADS)

Grossman, Arthur A.; Doerner, R. P.; Luckhardt, S. C.; Seraydarian, R.; Sze, D.; Burnham, A.

1998-11-01

The TMAP4 (G. Longhurst, et al. INEL 1992) model of hydrogen isotope transport in solid materials includes a particle diffusion calculation with Fick's Law modified for Soret Effect (Thermal Diffusion or Thermomigration), coupled to heat transport calculations which are needed because of the strong temperature dependence of diffusivity. These TMAP4 calculations applied to NIF show that high temperatures approaching the melting point and strong thermal gradients of 10^6 K/cm are reached in the first micron of wall material during the SXR pulse. These strong thermal gradients can drive hydrogen isotope migration up or down the thermal gradient depending on the sign of the heat of transport (Soret coefficient) which depends on whether the material dissolves hydrogen endothermically or exothermically. Two candidates for NIF wall material-boron carbide and stainless steel are compared. Boron carbide dissolves hydrogen exothermically so it may drive Soret migration down the thermal gradient deeper into the material, although the thermal gradient is not as large and hydrogen is not as mobile as in stainless steel. Stainless steel dissolves hydrogen endothermically, with a negative Soret coefficient which can drive hydrogen up the thermal gradient and out of the wall.

Hydrogen in tungsten as plasma-facing material

NASA Astrophysics Data System (ADS)

Roth, Joachim; Schmid, Klaus

2011-12-01

Materials facing plasmas in fusion experiments and future reactors are loaded with high fluxes (1020-1024 m-2 s-1) of H, D and T fuel particles at energies ranging from a few eV to keV. In this respect, the evolution of the radioactive T inventory in the first wall, the permeation of T through the armour into the coolant and the thermo-mechanical stability after long-term exposure are key parameters determining the applicability of a first wall material. Tungsten exhibits fast hydrogen diffusion, but an extremely low solubility limit. Due to the fast diffusion of hydrogen and the short ion range, most of the incident ions will quickly reach the surface and recycle into the plasma chamber. For steady-state operation the solute hydrogen for the typical fusion reactor geometry and wall conditions can reach an inventory of about 1 kg. However, in short-pulse operation typical of ITER, solute hydrogen will diffuse out after each pulse and the remaining inventory will consist of hydrogen trapped in lattice defects, such as dislocations, grain boundaries and irradiation-induced traps. In high-flux areas the hydrogen energies are too low to create displacement damage. However, under these conditions the solubility limit will be exceeded within the ion range and the formation of gas bubbles and stress-induced damage occurs. In addition, simultaneous neutron fluxes from the nuclear fusion reaction D(T,n)α will lead to damage in the materials and produce trapping sites for diffusing hydrogen atoms throughout the bulk. The formation and diffusive filling of these different traps will determine the evolution of the retained T inventory. This paper will concentrate on experimental evidence for the influence different trapping sites have on the hydrogen inventory in W as studied in ion beam experiments and low-temperature plasmas. Based on the extensive experimental data, models are validated and applied to estimate the contribution of different traps to the tritium inventory in future fusion reactors.

Studies on the electrodeposition of tin from acidic chloride-gluconate solutions

NASA Astrophysics Data System (ADS)

Rudnik, Ewa; Włoch, Grzegorz

2013-01-01

Electrodeposition of tin from acidic chloride-gluconate baths was investigated. Equilibrium distribution of tin(II) species showed domination of Sn(II)-gluconate complexes, but for Sn2+ concentrations 50 mM or higher increased percentage of Sn(II)-chloride complexes was found. Cyclic voltammetry, anodic stripping analysis and potentiostatic measurements indicated that rate of the cathodic process is determined by the release of metal cations from gluconate complexes in diluted bath (5 mM), but for more concentrated solutions reduction of Sn(II) ions run under diffusion control. Studies of anodic response showed that it depends on the Sn(II)/Glu ratio in the bath and deposition potential due to development of different planes of metal crystal. Average effective diffusion coefficients of metal species were determined. Morphology and structure tin deposits were also presented.

Diffusion of gas mixtures in the sI hydrate structure

NASA Astrophysics Data System (ADS)

Waage, Magnus H.; Trinh, Thuat T.; van Erp, Titus S.

2018-06-01

Replacing methane with carbon dioxide in gas hydrates has been suggested as a way of harvesting methane, while at the same time storing carbon dioxide. Experimental evidence suggests that this process is facilitated if gas mixtures are used instead of pure carbon dioxide. We studied the free energy barriers for diffusion of methane, carbon dioxide, nitrogen, and hydrogen in the sI hydrate structure using molecular simulation techniques. Cage hops between neighboring cages were considered with and without a water vacancy and with a potential inclusion of an additional gas molecule in either the initial or final cage. Our results give little evidence for enhanced methane and carbon dioxide diffusion if nitrogen is present as well. However, the inclusion of hydrogen seems to have a substantial effect as it diffuses rapidly and can easily enter occupied cages, which reduces the barriers of diffusion for the gas molecules that co-occupy a cage with hydrogen.

Understanding the impact of flow rate and recycle on the conversion of a complex biorefinery stream using a flow-through microbial electrolysis cell

DOE PAGES

Lewis, Alex J.; Borole, Abhijeet P.

2016-06-16

We investigated the effect of flow rate and recycle on the conversion of a biomass-derived pyrolysis aqueous phase in amicrobial electrolysis cell (MEC) to demonstrate production of renewable hydrogen in biorefinery. A continuous MEC operation was investigated under one-pass and recycle conditions usingthe complex, biomass-derived, fermentable, mixed substrate feed at a constant concentration of 0.026 g/L,while testing flow rates ranging from 0.19 to 3.6 mL/min. This corresponds to an organic loading rate (OLR) of 0.54₋10 g/L-day. Mass transfer issues observed at low flow rates were alleviated using high flow rates.Increasing the flow rate to 3.6 mL/min (3.7 min HRT) duringmore » one-pass operation increased the hydrogen productivity 3-fold, but anode conversion efficiency (ACE) decreased from 57.9% to 9.9%. Recycle of the anode liquid helped to alleviate kinetic limitations and the ACE increased by 1.8-fold and the hydrogen productivity by 1.2-fold compared to the one-pass condition at the flow rate of 3.6 mL/min (10 g/L-d OLR). High COD removal was also achieved under recycle conditions, reaching 74.2 1.1%, with hydrogen production rate of 2.92 ± 0.51 L/L-day. This study demonstrates the advantages of combining faster flow rates with a recycle process to improve rate of hydrogen production from a switchgrass-derived stream in the biorefinery.« less

Hydrogen diffusion and electronic structure in crystalline and amorphous Ti/sub y/CuH/sub x/

NASA Technical Reports Server (NTRS)

Bowman, R. C., Jr.; Rhim, W. K.; Maeland, A. J.; Lynch, J. F.

1982-01-01

Hydrogen diffusion behavior and electronic properties of crystalline TiCuHo94, Ti2CuH1.90, and Ti2CuH2.63 and amorphous a-TiCuH1.4 were studied using proton relaxation times, proton Knight shifts, and magnetic susceptibilities. Crystal structure and hydrogen site occupancy have major roles in hydrogen mobility. The density of electron states at E sub F is reduced in amorphous a-TiCuH1.4 compared to the crystalline hydrides.

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.

Dependence of hydrogen arcjet operation on electrode geometry

NASA Technical Reports Server (NTRS)

Pencil, Eric J.; Sankovic, John M.; Sarmiento, Charles J.; Hamley, John A.

1992-01-01

The dependence of 2kW hydrogen arcjet performance on cathode to anode electrode spacing was evaluated at specific impulses of 900 and 1000 s. Less than 2 absolute percent change in efficiency was measured for the spacings tested which did not repeat the 14 absolute percent variation reported in earlier work with similar electrode designs. A different nozzle configuration was used to quantify the variation in hydrogen arcjet performance over an extended range of electrode spacing. Electrode gap variation resulted in less than 3 absolute percent change in efficiency. These null results suggested that electrode spacing is decoupled from hydrogen arcjet ignition. The dependence of breakdown voltage on mass flow rate and electrode agreed with Paschen curves for hydrogen. Preliminary characterization of the dependence of hydrogen arcjet ignition on rates of pulse repetition and pulse voltage rise were also included for comparison with previous results obtained using simulated hydrazine.

Dependence of hydrogen arcjet operation on electrode geometry

NASA Technical Reports Server (NTRS)

Pencil, Eric J.; Sankovic, John M.; Sarmiento, Charles J.; Hamley, John A.

1992-01-01

The dependence of 2 kW hydrogen arcjet performance on cathode to anode electrode spacing was evaluated at specific impulses of 900 and 1000 s. Less than 2 absolute percent change in efficiency was measured for the spacings tested which did not repeat the 14 absolute percent variation reported in earlier work with similar electrode designs. A different nozzle configuration was used to quantify the variation in hydrogen arcjet performance over an extended range of electrode spacing. Electrode gap variation resulted in less than 3 absolute percent change in efficiency. These null results suggested that electrode spacing is decoupled from hydrogen arcjet performance considerations over the ranges tested. Initial studies were conducted on hydrogen arcjet ignition. The dependence of breakdown voltage on mass flow rate and hydrogen arcjet ignition on rates of pulse repetition and pulse voltage rise were also included for comparison with previous results obtained using simulated hydrazine.

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

Chen, Yun; Chen, Song; Hackett, Gregory

The interaction of trace (ppm) phosphine with the nickel/yttria stabilized zirconia (YSZ) anode of commercial solid oxide fuel cells has been investigated and evaluated for both synthesis gas and hydrogen fuels in an effort to examine P–Y reactions. The Ni poisoning effects reported in literature were confirmed and degradation was examined by electrochemical methods and post-test microstructural and chemical analyses. The results indicate that P-induced degradation rates and mechanisms are fuel dependent and that degradation of cells operated in synthesis gas (syngas) with phosphine is more severe than that of cells operated in hydrogen with phosphine. As reported in publishedmore » literature, a cell operated in syngas containing 10 ppm phosphine demonstrated significant microstructural degradation within the Ni phase, including formation of Ni–P phases concentrated on the outer layer of the anode and significant pitting corrosion in the Ni grains. In this research, a previously undetected YPO{sub 4} phase is observed at the YSZ/YSZ/Ni triple grain junctions located at the interface with the YSZ electrolyte. Tetragonal YSZ (t-YSZ) and cubic-YSZ (c-YSZ) domains with sizes of several tens of nanometers are also newly observed along the Ni/YSZ interface. These observations contrast with data obtained for a cell operated in dry hydrogen with phosphine, where no YPO{sub 4} phase is observed and the alternating t-YSZ and c-YSZ domains at the Ni/YSZ interface are smaller with typical sizes of 5–10 nm. The data imply that electrolyte attack by P is a potentially debilitating mode of degradation in SOFC anodes, and that the associated reaction mechanisms and rates are worthy of further examination.« less

Generation and delivery device for ozone gas and ozone dissolved in water

NASA Technical Reports Server (NTRS)

Andrews, Craig C. (Inventor); Murphy, Oliver J. (Inventor)

2006-01-01

The present invention provides an ozone generation and delivery system that lends itself to small scale applications and requires very low maintenance. The system includes an anode reservoir and a cathode phase separator each having a hydrophobic membrane to allow phase separation of produced gases from water. The system may be configured to operate passively with no moving parts or in a self-pressurizing manner with the inclusion of a pressure controlling device or valve in the gas outlet of the anode reservoir. The hydrogen gas, ozone gas and water containing ozone may be delivered under pressure.

Generation and delivery device for ozone gas and ozone dissolved in water

NASA Technical Reports Server (NTRS)

Andrews, Craig C. (Inventor); Rogers, Thomas D. (Inventor); Murphy, Oliver J. (Inventor)

1999-01-01

The present invention provides an ozone generation and delivery system that lends itself to small scale applications and requires very low maintenance. The system includes an anode reservoir and a cathode phase separator each having a hydrophobic membrane to allow phase separation of produced gases from water. The system may be configured to operate passively with no moving parts or in a self-pressurizing manner with the inclusion of a pressure controlling device or valve in the gas outlet of the anode reservoir. The hydrogen gas, ozone gas and water containing ozone may be delivered under pressure.

Electrochemical incineration of wastes

NASA Technical Reports Server (NTRS)

Kaba, L.; Hitchens, G. D.; Bockris, J. O'M.

1989-01-01

A low temperature electrolysis process has been developed for the treatment of solid waste material and urine. Experiments are described in which organic materials are oxidized directly at the surface of an electrode. Also, hypochlorite is generated electrochemically from chloride component of urine. Hypochlorite can act as a strong oxidizing agent in solution. The oxidation takes place at 30-60 C and the gaseous products from the anodic reaction are carbon dioxide, nitrogen, oxygen. Hydrogen is formed at the cathode. Carbon monoxide, and nitrogen oxides and methane were not detected in the off gases. Chlorine was evolved at the anode in relatively low amounts.

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

PubMed

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

2014-06-01

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

International Space Station United States Oxygen Generator Development Testing

NASA Technical Reports Server (NTRS)

Erickson, Robert J.; Mason, Richard K.

2000-01-01

A life test of a liquid anode feed oxygen generator assembly (OGA) using SPE(R) (United Technologies Corporation, Hamilton Sundstrand Division) membrane technology was terminated in June of 1999. In the total 15,658 hours of operation at MSFC since delivery in 1995, the OGA has produced 2,103 kilograms (kg) (4,632 pounds mass (lbm)) of oxygen, and 263 kg (579 lbm) of hydrogen. Evaluation of cell stack characteristics and oxygen and hydrogen hydrophilic/hydrophobic membrane separators will be discussed.

Studies of Hydrogen Production by the Water Gas Shift Reaction and Related Chemistry

DTIC Science & Technology

1983-04-15

HYDROGEN PRODUCTION BY THE WATER GAS SHIFT REACTION AND RELATED CHEMISTRY Institution: The University of Rochester Department of Chemistry -. Rochester...been in siated for the catalysis of the water gas shift reaction, W20 + CO H𔃼 + C02, and for electrocatalytic oxidation of CO, CO + H󈧘 C02 + 2H...particular interest in adopting water gas shift catalysts to act as electrocatalysts for the anode reaction of CO fuel cells. Under these conditions the best

Effect of hydrogen on cathodic corrosion of titanium aluminide

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

Gao, K.W.; Jin, J.W.; Qiao, L.J.

1996-01-01

Cathodic corrosion of titanium aluminide (TiAl) during hydrogen charging in various acidic aqueous solutions and in molten salt at 160 C was studied. At constant potential, the rate of cathodic corrosion (V) was much higher than during anodic dissolution, and V increased linearly with increasing current. V was 10 times higher in the acid solution than in the salt solution under the same current. Disruption of the surface film by local hydride formation during cathodic polarization was shown to be the key step.

Laser Surface Melting of Stainless Steel Anodes for Reduced Hydrogen Outgassing (Postprint)

DTIC Science & Technology

2016-12-29

including baking [8– 12], vacuum baking [8,11,13,14], polishing [8,14], and surface treatments to create oxide or other protective surface films. Elec...quantity [15] and may necessitate an additional bake to thoroughly degas the surface [8]. The purpose of the work described here was to determine the...9] M. Bernardini, Air bake -out to reduce hydrogen outgassing from stainless steel, J. Vac. Sci. Technol. A Vacuum, Surfaces, Film 16 (1998) 188–193.4

Water Splitting Using Porous Silicon Photo-electrodes for Hydrogen Production

NASA Astrophysics Data System (ADS)

Ali, M.; Starkov, V. V.; Gosteva, E. A.; Druzhinin, A. V.; Sattar, S.

2017-11-01

This paper presents the efficiency study results of using gradient-porous silicon structures with different morphology, as photo-anodes for photo-electrochemical dissociation of water. The results of a study of the physicochemical properties of gradient-porous silicon structures show the relatively low cost and simplicity of the technological process, as well as the possibility of forming structures with predefined properties, allow the creation of effective devices for artificial photosynthesis based on porous silicon for subsequent use in hydrogen energy.

Anodic Oxidative Modification of Egg White for Heat Treatment.

PubMed

Takahashi, Masahito; Handa, Akihiro; Yamaguchi, Yusuke; Kodama, Risa; Chiba, Kazuhiro

2016-08-31

A new functionalization of egg white was achieved by an electrochemical reaction. The method involves electron transfer from thiol groups of egg white protein to form disulfide bonds. The oxidized egg white produced less hydrogen sulfide during heat treatment; with sufficient application of electricity, almost no hydrogen sulfide was produced. In addition, gels formed by heating electrochemically oxidized egg white exhibited unique properties, such as a lower gelation temperature and a softened texture, presumably due to protein aggregation and electrochemically mediated intramolecular disulfide bond formation.

Optimizing membrane electrode assembly of direct methanol fuel cells for portable power

NASA Astrophysics Data System (ADS)

Liu, Fuqiang

Direct methanol fuel cells (DMFCs) for portable power applications require high power density, high-energy conversion efficiency and compactness. These requirements translate to fundamental properties of high methanol oxidation and oxygen reduction kinetics, as well as low methanol and water crossover. In this thesis a novel membrane electrode assembly (MEA) for direct methanol fuel cells has been developed, aiming to improve these fundamental properties. Firstly, methanol oxidation kinetics has been enhanced and methanol crossover has been minimized by proper control of ionomer crystallinity and its swelling in the anode catalyst layer through heat-treatment. Heat-treatment has a major impact on anode characteristics. The short-cured anode has low ionomer crystallinity, and thus swells easily when in contact with methanol solution to create a much denser anode structure, giving rise to higher methanol transport resistance than the long-cured anode. Variations in interfacial properties in the anode catalyst layer (CL) during cell conditioning were also characterized, and enhanced kinetics of methanol oxidation and severe limiting current phenomenon were found to be caused by a combination of interfacial property variations and swelling of ionomer over time. Secondly, much effort has been expended to develop a cathode CL suitable for operation under low air stoichiometry. The effects of fabrication procedure, ionomer content, and porosity distribution on the microstructure and cathode performance under low air stoichiometry are investigated using electrochemical and surface morphology characterizations to reveal the correlation between microstructure and electrochemical behavior. At the same time, computational fluid dynamics (CFD) models of DMFC cathodes have been developed to theoretically interpret the experimental results, to investigate two-phase transport, and to elucidate mechanism of cathode mixed potential due to methanol crossover. Thirdly, a MEA with low water crossover has been developed by employing a highly-hydrophobic microporous layer (MPL) to build up hydraulic pressure at the cathode, promoting product water permeation from the cathode to anode to offset water dragged by electro-osmosis. Water crossover through the MEA is further reduced by an anode hydrophobic MPL through facilitating water back diffusion. Under different current densities, the MEA with hydrophobic MPL has consistently low alpha, several times smaller than those with hydrophilic or without MPL. A simulation study of anode water transport by a two-phase model shows that anode MPL wettability strongly determines liquid saturation in the anode, and thus is identified as playing a crucial role in promoting water back diffusion. Finally, direct feed of highly-concentrated methanol using the optimized MEA has been successfully demonstrated by a face-feed anode plate, which minimizes methanol crossover by controlling the fuel delivery rate. Using 10 M methanol, a steady-state power density of ˜67mW/cm2 is reached at 60°C and 175mA/cm2, which is almost identical to that with 2M methanol.

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

Dubey, P., E-mail: purushd@barc.gov.in; Sharma, V. K.; Mitra, S.

Synthetic hydroxyapatite (HAp) is an important material in biomedical engineering due to its excellent biocompatibility and bioactivity. Here we report dynamics of cetyltrimethylammonium bromide (CTAB) in HAp composite, prepared by co-precipitation method, as studied by quasielastic neutron scattering (QENS) technique. It is found that the observed dynamics involved two time scales associated with fast torsional motion and segmental motion of the CTAB monomers. In addition to segmental motion of the hydrogen atoms, few undergo torsional motion as well. Torsional dynamics was described by a 2-fold jump diffusion model. The segmental dynamics of CTAB has been described assumimg the hydrogen atomsmore » undergoing diffusion inside a sphere of confined volume. While the diffusivity is found to increase with temperature, the spherical volumes within which the hydrogen atoms are undergoing diffusion remain almost unchanged.« less

Application of low-temperature plasma for the synthesis of hydrogenated graphene (graphane)

NASA Astrophysics Data System (ADS)

Shavelkina, M. B.; Amirov, R. H.; Katarzhis, V. A.; Kiselev, V. I.

2017-12-01

The possibility of a direct synthesis of hydrogenated graphene in decomposition of methane by means of low-temperature plasma was investigated. A DC plasma torch with an expanding channel-anode, a vortex gas supply and a self-setting arc length was used as a generator of low-temperature plasma. Argon was used as the plasma-forming gas. The temperatures of argon plasma and with methane addition to it were determined on the basis of spectral measurements. The synthesis products were characterized by electron microscopy and thermogravimetry. The effect of hydrogenated graphene as a nanomodifier on the properties of the cubic boron nitride based functional ceramics was investigated.

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.

Understanding the impact of operational conditions on performance of microbial peroxide producing cells

NASA Astrophysics Data System (ADS)

Young, Michelle N.; Chowdhury, Nadrat; Garver, Emily; Evans, Patrick J.; Popat, Sudeep C.; Rittmann, Bruce E.; Torres, César I.

2017-07-01

Microbial peroxide producing cells (MPPCs) are microbial electrochemical cells used to synthesize hydrogen peroxide (H2O2) in the cathode chamber. Catholyte hydraulic retention time (HRT), different catholytes and their concentrations, and a ferrochelating stabilizer are varied in a continuous-flow cathode MPPC to evaluate their impacts on performance. Using NaCl catholytes, the MPPC produced as high as 3.1 ± 0.37 g H2O2 L-1 at a 4-h HRT with as little as 1.13 W-h g-1 H2O2 energy input and with up to 57 g Lcathode-1 d-1 at a 1-h HRT. For these conditions, the H2O2 production rate provides more than 3 times the H2O2 required for disinfection or micro-pollutant removal while using 5-25% of the power used in conventional H2O2 production processes. Attempts to improve H2O2-production by adding weak acid buffers or H2O2-stabilizing EDTA fail for different reasons. The addition of the ferrochelator EDTA to prevent H2O2 auto-decay deteriorates MPPC performance, because EDTA diffuses from the cathode to the anode, inhibiting iron utilization by anode-respiring bacteria. Weak acid buffers failed to reduce cathode concentration overpotentials. Buffering catholytes lowered the H2O2 yield due to large pH gradients at the cathode chamber entrance, causing the formation of H2O instead of H2O2 or O2 re-formation from H2O2 auto-decay.

Performance testing of a prototype Pd-Ag diffuser

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

Morgan, G. A.; Hodge, B. J.

The fusion fuel cycle has gained significant attention over the last decade as interest in fusion programs has increased. One of the critical components of the fusion process is the tritium fuel cycle. The tritium fuel cycle is designed to supply and recycle process tritium at a specific throughput rate. One of the most important processes within the tritium fuel cycle is the clean-up of the of the process tritium. This step will initially separate the hydrogen isotopes (H2, D2, and T2) from the rest of the process gas using Pd-Ag diffusers or permeators. The Pd-Ag diffuser is an integralmore » component for any tritium purification system; whether part of the United States’ defense mission or fusion programs. Domestic manufacturers of Pd-Ag diffusers are extremely limited and only a few manufacturers exist. Johnson-Matthey (JM) Pd-Ag diffusers (permeators) have previously been evaluated for the separation of hydrogen isotopes from non-hydrogen gas species in the process. JM is no longer manufacturing Pd-Ag diffusers and a replacement vendor needs to be identified to support future needs. A prototype Pd-Ag diffuser has been manufactured by Power and Energy, and is considered a potential replacement for the JM diffuser for tritium service. New diffuser designs for a tritium facility for any fusion energy applications must be characterized by evaluating their operating envelope prior to installation in a tritium processing facility. The prototype Pd-Ag diffuser was characterized to determine the overall performance as a function of the permeation of hydrogen through the membrane. The tests described in this report consider the effects of feed gas compositions, feed flow rates, pump configuration and internal tube pressure on the permeation of H2 through the Pd-Ag tubes.« less

Fuel cell anode configuration for CO tolerance

DOEpatents

Uribe, Francisco A.; Zawodzinski, Thomas A.

2004-11-16

A polymer electrolyte fuel cell (PEFC) is designed to operate on a reformate fuel stream containing oxygen and diluted hydrogen fuel with CO impurities. A polymer electrolyte membrane has an electrocatalytic surface formed from an electrocatalyst mixed with the polymer and bonded on an anode side of the membrane. An anode backing is formed of a porous electrically conductive material and has a first surface abutting the electrocatalytic surface and a second surface facing away from the membrane. The second surface has an oxidation catalyst layer effective to catalyze the oxidation of CO by oxygen present in the fuel stream where at least the layer of oxidation catalyst is formed of a non-precious metal oxidation catalyst selected from the group consisting of Cu, Fe, Co, Tb, W, Mo, Sn, and oxides thereof, and other metals having at least two low oxidation states.

A high energy and power sodium-ion hybrid capacitor based on nitrogen-doped hollow carbon nanowires anode

NASA Astrophysics Data System (ADS)

Li, Dongdong; Ye, Chao; Chen, Xinzhi; Wang, Suqing; Wang, Haihui

2018-04-01

The sodium ion hybrid capacitor (SHC) has been attracting much attention. However, the SHC's power density is significantly confined to a low level due to the sluggish ion diffusion in the anode. Herein, we propose to use an electrode with a high double layer capacitance as the anode in the SHC instead of insertion anodes. To this aim, nitrogen doped hollow carbon nanowires (N-HCNWs) with a high specific surface area are prepared, and the high capacitive contribution during the sodium ion storage process is confirmed by a series of electrochemical measurements. A new SHC consisting of a N-HCNW anode and a commercial active carbon (AC) cathode is fabricated for the first time. Due to the hybrid charge storage mechanism combining ion insertion and capacitive process, the as-fabricated SHC strikes a balance between the energy density and power density, a energy density of 108 Wh kg-1 and a power density of 9 kW kg-1 can be achieved, which overwhelms the electrochemical performances of most reported AC-based SHCs.

Origin of electrochemical, structural and transport properties in non-aqueous zinc electrolytes

DOE PAGES

Han, Sang -Don; Rajput, Nav Nidhi; Qu, Xiaohui; ...

2016-01-14

Through coupled experimental analysis and computational techniques, we uncover the origin of anodic stability for a range of nonaqueous zinc electrolytes. By examination of electrochemical, structural, and transport properties of nonaqueous zinc electrolytes with varying concentrations, it is demonstrated that the acetonitrile Zn(TFSI) 2, acetonitrile Zn(CF 3SO 3) 2, and propylene carbonate Zn(TFSI) 2 electrolytes can not only support highly reversible Zn deposition behavior on a Zn metal anode (≥99% of Coulombic efficiency), but also provide high anodic stability (up to ~3.8 V). The predicted anodic stability from DFT calculations is well in accordance with experimental results, and elucidates thatmore » the solvents play an important role in anodic stability of most electrolytes. Molecular dynamics (MD) simulations were used to understand the solvation structure (e.g., ion solvation and ionic association) and its effect on dynamics and transport properties (e.g., diffusion coefficient and ionic conductivity) of the electrolytes. Lastly, the combination of these techniques provides unprecedented insight into the origin of the electrochemical, structural, and transport properties in nonaqueous zinc electrolytes« less

Self Regulating Fiber Fuel Cell

DTIC Science & Technology

2010-08-16

12000 68.2 77.4 24/7 Extreme Rigid liquid hydrogen fuel cell Medis 68 X 97 X 57 20000 53.2 108.1 Fiber Fuel Cell Flexible Individual fiber Honeywell...which allows hydrogen and water vapor to permeate freely but prevents liquids from entering or fuel particles from escaping. The SPM permeability...S is the solubility and D is the diffusivity. Solubility and diffusivity data vs. pressure for hydrogen in Nafion is not available in the literature

Unique Fe2P Nanoparticles Enveloped in Sandwichlike Graphited Carbon Sheets as Excellent Hydrogen Evolution Reaction Catalyst and Lithium-Ion Battery Anode.

PubMed

Zhang, Yan; Zhang, Huijuan; Feng, Yangyang; Liu, Li; Wang, Yu

2015-12-09

The novel Fe2P nanoparticles encapsulated in sandwichlike graphited carbon envelope nanocomposite (Fe2P/GCS) that can be first applied in hydrogen evolution reaction (HER) as well as lithium-ion batteries (LIBs) has been designed and fabricated. The unique sandwiched Fe2P/GCS is characterized with several prominent merits, including large specific surface area, nanoporous structure, excellent electronic conductivity, enhanced structural integrity and so on. All of these endow the Fe2P/GCS with brilliant electrochemical performance. When used as a HER electrocatalyst in acidic media, the harvested Fe2P/GCS demonstrates low onset overpotential and Tafel slope as well as particularly outstanding durability. Moreover, as an anode material for LIBs, the sandwiched Fe2P/GCS presents high specific capacity and excellent cyclability and rate capability. As a consequence, the acquired Fe2P/GCS is a promising material for energy applications, especially HER and LIBs.

Hydrogen-permeable composite metal membrane and uses thereof

DOEpatents

Edlund, D.J.; Friesen, D.T.

1993-06-08

Various hydrogen production and hydrogen sulfide decomposition processes are disclosed that utilize composite metal membranes that contain an intermetallic diffusion barrier separating a hydrogen-permeable base metal and a hydrogen-permeable coating metal. The barrier is a thermally stable inorganic proton conductor.

Preparation and Evaluation of Multi-Layer Anodes of Solid Oxide Fuel Cell

NASA Technical Reports Server (NTRS)

Santiago, Diana; Farmer, Serene C.; Setlock, John A.

2012-01-01

The development of an energy device with abundant energy generation, ultra-high specific power density, high stability and long life is critical for enabling longer missions and for reducing mission costs. Of all different types of fuel cells, the solid oxide fuel cells (SOFC) is a promising high temperature device that can generate electricity as a byproduct of a chemical reaction in a clean way and produce high quality heat that can be used for other purposes. For aerospace applications, a power-to-weight of (is) greater than 1.0 kW/kg is required. NASA has a patented fuel cell technology under development, capable of achieving the 1.0 kW/kg figure of merit. The first step toward achieving these goals is increasing anode durability. The catalyst plays an important role in the fuel cells for power generation, stability, efficiency and long life. Not only the anode composition, but its preparation and reduction are key to achieving better cell performance. In this research, multi-layer anodes were prepared varying the chemistry of each layer to optimize the performance of the cells. Microstructure analyses were done to the new anodes before and after fuel cell operation. The cells' durability and performance were evaluated in 200 hrs life tests in hydrogen at 850 C. The chemistry of the standard nickel anode was modified successfully reducing the anode degradation from 40% to 8.4% in 1000 hrs and retaining its microstructure.

Enhancing Sulfur Tolerance of Ni-Based Cermet Anodes of Solid Oxide Fuel Cells by Ytterbium-Doped Barium Cerate Infiltration.

PubMed

Li, Meng; Hua, Bin; Luo, Jing-Li; Jiang, San Ping; Pu, Jian; Chi, Bo; Li, Jian

2016-04-27

Conventional anode materials for solid oxide fuel cells (SOFCs) are Ni-based cermets, which are highly susceptible to deactivation by contaminants in hydrocarbon fuels. Hydrogen sulfide is one of the commonly existed contaminants in readily available natural gas and gasification product gases of pyrolysis of biomasses. Development of sulfur tolerant anode materials is thus one of the critical challenges for commercial viability and practical application of SOFC technologies. Here we report a viable approach to enhance substantially the sulfur poisoning resistance of a Ni-gadolinia-doped ceria (Ni-GDC) anode through impregnation of proton conducting perovskite BaCe0.9Yb0.1O3-δ (BCYb). The impregnation of BCYb nanoparticles improves the electrochemical performance of the Ni-GDC anode in both H2 and H2S containing fuels. Moreover, more importantly, the enhanced stability is observed in 500 ppm of H2S/H2. The SEM and XPS analysis indicate that the infiltrated BCYb fine particles inhibit the adsorption of sulfur and facilitate sulfur removal from active sites, thus preventing the detrimental interaction between sulfur and Ni-GDC and the formation of cerium sulfide. The preliminary results of the cell with the BCYb+Ni-GDC anode in methane fuel containing 5000 ppm of H2S show the promising potential of the BCYb infiltration approach in the development of highly active and stable Ni-GDC-based anodes fed with hydrocarbon fuels containing a high concentration of sulfur compounds.

Sorption of hydrogen by silica aerogel at low-temperatures

NASA Astrophysics Data System (ADS)

Dolbin, A. V.; Khlistyuck, M. V.; Esel'son, V. B.; Gavrilko, V. G.; Vinnikov, N. A.; Basnukaeva, R. M.; Martsenuk, V. E.; Veselova, N. V.; Kaliuzhnyi, I. A.; Storozhko, A. V.

2018-02-01

The programmed thermal desorption method is used at temperatures of 7-95 K to study the sorption and subsequent desorption of hydrogen by a sample of silica aerogel. Physical sorption of hydrogen owing to the weak van-der-Waals interaction of hydrogen molecules with the silicon dioxide walls of the pores of the sample was observed over the entire temperature range. The total capacity of the aerogel sample for hydrogen was ˜1.5 mass %. It was found that when the sample temperature was lowered from 95 to 60 K, the characteristic sorption times for hydrogen by the silica aerogel increase; this is typical of thermally activated diffusion (Ea ≈ 408 K). For temperatures of 15-45 K the characteristic H2 sorption times depended weakly on temperature, presumably because of the predominance of a tunnel mechanism for diffusion over thermally activated diffusion. Below 15 K the characteristic sorption times increase somewhat as the temperature is lowered; this may be explained by the formation of a monolayer of H2 molecules on the surface of the aerogel grains.

Determination of hydrogen permeability in uncoated and coated superalloys

NASA Technical Reports Server (NTRS)

Bhattacharyya, S.; Vesely, E. J., Jr.; Hill, V. L.

1981-01-01

Hydrogen permeability, diffusivity, and solubility data were obtained for eight wrought and cast high temperature alloys over the range 650 to 815 C. Data were obtained for both uncoated alloys and wrought alloys coated with four commercially available coatings. Activation energies for permeability, diffusivity and solubility were calculated.

Chemisorption and Diffusion of H on a Graphene Sheet and Single-Wall Carbon Nanotubes

NASA Technical Reports Server (NTRS)

Srivastava, Deepak; Dzegilenko, Fedor; Menon, Madhu

2000-01-01

Recent experiments on hydrogen storage in single wall nanotubes and nanotube bundles have reported large fractional weight of stored molecular hydrogen which are not in agreement with theoretical estimates based of simulation of hydrogen storage by physisorption mechanisms. Hydrogen storage in catalytically doped nanotube bundles indicate that atomic H might undergo chemisorption changing the basic nature of the storage mechanism under investigation by many groups. Using a generalized tight-binding molecular dynamics (GTBMD) method for reactive C-H dynamics, we investigate chemisorption and diffusion of atomic H on graphene sheet and C nanotubes. Effective potential energy surfaces (EPS) for chemisorption and diffusion are calculated for graphene sheet and nanotubes of different curvatures. Analysis of the activation barriers and quantum rate constants, computed via wave-packet dynamics method, will be discussed in this presentation.

In situ transmission electron microscopic observations of redox cycling of a Ni-ScSZ cermet fuel cell anode.

PubMed

Matsuda, Junko; Kawasaki, Tatsuya; Futamura, Shotaro; Kawabata, Tsutomu; Taniguchi, Shunsuke; Sasaki, Kazunari

2018-05-19

In situ transmission electron microscopy (TEM) observations of a Ni(O)-Sc2O3-stabilized ZrO2 (ScSZ; 10 mol% Sc2O3, 1 mol% CeO2, 89 mol% ZrO2) anode in a solid oxide fuel cell (SOFC) have been performed at high temperatures under a hydrogen/oxygen gas atmosphere using an environmental transmission electron microscope (ETEM); the specimens were removed from cross-sections of the real SOFC by focused ion beam milling and lifting. When heating the NiO-ScSZ anode under a hydrogen atmosphere of 3 mbar in ETEM, nano-pores were formed at the grain boundaries and on the surface of NiO particles at around 400°C due to the volume shrinkage accompanying the reduction of NiO to Ni. Moreover, densification of Ni occurred when increasing the temperature from 600 to 700°C. High-magnification TEM images obtained in the early stages of NiO reduction revealed that the (111) planes of Ni grew almost parallel to the (111) planes of NiO. In the case of heating Ni-ScSZ under an oxygen atmosphere of 3 mbar in ETEM, oxidation of Ni starting from the surface of the particles occurred above 300°C. All Ni particles became polycrystalline NiO after the temperature was increased to 800°C. Volume expansion/contraction by mass transfer to the outside/inside of the Ni particles in the anode during repeated oxidation/reduction seems to result in the agglomeration of Ni catalysts during long-term SOFC operation. We emphasize that our in situ TEM observations will be applied to observe electrochemical reactions in SOFCs under applied electric fields.

Vacuum ultraviolet photolysis of hydrogenated amorphous carbons. III. Diffusion of photo-produced H2 as a function of temperature

NASA Astrophysics Data System (ADS)

Martín-Doménech, R.; Dartois, E.; Muñoz Caro, G. M.

2016-06-01

Context. Hydrogenated amorphous carbon (a-C:H) has been proposed as one of the carbonaceous solids detected in the interstellar medium. Energetic processing of the a-C:H particles leads to the dissociation of the C-H bonds and the formation of hydrogen molecules and small hydrocarbons. Photo-produced H2 molecules in the bulk of the dust particles can diffuse out to the gas phase and contribute to the total H2 abundance. Aims: We have simulated this process in the laboratory with plasma-produced a-C:H and a-C:D analogs under astrophysically relevant conditions to investigate the dependence of the diffusion as a function of temperature. Methods: Experimental simulations were performed in a high-vacuum chamber, with complementary experiments carried out in an ultra-high-vacuum chamber. Plasma-produced a-C:H and a-C:D analogs were UV-irradiated using a microwave-discharged hydrogen flow lamp. Molecules diffusing to the gas-phase were detected by a quadrupole mass spectrometer, providing a measurement of the outgoing H2 or D2 flux. By comparing the experimental measurements with the expected flux from a one-dimensional diffusion model, a diffusion coefficient D could be derived for experiments carried out at different temperatures. Results: Dependence on the diffusion coefficient D with the temperature followed an Arrhenius-type equation. The activation energy for the diffusion process was estimated (ED(H2) = 1660 ± 110 K, ED(D2) = 2090 ± 90 K), as well as the pre-exponential factor (D0(H2) = 0.0007 cm2 s-1, D0(D2) = 0.0045 cm2 s-1). Conclusions: The strong decrease of the diffusion coefficient at low dust particle temperatures exponentially increases the diffusion times in astrophysical environments. Therefore, transient dust heating by cosmic rays needs to be invoked for the release of the photo-produced H2 molecules in cold photon-dominated regions, where destruction of the aliphatic component in hydrogenated amorphous carbons most probably takes place.

Electron-stimulated reactions in layered CO/H2O films: Hydrogen atom diffusion and the sequential hydrogenation of CO to methanol

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

Petrik, Nikolay G.; Monckton, Rhiannon J.; Koehler, Sven

Low-energy (100 eV) electron-stimulated reactions in layered H2O/CO/H2O ices are investigated. For CO trapped within approximately 50 ML of the vacuum interface in the amorphous solid water (ASW) films, both oxidation and reduction reactions are observed. However for CO buried more deeply in the film, only the reduction of CO to methanol is observed. Experiments with layered films of H2O and D2O show that the hydrogen atoms participating in the reduction of the buried CO originate in region from ~10 – 40 ML below the surface of the ASW films and subsequently diffuse through the film. For deeply buried COmore » layers, the CO reduction reactions quickly increase with temperature above ~60 K. We present a simple chemical kinetic model that treats the diffusion of hydrogen atoms in the ASW and sequential hydrogenation of the CO to methanol that accounts for the observations.« less

Transport equations in an enzymatic glucose fuel cell

NASA Astrophysics Data System (ADS)

Jariwala, Soham; Krishnamurthy, Balaji

2018-01-01

A mathematical model is developed to study the effects of convective flux and operating temperature on the performance of an enzymatic glucose fuel cell with a membrane. The model assumes isothermal operating conditions and constant feed rate of glucose. The glucose fuel cell domain is divided into five sections, with governing equations describing transport characteristics in each region, namely - anode diffusion layer, anode catalyst layer (enzyme layer), membrane, cathode catalyst layer and cathode diffusion layer. The mass transport is assumed to be one-dimensional and the governing equations are solved numerically. The effects flow rate of glucose feed on the performance of the fuel cell are studied as it contributes significantly to the convective flux. The effects of operating temperature on the performance of a glucose fuel cell are also modeled. The cell performances are compared using cell polarization curves, which were found compliant with experimental observations.

Si/Ge double-layered nanotube array as a lithium ion battery anode.

PubMed

Song, Taeseup; Cheng, Huanyu; Choi, Heechae; Lee, Jin-Hyon; Han, Hyungkyu; Lee, Dong Hyun; Yoo, Dong Su; Kwon, Moon-Seok; Choi, Jae-Man; Doo, Seok Gwang; Chang, Hyuk; Xiao, Jianliang; Huang, Yonggang; Park, Won Il; Chung, Yong-Chae; Kim, Hansu; Rogers, John A; Paik, Ungyu

2012-01-24

Problems related to tremendous volume changes associated with cycling and the low electron conductivity and ion diffusivity of Si represent major obstacles to its use in high-capacity anodes for lithium ion batteries. We have developed a group IVA based nanotube heterostructure array, consisting of a high-capacity Si inner layer and a highly conductive Ge outer layer, to yield both favorable mechanics and kinetics in battery applications. This type of Si/Ge double-layered nanotube array electrode exhibits improved electrochemical performances over the analogous homogeneous Si system, including stable capacity retention (85% after 50 cycles) and doubled capacity at a 3C rate. These results stem from reduced maximum hoop strain in the nanotubes, supported by theoretical mechanics modeling, and lowered activation energy barrier for Li diffusion. This electrode technology creates opportunities in the development of group IVA nanotube heterostructures for next generation lithium ion batteries. © 2011 American Chemical Society

Observation of copper atoms behavior in a vacuum arc discharge using laser spectroscopy

NASA Astrophysics Data System (ADS)

Sung, Y. M.; Hayashi, Y.; Okraku-Yirenkyi, Y.; Otsubo, M.; Honda, C.; Sakoda, T.

2003-01-01

In order to investigate the most important parameters influencing the breaking characteristic of a vacuum circuit breaker (VCB), the behavior of copper (Cu) particles emitted from electrodes designed as an imitation of a vacuum valve of the VCB was observed. The temporal-spatial intensity distributions due to Cu particles in an excited state or a neutral state were measured using the laser induced fluorescence (LIF) technique and a charge coupled device camera attached with a special filter. The diffusion velocity of a Cu atom was also investigated by evaluating a Doppler shift of the LIF signal. The results showed that most Cu particles were emitted from the anode and were in an excited state or an ionized state during an arc discharge. Also, Cu particles were distributed between electrodes even after the discharge chocked, and its diffusion velocity in the direction of the cathode from the anode was about 2.6 km/s.

A High-Performing Sulfur-Tolerant and Redox-Stable Layered Perovskite Anode for Direct Hydrocarbon Solid Oxide Fuel Cells

PubMed Central

Ding, Hanping; Tao, Zetian; Liu, Shun; Zhang, Jiujun

2015-01-01

Development of alternative ceramic oxide anode materials is a key step for direct hydrocarbon solid oxide fuel cells (SOFCs). Several lanthanide based layered perovskite-structured oxides demonstrate outstanding oxygen diffusion rate, favorable electronic conductivity, and good oxygen surface exchange kinetics, owing to A-site ordered structure in which lanthanide and alkali-earth ions occupy alternate (001) layers and oxygen vacancies are mainly located in [LnOx] planes. Here we report a nickel-free cation deficient layered perovskite, (PrBa)0.95(Fe0.9Mo0.1)2O5 + δ (PBFM), for SOFC anode, and this anode shows an outstanding performance with high resistance against both carbon build-up and sulfur poisoning in hydrocarbon fuels. At 800 °C, the layered PBFM showed high electrical conductivity of 59.2 S cm−1 in 5% H2 and peak power densities of 1.72 and 0.54 W cm−2 using H2 and CH4 as fuel, respectively. The cell exhibits a very stable performance under a constant current load of 1.0 A cm−2. To our best knowledge, this is the highest performance of ceramic anodes operated in methane. In addition, the anode is structurally stable at various fuel and temperature conditions, suggesting that it is a feasible material candidate for high-performing SOFC anode. PMID:26648509

A High-Performing Sulfur-Tolerant and Redox-Stable Layered Perovskite Anode for Direct Hydrocarbon Solid Oxide Fuel Cells

NASA Astrophysics Data System (ADS)

Ding, Hanping; Tao, Zetian; Liu, Shun; Zhang, Jiujun

2015-12-01

Development of alternative ceramic oxide anode materials is a key step for direct hydrocarbon solid oxide fuel cells (SOFCs). Several lanthanide based layered perovskite-structured oxides demonstrate outstanding oxygen diffusion rate, favorable electronic conductivity, and good oxygen surface exchange kinetics, owing to A-site ordered structure in which lanthanide and alkali-earth ions occupy alternate (001) layers and oxygen vacancies are mainly located in [LnOx] planes. Here we report a nickel-free cation deficient layered perovskite, (PrBa)0.95(Fe0.9Mo0.1)2O5 + δ (PBFM), for SOFC anode, and this anode shows an outstanding performance with high resistance against both carbon build-up and sulfur poisoning in hydrocarbon fuels. At 800 °C, the layered PBFM showed high electrical conductivity of 59.2 S cm-1 in 5% H2 and peak power densities of 1.72 and 0.54 W cm-2 using H2 and CH4 as fuel, respectively. The cell exhibits a very stable performance under a constant current load of 1.0 A cm-2. To our best knowledge, this is the highest performance of ceramic anodes operated in methane. In addition, the anode is structurally stable at various fuel and temperature conditions, suggesting that it is a feasible material candidate for high-performing SOFC anode.

A High-Performing Sulfur-Tolerant and Redox-Stable Layered Perovskite Anode for Direct Hydrocarbon Solid Oxide Fuel Cells.

PubMed

Ding, Hanping; Tao, Zetian; Liu, Shun; Zhang, Jiujun

2015-12-09

Development of alternative ceramic oxide anode materials is a key step for direct hydrocarbon solid oxide fuel cells (SOFCs). Several lanthanide based layered perovskite-structured oxides demonstrate outstanding oxygen diffusion rate, favorable electronic conductivity, and good oxygen surface exchange kinetics, owing to A-site ordered structure in which lanthanide and alkali-earth ions occupy alternate (001) layers and oxygen vacancies are mainly located in [LnOx] planes. Here we report a nickel-free cation deficient layered perovskite, (PrBa)0.95(Fe0.9Mo0.1)2O5 + δ (PBFM), for SOFC anode, and this anode shows an outstanding performance with high resistance against both carbon build-up and sulfur poisoning in hydrocarbon fuels. At 800 °C, the layered PBFM showed high electrical conductivity of 59.2 S cm(-1) in 5% H2 and peak power densities of 1.72 and 0.54 W cm(-2) using H2 and CH4 as fuel, respectively. The cell exhibits a very stable performance under a constant current load of 1.0 A cm(-2). To our best knowledge, this is the highest performance of ceramic anodes operated in methane. In addition, the anode is structurally stable at various fuel and temperature conditions, suggesting that it is a feasible material candidate for high-performing SOFC anode.

The Electrochemical Properties of Sr(Ti,Fe)O 3-δ for Anodes in Solid Oxide Fuel Cells

DOE PAGES

Nenning, Andreas; Volgger, Lukas; Miller, Elizabeth; ...

2017-02-18

Reduction-stable mixed ionic and electronic conductors such as Sr(Ti,Fe)O 3-δ (STF) are promising materials for application in anodes of solid oxide fuel cells. The defect chemistry of STF and its properties as solid oxide fuel cell (SOFC) cathode have been studied thoroughly, while mechanistic investigations of its electrochemical properties as SOFC anode material are still scarce. In this study, thin film model electrodes of STF with 30% and 70% Fe content were investigated in H 2+H 2O atmosphere by electrochemical impedance spectroscopy. Lithographically patterned thin film Pt current collectors were applied on top or beneath the STF thin films tomore » compensate for the low electronic conductivity under reducing conditions. Oxygen exchange resistances, electronic and ionic conductivities and chemical capacitances were quantified and discussed in a defect chemical model. Increasing Fe content increases the electro-catalytic activity of the STF surface as well as the electronic and ionic conductivity. Current collectors on top also increase the electrochemical activity due to a highly active Pt-atmosphere-STF triple phase boundary. Furthermore, the electrochemical activity depends decisively on the H 2:H 2O mixing ratio and the polarization. Lastly, Fe 0 nanoparticles may evolve on the surface in hydrogen rich atmospheres and increase the hydrogen adsorption rate.« less

Effect of atomic layer deposition coatings on the surface structure of anodic aluminum oxide membranes.

PubMed

Xiong, Guang; Elam, Jeffrey W; Feng, Hao; Han, Catherine Y; Wang, Hsien-Hau; Iton, Lennox E; Curtiss, Larry A; Pellin, Michael J; Kung, Mayfair; Kung, Harold; Stair, Peter C

2005-07-28

Anodic aluminum oxide (AAO) membranes were characterized by UV Raman and FT-IR spectroscopies before and after coating the entire surface (including the interior pore walls) of the AAO membranes by atomic layer deposition (ALD). UV Raman reveals the presence of aluminum oxalate in bulk AAO, both before and after ALD coating with Al2O3, because of acid anion incorporation during the anodization process used to produce AAO membranes. The aluminum oxalate in AAO exhibits remarkable thermal stability, not totally decomposing in air until exposed to a temperature >900 degrees C. ALD was used to cover the surface of AAO with either Al2O3 or TiO2. Uncoated AAO have FT-IR spectra with two separate types of OH stretches that can be assigned to isolated OH groups and hydrogen-bonded surface OH groups, respectively. In contrast, AAO surfaces coated by ALD with Al2O3 display a single, broad band of hydrogen-bonded OH groups. AAO substrates coated with TiO2 show a more complicated behavior. UV Raman results show that very thin TiO2 coatings (1 nm) are not stable upon annealing to 500 degrees C. In contrast, thicker coatings can totally cover the contaminated alumina surface and are stable at temperatures in excess of 500 degrees C.

Solution-processed copper-nickel nanowire anodes for organic solar cells

NASA Astrophysics Data System (ADS)

Stewart, Ian E.; Rathmell, Aaron R.; Yan, Liang; Ye, Shengrong; Flowers, Patrick F.; You, Wei; Wiley, Benjamin J.

2014-05-01

This work describes a process to make anodes for organic solar cells from copper-nickel nanowires with solution-phase processing. Copper nanowire films were coated from solution onto glass and made conductive by dipping them in acetic acid. Acetic acid removes the passivating oxide from the surface of copper nanowires, thereby reducing the contact resistance between nanowires to nearly the same extent as hydrogen annealing. Films of copper nanowires were made as oxidation resistant as silver nanowires under dry and humid conditions by dipping them in an electroless nickel plating solution. Organic solar cells utilizing these completely solution-processed copper-nickel nanowire films exhibited efficiencies of 4.9%.This work describes a process to make anodes for organic solar cells from copper-nickel nanowires with solution-phase processing. Copper nanowire films were coated from solution onto glass and made conductive by dipping them in acetic acid. Acetic acid removes the passivating oxide from the surface of copper nanowires, thereby reducing the contact resistance between nanowires to nearly the same extent as hydrogen annealing. Films of copper nanowires were made as oxidation resistant as silver nanowires under dry and humid conditions by dipping them in an electroless nickel plating solution. Organic solar cells utilizing these completely solution-processed copper-nickel nanowire films exhibited efficiencies of 4.9%. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr01024h

Catalysis in high-temperature fuel cells.

PubMed

Föger, K; Ahmed, K

2005-02-17

Catalysis plays a critical role in solid oxide fuel cell systems. The electrochemical reactions within the cell--oxygen dissociation on the cathode and electrochemical fuel combustion on the anode--are catalytic reactions. The fuels used in high-temperature fuel cells, for example, natural gas, propane, or liquid hydrocarbons, need to be preprocessed to a form suitable for conversion on the anode-sulfur removal and pre-reforming. The unconverted fuel (economic fuel utilization around 85%) is commonly combusted using a catalytic burner. Ceramic Fuel Cells Ltd. has developed anodes that in addition to having electrochemical activity also are reactive for internal steam reforming of methane. This can simplify fuel preprocessing, but its main advantage is thermal management of the fuel cell stack by endothermic heat removal. Using this approach, the objective of fuel preprocessing is to produce a methane-rich fuel stream but with all higher hydrocarbons removed. Sulfur removal can be achieved by absorption or hydro-desulfurization (HDS). Depending on the system configuration, hydrogen is also required for start-up and shutdown. Reactor operating parameters are strongly tied to fuel cell operational regimes, thus often limiting optimization of the catalytic reactors. In this paper we discuss operation of an authothermal reforming reactor for hydrogen generation for HDS and start-up/shutdown, and development of a pre-reformer for converting propane to a methane-rich fuel stream.

Modelling of discrete TDS-spectrum of hydrogen desorption

NASA Astrophysics Data System (ADS)

Rodchenkova, Natalia I.; Zaika, Yury V.

2015-12-01

High concentration of hydrogen in metal leads to hydrogen embrittlement. One of the methods to evaluate the hydrogen content is the method of thermal desorption spectroscopy (TDS). As the sample is heated under vacuumization, atomic hydrogen diffuses inside the bulk and is desorbed from the surface in the molecular form. The extraction curve (measured by a mass-spectrometric analyzer) is recorded. In experiments with monotonous external heating it is observed that background hydrogen fluxes from the extractor walls and fluxes from the sample cannot be reliably distinguished. Thus, the extraction curve is doubtful. Therefore, in this case experimenters use discrete TDS-spectrum: the sample is removed from the analytical part of the device for the specified time interval, and external temperature is then increased stepwise. The paper is devoted to the mathematical modelling and simulation of experimental studies. In the corresponding boundary-value problem with nonlinear dynamic boundary conditions physical- chemical processes in the bulk and on the surface are taken into account: heating of the sample, diffusion in the bulk, hydrogen capture by defects, penetration from the bulk to the surface and desorption. The model aimed to analyze the dynamics of hydrogen concentrations without preliminary artificial sample saturation. Numerical modelling allows to choose the point on the extraction curve that corresponds to the initial quantity of the surface hydrogen, to estimate the values of the activation energies of diffusion, desorption, parameters of reversible capture and hydride phase decomposition.

Integrated conversion of food waste diluted with sewage into volatile fatty acids through fermentation and electricity through a fuel cell.

PubMed

Pant, Deepak; Arslan, Doga; Van Bogaert, Gilbert; Gallego, Yolanda Alvarez; De Wever, Heleen; Diels, Ludo; Vanbroekhoven, Karolien

2013-01-01

In this study, domestic wastewater was given a second life as dilution medium for concentrated organic waste streams, in particular artificial food waste. A two-step continuous process with first volatile fatty acid (VFA)/hydrogen production and second electricity production in microbial fuel cells (MFCs) was employed. For primary treatment, bioreactors were optimized to produce hydrogen and VFAs. Hydrolysis of the solids and formation of fermentation products and hydrogen was monitored. In the second step, MFCs were operated batch-wise using the effluent rich in VFAs specifically acetic acid from the continuous reactor of the first step. The combined system was able to reduce the chemical oxygen demand load by 90%. The concentration of VFAs was also monitored regularly in the MFCs and showed a decreasing trend over time. Further, the anode potential changed from -500 to OmV vs. Ag/AgCl when the VFAs (especially acetate) were depleted in the system. On feeding the system again with the effluent, the anode potential recovered back to -500 mV vs. Ag/AgCl. Thus, the overall aim of converting chemical energy into electrical energy was achieved with a columbic efficiency of 46% generating 65.33 mA/m2 at a specific cell potential of 148 mV.

Kinetics of Hydrogen Diffusion in LaNi(sub 5-x)Sn(sub x) Alloys

NASA Technical Reports Server (NTRS)

Ratnakumar, B. V.; Hightower, A.; Witham, C.; Bowman, R. C.; Fultz, B.

1996-01-01

Solid-state diffusion of hydrogen in metal hydride (MH) alloys is recognized as the rate determining step in the discharge of MH alloys in alkaline Ni-MH rechargeable cells. In our pursuit of new ternary solutes in LaNi(sub 5) for extended cycle lifetimes, we have observed noticeable improvement in the cycle life with small substitutions of Sn and Ge for Ni. Furthermore, these substituents also facilitate enhanced charge transfer kinetics for hydriding-dehydriding process. In this paper, we report our studies on the kinetics of hydrogen diffusion in LaNi(sub 5-x) Sn(sub x) alloys by electrochemical pulse techniques, chronoamperometry and chronocoulometry.

Electrochemically hydrogenated TiO2 nanotubes with improved photoelectrochemical water splitting performance

PubMed Central

2013-01-01

One-dimensional anodic titanium oxide (ATO) nanotube arrays hold great potential as photoanode for photoelectrochemical (PEC) water splitting. In this work, we report a facile and eco-friendly electrochemical hydrogenation method to modify the electronic and PEC properties of ATO nanotube films. The hydrogenated ATO (ATO-H) electrodes present a significantly improved photocurrent of 0.65 mA/cm2 in comparison with that of pristine ATO nanotubes (0.29 mA/cm2) recorded under air mass 1.5 global illumination. The incident photon-to-current efficiency measurement suggests that the enhanced photocurrent of ATO-H nanotubes is mainly ascribed to the improved photoactivity in the UV region. We propose that the electrochemical hydrogenation induced surface oxygen vacancies contribute to the substantially enhanced electrical conductivity and photoactivity. PMID:24047205

Quantum diffusion of H/D on Ni(111)—A partially adiabatic centroid MD study

NASA Astrophysics Data System (ADS)

Hopkinson, A. R.; Probert, M. I. J.

2018-03-01

We present the results of a theoretical study of H/D diffusion on a Ni(111) surface at a range of temperatures, from 250 K to 75 K. The diffusion is studied using both classical molecular dynamics and the partially adiabatic centroid molecular dynamics method. The calculations are performed with the hydrogen (or deuterium) moving in 3D across a static nickel surface using a novel Fourier interpolated potential energy surface which has been parameterized to density functional theory calculations. The results of the classical simulations are that the calculated diffusion coefficients are far too small and with too large a variation with temperature compared with experiment. By contrast, the quantum simulations are in much better agreement with experiment and show that quantum effects in the diffusion of hydrogen are significant at all temperatures studied. There is also a crossover to a quantum-dominated diffusive regime for temperatures below ˜150 K for hydrogen and ˜85 K for deuterium. The quantum diffusion coefficients are found to accurately reproduce the spread in values with temperature, but with an absolute value that is a little high compared with experiment.

Hydrogenated vacancies lock dislocations in aluminium

PubMed Central

Xie, Degang; Li, Suzhi; Li, Meng; Wang, Zhangjie; Gumbsch, Peter; Sun, Jun; Ma, Evan; Li, Ju; Shan, Zhiwei

2016-01-01

Due to its high diffusivity, hydrogen is often considered a weak inhibitor or even a promoter of dislocation movements in metals and alloys. By quantitative mechanical tests in an environmental transmission electron microscope, here we demonstrate that after exposing aluminium to hydrogen, mobile dislocations can lose mobility, with activating stress more than doubled. On degassing, the locked dislocations can be reactivated under cyclic loading to move in a stick-slip manner. However, relocking the dislocations thereafter requires a surprisingly long waiting time of ∼103 s, much longer than that expected from hydrogen interstitial diffusion. Both the observed slow relocking and strong locking strength can be attributed to superabundant hydrogenated vacancies, verified by our atomistic calculations. Vacancies therefore could be a key plastic flow localization agent as well as damage agent in hydrogen environment. PMID:27808099

Analysis of opposed jet hydrogen-air counter flow diffusion flame

NASA Technical Reports Server (NTRS)

Ho, Y. H.; Isaac, K. M.

1989-01-01

A computational simulation of the opposed-jet diffusion flame is performed to study its structure and extinction limits. The present analysis concentrates on the nitrogen-diluted hydrogen-air diffusion flame, which provides the basic information for many vehicle designs such as the aerospace plane for which hydrogen is a candidate as the fuel. The computer program uses the time-marching technique to solve the energy and species equations coupled with the momentum equation solved by the collocation method. The procedure is implemented in two stages. In the first stage, a one-step forward overal chemical reaction is chosen with the gas phase chemical reaction rate determined by comparison with experimental data. In the second stage, a complete chemical reaction mechanism is introduced with detailed thermodynamic and transport property calculations. Comparison between experimental extinction data and theoretical predictions is discussed. The effects of thermal diffusion as well as Lewis number and Prandtl number variations on the diffusion flame are also presented.

Electrode Reaction Pathway in Oxide Anode for Solid Oxide Fuel Cells

NASA Astrophysics Data System (ADS)

Li, Wenyuan

Oxide anodes for solid oxide fuel cells (SOFC) with the advantage of fuel flexibility, resistance to coarsening, small chemical expansion and etc. have been attracting increasing interest. Good performance has been reported with a few of perovskite structure anodes, such as (LaSr)(CrMn)O3. However, more improvements need to be made before meeting the application requirement. Understanding the oxidation mechanism is crucial for a directed optimization, but it is still on the early stage of investigation. In this study, reaction mechanism of oxide anodes is investigated on doped YCrO 3 with H2 fuel, in terms of the origin of electrochemical activity, rate-determining steps (RDS), extension of reactive zone, and the impact from overpotential under service condition to those properties. H2 oxidation on the YCs anodes is found to be limited by charge transfer and H surface diffusion. A model is presented to describe the elementary steps in H2 oxidation. From the reaction order results, it is suggested that any models without taking H into the charge transfer step are invalid. The nature of B site element determines the H2 oxidation kinetics primarily. Ni displays better adsorption ability than Co. However, H adsorption ability of such oxide anode is inferior to that of Ni metal anode. In addition, the charge transfer step is directly associated with the activity of electrons in the anode; therefore it can be significantly promoted by enhancement of the electron activity. It is found that A site Ca doping improves the polarization resistance about 10 times, by increasing the activity of electrons to promote the charge transfer process. For the active area in the oxide anode, besides the traditional three-phase boundary (3PB), the internal anode surface as two-phase boundary (2PB) is proven to be capable of catalytically oxidizing the H2 fuel also when the bulk lattice is activated depending on the B site elements. The contribution from each part is estimated by switching the electrolyte to change 3PB kinetics. Compared to Ni, Co doping activates the bulk oxygen more significantly, promoting the reaction at 2PB. The active surface reaction zone is found to be enlarged by the electrolyte with high oxygen activity (SSZ vs. YSZ) when charge transfer is one of the RDS. Due to the larger exchange current for charge transfer in 3PB with SSZ electrolyte, the adsorption gradient zone is broadened, leading to enhanced surface reaction kinetics. The potential application of such finding is demonstrated on SSZ/YSZ/SSZ sandwich, showing largely improved electrode performance, opening a wide door for the utilization of electrolytes that are too expensive, fragile or instable to be used before. The bulk path way in 2PB reaction can be affected by overpotential in terms of local vacancy concentration, built-in electrical field and stability. It is proven that an uneven distribution of lattice oxygen is established under operation conditions with overpotential by both qualitative analysis and analytic solution. An electrostatic field force is present besides the concentration gradient in the anode lattice to control the motion of oxygen ions. Compared to the usual estimation based on chemical diffusion mechanism, the real deviation of ionic defects concentration under polarization from the equilibrium state near electrode/electrolyte interface is smaller with the built-in electrical field. The overpotential is demonstrated to be able to open up or shut down the bulk pathway depending on the ionic defects of electrodes. The analysis on the bulk pathway in terms of local charged species and various potentials provides new insight in anion diffusion and electrode stability.

Effects of Zn-In-Sn elements on the electric properties of magnesium alloy anode materials.

PubMed

Yu, Zhan; Ju, Dongying; Zhao, Hongyang; Hu, Xiaodong

2011-06-01

A new magnesium alloy anode is based on an environmentally friendly electrode that contains none of mercury, lead and chromate, but it can enhance the electric properties of alloy significantly. Magnesium alloy adding eco-friendly elements Zn-In-Sn which was developed by orthogonal design were obtained by two casting methods. The effect of additive elements on performance of electrode material was studied. The effects of elements addition and casting method on electric properties and corrosive properties of Mg-Zn-In-Sn alloys were investigated by using electrochemical measurements, corrosive tests and observation of surface structure. The results show that Mg-Zn-In-Sn alloy anode has higher electromotive force and more stable work potential than that commercial magnesium alloy AZ91. It is suitable for anode material of magnesium battery for its small hydrogen evolution, less self-corrosion rate and easy to shed corrosive offspring off. Copyright © 2011 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Impact of cell design and operating conditions on the performances of SOFC fuelled with methane

NASA Astrophysics Data System (ADS)

Laurencin, J.; Lefebvre-Joud, F.; Delette, G.

An in-house-model has been developed to study the thermal and electrochemical behaviour of a planar SOFC fed directly with methane and incorporated in a boiler. The usual Ni-YSZ cermet has been considered for the anode material. It has been found that methane reforming into hydrogen occurs only at the cell inlet in a limited depth within the anode. A sensitivity analysis has allowed establishing that anode thicknesses higher than ∼400-500 μm are required to achieve both the optimal methane conversion and electrochemical performances. The direct internal reforming (DIR) mechanisms and the impact of operating conditions on temperature gradients and SOFC electrical efficiencies have been investigated considering the anode supported cell configuration. It has been shown that the temperature gradient is minimised in the autothermal mode of cell operation. Thermal equilibrium in the stack has been found to be strongly dependent on radiative heat losses with the stack envelope. Electrochemical performance and cell temperature maps have been established as a function of methane flow rates and cell voltages.

Synthesis of Li2Ti3O7 Anode Materials by Ultrasonic Spray Pyrolysis and Their Electrochemical Properties

PubMed Central

Ogihara, Takashi; Kodera, Takayuki

2013-01-01

Ramsdellite-type lithium titanate (Li2Ti3O7) powders were synthesized by performing ultrasonic spray pyrolysis, and their chemical and physical properties were characterized by performing Scanning Electron Microscope (SEM), powder X-ray Diffraction (XRD), and Inductively Coupled Plasma (ICP) analyses. The as-prepared Li2Ti3O7 precursor powders had spherical morphologies with hollow microstructures, but an irregularly shaped morphology was obtained after calcination above 900 °C. The ramsdellite Li2Ti3O7 crystal phase was obtained after the calcination at 1100 °C under an argon/hydrogen atmosphere. The first rechargeable capacity of the Li2Ti3O7 anode material was 168 mAh/g at 0.1 C and 82 mAh/g at 20 C, and the discharge capacity retention ratio was 99% at 1 C after the 500th cycle. The cycle performance of the Li2Ti3O7 anode was also highly stable at 50 °C, demonstrating the superiority of Li2Ti3O7 anode materials reported previously. PMID:28809274

Controlled surface diffusion in plasma-enhanced chemical vapor deposition of GaN nanowires.

PubMed

Hou, Wen Chi; Hong, Franklin Chau-Nan

2009-02-04

This study investigates the growth of GaN nanowires by controlling the surface diffusion of Ga species on sapphire in a plasma-enhanced chemical vapor deposition (CVD) system. Under nitrogen-rich growth conditions, Ga has a tendency to adsorb on the substrate surface diffusing to nanowires to contribute to their growth. The significance of surface diffusion on the growth of nanowires is dependent on the environment of the nanowire on the substrate surface as well as the gas phase species and compositions. Under nitrogen-rich growth conditions, the growth rate is strongly dependent on the surface diffusion of gallium, but the addition of 5% hydrogen in nitrogen plasma instantly diminishes the surface diffusion effect. Gallium desorbs easily from the surface by reaction with hydrogen. On the other hand, under gallium-rich growth conditions, nanowire growth is shown to be dominated by the gas phase deposition, with negligible contribution from surface diffusion. This is the first study reporting the inhibition of surface diffusion effects by hydrogen addition, which can be useful in tailoring the growth and characteristics of nanowires. Without any evidence of direct deposition on the nanowire surface, gallium and nitrogen are shown to dissolve into the catalyst for growing the nanowires at 900 degrees C.

Building one-dimensional oxide nanostructure arrays on conductive metal substrates for lithium-ion battery anodes.

PubMed

Jiang, Jian; Li, Yuanyuan; Liu, Jinping; Huang, Xintang

2011-01-01

Lithium ion battery (LIB) is potentially one of the most attractive energy storage devices. To meet the demands of future high-power and high-energy density requirements in both thin-film microbatteries and conventional batteries, it is challenging to explore novel nanostructured anode materials instead of conventional graphite. Compared to traditional electrodes based on nanostructure powder paste, directly grown ordered nanostructure array electrodes not only simplify the electrode processing, but also offer remarkable advantages such as fast electron transport/collection and ion diffusion, sufficient electrochemical reaction of individual nanostructures, enhanced material-electrolyte contact area and facile accommodation of the strains caused by lithium intercalation and de-intercalation. This article provides a brief overview of the present status in the area of LIB anodes based on one-dimensional nanostructure arrays growing directly on conductive inert metal substrates, with particular attention to metal oxides synthesized by an anodized alumina membrane (AAM)-free solution-based or hydrothermal methods. Both the scientific developments and the techniques and challenges are critically analyzed.

Building one-dimensional oxidenanostructure arrays on conductive metal substrates for lithium-ion battery anodes

NASA Astrophysics Data System (ADS)

Jiang, Jian; Li, Yuanyuan; Liu, Jinping; Huang, Xintang

2011-01-01

Lithium ion battery (LIB) is potentially one of the most attractive energy storage devices. To meet the demands of future high-power and high-energy density requirements in both thin-film microbatteries and conventional batteries, it is challenging to explore novel nanostructured anode materials instead of conventional graphite. Compared to traditional electrodes based on nanostructure powder paste, directly grown ordered nanostructure array electrodes not only simplify the electrode processing, but also offer remarkable advantages such as fast electron transport/collection and ion diffusion, sufficient electrochemical reaction of individual nanostructures, enhanced material-electrolyte contact area and facile accommodation of the strains caused by lithium intercalation and de-intercalation. This article provides a brief overview of the present status in the area of LIB anodes based on one-dimensional nanostructure arrays growing directly on conductive inert metal substrates, with particular attention to metal oxides synthesized by an anodized aluminamembrane (AAM)-free solution-based or hydrothermal methods. Both the scientific developments and the techniques and challenges are critically analyzed.

Atom-Level Understanding of the Sodiation Process in Silicon Anode Material.

PubMed

Jung, Sung Chul; Jung, Dae Soo; Choi, Jang Wook; Han, Young-Kyu

2014-04-03

Despite the exceptionally large capacities in Li ion batteries, Si has been considered inappropriate for applications in Na ion batteries. We report an atomic-level study on the applicability of a Si anode in Na ion batteries using ab initio molecular dynamics simulations. While crystalline Si is not suitable for alloying with Na atoms, amorphous Si can accommodate 0.76 Na atoms per Si atom, corresponding to a specific capacity of 725 mA h g(-1). Bader charge analyses reveal that the sodiation of an amorphous Si electrode continues until before the local Na-rich clusters containing neutral Na atoms are formed. The amorphous Na0.76Si phase undergoes a volume expansion of 114% and shows a Na diffusivity of 7 × 10(-10) cm(2) s(-1) at room temperature. Overall, the amorphous Si phase turns out quite attractive in performance compared to other alloy-type anode materials. This work suggests that amorphous Si might be a competitive candidate for Na ion battery anodes.

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.

Hydrogen generation having CO₂ removal with steam reforming

DOEpatents

Kandaswamy, Duraiswamy; Chellappa, Anand S.; Knobbe, Mack

2015-07-28

A method for producing hydrogen using fuel cell off gases, the method feeding hydrocarbon fuel to a sulfur adsorbent to produce a desulfurized fuel and a spent sulfur adsorbent; feeding said desulfurized fuel and water to an adsorption enhanced reformer that comprises of a plurality of reforming chambers or compartments; reforming said desulfurized fuel in the presence of a one or more of a reforming catalyst and one or more of a CO₂ adsorbent to produce hydrogen and a spent CO₂ adsorbent; feeding said hydrogen to the anode side of the fuel cell; regenerating said spent CO₂ adsorbents using the fuel cell cathode off-gases, producing a flow of hydrogen by cycling between said plurality of reforming chambers or compartments in a predetermined timing sequence; and, replacing the spent sulfur adsorbent with a fresh sulfur adsorbent at a predetermined time.

Electrolytic systems and methods for making metal halides and refining metals

DOEpatents

Holland, Justin M.; Cecala, David M.

2015-05-26

Disclosed are electrochemical cells and methods for producing a halide of a non-alkali metal and for electrorefining the halide. The systems typically involve an electrochemical cell having a cathode structure configured for dissolving a hydrogen halide that forms the halide into a molten salt of the halogen and an alkali metal. Typically a direct current voltage is applied across the cathode and an anode that is fabricated with the non-alkali metal such that the halide of the non-alkali metal is formed adjacent the anode. Electrorefining cells and methods involve applying a direct current voltage across the anode where the halide of the non-alkali metal is formed and the cathode where the non-alkali metal is electro-deposited. In a representative embodiment the halogen is chlorine, the alkali metal is lithium and the non-alkali metal is uranium.

Investigation of a subsonic-arc-attachment thruster using segmented anodes

NASA Technical Reports Server (NTRS)

Berns, Darren H.; Sankovic, John M.; Sarmiento, Charles J.

1993-01-01

To investigate high frequency arc instabilities observed in subsonic-arc-attachment thrusters, a 3 kW, segmented-anode arc jet was designed and tested using hydrogen as the propellant. The thruster nozzle geometry was scaled from a 30 kW design previously tested in the 1960's. By observing the current to each segment and the arc voltage, it was determined that the 75-200 kHz instabilities were results of axial movements of the arc anode attachment point. The arc attachment point was fully contained in the subsonic portion of the nozzle for nearly all flow rates. The effects of isolating selected segments were investigated. In some cases, forcing the arc downstream caused the restrike to cease. Finally, decreasing the background pressure from 18 to 0.05 Pa affected the pressure distribution in the nozzle including the pressure in the subsonic arc chamber.

Investigation of a subsonic-arc-attachment thruster using segmented anodes

NASA Technical Reports Server (NTRS)

Berns, Darren H.; Sankovic, John M.; Sarmiento, Charles J.

1993-01-01

To investigate high frequency arc instabilities observed in subsonic-arc-attachment thrusters, a 3 kW, segmented-anode arcjet was designed and tested using hydrogen as the propellant. The thruster nozzle geometry was scaled from a 30 kW design previously tested in the 1960's. By observing the current to each segment and the arc voltage, it was determined that the 75-200 kHz instabilities were results of axial movements of the arc anode attachment point. The arc attachment point was fully contained in the subsonic portion of the nozzle for nearly all flow rates. The effects of isolating selected segments were investigated. In some cases, forcing the arc downstream caused the restrike to cease. Finally, decreasing the background pressure from 18 Pa to 0.05 Pa affected the pressure distribution in the nozzle, including the pressure in the subsonic arc chamber.

Electrolytic Migration of Ag-Pd Alloy Wires with Various Pd Contents

NASA Astrophysics Data System (ADS)

Lin, Yan-Cheng; Chen, Chun-Hao; He, Yu-Zhen; Chen, Sheng-Chi; Chuang, Tung-Han

2018-07-01

During Ag ion migration in an aqueous water drop covering a pair of parallel Ag-Pd wires under current stressing, hydrogen bubbles form first from the cathode, followed by the appearance of pure Ag dendrites on the cathodic wire. In this study, Ag dendrites with a diameter of 0.2-0.4 μm grew toward the anodic wire. The growth rate ( v) of these dendrites decreased with the Pd content ( c) with a linear relationship of: v = 10.02 - 0.43 c . Accompanying the growth of pure Ag dendrites was the formation of a continuous layer of crystallographic Ag2O particles on the surface of the anodic wire. The deposition of such insulating Ag2O products did not prevent the contact of Ag dendrites with the anodic Ag-Pd wire or the short circuit of the wire couple.

Electrolytic Migration of Ag-Pd Alloy Wires with Various Pd Contents

NASA Astrophysics Data System (ADS)

Lin, Yan-Cheng; Chen, Chun-Hao; He, Yu-Zhen; Chen, Sheng-Chi; Chuang, Tung-Han

2018-03-01

During Ag ion migration in an aqueous water drop covering a pair of parallel Ag-Pd wires under current stressing, hydrogen bubbles form first from the cathode, followed by the appearance of pure Ag dendrites on the cathodic wire. In this study, Ag dendrites with a diameter of 0.2-0.4 μm grew toward the anodic wire. The growth rate (v) of these dendrites decreased with the Pd content (c) with a linear relationship of: v = 10.02 - 0.43 c . Accompanying the growth of pure Ag dendrites was the formation of a continuous layer of crystallographic Ag2O particles on the surface of the anodic wire. The deposition of such insulating Ag2O products did not prevent the contact of Ag dendrites with the anodic Ag-Pd wire or the short circuit of the wire couple.

Electrochemical separation and concentration of sulfur containing gases from gas mixtures

DOEpatents

Winnick, Jack

1981-01-01

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.sup.= or, in the case of H.sub.2 S, to S.sup.=. 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.

Ni-Al Protective Coating of Steel Electrodes in Dc Electrolysis for Hydrogen Production / Ni-Al Pārklājuma Ietekme Uz Tērauda Elektrodiem Līdzstrāvas Elektrolīzē Ūdeņraža Ražošanai

NASA Astrophysics Data System (ADS)

Aizpurietis, P.; Vanags, M.; Kleperis, J.; Bajars, G.

2013-04-01

Hydrogen can be a good alternative to fossil fuels under the conditions of world's crisis as an effective energy carrier derived from renewable resources. Among all the known methods of hydrogen production, water electrolysis gives the ecologically purest hydrogen, so it is of importance to maximize the efficiency of this process. The authors consider the influence of plasma sprayed Ni-Al protective coating of 316L steel anode-cathode electrodes in DC electrolysis. In a long-term (24 h) process the anode corrodes strongly, losing Cr and Ni ions which are transferred to the electrolyte, while only minor corrosion of the cathode occurs. At the same time, the composition of anode and cathode electrodes protected by Ni-Al coating changes only slightly during a prolonged electrolysis. As the voltammetry and Tafel plots evidence, the Ni-Al coating protects both the anode and cathode from the corrosion and reduces the potential of hydrogen evolution. The results obtained show that such a coating works best in the case of steel electrodes. Darbā pētīts, kā līdzstrāvas elektrolīzē tērauda 316L elektrodus (anods un katods) ietekmē ar plazmas izputināšanas metodi iegūts Ni-Al pārklājums. Tikko uznestam pārklājumam ir mikrostrukturēta virsma, kas kodināšanas laikā mainās, gan pēc reljefa, gan elementu sastāva. Veicot ilgstošu (24 stundas elektrolīzi), atrasts, ka tikai tērauda elektrods anoda lomā intensīvi korodē un zaudē hroma un niķeļa jonus, kas pāriet elektrolītā, turpretī katods mainās relatīvi maz. Pārklājums Ni-Al pēc uznešanas tiek kodināts karstā sārmā, kad tiek izšķīdināta daļa sastāvā esošo elementu (Al, Si, Cd), bet ilgstošas elektrolīzes laikā pārklājuma sastāvs mainās maz gan anodam, gan katodam. Elektrodu elektroķīmiskie raksturlielumi noteikti ar voltamperometrijas un Tāfeļa līkņu analīzes metodēm. Atrasts, ka Ni-Al pārklājums aizsargā gan anodu, gan katodu no korozijas un samazina ūdeņraža izdalīšanās potenciālu, lai gan ilgstošas elektrolīzes laikā katoda pārklājumā parādās plaisas. No iegūtajiem rezultātiem ieteikts reālai elektrolīzes šūnai par anodu un katodu izmantot tēraudu, kas pārklāts ar plazmas izputināšanas metodē iegūtu Ni-Al aizsargpārklājumu.

Ambient pressure fuel cell system

DOEpatents

Wilson, Mahlon S.

2000-01-01

An ambient pressure fuel cell system is provided with a fuel cell stack formed from a plurality of fuel cells having membrane/electrode assemblies (MEAs) that are hydrated with liquid water and bipolar plates with anode and cathode sides for distributing hydrogen fuel gas and water to a first side of each one of the MEAs and air with reactant oxygen gas to a second side of each one of the MEAs. A pump supplies liquid water to the fuel cells. A recirculating system may be used to return unused hydrogen fuel gas to the stack. A near-ambient pressure blower blows air through the fuel cell stack in excess of reaction stoichiometric amounts to react with the hydrogen fuel gas.

Preparation and evaluation of advanced electrocatalysts for phosphoric acid fuel cells

NASA Technical Reports Server (NTRS)

Stonehart, P.; Baris, J.; Hochmuth, J.; Pagliaro, P.

1981-01-01

A number of electrocatalyst combinations were prepared and characterized. These electrocatalysts were formulated to contain platinum combined with transition metal carbide forming elements (W, Mo, V) for cathodes and platinum combined with palladium for anodes. High resolution electron microscopy was used to determine the crystallite size and dispersion of platinum-palladium alloy electrocatalysts in order to provide analytical support for the electrochemical determinations of the particle dispersions. An equation was derived which correlates palladium crystallite size with electrochemical hydrogen adsorption. Based on comparisons of electrocatalyst performances in the presence of pure hydrogen and hydrogen containing carbon monoxide, it was shown that the apparent poisoning of the electrocatalyst by carbon monoxide is influenced by the electrode structure.

Life test results for an ensemble of CO2 lasers

NASA Technical Reports Server (NTRS)

Peruso, C. J.; Degnan, J. J.; Hochuli, U. E.

1978-01-01

The effects of cathode material, cathode operating temperature, anode configuration, window materials, and hydrogen additives on laser lifetime are determined. Internally oxidized copper and silber-copper alloy cathodes were tested. The cathode operating temperature was raised in some tubes through the use of thermal insulation. Lasers incorporating thermally insulated silver copper oxide cathodes clearly yielded the longest lifetimes-typically in excess of 22,000 hours. The use of platinum sheet versus platinum pin anodes had no observable effect on laser lifetime. Similarly, the choice of germanium, cadmium telluride, or zinc selenide as the optical window material appears to have no impact on lifetime.

100-kW class applied-field MPD thruster component wear

NASA Technical Reports Server (NTRS)

Mantenieks, Maris A.; Myers, Roger M.

1993-01-01

Component erosion and material deposition sites were identified and analyzed during tests of various configurations of 100 kW class, applied-field, water-cooled magnetoplasmadynamic (MPD) thrusters. Severe erosion of the cathode and the boron nitride insulator was observed for the first series of tests, which was significantly decreased by reducing the levels of propellant contamination. Severe erosion of the copper anode resulting from sputtering by the propellant was also observed. This is the first observation of this phenomenon in MPD thrusters. The anode erosion indicates that development of long life MPD thrusters requires the use of light gas propellants such as hydrogen, deuterium, or lithium.

Computer simulations of adsorption and diffusion for binary mixtures of methane and hydrogen in titanosilicates.

PubMed

Mitchell, Martha C; Gallo, Marco; Nenoff, Tina M

2004-07-22

Equilibrium molecular dynamics (MD) simulations of equimolar mixtures of hydrogen and methane were performed in three different titanosilicates: naturally occurring zorite and two synthetic titanosilicates, ETS-4 and ETS-10. In addition, single-component MD simulations and adsorption isotherms generated using grand canonical Monte Carlo simulations were performed to support the mixture simulations. The goal of this study was to determine the best membrane material to carry out hydrogen/methane separations. ETS-10 has a three-dimensional pore network. ETS-4 and zorite have two-dimensional pore networks. The simulations carried out in this study show that the increased porosity of ETS-10 results in self-diffusion coefficients for both hydrogen and methane that are higher in ETS-10 than in either ETS-4 or zorite. Methane only showed appreciable displacement in ETS-10. The ability of the methane molecules to move in all three directions in ETS-10 was demonstrated by the high degree of isotropy shown in the values of the x, y, and z components of the self-diffusion coefficient for methane in ETS-10. From our simulations we conclude that ETS-10 would be better suited for fast industrial separations of hydrogen and methane. However, the separation would not result in a pure hydrogen stream. In contrast, ETS-4 and zorite would act as true molecular sieves for separations of hydrogen and methane, as the methane would not move through membranes made of these materials. This was indicated by the near-zero self-diffusion coefficient of methane in ETS-4 and zorite.

Computer simulations of adsorption and diffusion for binary mixtures of methane and hydrogen in titanosilicates

NASA Astrophysics Data System (ADS)

Mitchell, Martha C.; Gallo, Marco; Nenoff, Tina M.

2004-07-01

Equilibrium molecular dynamics (MD) simulations of equimolar mixtures of hydrogen and methane were performed in three different titanosilicates: naturally occurring zorite and two synthetic titanosilicates, ETS-4 and ETS-10. In addition, single-component MD simulations and adsorption isotherms generated using grand canonical Monte Carlo simulations were performed to support the mixture simulations. The goal of this study was to determine the best membrane material to carry out hydrogen/methane separations. ETS-10 has a three-dimensional pore network. ETS-4 and zorite have two-dimensional pore networks. The simulations carried out in this study show that the increased porosity of ETS-10 results in self-diffusion coefficients for both hydrogen and methane that are higher in ETS-10 than in either ETS-4 or zorite. Methane only showed appreciable displacement in ETS-10. The ability of the methane molecules to move in all three directions in ETS-10 was demonstrated by the high degree of isotropy shown in the values of the x, y, and z components of the self-diffusion coefficient for methane in ETS-10. From our simulations we conclude that ETS-10 would be better suited for fast industrial separations of hydrogen and methane. However, the separation would not result in a pure hydrogen stream. In contrast, ETS-4 and zorite would act as true molecular sieves for separations of hydrogen and methane, as the methane would not move through membranes made of these materials. This was indicated by the near-zero self-diffusion coefficient of methane in ETS-4 and zorite.

Enhancement in hydrogen evolution using Au-TiO2 hollow spheres with microbial devices modified with conjugated oligoelectrolytes

PubMed Central

Ngaw, Chee Keong; Wang, Victor Bochuan; Liu, Zhengyi; Zhou, Yi; Kjelleberg, Staffan; Zhang, Qichun; Tan, Timothy Thatt Yang; Loo, Say Chye Joachim

2015-01-01

Objective: Although photoelectrochemical (PEC) water splitting heralds the emergence of the hydrogen economy, the need for external bias and low efficiency stymies the widespread application of this technology. By coupling water splitting (in a PEC cell) to a microbial fuel cell (MFC) using Escherichia coli as the biocatalyst, this work aims to successfully demonstrate a sustainable hybrid PEC–MFC platform functioning solely by biocatalysis and solar energy, at zero bias. Through further chemical modification of the photo-anode (in the PEC cell) and biofilm (in the MFC), the performance of the hybrid system is expected to improve in terms of the photocurrent generated and hydrogen evolved. Methods: The hybrid system constitutes the interconnected PEC cell with the MFC. Both PEC cell and MFC are typical two-chambered systems housing the anode and cathode. Au-TiO2 hollow spheres and conjugated oligoelectrolytes were synthesised chemically and introduced to the PEC cell and MFC, respectively. Hydrogen evolution measurements were performed in triplicates. Results: The hybrid PEC–MFC platform generated a photocurrent density of 0.35 mA/cm2 (~70× enhancement) as compared with the stand-alone P25 standard PEC cell (0.005 mA/cm2) under one-sun illumination (100 mW/cm2) at zero bias (0 V vs. Pt). This increase in photocurrent density was accompanied by continuous H2 production. No H2 was observed in the P25 standard PEC cell whereas H2 evolution rate was ~3.4 μmol/h in the hybrid system. The remarkable performance is attributed to the chemical modification of E. coli through the incorporation of novel conjugated oligoelectrolytes in the MFC as well as the lower recombination rate and higher photoabsorption capabilities in the Au-TiO2 hollow spheres electrode. Conclusions: The combined strategy of photo-anode modification in PEC cells and chemically modified MFCs shows great promise for future exploitation of such synergistic effects between MFCs and semiconductor-based PEC water splitting. PMID:28721235

Electrochemical investigation of stainless steel corrosion in a proton exchange membrane electrolyzer cell

DOE PAGES

Mo, Jingke; Steen, Stuart M.; Zhang, Feng-Yuan; ...

2015-08-05

The lack of a fundamental understanding of the corrosion mechanisms in the electrochemical environments of proton exchange membrane (PEM) electrolyzer and/or fuel cells (ECs/FCs) has seriously hindered the improvement of performance and efficiency of PEM ECs/FCs. In this study, a stainless steel mesh was purposely used as an anode gas diffusion layer that was intentionally operated with high positive potentials under harsh oxidative environments in a PEMEC to study the corrosion mechanism of metal migration. A significant amount of iron and nickel cations were determined to transport through the anode catalyst layer, the PEM and the cathode catalyst layer duringmore » the PEMEC operation. The formation/deposition of iron oxide and nickel oxide on the carbon paper gas diffusion layer at the cathode side is first revealed by both scanning electron microscope and X-ray diffraction. The results indicate the corrosion elements of iron and nickel are transported from anode to cathode through the catalyst-coated membrane, and deposited on carbon fibers as oxides. This phenomenon could also open a new corrosion-based processing approach to potentially fabricate multifunctional oxide structures on carbon fiber devices. This study has demonstrated a new accelerated test method for investigating the corrosion and durability of metallic materials as well.« less

Electrochemical investigation of stainless steel corrosion in a proton exchange membrane electrolyzer cell

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

Mo, Jingke; Steen, Stuart M.; Zhang, Feng-Yuan

The lack of a fundamental understanding of the corrosion mechanisms in the electrochemical environments of proton exchange membrane (PEM) electrolyzer and/or fuel cells (ECs/FCs) has seriously hindered the improvement of performance and efficiency of PEM ECs/FCs. In this study, a stainless steel mesh was purposely used as an anode gas diffusion layer that was intentionally operated with high positive potentials under harsh oxidative environments in a PEMEC to study the corrosion mechanism of metal migration. A significant amount of iron and nickel cations were determined to transport through the anode catalyst layer, the PEM and the cathode catalyst layer duringmore » the PEMEC operation. The formation/deposition of iron oxide and nickel oxide on the carbon paper gas diffusion layer at the cathode side is first revealed by both scanning electron microscope and X-ray diffraction. The results indicate the corrosion elements of iron and nickel are transported from anode to cathode through the catalyst-coated membrane, and deposited on carbon fibers as oxides. This phenomenon could also open a new corrosion-based processing approach to potentially fabricate multifunctional oxide structures on carbon fiber devices. This study has demonstrated a new accelerated test method for investigating the corrosion and durability of metallic materials as well.« less

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

Chen, Yinshan; Zhu, Men; Laventure, Audrey

Surface grating decay measurements have been performed on three closely related molecular glasses to study the effect of intermolecular hydrogen bonds on surface diffusion. The three molecules are derivatives of bis(3,5-dimethyl-phenylamino)-1,3,5-triazine and differ only in the functional group R at the 2-position, with R being C 2H 5, OCH 3, and NHCH 3, and referred to as “Et”, “OMe”, and “NHMe”, respectively. Of the three molecules, NHMe forms more extensive intermolecular hydrogen bonds than Et and OMe and was found to have slower surface diffusion. For Et and OMe, surface diffusion is so fast that it replaces viscous flow asmore » the mechanism of surface grating decay as temperature is lowered. In contrast, no such transition was observed for NHMe under the same conditions, indicating significantly slower surface diffusion. This result is consistent with the previous finding that extensive intermolecular hydrogen bonds slow down surface diffusion in molecular glasses and is attributed to the persistence of hydrogen bonds even in the surface environment. Here, this result is also consistent with the lower stability of the vapor-deposited glass of NHMe relative to those of Et and OMe and supports the view that surface mobility controls the stability of vapor-deposited glasses.« less

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.

Investigation of Local Hydrogen Uptake in Rescaled Model Occluded Sites Using Crevice Scaling Laws

DTIC Science & Technology

2005-04-01

13- 8 Mo . Under anodic polarization, there is a combination of x and G in a crevice or crack where the stainless steel would be passive and remain...2004). 8 . G.A. Young, Jr., J.R. Scully, "The Effects of Test Temperature , Temper and Alloyed Copper on Hydrogen Controlled Crack Growth of an A1-Zn-Mg...sharp crack tip.[16] Precipitation-aged hardened martensitic stainless steels (i.e., Fe-Cr-Ni- Mo alloys) that release hydrolysable Cr and Fe cations

Optimization of the electrochemical performance of a Ni/Ce0.9Gd0.1O2-δ-impregnated La0.57Sr0.15TiO3 anode in hydrogen

NASA Astrophysics Data System (ADS)

Xia, Tian; Brüll, Annelise; Grimaud, Alexis; Fourcade, Sébastien; Mauvy, Fabrice; Zhao, Hui; Grenier, Jean-Claude; Bassat, Jean-Marc

2014-09-01

A-site deficient perovskite La0.57Sr0.15TiO3 (LSTO) materials are synthesized by a modified polyacrylamide gel route. X-ray diffraction pattern of LSTO indicates an orthorhombic structure. The thermal expansion coefficient of LSTO is 10.0 × 10-6 K-1 at 600 °C in 5%H2/Ar. LSTO shows an electrical conductivity of 2 S cm-1 at 600 °C in 3%H2O/H2. A new composite material, containing the porous LSTO backbone impregnated with small amounts of Ce0.9Gd0.1O2-δ (CGO) (3.4-8.3 wt.%) and Ni/Cu (2.0-6.3 wt.%), is investigated as an alternative anode for solid oxide fuel cells (SOFCs). Because of the substantial electro-catalytic activity of the fine and well-dispersed Ni particles on the surface of the ceramic framework, the polarization resistance of 6.3%Ni-8.3%CGO-LSTO anode reaches 0.73 Ω cm2 at 800 °C in 3%H2O/H2. In order to further improve the anodic performance, corn starch and carbon black are used as pore-formers to optimize the microstructure of anodes.

Advances in catalysts for internal reforming in high temperature fuel cells

NASA Astrophysics Data System (ADS)

Dicks, A. L.

Catalytic steam reforming of natural gas is an attractive method of producing the hydrogen required by the present generation of fuel cells. The molten carbonate (MCFC) and solid oxide (SOFC) fuel cells operate at high enough temperatures for the endothermic steam reforming reaction to be carried out within the stack. For the MCFC, the conventional anodes have insufficient activity to catalyse the steam reforming of natural gas. For these cells, internal reforming can be achieved only with the addition of a separate catalyst, preferably located in close proximity to the anode. However, in the so-called `Direct Internal Reforming' configuration, attack from alkali in the MCFC may severely limit catalyst lifetime. In the case of the state-of-the-art SOFC, natural gas can be reformed directly on the nickel cermet anode. However, in the SOFC, temperature variations in the cell caused by the reforming reaction may limit the amount of internal reforming that can be allowed in practice. In addition, some external pre-reforming may be desirable to remove high molecular weight hydrocarbons from the fuel gas, which would otherwise crack to produce elemental carbon. Degradation of the SOFC anode may also be a problem when internal reforming is carried out. This has prompted several research groups to investigate the use of alternative anode materials.

Molecular dynamics investigation of dynamical properties of phosphatidylethanolamine lipid bilayers

NASA Astrophysics Data System (ADS)

Pitman, Michael C.; Suits, Frank; Gawrisch, Klaus; Feller, Scott E.

2005-06-01

We describe the dynamic behavior of a 1-stearoyl-2-oleoyl-phosphatidylethanolamine (SOPE) bilayer from a 20ns molecular dynamics simulation. The dynamics of individual molecules are characterized in terms of H2 spin-lattice relaxation rates, nuclear overhauser enhancement spectroscopy (NOESY) cross-relaxation rates, and lateral diffusion coefficients. Additionally, we describe the dynamics of hydrogen bonding through an analysis of hydrogen bond lifetimes and the time evolution of clusters of hydrogen bonded lipids. The simulated trajectory is shown to be consistent with experimental measures of internal, intermolecular, and diffusive motion. Consistent with our analysis of SOPE structure in the companion paper, we see hydrogen bonding dominating the dynamics of the interface region. Comparison of H2 T1 relaxation rates for chain methylene segments in phosphatidylcholine and phosphatidylethanolamine bilayers indicates that slower motion resulting from hydrogen bonding extends at least three carbons into the hydrophobic core. NOESY cross-relaxation rates compare well with experimental values, indicating the observed hydrogen bonding dynamics are realistic. Calculated lateral diffusion rates (4±1×10-8cm2/s) are comparable, though somewhat lower than, those determined by pulsed field gradient NMR methods.

Hydrogen Diffusion and Trapping in α -Iron: The Role of Quantum and Anharmonic Fluctuations

NASA Astrophysics Data System (ADS)

Cheng, Bingqing; Paxton, Anthony T.; Ceriotti, Michele

2018-06-01

We investigate the thermodynamics and kinetics of a hydrogen interstitial in magnetic α -iron, taking account of the quantum fluctuations of the proton as well as the anharmonicities of lattice vibrations and hydrogen hopping. We show that the diffusivity of hydrogen in the lattice of bcc iron deviates strongly from an Arrhenius behavior at and below room temperature. We compare a quantum transition state theory to explicit ring polymer molecular dynamics in the calculation of diffusivity. We then address the trapping of hydrogen by a vacancy as a prototype lattice defect. By a sequence of steps in a thought experiment, each involving a thermodynamic integration, we are able to separate out the binding free energy of a proton to a defect into harmonic and anharmonic, and classical and quantum contributions. We find that about 30% of a typical binding free energy of hydrogen to a lattice defect in iron is accounted for by finite temperature effects, and about half of these arise from quantum proton fluctuations. This has huge implications for the comparison between thermal desorption and permeation experiments and standard electronic structure theory. The implications are even greater for the interpretation of muon spin resonance experiments.

Hydrogenated vacancies lock dislocations in aluminium

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

Xie, Degang; Li, Suzhi; Li, Meng

Due to its high diffusivity, hydrogen is often considered a weak inhibitor or even a promoter of dislocation movements in metals and alloys. By quantitative mechanical tests in an environmental transmission electron microscope, here we demonstrate that after exposing aluminium to hydrogen, mobile dislocations can lose mobility, with activating stress more than doubled. On degassing, the locked dislocations can be reactivated under cyclic loading to move in a stick-slip manner. However, relocking the dislocations thereafter requires a surprisingly long waiting time of ~10 3 s, much longer than that expected from hydrogen interstitial diffusion. Both the observed slow relocking andmore » strong locking strength can be attributed to superabundant hydrogenated vacancies, verified by our atomistic calculations. In conclusion, vacancies therefore could be a key plastic flow localization agent as well as damage agent in hydrogen environment.« less

Hydrogenated vacancies lock dislocations in aluminium

DOE PAGES

Xie, Degang; Li, Suzhi; Li, Meng; ...

2016-11-03

Due to its high diffusivity, hydrogen is often considered a weak inhibitor or even a promoter of dislocation movements in metals and alloys. By quantitative mechanical tests in an environmental transmission electron microscope, here we demonstrate that after exposing aluminium to hydrogen, mobile dislocations can lose mobility, with activating stress more than doubled. On degassing, the locked dislocations can be reactivated under cyclic loading to move in a stick-slip manner. However, relocking the dislocations thereafter requires a surprisingly long waiting time of ~10 3 s, much longer than that expected from hydrogen interstitial diffusion. Both the observed slow relocking andmore » strong locking strength can be attributed to superabundant hydrogenated vacancies, verified by our atomistic calculations. In conclusion, vacancies therefore could be a key plastic flow localization agent as well as damage agent in hydrogen environment.« less

Effect of Ti Substrate Ion Implantation on the Physical Properties of Anodic TiO2 Nanotubes

NASA Astrophysics Data System (ADS)

Jedi-Soltanabadi, Zahra; Ghoranneviss, Mahmood; Ghorannevis, Zohreh; Akbari, Hossein

2018-03-01

The influence of nitrogen-ion implantation on the titanium (Ti) surface is studied. The nontreated Ti and the Ti treated with ion implantation were anodized in an ethylene-glycol-based electrolyte solution containing 0.3 wt% ammonium fluoride (NH4F) and 3 vol% deionized (DI) water at a potential of 60 V for 1 h at room temperature. The current density during the growth of the TiO2 nanotubes was monitored in-situ. The surface roughnesses of the Ti substrates before and after the ion implantation were investigated with atomic force microscopy (AFM). The surface roughness was lower for the treated Ti substrate. The morphology of the anodic TiO2 nanotubes was studied by using field-emission scanning electron microscopy (FESEM). Clearly, the titanium nanotubes grown on the treated substrate were longer. In addition, some ribs were observed on their walls. The optical band gap of the anodic TiO2 nanotubes was characterized by using a diffuse reflection spectral (DRS) analysis. The anodic TiO2 nanotubes grown on the treated Ti substrate revealed a band gap energy of approximately 3.02 eV.

Elaborate strategy for preparing Li4Ti5O12-based anode materials with significantly improved lithium storage: TiO2 nanodots in-situ decoration and hierarchical structure construction

NASA Astrophysics Data System (ADS)

Xu, Hui; Tian, Qinghua; Huang, Jun; Bao, Dongmei; Zhang, Zhengxi; Yang, Li

2017-11-01

Spinel Li4Ti5O12 (LTO) has attracted extensive attention as potential anode materials for power lithium-ion batteries due to its outstanding structural stability and remarkable safety. However, it's practical application yet be limited by such disadvantages of dissatisfied specific capacity, poor electron conductivity and low lithium-ion diffusion coefficient. Thus, design and preparation of LTO anodes with desirable performance is still a challenge. Herein, we have successfully and greatly improved the performance of LTO anodes, in terms of rate capability, life and specific capacity in particular via dot-to-face anatase TiO2in-situ decoration and hierarchical structure construction under a facile approach (directly using the tetrabutyl titanate as titanium source instead of specially prepared titanium oxide precursors). The as-prepared LTO-based anode (denoted as T-LTO) delivers an ultra-high reversible specific capacity of 196.5 mAh g-1 after 300 cycles at 20 mA g-1, and superior rate performance and even ultra-long life of more than 145.8 mAh g-1 at 28.5C between 1.0 and 3.0 V. The achieved outstanding electrochemical performance largely surpasses that of reportedly state-of-the-art LTO-based anode materials. This work may open up a broader vision into developing advanced LTO-based anode materials for lithium-ion batteries.

Understanding of ammonia transport in PEM fuel cells

NASA Astrophysics Data System (ADS)

Jung, Myunghee

This dissertation investigates ammonia (NH3) as a fuel contaminant to the anode in Proton Exchange Membrane Fuel Cells (PEMFCs). Since NH 3 is fed to the anode in a gas phase and transferred to the cathode, the effect of a contaminant is distributed through MEA and quite complicated. This study is focused on the investigation of mechanism of NH3 transport and the isolation of multiple effects to degrade the performance of fuel cell. An External Reference Electrode (ERE) was employed to decouple the effect of individual electrode and explain the mechanism of NH3 contamination. A mechanism of NH3 transport is proposed and supported by data for various inlet conditions in a N2/N2 laboratory-scale fuel cell at Open Circuit Conditions (OCC). With a commercialized GORE(TM) PRIMEA RTM 5631 MEAs at 70°C, data were obtained utilizing a material balance technique, which uses an ion selective electrode (ISE) to determine the concentration of ammonium ion in the process streams. The results indicate that ammonia is not transported across the membrane when the feeds to both electrodes are dry. However, with humidified feeds ammonia was transported from the anode to the cathode. The data also indicate the water content of in the MEA is the critical factor that causes NH3 crossover in the MEA. Diffusion coefficients of NH3 in MEA are also calculated at different relative humilities. An ERE was developed for PEM fuel cell by using a NafionRTM strip which was used to understand contamination mechanism. The voltage of anode electrode relative to ERE was measured during a polarization curve. The data showed the measurement of individual electrode potential was extremely affected by the misalignment between two electrodes. We compare the overpotential measured from the reference electrode and the calculated overpotential from subtracting the cell voltages between neat hydrogen and a 25 ppm CO in H 2 stream at same current. The studies indicated that the overpotentials obtained from two different methods were same and the location of a Nafion RTM strip on MEA did not affect the measured overpotentials. When NH3 was introduced as a contaminant to the cell at OCC, the thermodynamic potential of the anode electrode was measured for GORETM PRIMEARTM 57 series MEA at 80°C. High Frequency Resistance (HFR) and material balance were also analyzed during the change of thermodynamic potential. The results show that the injected NH3 was absorbed in the MEA until the ion exchange capacity was fully saturated and then NH 3 reaction occurred on the electrode. Finally, we studied how NH 3 contamination process occurs from transient voltage changes of the cell and an individual electrode.

Effects of direct current on dog liver: Possible mechanisms for tumor electrochemical treatment

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

Li, K.H.; Gu, Y.N.; Xu, B.I.

1997-03-01

Mechanisms of tumor electrochemical treatment (ECT) were studied using normal dog liver. Five physical and chemical methods were used. Two platinum electrodes were inserted into an anesthetized dog`s liver at 3 cm separation. A voltage of 8.5 V direct current (DC) at an average current of 30 mA was applied for 69 min; total charge was 124 coulombs. Concentrations of selected ions near the anode and cathode were measured. The concentrations of Na{sup +} and K{sup +} ions were higher around the cathode, whereas the concentration of Cl{sup {minus}} ions was higher around the anode. Water contents and pH weremore » determined near the anode and the cathode at the midpoint between the two electrodes and in an untreated area away from the electrodes. Hydration occurred around the cathode, and dehydration occurred around the anode. The pH values were 2.1 near the anode and 12.9 near the cathode. Spectrophotometric scans of the liver sample extract were obtained, and the released gases were identified by gas chromatography as chlorine at the anode and hydrogen at the cathode. These results indicate that a series of electrochemical reactions take place during ECT. The cell metabolism and its environment are severely disturbed. Both normal and tumor cells are rapidly and completely destroyed in this altered environment. The authors believe that the above reactions are the ECT mechanisms for treating tumors.« less

A Review: Enhanced Anodes of Li/Na-Ion Batteries Based on Yolk-Shell Structured Nanomaterials

NASA Astrophysics Data System (ADS)

Wu, Cuo; Tong, Xin; Ai, Yuanfei; Liu, De-Sheng; Yu, Peng; Wu, Jiang; Wang, Zhiming M.

2018-09-01

Lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs) have received much attention in energy storage system. In particular, among the great efforts on enhancing the performance of LIBs and SIBs, yolk-shell (YS) structured materials have emerged as a promising strategy toward improving lithium and sodium storage. YS structures possess unique interior void space, large surface area and short diffusion distance, which can solve the problems of volume expansion and aggregation of anode materials, thus enhancing the performance of LIBs and SIBs. In this review, we present a brief overview of recent advances in the novel YS structures of spheres, polyhedrons and rods with controllable morphology and compositions. Enhanced electrochemical performance of LIBs and SIBs based on these novel YS structured anode materials was discussed in detail. [Figure not available: see fulltext.

Fluorinated Electrolytes for Li-S Battery: Suppressing the Self-Discharge with an Electrolyte Containing Fluoroether Solvent

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

Azimi, N.; Xue, Z.; Rago, N. D.

The fluorinated electrolyte containing a fluoroether 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) was investigated as a new electrolyte for lithium-sulfur (Li-S) batteries. The low solubility of lithium polysulfides (LiPS) in the fluorinated electrolyte reduced the parasitic reactions with Li anode and mitigated the self-discharge by limiting their diffusion from the cathode to the anode. The use of fluorinated ether as a co-solvent and LiNO3 as an additive in the electrolyte shows synergetic effect in suppressing the self-discharge of Li-S battery due to the formation of the solid electrolyte interphase (SEI) on both sulfur cathode and the lithium anode. The Li-S cell with themore » fluorinated electrolyte showed prolonged shelf life at fully charged state.« less

Oxygen-consuming chlor alkali cell configured to minimize peroxide formation

DOEpatents

Chlistunoff, Jerzy B [Los Alamos, NM; Lipp, Ludwig [Brookfield, CT; Gottesfeld, Shimshon [Niskayuna, NY

2006-08-01

Oxygen-consuming zero gap chlor-alkali cell was configured to minimize peroxide formation. The cell included an ion-exchange membrane that divided the cell into an anode chamber including an anode and a cathode chamber including an oxygen gas diffusion cathode. The cathode included a single-piece of electrically conducting graphitized carbon cloth. Catalyst and polytetrafluoroethylene were attached to only one side of the cloth. When the cathode was positioned against the cation exchange membrane with the catalyst side away from the membrane, electrolysis of sodium chloride to chlorine and caustic (sodium hydroxide) proceeded with minimal peroxide formation.

Polarization-Induced Interfacial Reactions between Nickel and Selenium in Ni/Zirconia SOFC Anodes and Comparison with Sulfur Poisoning

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

Marina, Olga A.; Pederson, Larry R.; Coyle, Christopher A.

2011-01-10

Three distinctly different characteristic responses of a nickel/yttria-stabilized zirconia (Ni/YSZ) cermet anode to the presence of hydrogen selenide in synthetic coal gas were observed, depending on temperature (650-800oC), H2Se concentration (0-40 ppm), and especially on the extent of anodic polarization (0 to ~0.5 V). The first level of response was characterized by a rapid but modest decrease in power density to a new steady state, with no further degradation observed in tests up to 700 hours in duration. Mostly observed at high temperatures, low H2Se concentrations, and low anodic polarizations, this response level was similar to effects caused by themore » presence of H2S, but with slower onset and lower reversibility. Higher anodic polarization at a constant current could trigger a second level of response characterized by oscillatory behavior involving cycles of rapid performance loss followed by rapid recovery. Oscillations at the constant current density were accompanied by the appearance and disappearance of a new feature in the electrochemical impedance spectrum with a summit frequency of ~100 Hz. Oscillatory behavior ceased when the current density was lowered. Such behavior was not observed for cells operated at a constant potential of similar magnitude, though. A third level of response, irreversible cell failure, could be induced by further increases in anodic polarization, additionally favored by low temperature and high H2Se concentration. Post-test analyses of failed cells by electron microscopy revealed the extensive microstructural changes including the appearance of nickel oxide and nickel selenide alteration phases, only at the anode/electrolyte interface. From bulk thermochemical considerations the formation of nickel selenides could not be expected. Local chemical conditions created at the anode/electrolyte interface appear to be of overriding importance with respect to the extent of Ni/YSZ anode interactions with H2Se in coal gas.« less