Kinetic Monte Carlo simulations of electrodeposition: Crossover from continuous to instantaneous homogeneous nucleation within Avrami’s law

NASA Astrophysics Data System (ADS)

Frank, Stefan; Rikvold, Per Arne

2006-06-01

The influence of lateral adsorbate diffusion on the dynamics of the first-order phase transition in a two-dimensional Ising lattice gas with attractive nearest-neighbor interactions is investigated by means of kinetic Monte Carlo simulations. For example, electrochemical underpotential deposition proceeds by this mechanism. One major difference from adsorption in vacuum surface science is that under control of the electrode potential and in the absence of mass-transport limitations, local adsorption equilibrium is approximately established. We analyze our results using the theory of Kolmogorov, Johnson and Mehl, and Avrami (KJMA), which we extend to an exponentially decaying nucleation rate. Such a decay may occur due to a suppression of nucleation around existing clusters in the presence of lateral adsorbate diffusion. Correlation functions prove the existence of such exclusion zones. By comparison with microscopic results for the nucleation rate I and the interface velocity of the growing clusters v, we can show that the KJMA theory yields the correct order of magnitude for Iv2. This is true even though the spatial correlations mediated by diffusion are neglected. The decaying nucleation rate causes a gradual crossover from continuous to instantaneous nucleation, which is complete when the decay of the nucleation rate is very fast on the time scale of the phase transformation. Hence, instantaneous nucleation can be homogeneous, producing negative minima in the two-point correlation functions. We also present in this paper an n-fold way Monte Carlo algorithm for a square lattice gas with adsorption/desorption and lateral diffusion.

CAD/CAM-designed 3D-printed electroanalytical cell for the evaluation of nanostructured gas-diffusion electrodes.

PubMed

Chervin, Christopher N; Parker, Joseph F; Nelson, Eric S; Rolison, Debra R; Long, Jeffrey W

2016-04-29

The ability to effectively screen and validate gas-diffusion electrodes is critical to the development of next-generation metal-air batteries and regenerative fuel cells. The limiting electrode in a classic two-terminal device such as a battery or fuel cell is difficult to discern without an internal reference electrode, but the flooded electrolyte characteristic of three-electrode electroanalytical cells negates the prime function of an air electrode-a void volume freely accessible to gases. The nanostructured catalysts that drive the energy-conversion reactions (e.g., oxygen reduction and evolution in the air electrode of metal-air batteries) are best evaluated in the electrode structure as-used in the practical device. We have designed, 3D-printed, and characterized an air-breathing, thermodynamically referenced electroanalytical cell that allows us to mimic the Janus arrangement of the gas-diffusion electrode in a metal-air cell: one face freely exposed to gases, the other wetted by electrolyte.

CAD/CAM-designed 3D-printed electroanalytical cell for the evaluation of nanostructured gas-diffusion electrodes

NASA Astrophysics Data System (ADS)

Chervin, Christopher N.; Parker, Joseph F.; Nelson, Eric S.; Rolison, Debra R.; Long, Jeffrey W.

2016-04-01

The ability to effectively screen and validate gas-diffusion electrodes is critical to the development of next-generation metal-air batteries and regenerative fuel cells. The limiting electrode in a classic two-terminal device such as a battery or fuel cell is difficult to discern without an internal reference electrode, but the flooded electrolyte characteristic of three-electrode electroanalytical cells negates the prime function of an air electrode—a void volume freely accessible to gases. The nanostructured catalysts that drive the energy-conversion reactions (e.g., oxygen reduction and evolution in the air electrode of metal-air batteries) are best evaluated in the electrode structure as-used in the practical device. We have designed, 3D-printed, and characterized an air-breathing, thermodynamically referenced electroanalytical cell that allows us to mimic the Janus arrangement of the gas-diffusion electrode in a metal-air cell: one face freely exposed to gases, the other wetted by electrolyte.

Core-shell fuel cell electrodes

DOEpatents

Adzic, Radoslav; Bliznakov, Stoyan; Vukmirovic, Miomir

2017-12-26

Embodiments of the disclosure relate to membrane electrode assemblies. The membrane electrode assembly may include at least one gas-diffusion layer having a first side and a second side, and particle cores adhered to at least one of the first and second sides of the at least one gas-diffusion layer. The particle cores includes surfaces adhered to the at least one of the first and second sides of the at least one gas-diffusion layer and surfaces not in contact with the at least one gas-diffusion layer. Furthermore, a thin layer of catalytically atoms may be adhered to the surfaces of the particle cores not in contact with the at least one gas-diffusion layer.

Protein Electrochemistry: Questions and Answers.

PubMed

Fourmond, V; Léger, C

This chapter presents the fundamentals of electrochemistry in the context of protein electrochemistry. We discuss redox proteins and enzymes that are not photoactive. Of course, the principles described herein also apply to photobioelectrochemistry, as discussed in later chapters of this book. Depending on which experiment is considered, electron transfer between proteins and electrodes can be either direct or mediated, and achieved in a variety of configurations: with the protein and/or the mediator free to diffuse in solution, immobilized in a thick, hydrated film, or adsorbed as a sub-monolayer on the electrode. The experiments can be performed with the goal to study the protein or to use it. Here emphasis is on mechanistic studies, which are easier in the configuration where the protein is adsorbed and electron transfer is direct, but we also explain the interpretation of signals obtained when diffusion processes affect the response.This chapter is organized as a series of responses to questions. Questions 1-5 are related to the basics of electrochemistry: what does "potential" or "current" mean, what does an electrochemical set-up look like? Questions 6-9 are related to the distinction between adsorbed and diffusive redox species. The answers to questions 10-13 explain the interpretation of slow and fast scan voltammetry with redox proteins. Questions 14-19 deal with catalytic electrochemistry, when the protein studied is actually an enzyme. Questions 20, 21 and 22 are general.

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.

Transient nanobubbles in short-time electrolysis

NASA Astrophysics Data System (ADS)

Svetovoy, Vitaly B.; Sanders, Remco G. P.; Elwenspoek, Miko C.

2013-05-01

Water electrolysis in a microsystem is observed and analyzed on a short-time scale of ∼10 μs. The very unusual properties of the process are stressed. An extremely high current density is observed because the process is not limited by the diffusion of electroactive species. The high current is accompanied by a high relative supersaturation, S > 1000, that results in homogeneous nucleation of bubbles. On the short-time scale only nanobubbles can be formed. These nanobubbles densely cover the electrodes and aggregate at a later time to microbubbles. The effect is significantly intensified with a small increase of temperature. Application of alternating polarity voltage pulses produces bubbles containing a mixture of hydrogen and oxygen. Spontaneous reaction between gases is observed for stoichiometric bubbles with sizes smaller than ∼150 nm. Such bubbles disintegrate violently affecting the surfaces of the electrodes.

Effect of Electrode Configuration on Nitric Oxide Gas Sensor Behavior.

PubMed

Cui, Ling; Murray, Erica P

2015-09-23

The influence of electrode configuration on the impedancemetric response of nitric oxide (NO) gas sensors was investigated for solid electrochemical cells [Au/yttria-stabilized zirconia (YSZ)/Au)]. Fabrication of the sensors was carried out at 1050 °C in order to establish a porous YSZ electrolyte that enabled gas diffusion. Two electrode configurations were studied where Au wire electrodes were either embedded within or wrapped around the YSZ electrolyte. The electrical response of the sensors was collected via impedance spectroscopy under various operating conditions where gas concentrations ranged from 0 to 100 ppm NO and 1%-18% O₂ at temperatures varying from 600 to 700 °C. Gas diffusion appeared to be a rate-limiting mechanism in sensors where the electrode configuration resulted in longer diffusion pathways. The temperature dependence of the NO sensors studied was independent of the electrode configuration. Analysis of the impedance data, along with equivalent circuit modeling indicated the electrode configuration of the sensor effected gas and ionic transport pathways, capacitance behavior, and NO sensitivity.

Recipes for lateral spin transport between magnetic contacts, advantage of carbon-based materials.

NASA Astrophysics Data System (ADS)

Fert, Albert

2010-03-01

After the presentation of magneto-transport results [1] on metallic carbon nanotubes (CNT) between LSMO electrodes (MR 60-70%, [VAP -- VP] 60mV), I will discuss the general problem of spin transport in a nonmagnetic lateral channel between spin-polarized contacts in both the diffusive and ballistic regimes. In the diffusive regime, a treatment by the classical drift-diffusion equations applied to a multi-terminal structure is used to calculate what can be expected for the output signal with local or non-local voltage probes. A general result is that the output signal (δR = δV/I where δV is the local or non-local output voltage), directly related to the spin accumulation splitting in the channel, scales with the smallest of the relevant spin and interfaces resistances. In the best situation, that is with only tunnel contacts having the same (large) resistance RT and separated by less than the spin diffusion length (λ) in a lateral channel limited to the zone of the contacts, the signal δR increases in proportion of RT as long as the dwell time is smaller than the spin lifetime. δR can be thus much larger than the spin resistance of the channel (product of its resistivity by the ratio λ/section ). This explain why, in the experiments of Ref.[1] on CNT, δR can be as large as 90 Mφ, that is of the order of the tunnel contact resistances and much larger than the spin resistance of the CNT (smaller signals in experiments with CNT or graphene are often due the leak of spin accumulation in lateral channels extending too far outside the contacts). The relative disadvantage for semiconductors comes from the too long dwell time due to much smaller electron velocities than in metallic CNTs (and graphene). We will conclude by a similar analysis of the ballistic regime and a discussion of experiments with graphene. [4pt] [1] Hueso et al, Nature 445, 410 (2007).

Nickel-hydrogen battery with oxygen and electrolyte management features

DOEpatents

Sindorf, John F.

1991-10-22

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

Diffusion welded nonconsumable electrode assembly and use thereof for electrolytic production of metals and silicon

DOEpatents

Byrne, Stephen C.; Vasudevan, Asuri K.

1984-01-01

A nonconsumable electrode assembly suitable for use in the production of metal by electrolytic reduction of a metal compound dissolved in a molten salt, the assembly comprising a metal conductor diffusion welded to a portion of a ceramic electrode body having a level of free metal or metal alloy sufficient to effect a metal bond.

Electrocatalytic performance of fuel cell reactions at low catalyst loading and high mass transport.

PubMed

Zalitis, Christopher M; Kramer, Denis; Kucernak, Anthony R

2013-03-28

An alternative approach to the rotating disk electrode (RDE) for characterising fuel cell electrocatalysts is presented. The approach combines high mass transport with a flat, uniform, and homogeneous catalyst deposition process, well suited for studying intrinsic catalyst properties at realistic operating conditions of a polymer electrolyte fuel cell (PEFC). Uniform catalyst layers were produced with loadings as low as 0.16 μgPt cm(-2) and thicknesses as low as 200 nm. Such ultra thin catalyst layers are considered advantageous to minimize internal resistances and mass transport limitations. Geometric current densities as high as 5.7 A cm(-2)Geo were experimentally achieved at a loading of 10.15 μgPt cm(-2) for the hydrogen oxidation reaction (HOR) at room temperature, which is three orders of magnitude higher than current densities achievable with the RDE. Modelling of the associated diffusion field suggests that such high performance is enabled by fast lateral diffusion within the electrode. The electrodes operate over a wide potential range with insignificant mass transport losses, allowing the study of the ORR at high overpotentials. Electrodes produced a specific current density of 31 ± 9 mA cm(-2)Spec at a potential of 0.65 V vs. RHE for the oxygen reduction reaction (ORR) and 600 ± 60 mA cm(-2)Spec for the peak potential of the HOR. The mass activity of a commercial 60 wt% Pt/C catalyst towards the ORR was found to exceed a range of literature PEFC mass activities across the entire potential range. The HOR also revealed fine structure in the limiting current range and an asymptotic current decay for potentials above 0.36 V. These characteristics are not visible with techniques limited by mass transport in aqueous media such as the RDE.

High Speed, Low Cost Fabrication of Gas Diffusion Electrodes for Membrane Electrode Assemblies

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

DeCastro, Emory S.; Tsou, Yu-Min; Liu, Zhenyu

Fabrication of membrane electrode assemblies (MEAs) depends on creating inks or pastes of catalyst and binder, and applying this suspension to either the membrane (catalyst coated membrane) or gas diffusion media (gas diffusion electrode) and respectively laminating either gas diffusion media or gas diffusion electrodes (GDEs) to the membrane. One barrier to cost effective fabrication for either of these approaches is the development of stable and consistent suspensions. This program investigated the fundamental forces that destabilize the suspensions and developed innovative approaches to create new, highly stable formulations. These more concentrated formulations needed fewer application passes, could be coated overmore » longer and wider substrates, and resulted in significantly lower coating defects. In March of 2012 BASF Fuel Cell released a new high temperature product based on these advances, whereby our customers received higher performing, more uniform MEAs resulting in higher stack build yields. Furthermore, these new materials resulted in an “instant” increase in capacity due to higher product yields and material throughput. Although not part of the original scope of this program, these new formulations have also led us to materials that demonstrate equivalent performance with 30% less precious metal in the anode. This program has achieved two key milestones in DOE’s Manufacturing R&D program: demonstration of processes for direct coating of electrodes and continuous in-line measurement for component fabrication.« less

Native and sodium dodecyl sulfate-capillary gel electrophoresis of proteins on a single microchip.

PubMed

Tsai, Shuo-Wen; Loughran, Michael; Suzuki, Hiroaki; Karube, Isao

2004-02-01

Simultaneous electrophoresis of both native and Sodium dodecyl sulfate (SDS) proteins was observed on a single microchip within 20 min. The capillary array prevented lateral diffusion of SDS components and avoided cross contamination of native protein samples. The planar sputtered electrode format provided a more uniform distribution of separation voltage into each of the 36 parallel microchannel capillaries than platinum wire electrodes commonly used in conventional electrophoresis. The customized geometry of the stacking capillary machined into the cover plate of the microchip facilitated reproducible sample injection without the requirement for stacking gel. Polyimide served as a mask and facilitated insulation of the anode and cathode to prevent electrode lift off and deterioration during continuous electrophoresis, even at a constant current of 8 mA. Improved protein separation was observed during capillary electrophoresis at lower currents. Ferguson plot analysis confirmed the electrophoretic mobility of native globular proteins in accordance with their charge and size. Corresponding Ferguson plot analysis of SDS-associated proteins on the same chip confirmed separation of marker proteins according to their molecular weight.

Electrodes for microfluidic applications

DOEpatents

Crocker, Robert W [Fremont, CA; Harnett, Cindy K [Livermore, CA; Rognlien, Judith L [Livermore, CA

2006-08-22

An electrode device for high pressure applications. These electrodes, designed to withstand pressure of greater than 10,000 psi, are adapted for use in microfluidic devices that employ electrokinetic or electrophoretic flow. The electrode is composed, generally, of an outer electrically insulating tubular body having a porous ceramic frit material disposed in one end of the outer body. The pores of the porous ceramic material are filled with an ion conductive polymer resin. A conductive material situated on the upper surface of the porous ceramic frit material and, thus isolated from direct contact with the electrolyte, forms a gas diffusion electrode. A metal current collector, in contact with the gas diffusion electrode, provides connection to a voltage source.

Superstructures and multijunction cells for high efficiency energy conversion

NASA Technical Reports Server (NTRS)

Wagner, M.; Leburton, J. P.

1985-01-01

Potential applications of superlattices to photovoltaic structures are discussed. A single-bandgap, multijunction cell with selective electrodes for lateral transport of collected carriers is proposed. The concept is based on similar doping superlattice (NIPI) structures. Computer simulations show that by reducing bulk recombination losses, the spectral response of such cells is enhanced, particularly for poor quality materials with short diffusion lengths. Dark current contributions of additional junctions result in a trade-off between short-circuit current and open-circuit voltage as the number of layers is increased. One or two extra junctions appear to be optimal.

Understanding and improving lithium ion batteries through mathematical modeling and experiments

NASA Astrophysics Data System (ADS)

Deshpande, Rutooj D.

There is an intense, worldwide effort to develop durable lithium ion batteries with high energy and power densities for a wide range of applications, including electric and hybrid electric vehicles. For improvement of battery technology understanding the capacity fading mechanism in batteries is of utmost importance. Novel electrode material and improved electrode designs are needed for high energy- high power batteries with less capacity fading. Furthermore, for applications such as automotive applications, precise cycle-life prediction of batteries is necessary. One of the critical challenges in advancing lithium ion battery technologies is fracture and decrepitation of the electrodes as a result of lithium diffusion during charging and discharging operations. When lithium is inserted in either the positive or negative electrode, there is a volume change associated with insertion or de-insertion. Diffusion-induced stresses (DISs) can therefore cause the nucleation and growth of cracks, leading to mechanical degradation of the batteries. With different mathematical models we studied the behavior of diffusion induces stresses and effects of electrode shape, size, concentration dependent material properties, pre-existing cracks, phase transformations, operating conditions etc. on the diffusion induced stresses. Thus we develop tools to guide the design of the electrode material with better mechanical stability for durable batteries. Along with mechanical degradation, chemical degradation of batteries also plays an important role in deciding battery cycle life. The instability of commonly employed electrolytes results in solid electrolyte interphase (SEI) formation. Although SEI formation contributes to irreversible capacity loss, the SEI layer is necessary, as it passivates the electrode-electrolyte interface from further solvent decomposition. SEI layer and diffusion induced stresses are inter-dependent and affect each-other. We study coupled chemical-mechanical degradation of electrode materials to understand the capacity fading of the battery with cycling. With the understanding of chemical and mechanical degradation, we develop a simple phenomenological model to predict battery life. On the experimental part we come up with a novel concept of using liquid metal alloy as a self-healing battery electrode. We develop a method to prepare thin film liquid gallium electrode on a conductive substrate. This enabled us to perform a series of electrochemical and characterization experiments which certify that liquid electrode undergo liquid-solid-liquid transition and thus self-heals the cracks formed during de-insertion. Thus the mechanical degradation can be avoided. We also perform ab-initio calculations to understand the equilibrium potential of various lithium-gallium phases. KEYWORDS: Lithium ion batteries, diffusion induced stresses, self-healing electrode, coupled chemical and mechanical degradation, life-prediction model.

Layered materials with improved magnesium intercalation for rechargeable magnesium ion cells

DOEpatents

Doe, Robert Ellis; Downie, Craig Michael; Fischer, Christopher; Lane, George Hamilton; Morgan, Dane; Nevin, Josh; Ceder, Gerbrand; Persson, Kristin Aslaug; Eaglesham, David

2015-10-27

Electrochemical devices which incorporate cathode materials that include layered crystalline compounds for which a structural modification has been achieved which increases the diffusion rate of multi-valent ions into and out of the cathode materials. Examples in which the layer spacing of the layered electrode materials is modified to have a specific spacing range such that the spacing is optimal for diffusion of magnesium ions are presented. An electrochemical cell comprised of a positive intercalation electrode, a negative metal electrode, and a separator impregnated with a nonaqeuous electrolyte solution containing multi-valent ions and arranged between the positive electrode and the negative electrode active material is described.

On the meaning of the diffusion layer thickness for slow electrode reactions.

PubMed

Molina, A; González, J; Laborda, E; Compton, R G

2013-02-21

A key concept underpinning electrochemical science is that of the diffusion layer - the zone of depletion around an electrode accompanying electrolysis. The size of this zone can be found either from the simulated or measured concentration profiles (yielding the 'true' diffusion layer thickness) or, in the case of the Nernst ('linear') diffusion layer by extrapolating the concentration gradient at the electrode surface to the distance at which the concentration takes its bulk value. The latter concept is very well developed in the case of fast (so-called reversible) electrode processes, however the study of the linear diffusion layer has received scant attention in the case of slow charge transfer processes, despite its study being of great interest in the analysis of the influence of different experimental variables which determine the electrochemical response. Analytical explicit solutions for the concentration profiles, surface concentrations and real and linear diffusion layers corresponding to the application of a potential step to a slow charge transfer process are presented. From these expressions the dependence of the diffusion layer thickness on the potential, pulse time, heterogeneous rate constant and ratio of bulk concentrations of electroactive species and of diffusion coefficients is quantified. A profound influence of the reversibility degree of the charge transfer on the diffusion layer thickness is clear, showing that for non-reversible processes the real and linear diffusion layers reveal a minimum thickness which coincides with the equilibrium potential of the redox couple in the former case and with the reversible half-wave potential in the latter one.

Twenty kW fuel cell units of compact design. Part 4: Accompanying research and development

NASA Astrophysics Data System (ADS)

Mund, K.

1980-10-01

Models describing the electrochemical kinetics at porous H2 and O2 electrodes using Raney nickel and silver catalysts were developed and their parameters determined by means of stationary and impedance measurements. A correct description of the hydrogen electrode with a Raney nickel catalyst is shown to encompass proper consideration of both diffusion in the pore electrolyte and surface diffusion. Impedance measurements yield a surface diffusion coefficient of 10 sub-8 cm2 S sub-1. The addition of titanium to the catalyst results in decreased electrode polarization and higher stability. Highly active doped silver catalysts are shown to allow high current densities and diaphragm resistances as low as 3 ohm cm at the oxygen electrode. Service tests show adequate stability of the catalysts.

Irreversible Electroporation in a Swine Lung Model

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

Dupuy, Damian E., E-mail: ddupuy@lifespan.org; Aswad, Bassam, E-mail: baswad@lifespan.org; Ng, Thomas, E-mail: tng@usasurg.org

2011-04-15

Purpose: This study was designed to evaluate the safety and tissue effects of IRE in a swine lung model. Methods: This study was approved by the institutional animal care committee. Nine anesthetized domestic swine underwent 15 percutaneous irreversible electroporation (IRE) lesion creations (6 with bipolar and 3 with 3-4 monopolar electrodes) under fluoroscopic guidance and with pancuronium neuromuscular blockade and EKG gating. IRE electrodes were placed into the central and middle third of the right mid and lower lobes in all animals. Postprocedure PA and lateral chest radiographs were obtained to evaluate for pneumothorax. Three animals were sacrificed at 2more » weeks and six at 4 weeks. Animals underwent high-resolution CT scanning and PA and lateral radiographs 1 h before sacrifice. The treated lungs were removed en bloc, perfused with formalin, and sectioned. Gross pathologic and microscopic changes after standard hematoxylin and eosin staining were analyzed within the areas of IRE lesion creation. Results: No significant adverse events were identified. CT showed focal areas of spiculated high density ranging in greatest diameter from 1.1-2.2 cm. On gross inspection of the sectioned lung, focal areas of tan discoloration and increased density were palpated in the areas of IRE. Histological analysis revealed focal areas of diffuse alveolar damage with fibrosis and inflammatory infiltration that respected the boundaries of the interlobular septae. No pathological difference could be discerned between the 2- and 4-week time points. The bronchioles and blood vessels within the areas of IRE were intact and did not show signs of tissue injury. Conclusion: IRE creates focal areas of diffuse alveolar damage without creating damage to the bronchioles or blood vessels. Short-term safety in a swine model appears to be satisfactory.« less

Development And Testing Of The Inertial Electrostatic Confinement Diffusion Thruster

NASA Technical Reports Server (NTRS)

Becnel, Mark D.; Polzin, Kurt A.

2013-01-01

The Inertial Electrostatic Confinement (IEC) diffusion thruster is an experiment in active development that takes advantage of physical phenomenon that occurs during operation of an IEC device. The IEC device has been proposed as a fusion reactor design that relies on traditional electrostatic ion acceleration and is typically arranged in a spherical geometry. The design incorporates two radially-symmetric spherical electrodes. Often the inner electrode utilizes a grid of wire shaped in a sphere with a radius 15 to 50 percent of the radius of the outer electrode. The inner electrode traditionally has 90 percent or more transparency to allow particles (ions) to pass to the center of the spheres and collide/recombine in the dense plasma core at r=0. When operating the IEC, an unsteady plasma leak is typically observed passing out one of the gaps in the lattice grid of the inner electrode. The IED diffusion thruster is based upon the idea that this plasma leak can be used for propulsive purposes. The IEC diffusion thruster utilizes the radial symmetry found in the IEC device. A cylindrical configuration is employed here as it will produce a dense core of plasma the length of the cylindrical grid while promoting the plasma leak to exhaust through an electromagnetic nozzle at one end of the apparatus. A proof-of-concept IEC diffusion thruster is operational and under testing using argon as propellant (Figure 1).

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.

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.

Numerical Simulation of the Diffusion Processes in Nanoelectrode Arrays Using an Axial Neighbor Symmetry Approximation.

PubMed

Peinetti, Ana Sol; Gilardoni, Rodrigo S; Mizrahi, Martín; Requejo, Felix G; González, Graciela A; Battaglini, Fernando

2016-06-07

Nanoelectrode arrays have introduced a complete new battery of devices with fascinating electrocatalytic, sensitivity, and selectivity properties. To understand and predict the electrochemical response of these arrays, a theoretical framework is needed. Cyclic voltammetry is a well-fitted experimental technique to understand the undergoing diffusion and kinetics processes. Previous works describing microelectrode arrays have exploited the interelectrode distance to simulate its behavior as the summation of individual electrodes. This approach becomes limited when the size of the electrodes decreases to the nanometer scale due to their strong radial effect with the consequent overlapping of the diffusional fields. In this work, we present a computational model able to simulate the electrochemical behavior of arrays working either as the summation of individual electrodes or being affected by the overlapping of the diffusional fields without previous considerations. Our computational model relays in dividing a regular electrode array in cells. In each of them, there is a central electrode surrounded by neighbor electrodes; these neighbor electrodes are transformed in a ring maintaining the same active electrode area than the summation of the closest neighbor electrodes. Using this axial neighbor symmetry approximation, the problem acquires a cylindrical symmetry, being applicable to any diffusion pattern. The model is validated against micro- and nanoelectrode arrays showing its ability to predict their behavior and therefore to be used as a designing tool.

Layered materials with improved magnesium intercalation for rechargeable magnesium ion cells

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

Doe, Robert E.; Downie, Craig M.; Fischer, Christopher

2016-01-19

Electrochemical devices which incorporate cathode materials that include layered crystalline compounds for which a structural modification has been achieved which increases the diffusion rate of multi-valent ions into and out of the cathode materials. Examples in which the layer spacing of the layered electrode materials is modified to have a specific spacing range such that the spacing is optimal for diffusion of magnesium ions are presented. An electrochemical cell comprised of a positive intercalation electrode, a negative metal electrode, and a separator impregnated with a nonaqueous electrolyte solution containing multi-valent ions and arranged between the positive electrode and the negativemore » electrode active material is described.« less

Layered materials with improved magnesium intercalation for rechargeable magnesium ion cells

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

Doe, Robert Ellis; Downie, Craig Michael; Fischer, Christopher

2016-07-26

Electrochemical devices which incorporate cathode materials that include layered crystalline compounds for which a structural modification has been achieved which increases the diffusion rate of multi-valent ions into and out of the cathode materials. Examples in which the layer spacing of the layered electrode materials is modified to have a specific spacing range such that the spacing is optimal for diffusion of magnesium ions are presented. An electrochemical cell comprised of a positive intercalation electrode, a negative metal electrode, and a separator impregnated with a nonaqueous electrolyte solution containing multi-valent ions and arranged between the positive electrode and the negativemore » electrode active material is described.« less

Fabrication of lateral electrodes on semiconductor nanowires through structurally matched insulation for functional optoelectronics.

PubMed

Sheng, Yun; Sun, Huabin; Wang, Jianyu; Gao, Fan; Wang, Junzhuan; Pan, Lijia; Pu, Lin; Zheng, Youdou; Shi, Yi

2013-01-18

A strategy of using structurally matched alumina insulation to produce lateral electrodes on semiconductor nanowires is presented. Nanowires in the architecture are structurally matched with alumina insulation using selective anodic oxidation. Lateral electrodes are fabricated by directly evaporating metallic atoms onto the opposite sides of the nanowires. The integrated architecture with lateral electrodes propels carriers to transport them across nanowires and is crucially beneficial to the injection/extraction in optoelectronics. The matched architecture and the insulating properties of the alumina layer are investigated experimentally. ZnO nanowires are functionalized into an ultraviolet photodiode as an example. The present strategy successfully implements an advantageous architecture and is significant in developing diverse semiconductor nanowires in optoelectronic applications.

How to Enhance Gas Removal from Porous Electrodes?

PubMed Central

Kadyk, Thomas; Bruce, David; Eikerling, Michael

2016-01-01

This article presents a structure-based modeling approach to optimize gas evolution at an electrolyte-flooded porous electrode. By providing hydrophobic islands as preferential nucleation sites on the surface of the electrode, it is possible to nucleate and grow bubbles outside of the pore space, facilitating their release into the electrolyte. Bubbles that grow at preferential nucleation sites act as a sink for dissolved gas produced in electrode reactions, effectively suctioning it from the electrolyte-filled pores. According to the model, high oversaturation is necessary to nucleate bubbles inside of the pores. The high oversaturation allows establishing large concentration gradients in the pores that drive a diffusion flux towards the preferential nucleation sites. This diffusion flux keeps the pores bubble-free, avoiding deactivation of the electrochemically active surface area of the electrode as well as mechanical stress that would otherwise lead to catalyst degradation. The transport regime of the dissolved gas, viz. diffusion control vs. transfer control at the liquid-gas interface, determines the bubble growth law. PMID:28008914

Ionic liquid structure, dynamics, and electrosorption in carbon electrodes with bimodal pores and heterogeneous surfaces

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

Dyatkin, Boris; Osti, Naresh C.; Zhang, Yu

In this paper, we investigate the aggregation, diffusion, and resulting electrochemical behavior of ionic liquids inside carbon electrodes with complex pore architectures and surface chemistries. Carbide-derived carbons (CDCs) with bimodal porosities and defunctionalized or oxidized electrode surfaces served as model electrode materials. Our goal was to obtain a fundamental understanding of room-temperature ionic liquid ion orientation, mobility, and electrosorption behavior. Neat 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide confined in CDCs was studied using an integrated experimental and modeling approach, consisting of quasielastic neutron scattering, small-angle neutron scattering, X-ray pair distribution function analysis, and electrochemical measurements, which were combined with molecular dynamics simulations. Our analysismore » shows that surface oxygen groups increase the diffusion of confined electrolytes. Consequently, the ions become more than twice as mobile in oxygen-rich pores. Although greater self-diffusion of ions translates into higher electrochemical mobilities in oxidized pores, bulk-like behavior of ions dominates in the larger mesopores and increases the overall capacitance in defunctionalized pores. Experimental results highlight strong confinement and surface effects of carbon electrodes on electrolyte behavior, and molecular dynamics simulations yield insight into diffusion and capacitance differences in specific pore regions. Finally, we demonstrate the significance of surface defects on electrosorption dynamics of complex electrolytes in hierarchical pore architectures of supercapacitor electrodes.« less

Ionic liquid structure, dynamics, and electrosorption in carbon electrodes with bimodal pores and heterogeneous surfaces

DOE PAGES

Dyatkin, Boris; Osti, Naresh C.; Zhang, Yu; ...

2017-12-05

In this paper, we investigate the aggregation, diffusion, and resulting electrochemical behavior of ionic liquids inside carbon electrodes with complex pore architectures and surface chemistries. Carbide-derived carbons (CDCs) with bimodal porosities and defunctionalized or oxidized electrode surfaces served as model electrode materials. Our goal was to obtain a fundamental understanding of room-temperature ionic liquid ion orientation, mobility, and electrosorption behavior. Neat 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide confined in CDCs was studied using an integrated experimental and modeling approach, consisting of quasielastic neutron scattering, small-angle neutron scattering, X-ray pair distribution function analysis, and electrochemical measurements, which were combined with molecular dynamics simulations. Our analysismore » shows that surface oxygen groups increase the diffusion of confined electrolytes. Consequently, the ions become more than twice as mobile in oxygen-rich pores. Although greater self-diffusion of ions translates into higher electrochemical mobilities in oxidized pores, bulk-like behavior of ions dominates in the larger mesopores and increases the overall capacitance in defunctionalized pores. Experimental results highlight strong confinement and surface effects of carbon electrodes on electrolyte behavior, and molecular dynamics simulations yield insight into diffusion and capacitance differences in specific pore regions. Finally, we demonstrate the significance of surface defects on electrosorption dynamics of complex electrolytes in hierarchical pore architectures of supercapacitor electrodes.« less

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.

Interstitial pneumonitis after acetylene welding: a case report.

PubMed

Brvar, Miran

2014-01-01

Acetylene is a colorless gas commonly used for welding. It acts mainly as a simple asphyxiant. In this paper, however, we present a patient who developed a severe interstitial pneumonitis after acetylene exposure during aluminum welding. A 44-year old man was welding with acetylene, argon and aluminum electrode sticks in a non-ventilated aluminum tank for 2 h. Four hours after welding dyspnea appeared and 22 h later he was admitted at the Emergency Department due to severe respiratory insufficiency with pO2 = 6.7 kPa. Chest X-ray showed diffuse interstitial infiltration. Pulmonary function and gas diffusion tests revealed a severe restriction (55% of predictive volume) and impaired diffusion capacity (47% of predicted capacity). Toxic interstitial pneumonitis was diagnosed and high-dose systemic corticosteroid methylprednisolone and inhalatory corticosteroid fluticasone therapy was started. Computed Tomography (CT) of the lungs showed a diffuse patchy ground-glass opacity with no signs of small airway disease associated with interstitial pneumonitis. Corticosteroid therapy was continued for the next 8 weeks gradually reducing the doses. The patient's follow-up did not show any deterioration of respiratory function. In conclusion, acetylene welding might result in severe toxic interstitial pneumonitis that improves after an early systemic and inhalatory corticosteroid therapy.

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

Application of gas diffusion electrodes in bioelectrochemical syntheses and energy conversion.

PubMed

Horst, Angelika E W; Mangold, Klaus-Michael; Holtmann, Dirk

2016-02-01

Combining the advantages of biological components (e.g., reaction specificity, self-replication) and electrochemical techniques in bioelectrochemical systems offers the opportunity to develop novel efficient and sustainable processes for the production of a number of valuable products. The choice of electrode material has a great impact on the performance of bioelectrochemical systems. In addition to the redox process at the electrodes, interactions of biocatalysts with electrodes (e.g., enzyme denaturation or biofouling) need to be considered. In recent years, gas diffusion electrodes (GDEs) have proved to be very attractive electrodes for bioelectrochemical purposes. GDEs are porous electrodes, that posses a large three-phase boundary surface. At this interface, a solid catalyst supports the electrochemical reaction between gaseous and liquid phase. This mini-review discusses the application of GDEs in microbial and enzymatic fuel cells, for microbial electrolysis, in biosensors and for electroenzymatic synthesis reactions. © 2015 Wiley Periodicals, Inc.

Roles of Bulk and Surface Chemistry in the Oxygen Exchange Kinetics and Related Properties of Mixed Conducting Perovskite Oxide Electrodes

PubMed Central

Perry, Nicola H.; Ishihara, Tatsumi

2016-01-01

Mixed conducting perovskite oxides and related structures serving as electrodes for electrochemical oxygen incorporation and evolution in solid oxide fuel and electrolysis cells, respectively, play a significant role in determining the cell efficiency and lifetime. Desired improvements in catalytic activity for rapid surface oxygen exchange, fast bulk transport (electronic and ionic), and thermo-chemo-mechanical stability of oxygen electrodes will require increased understanding of the impact of both bulk and surface chemistry on these properties. This review highlights selected work at the International Institute for Carbon-Neutral Energy Research (I2CNER), Kyushu University, set in the context of work in the broader community, aiming to characterize and understand relationships between bulk and surface composition and oxygen electrode performance. Insights into aspects of bulk point defect chemistry, electronic structure, crystal structure, and cation choice that impact carrier concentrations and mobilities, surface exchange kinetics, and chemical expansion coefficients are emerging. At the same time, an understanding of the relationship between bulk and surface chemistry is being developed that may assist design of electrodes with more robust surface chemistries, e.g., impurity tolerance or limited surface segregation. Ion scattering techniques (e.g., secondary ion mass spectrometry, SIMS, or low energy ion scattering spectroscopy, LEIS) with high surface sensitivity and increasing lateral resolution are proving useful for measuring surface exchange kinetics, diffusivity, and corresponding outer monolayer chemistry of electrodes exposed to typical operating conditions. Beyond consideration of chemical composition, the use of strain and/or a high density of active interfaces also show promise for enhancing performance. PMID:28773978

The Nature of Electrochemical Delithiation of Li-Mg Alloy Electrodes: Neutron Computed Tomography and Modeling of Li Diffusion and Delithiation Phenomenon

DOE PAGES

Zhang, Yuxuan; Chandran, K.S. Ravi; Jagannathan, M.; ...

2016-12-05

Li-Mg alloys are promising as positive electrodes (anodes) for Li-ion batteries due to the high Li storage capacity and the relatively lower volume change during the lithiation/delithiation process. They also present a unique opportunity to image the Li distribution through the electrode thickness at various delithiation states. In this work, spatial distributions of Li in electrochemically delithiated Li-Mg alloy electrodes have been quantitatively determined using neutron tomography. Specifically, the Li concentration profiles along thickness direction are determined. A rigorous analytical model to quantify the diffusion-controlled delithiation, accompanied by phase transition and boundary movement, has also been developed to explain themore » delithiation mechanism. The analytical modeling scheme successfully predicted the Li concentration profiles which agreed well with the experimental data. It is demonstrated that during discharge Li is removed by diffusion through the solid solution Li-Mg phases and this proceeds with β→α phase transition and the associated phase boundary movement through the thickness of the electrode. This is also accompanied by electrode thinning due to the change in molar volume during delithiation. In conclusion, following the approaches developed here, one can develop a rigorous and quantitative understanding of electrochemical delithiation in electrodes of electrochemical cells, similar to that in the present Li-Mg electrodes.« less

The Nature of Electrochemical Delithiation of Li-Mg Alloy Electrodes: Neutron Computed Tomography and Modeling of Li Diffusion and Delithiation Phenomenon

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

Zhang, Yuxuan; Chandran, K.S. Ravi; Jagannathan, M.

Li-Mg alloys are promising as positive electrodes (anodes) for Li-ion batteries due to the high Li storage capacity and the relatively lower volume change during the lithiation/delithiation process. They also present a unique opportunity to image the Li distribution through the electrode thickness at various delithiation states. In this work, spatial distributions of Li in electrochemically delithiated Li-Mg alloy electrodes have been quantitatively determined using neutron tomography. Specifically, the Li concentration profiles along thickness direction are determined. A rigorous analytical model to quantify the diffusion-controlled delithiation, accompanied by phase transition and boundary movement, has also been developed to explain themore » delithiation mechanism. The analytical modeling scheme successfully predicted the Li concentration profiles which agreed well with the experimental data. It is demonstrated that during discharge Li is removed by diffusion through the solid solution Li-Mg phases and this proceeds with β→α phase transition and the associated phase boundary movement through the thickness of the electrode. This is also accompanied by electrode thinning due to the change in molar volume during delithiation. In conclusion, following the approaches developed here, one can develop a rigorous and quantitative understanding of electrochemical delithiation in electrodes of electrochemical cells, similar to that in the present Li-Mg electrodes.« less

Effect of porosity and tortuosity of electrodes on carbon polymer soft actuators

NASA Astrophysics Data System (ADS)

S, Sunjai Nakshatharan; Punning, Andres; Johanson, Urmas; Aabloo, Alvo

2018-01-01

This work presents an electro-mechanical model and simulation of ionic electroactive polymer soft actuators with a porous carbon electrode, polymer membrane, and ionic liquid electrolyte. An attempt is made to understand the effects of specific properties of the porous electrodes such as porosity and tortuosity on the charge dynamics and mechanical performance of the actuator. The model uses porous electrode theory to study the electrochemical response of the system. The mechanical response of the whole laminate is attributed to the evolution of local stresses caused by diffusion of ions (diffusion-induced stresses or chemical stresses). The model indicates that in actuators with porous electrode, the diffusion coefficient of ions, conductivity of the electrodes, and ionic conductivity in both electrodes and separator are altered significantly. In addition, the model leads to an obvious deduction that the ions that are highly active in terms of mobility will dominate the whole system in terms of resulting mechanical deformation direction and rate of deformation. Finally, to validate the model, simulations are conducted using the finite element method, and the outcomes are compared with the experimental data. Significant effort has been put forward to experimentally measure the key parameters essential for the validation of the model. The results show that the model developed is able to well predict the behavior of the actuator, providing a comprehensive understanding of charge dynamics in ionic polymer actuator with porous electrodes.

Embedding of electrodes within a microchannel interfacing a permselective medium for sensing and active control of the concentration-polarization layer

NASA Astrophysics Data System (ADS)

Yossifon, Gilad; Park, Sinwook

2016-11-01

Previously, it has been shown that for a prescribed system, the diffusion length may be affected by any number of mechanisms including natural and forced convection, electroosmotic flow of the second kind and electro-convective instability. In all of the above mentioned cases the length of the diffusion layer is indirectly prescribed by the complicated competition between several mechanisms which are primarily dictated by the various system parameters and applied voltage. In contrast, we suggest that by embedding electrodes/heaters within a microchannel interfacing a permselective medium, the diffusion layer length may be controlled regardless of the dominating overlimiting current mechanism and system parameters. As well as demonstrating that the simple presence of electrodes can enhance mixing via induced-charge electrokinetic effects, we also offer a means of externally activating embedded electrodes and heaters to maintain external, dynamic control of the diffusion length. Such control is particularly important in applications requiring intense ion transport, such as electrodialysis. At the same time, we will also investigate means of suppressing these mechanisms which is of fundamental importance for sensing applications.

Theory of linear sweep voltammetry with diffuse charge: Unsupported electrolytes, thin films, and leaky membranes

NASA Astrophysics Data System (ADS)

Yan, David; Bazant, Martin Z.; Biesheuvel, P. M.; Pugh, Mary C.; Dawson, Francis P.

2017-03-01

Linear sweep and cyclic voltammetry techniques are important tools for electrochemists and have a variety of applications in engineering. Voltammetry has classically been treated with the Randles-Sevcik equation, which assumes an electroneutral supported electrolyte. In this paper, we provide a comprehensive mathematical theory of voltammetry in electrochemical cells with unsupported electrolytes and for other situations where diffuse charge effects play a role, and present analytical and simulated solutions of the time-dependent Poisson-Nernst-Planck equations with generalized Frumkin-Butler-Volmer boundary conditions for a 1:1 electrolyte and a simple reaction. Using these solutions, we construct theoretical and simulated current-voltage curves for liquid and solid thin films, membranes with fixed background charge, and cells with blocking electrodes. The full range of dimensionless parameters is considered, including the dimensionless Debye screening length (scaled to the electrode separation), Damkohler number (ratio of characteristic diffusion and reaction times), and dimensionless sweep rate (scaled to the thermal voltage per diffusion time). The analysis focuses on the coupling of Faradaic reactions and diffuse charge dynamics, although capacitive charging of the electrical double layers is also studied, for early time transients at reactive electrodes and for nonreactive blocking electrodes. Our work highlights cases where diffuse charge effects are important in the context of voltammetry, and illustrates which regimes can be approximated using simple analytical expressions and which require more careful consideration.

Large amplitude Fourier transformed ac voltammetry at a rotating disc electrode: a versatile technique for covering Levich and flow rate insensitive regimes in a single experiment.

PubMed

Bano, Kiran; Kennedy, Gareth F; Zhang, Jie; Bond, Alan M

2012-04-14

The theory for large amplitude Fourier transformed ac voltammetry at a rotating disc electrode is described. Resolution of time domain data into dc and ac harmonic components reveals that the mass transport for the dc component is controlled by convective-diffusion, while the background free higher order harmonic components are flow rate insensitive and mainly governed by linear diffusion. Thus, remarkable versatility is available; Levich behaviour of the dc component limiting current provides diffusion coefficient values and access to higher harmonics allows fast electrode kinetics to be probed. Two series of experiments (dc and ac voltammetry) have been required to extract these parameters; here large amplitude ac voltammetry with RDE methodology is used to demonstrate that kinetics and diffusion coefficient information can be extracted from a single experiment. To demonstrate the power of this approach, theoretical and experimental comparisons of data obtained for the reversible [Ru(NH(3))(6)](3+/2+) and quasi-reversible [Fe(CN)(6)](3-/4-) electron transfer processes are presented over a wide range of electrode rotation rates and with different concentrations and electrode materials. Excellent agreement of experimental and simulated data is achieved, which allows parameters such as electron transfer rate, diffusion coefficient, uncompensated resistance and others to be determined using a strategically applied approach that takes into account the different levels of sensitivity of each parameter to the dc or the ac harmonic.

Electrochemical mercerization, souring, and bleaching of textiles

DOEpatents

Cooper, J.F.

1995-10-10

Economical, pollution-free treatment of textiles occurs in a low voltage electrochemical cell that mercerizes (or scours), sours, and optionally bleaches without effluents and without the purchase of bulk caustic, neutralizing acids, or bleaches. The cell produces base in the cathodic chamber for mercerization and an equivalent amount of acid in the anodic chamber for neutralizing the fabric. Gas diffusion electrodes are used for one or both electrodes and may simultaneously generate hydrogen peroxide for bleaching. The preferred configuration is a stack of bipolar electrodes, in which one or both of the anode and cathode are gas diffusion electrodes, and where no hydrogen gas is evolved at the cathode. 5 figs.

Electrochemical mercerization, souring, and bleaching of textiles

DOEpatents

Cooper, John F.

1995-01-01

Economical, pollution-free treatment of textiles occurs in a low voltage electrochemical cell that mercerizes (or scours), sours, and optionally bleaches without effluents and without the purchase of bulk caustic, neutralizing acids, or bleaches. The cell produces base in the cathodic chamber for mercerization and an equivalent amount of acid in the anodic chamber for neutralizing the fabric. Gas diffusion electrodes are used for one or both electrodes and may simultaneously generate hydrogen peroxide for bleaching. The preferred configuration is a stack of bipolar electrodes, in which one or both of the anode and cathode are gas diffusion electrodes, and where no hydrogen gas is evolved at the cathode.

Carbon nanotube macrofilm-based nanocomposite electrodes for energy applications

NASA Astrophysics Data System (ADS)

Cao, Zeyuan

Finding new electrode materials for energy conversion and storage devices have been the focus of recent research in the fields of science and engineering. Suffering from poor electronic conductivity, chemical and mechanical stability, active electrode materials are usually coupled with different carbon nanostructured materials to form nanocomposite electrodes, showing promising electrochemical performance. Among the carbon nanostructured materials, carbon nanotube (CNT) macrofilms draw great attention owing to their extraordinary properties, such as a large specific surface area, exceptionally high conductivity, porous structure, flexibility, mechanical robustness, and adhesion. They could effectively enhance the electrochemical performance of the incorporated active materials in the nanocomposites. In this dissertation, CNT macrofilm-based nanocomposites are investigated for rechargeable lithium-ion batteries, supercapacitors, and electrocatalysts of fuel cells. The progressive research developed various nanocomposites from cathode materials to anode materials followed by a general nanocomposite solution due to the unique adhesive property of the fragmented CNT macrofilms. The in-situ synthesis strategy are explored to in-situ deposit unlithiated cathode materials V2O5 and lithiated cathode materials LiMn2O4 nanocrystals in the matrix of the CNT macrofilms as nanocomposites to be paired with metallic lithium in half cells. The presence of oxygen-containing functional groups on the surface of the CNT macrofilms after purification can enhance the association with the active materials to enable the facilitated transport of solvated ions to the electrolyte/electrode interfaces and increase the diffusion kinetics, consequently enhancing the battery performance in terms of high specific capacity, rate capability, and cycling stability. It is also significant to demonstrate a reliable, low-cost, and effective route to synthesize the family of metal oxides (MxOy (M=Fe, Co, Ni)) with CNT macofilms as high performance anodes for rechargeable lithium-ion batteries and as catalysts for oxygen reduction/evolution (ORR/OER). All MxOy-CNT macrofilm nanocomposites inherit the high specific capacity and cycling stability for lithium-ion batteries. NiO/SWNT and Co3O4/SWNT (200 °C) have their specialized high catalytic activities for ORR and OER in alkaline solutions, respectively. NiO/SWNT also exhibits an excellent electrochemical performance in asymmetric supercapacitors with a high power and energy density. Experimental measurements on electrochemical kinetics such as potentiostatic/galvanostatic intermittent titration techniques (PITT/GITT) are depended to understand the underlying improved Li+ diffusion behavior of nanocomposites. Critical effects of the film thickness have been identified. The CNT macrofilm with a thickness that is comparable to the characteristic diffusion length of 300~500 nm enables the nanocomposite with the highest Li+ chemical diffusion coefficient and thus an optimal electrochemical performance. The adhesive characteristic of CNT macrofilms is noticed for the first time after fragmentation by ultrasound that origins from irregular structures of laterally 2-D distributed CNT segments. The fragmented CNT macrofilms (FCNT) as "bifunctional" adhesive conductors promote a general approach to construct nanocomposite electrodes with both cathode and anode materials for lithium-ion batteries. An in-situ tribology method combining the wear track imaging and force measurement is employed to evaluate the adhesion strength of the adhesive FCNT conductors. The results show that the FCNT macrofilms have a higher adhesion strength than the conventional polymer binder polyvinylidene fluoride (PVDF). It is confirmed that the fabricated nanocomposite electrodes exhibit high rate and retention capabilities, superior to the electrodes using PVDF and carbon black. Thus, FCNT is recognized to be a competent substitute for polymer binders to maintain mechanical integrity and meanwhile to improve electrical connectivity of active materials in the nanocomposite electrodes. In addition, this new electrode manufacturing technique avoids the utilization of toxic organic solvents and could provide a revolution to traditional battery industry.

Submersed sensing electrode used in fuel-cell type hydrogen detector

NASA Technical Reports Server (NTRS)

Niedrach, L. W.; Rudek, F. P.; Rutkoneski, M. D.

1971-01-01

Electrode has silicone rubber diffusion barrier with fixed permeation constant for hydrogen. Barrier controls flow of hydrogen to anode and Faraday relationship establishes upper limit for current through cell. Electrode fabrication is described.

Electrocatalytic cermet gas detector/sensor

DOEpatents

Vogt, Michael C.; Shoemarker, Erika L.; Fraioli, deceased, Anthony V.

1995-01-01

An electrocatalytic device for sensing gases. The gas sensing device includes a substrate layer, a reference electrode disposed on the substrate layer comprised of a nonstoichiometric chemical compound enabling oxygen diffusion therethrough, a lower reference electrode coupled to the reference electrode, a solid electrolyte coupled to the lower reference electrode and an upper catalytically active electrode coupled to the solid electrolyte.

Simulation of diffuse-charge capacitance in electric double layer capacitors

NASA Astrophysics Data System (ADS)

Sun, Ning; Gersappe, Dilip

2017-01-01

We use a Lattice Boltzmann Model (LBM) in order to simulate diffuse-charge dynamics in Electric Double Layer Capacitors (EDLCs). Simulations are carried out for both the charge and the discharge processes on 2D systems of complex random electrode geometries (pure random, random spheres and random fibers). The steric effect of concentrated solutions is considered by using a Modified Poisson-Nernst-Planck (MPNP) equations and compared with regular Poisson-Nernst-Planck (PNP) systems. The effects of electrode microstructures (electrode density, electrode filler morphology, filler size, etc.) on the net charge distribution and charge/discharge time are studied in detail. The influence of applied potential during discharging process is also discussed. Our studies show how electrode morphology can be used to tailor the properties of supercapacitors.

Positive electrodes of nickel-cadmium batteries

NASA Technical Reports Server (NTRS)

Wabner, D. W.; Kandler, L.; Krienke, W.

1985-01-01

Ni hydroxide sintered electrodes which are filled electrochemically are superior to chemically treated electrodes. In the electrochemical process, the hydroxide grows on the Ni grains and possesses a well-defined porous structure. Diffusion and conducting mechanisms are therefore facilitated.

Variable-order fractional MSD function to describe the evolution of protein lateral diffusion ability in cell membranes

NASA Astrophysics Data System (ADS)

Yin, Deshun; Qu, Pengfei

2018-02-01

Protein lateral diffusion is considered anomalous in the plasma membrane. And this diffusion is related to membrane microstructure. In order to better describe the property of protein lateral diffusion and find out the inner relationship between protein lateral diffusion and membrane microstructure, this article applies variable-order fractional mean square displacement (f-MSD) function for characterizing the anomalous diffusion. It is found that the variable order can reflect the evolution of diffusion ability. The results of numerical simulation demonstrate variable-order f-MSD function can predict the tendency of anomalous diffusion during the process of confined diffusion. It is also noted that protein lateral diffusion ability during the processes of confined and hop diffusion can be split into three parts. In addition, the comparative analyses reveal that the variable order is related to the confinement-domain size and microstructure of compartment boundary too.

Acceleration of metal-atom diffusion in electric field at metal/insulator interfaces: First-principles study

NASA Astrophysics Data System (ADS)

Nagasawa, Riki; Asayama, Yoshihiro; Nakayama, Takashi

2018-04-01

Metal-atom diffusion from metal electrodes into SiO2 in electric fields was studied using first-principles calculations. It was shown in the case without electric field that the diffusion barrier of a metal atom is mainly made of the cohesive energy of bulk metal layers, while the shape of the diffusion potential reflects the hybridization of the metal-atom state with metal-induced gap states (MIGSs) and the electron transfer between the metal atom and the electrode. We found that the metal-atom diffusion is markedly accelerated by the applied electric field, such that the diffusion barrier ϕB(E) decreases almost linearly with increasing electric field strength E. By analyzing the physical origins of the metal-atom diffusion, we derived the universal formula to estimate the diffusion barrier in the electric field, which is closely related to MIGSs.

Electrocatalytic cermet gas detector/sensor

DOEpatents

Vogt, M.C.; Shoemarker, E.L.; Fraioli, A.V.

1995-07-04

An electrocatalytic device for sensing gases is described. The gas sensing device includes a substrate layer, a reference electrode disposed on the substrate layer comprised of a nonstoichiometric chemical compound enabling oxygen diffusion therethrough, a lower reference electrode coupled to the reference electrode, a solid electrolyte coupled to the lower reference electrode and an upper catalytically active electrode coupled to the solid electrolyte. 41 figs.

Numerical Evaluation of Lateral Diffusion Inside Diffusive Gradients in Thin Films Samplers

PubMed Central

2015-01-01

Using numerical simulation of diffusion inside diffusive gradients in thin films (DGT) samplers, we show that the effect of lateral diffusion inside the sampler on the solute flux into the sampler is a nonlinear function of the diffusion layer thickness and the physical sampling window size. In contrast, earlier work concluded that this effect was constant irrespective of parameters of the sampler geometry. The flux increase caused by lateral diffusion inside the sampler was determined to be ∼8.8% for standard samplers, which is considerably lower than the previous estimate of ∼20%. Lateral diffusion is also propagated to the diffusive boundary layer (DBL), where it leads to a slightly stronger decrease in the mass uptake than suggested by the common 1D diffusion model that is applied for evaluating DGT results. We introduce a simple correction procedure for lateral diffusion and demonstrate how the effect of lateral diffusion on diffusion in the DBL can be accounted for. These corrections often result in better estimates of the DBL thickness (δ) and the DGT-measured concentration than earlier approaches and will contribute to more accurate concentration measurements in solute monitoring in waters. PMID:25877251

Combining phase-field crystal methods with a Cahn-Hilliard model for binary alloys

NASA Astrophysics Data System (ADS)

Balakrishna, Ananya Renuka; Carter, W. Craig

2018-04-01

Diffusion-induced phase transitions typically change the lattice symmetry of the host material. In battery electrodes, for example, Li ions (diffusing species) are inserted between layers in a crystalline electrode material (host). This diffusion induces lattice distortions and defect formations in the electrode. The structural changes to the lattice symmetry affect the host material's properties. Here, we propose a 2D theoretical framework that couples a Cahn-Hilliard (CH) model, which describes the composition field of a diffusing species, with a phase-field crystal (PFC) model, which describes the host-material lattice symmetry. We couple the two continuum models via coordinate transformation coefficients. We introduce the transformation coefficients in the PFC method to describe affine lattice deformations. These transformation coefficients are modeled as functions of the composition field. Using this coupled approach, we explore the effects of coarse-grained lattice symmetry and distortions on a diffusion-induced phase transition process. In this paper, we demonstrate the working of the CH-PFC model through three representative examples: First, we describe base cases with hexagonal and square symmetries for two composition fields. Next, we illustrate how the CH-PFC method interpolates lattice symmetry across a diffuse phase boundary. Finally, we compute a Cahn-Hilliard type of diffusion and model the accompanying changes to lattice symmetry during a phase transition process.

Stress analysis in cylindrical composition-gradient electrodes of lithium-ion battery

NASA Astrophysics Data System (ADS)

Zhong, Yaotian; Liu, Yulan; Wang, B.

2017-07-01

In recent years, the composition-gradient electrode material has been verified to be one of the most promising materials in lithium-ion battery. To investigate diffusion-induced stresses (DIS) generated in a cylindrical composition-gradient electrode, the finite deformation theory and the stress-induced diffusion hypothesis are adopted to establish the constitutive equations. Compared with stress distributions in a homogeneous electrode, the increasing forms of Young's modulus E(R) and partial molar volume Ω(R) from the electrode center to the surface along the radial direction drastically increase the maximal magnitudes of hoop and axial stresses, while both of the decreasing forms are able to make the stress fields smaller and flatter. Also, it is found that the slope of -1 for E(R) with that of -0.5 for Ω(R) is a preferable strategy to prevent the inhomogeneous electrode from cracking, while for the sake of protecting the electrode from compression failure, the optimal slope for inhomogeneous E(R) and the preferential one for Ω(R) are both -0.5. The results provide a theoretical guidance for the design of composition-gradient electrode materials.

Recent advancements in 2D-materials interface based magnetic junctions for spintronics

NASA Astrophysics Data System (ADS)

Iqbal, Muhammad Zahir; Qureshi, Nabeel Anwar; Hussain, Ghulam

2018-07-01

Two-dimensional (2D) materials comprising of graphene, hexagonal boron nitride (hBN) and transition metal dichalcogenides (TMDs) have revealed fascinating properties in various spintronic architectures. Here, we review spin valve effect in lateral and vertical magnetic junctions incorporating 2D materials as non-magnetic layer between ferromagnetic (FM) electrodes. The magnetic field dependent spin transport properties are studied by measuring non-local resistance (RNL) and relative magnetoresistance ratio (MR) for lateral and vertical structures, respectively. The review consists of (i) studying spin lifetimes and spin diffusion length thereby exploring the effect of tunneling and transparent contacts in lateral spin valve structures, temperature dependence, gate tunability and contrasting mechanisms of spin relaxation in single layer graphene (SLG) and bilayer graphene (BLG) devices. (ii) Perpendicular spin valve devices are thoroughly investigated thereby studying the role of different 2D materials in vertical spin dynamics. The dependence of spin valve signal on interface quality, temperature and various other parameters is also investigated. Furthermore, the spin reversal in graphene-hBN hybrid system is examined on the basis of Julliere model.

Mesoscale elucidation of laser-assisted chemical deposition of Sn nanostructured electrodes

NASA Astrophysics Data System (ADS)

Liu, Zhixiao; Deng, Biwei; Cheng, Gary J.; Deng, Huiqiu; Mukherjee, Partha P.

2015-06-01

Nanostructured tin (Sn) is a promising high-capacity electrode for improved performance in lithium-ion batteries for electric vehicles. In this work, Sn nanoisland growth for nanostructured electrodes assisted by the pulse laser irradiation has been investigated based on a mesoscale modeling formalism. The influence of pertinent processing conditions, such as pulse duration, heating/cooling rates, and atom flux, on the Sn nanostructure formation is specifically considered. The interaction between the adsorbed atom and the substrate, represented by the adatom diffusion barrier, is carefully studied. It is found that the diffusion barrier predominantly affects the distribution of Sn atoms. For both α-Sn and β-Sn, the averaged coordination number is larger than 3 when the diffusion barrier equals to 0.15 eV. The averaged coordination number decreases as the diffusion barrier increases. The substrate temperature, which is determined by heating/cooling rates and pulse duration, can also affect the formation of Sn nanoislands. For α-Sn, when applied low heating/cooling rates, nanoislands cannot form if the diffusion barrier is larger than 0.35 eV.

High Rate Oxygen Reduction in Non-aqueous Electrolytes with the Addition of Perfluorinated Additives

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

Wang, Y.; Yang, X.; Zheng, D.

2011-08-04

The discharge rate capability of Li-air batteries is substantially increased by using perfluorinated compounds as oxygen carriers. The solubility of oxygen in a non-aqueous electrolyte can be significantly increased by the introduction of such compounds, which leads to the increase in the diffusion-limited current of oxygen reduction on the gas diffusion electrode in a Li-air battery. The perfluorinated compound is found to be stable within the electrochemical window of the electrolyte. A powder microelectrode and a rotating disk electrode were used to study the gas diffusion-limited current together with a rotating disk electrode. A 5 mA cm{sup -2} discharge ratemore » is demonstrated in a lab Li-O{sub 2} cell.« less

Measurement of absorbed dose with a bone-equivalent extrapolation chamber.

PubMed

DeBlois, François; Abdel-Rahman, Wamied; Seuntjens, Jan P; Podgorsak, Ervin B

2002-03-01

A hybrid phantom-embedded extrapolation chamber (PEEC) made of Solid Water and bone-equivalent material was used for determining absorbed dose in a bone-equivalent phantom irradiated with clinical radiation beams (cobalt-60 gamma rays; 6 and 18 MV x rays; and 9 and 15 MeV electrons). The dose was determined with the Spencer-Attix cavity theory, using ionization gradient measurements and an indirect determination of the chamber air-mass through measurements of chamber capacitance. The collected charge was corrected for ionic recombination and diffusion in the chamber air volume following the standard two-voltage technique. Due to the hybrid chamber design, correction factors accounting for scatter deficit and electrode composition were determined and applied in the dose equation to obtain absorbed dose in bone for the equivalent homogeneous bone phantom. Correction factors for graphite electrodes were calculated with Monte Carlo techniques and the calculated results were verified through relative air cavity dose measurements for three different polarizing electrode materials: graphite, steel, and brass in conjunction with a graphite collecting electrode. Scatter deficit, due mainly to loss of lateral scatter in the hybrid chamber, reduces the dose to the air cavity in the hybrid PEEC in comparison with full bone PEEC by 0.7% to approximately 2% depending on beam quality and energy. In megavoltage photon and electron beams, graphite electrodes do not affect the dose measurement in the Solid Water PEEC but decrease the cavity dose by up to 5% in the bone-equivalent PEEC even for very thin graphite electrodes (<0.0025 cm). In conjunction with appropriate correction factors determined with Monte Carlo techniques, the uncalibrated hybrid PEEC can be used for measuring absorbed dose in bone material to within 2% for high-energy photon and electron beams.

Improved Ionic Diffusion through the Mesoporous Carbon Skin on Silicon Nanoparticles Embedded in Carbon for Ultrafast Lithium Storage.

PubMed

An, Geon-Hyoung; Kim, Hyeonjin; Ahn, Hyo-Jin

2018-02-21

Because of their combined effects of outstanding mechanical stability, high electrical conductivity, and high theoretical capacity, silicon (Si) nanoparticles embedded in carbon are a promising candidate as electrode material for practical utilization in Li-ion batteries (LIBs) to replace the conventional graphite. However, because of the poor ionic diffusion of electrode materials, the low-grade ultrafast cycling performance at high current densities remains a considerable challenge. In the present study, seeking to improve the ionic diffusion, we propose a novel design of mesoporous carbon skin on the Si nanoparticles embedded in carbon by hydrothermal reaction, poly(methyl methacrylate) coating process, and carbonization. The resultant electrode offers a high specific discharge capacity with excellent cycling stability (1140 mA h g -1 at 100 mA g -1 after 100 cycles), superb high-rate performance (969 mA h g -1 at 2000 mA g -1 ), and outstanding ultrafast cycling stability (532 mA h g -1 at 2000 mA g -1 after 500 cycles). The battery performances are surpassing the previously reported results for carbon and Si composite-based electrodes on LIBs. Therefore, this novel approach provides multiple benefits in terms of the effective accommodation of large volume expansions of the Si nanoparticles, a shorter Li-ion diffusion pathway, and stable electrochemical conditions from a faster ionic diffusion during cycling.

Microencephaloceles: another dual pathology of intractable temporal lobe epilepsy in childhood.

PubMed

Aquilina, Kristian; Clarke, Dave F; Wheless, James W; Boop, Frederick A

2010-04-01

Temporal lobe encephaloceles can be associated with temporal lobe epilepsy. The authors report on the case of an adolescent with multiple microencephaloceles, in the anterolateral middle fossa floor, identified at surgery (temporal lobectomy) for intractable partial-onset seizures of temporal origin. Magnetic resonance imaging revealed only hippocampal atrophy. Subdural electrodes demonstrated ictal activity arising primarily from the anterior and lateral temporal lobe, close to the microencephaloceles, spreading to the anterior and posterior mesial structures. Pathological examination revealed diffuse temporal gliosis involving the hippocampus, together with microdysgenesis of the amygdala. The literature on epilepsy secondary to encephaloceles is reviewed and the contribution of the microencephaloceles to the seizure disorder in this patient is discussed.

Influence of implantation on the electrochemical properties of smooth and porous TiN coatings for stimulation electrodes

NASA Astrophysics Data System (ADS)

Meijs, S.; Sørensen, C.; Sørensen, S.; Rechendorff, K.; Fjorback, M.; Rijkhoff, N. J. M.

2016-04-01

Objective. To determine whether changes in electrochemical properties of porous titanium nitride (TiN) electrodes as a function of time after implantation are different from those of smooth TiN electrodes. Approach. Eight smooth and 8 porous TiN coated electrodes were implanted in 8 rats. Before implantation, voltage transients, cyclic voltammograms and impedance spectra were recorded in phosphate buffered saline (PBS). After implantation, these measurements were done weekly to investigate how smooth and porous electrodes were affected by implantation. Main results. The electrode capacitance of the porous TiN electrodes decreased more than the capacitance of the smooth electrodes due to acute implantation under fast measurement conditions (such as stimulation pulses). This indicates that protein adhesion presents a greater diffusion limitation for counter-ions for the porous than for the smooth electrodes. The changes in electrochemical properties during the implanted period were similar for smooth and porous TiN electrodes, indicating that cell adhesion poses a similar diffusion limitation for smooth and porous electrodes. Significance. This knowledge can be used to optimize the porous structure of the TiN film, so that the effect of protein adhesion on the electrochemical properties is diminished. Alternatively, an additional coating could be applied on the porous TiN that would prevent or minimize protein adhesion.

Diffuse charge dynamics in ionic thermoelectrochemical systems.

PubMed

Stout, Robert F; Khair, Aditya S

2017-08-01

Thermoelectrics are increasingly being studied as promising electrical generators in the ongoing search for alternative energy sources. In particular, recent experimental work has examined thermoelectric materials containing ionic charge carriers; however, the majority of mathematical modeling has been focused on their steady-state behavior. Here, we determine the time scales over which the diffuse charge dynamics in ionic thermoelectrochemical systems occur by analyzing the simplest model thermoelectric cell: a binary electrolyte between two parallel, blocking electrodes. We consider the application of a temperature gradient across the device while the electrodes remain electrically isolated from each other. This results in a net voltage, called the thermovoltage, via the Seebeck effect. At the same time, the Soret effect results in migration of the ions toward the cold electrode. The charge dynamics are described mathematically by the Poisson-Nernst-Planck equations for dilute solutions, in which the ion flux is driven by electromigration, Brownian diffusion, and thermal diffusion under a temperature gradient. The temperature evolves according to the heat equation. This nonlinear set of equations is linearized in the (experimentally relevant) limit of a "weak" temperature gradient. From this, we show that the time scale on which the thermovoltage develops is the Debye time, 1/Dκ^{2}, where D is the Brownian diffusion coefficient of both ion species, and κ^{-1} is the Debye length. However, the concentration gradient due to the Soret effect develops on the bulk diffusion time, L^{2}/D, where L is the distance between the electrodes. For thin diffuse layers, which is the condition under which most real devices operate, the Debye time is orders of magnitude less than the diffusion time. Therefore, rather surprisingly, the majority of ion motion occurs after the steady thermovoltage has developed. Moreover, the dynamics are independent of the thermal diffusion coefficients, which simply set the magnitude of the steady-state thermovoltage.

Diffuse charge dynamics in ionic thermoelectrochemical systems

NASA Astrophysics Data System (ADS)

Stout, Robert F.; Khair, Aditya S.

2017-08-01

Thermoelectrics are increasingly being studied as promising electrical generators in the ongoing search for alternative energy sources. In particular, recent experimental work has examined thermoelectric materials containing ionic charge carriers; however, the majority of mathematical modeling has been focused on their steady-state behavior. Here, we determine the time scales over which the diffuse charge dynamics in ionic thermoelectrochemical systems occur by analyzing the simplest model thermoelectric cell: a binary electrolyte between two parallel, blocking electrodes. We consider the application of a temperature gradient across the device while the electrodes remain electrically isolated from each other. This results in a net voltage, called the thermovoltage, via the Seebeck effect. At the same time, the Soret effect results in migration of the ions toward the cold electrode. The charge dynamics are described mathematically by the Poisson-Nernst-Planck equations for dilute solutions, in which the ion flux is driven by electromigration, Brownian diffusion, and thermal diffusion under a temperature gradient. The temperature evolves according to the heat equation. This nonlinear set of equations is linearized in the (experimentally relevant) limit of a "weak" temperature gradient. From this, we show that the time scale on which the thermovoltage develops is the Debye time, 1 /D κ2 , where D is the Brownian diffusion coefficient of both ion species, and κ-1 is the Debye length. However, the concentration gradient due to the Soret effect develops on the bulk diffusion time, L2/D , where L is the distance between the electrodes. For thin diffuse layers, which is the condition under which most real devices operate, the Debye time is orders of magnitude less than the diffusion time. Therefore, rather surprisingly, the majority of ion motion occurs after the steady thermovoltage has developed. Moreover, the dynamics are independent of the thermal diffusion coefficients, which simply set the magnitude of the steady-state thermovoltage.

The mixing mechanism during lithiation of Si negative electrode in Li-ion batteries: an ab initio molecular dynamics study.

PubMed

Johari, Priya; Qi, Yue; Shenoy, Vivek B

2011-12-14

In order to realize Si as a negative electrode material in commercial Li-ion batteries, it is important to understand the mixing mechanism of Li and Si, and stress evolution during lithiation in Si negative electrode of Li-ion batteries. Available experiments mainly provide the diffusivity of Li in Si as an averaged property, neglecting information regarding diffusivity of Si. However, if Si can diffuse as fast as Li, the stress generated during Li diffusion can be reduced. We, therefore, studied the diffusivity of Li as well as Si atoms in the Si-anode of Li-ion battery using an ab initio molecular dynamics-based methodology. The electrochemical insertion of Li into crystalline Si prompts a crystalline-to-amorphous phase transition. We considered this situation and thus examined the diffusion kinetics of Li and Si atoms in both crystalline and amorphous Si. We find that Li diffuses faster in amorphous Si as compared to crystalline Si, while Si remains relatively immobile in both cases and generates stresses during lithiation. To further understand the mixing mechanism and to relate the structure with electrochemical mixing, we analyzed the evolution of the structure during lithiation and studied the mechanism of breaking of Si-Si network by Li. We find that Li atoms break the Si rings and chains and create ephemeral structures such as stars and boomerangs, which eventually transform to Si-Si dumbbells and isolated Si atoms in the LiSi phase. Our results are found to be in agreement with the available experimental data and provide insights into the mixing mechanism of Li and Si in Si negative electrode of Li-ion batteries.

Electrochemical Ionization and Analyte Charging in the Array of Micromachined UltraSonic Electrospray (AMUSE) Ion Source

PubMed Central

Forbes, Thomas P.; Degertekin, F. Levent; Fedorov, Andrei G.

2010-01-01

Electrochemistry and ion transport in a planar array of mechanically-driven, droplet-based ion sources are investigated using an approximate time scale analysis and in-depth computational simulations. The ion source is modeled as a controlled-current electrolytic cell, in which the piezoelectric transducer electrode, which mechanically drives the charged droplet generation using ultrasonic atomization, also acts as the oxidizing/corroding anode (positive mode). The interplay between advective and diffusive ion transport of electrochemically generated ions is analyzed as a function of the transducer duty cycle and electrode location. A time scale analysis of the relative importance of advective vs. diffusive ion transport provides valuable insight into optimality, from the ionization prospective, of alternative design and operation modes of the ion source operation. A computational model based on the solution of time-averaged, quasi-steady advection-diffusion equations for electroactive species transport is used to substantiate the conclusions of the time scale analysis. The results show that electrochemical ion generation at the piezoelectric transducer electrodes located at the back-side of the ion source reservoir results in poor ionization efficiency due to insufficient time for the charged analyte to diffuse away from the electrode surface to the ejection location, especially at near 100% duty cycle operation. Reducing the duty cycle of droplet/analyte ejection increases the analyte residence time and, in turn, improves ionization efficiency, but at an expense of the reduced device throughput. For applications where this is undesirable, i.e., multiplexed and disposable device configurations, an alternative electrode location is incorporated. By moving the charging electrode to the nozzle surface, the diffusion length scale is greatly reduced, drastically improving ionization efficiency. The ionization efficiency of all operating conditions considered is expressed as a function of the dimensionless Peclet number, which defines the relative effect of advection as compared to diffusion. This analysis is general enough to elucidate an important role of electrochemistry in ionization efficiency of any arrayed ion sources, be they mechanically-driven or electrosprays, and is vital for determining optimal design and operation conditions. PMID:20607111

Electrodics: mesoscale physicochemical interactions in lithium-ion batteries

NASA Astrophysics Data System (ADS)

Mukherjee, Partha P.; Chen, Chien-Fan

2014-06-01

Recent years have witnessed an explosion of interest and research endeavor in lithium-ion batteries to enable vehicle electrification. In particular, a critical imperative is to accelerate innovation for improved performance, life and safety of lithium-ion batteries for electric drive vehicles. Lithium ion batteries are complex, dynamical systems which include a multitude of coupled physicochemical processes encompassing electronic/ionic/diffusive transport in solid/electrolyte phases, electrochemical and phase change reactions and diffusion induced stress generation in multi-scale porous electrode microstructures. While innovations in nanomaterials and nanostructures have spurred the recent advancements, fundamental understanding of the electrode processing - microstructure - performance interplay is of paramount importance. In this presentation, mesoscale physicochemical interactions in lithium-ion battery electrodes will be elucidated.

Defect Detection in Fuel Cell Gas Diffusion Electrodes Using Infrared Thermography

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

Ulsh, Michael; Porter, Jason M.; Bittinat, Daniel C.

2016-04-01

Polymer electrolyte membrane fuel cells are energy conversion devices that offer high power densities and high efficiencies for mobile and other applications. Successful introduction into the marketplace requires addressing cost barriers such as production volumes and platinum loading. For cost reduction, it is vital to minimize waste and maximize quality during the manufacturing of platinum-containing electrodes, including gas diffusion electrodes (GDEs). In this work, we report on developing a quality control diagnostic for GDEs, involving creating an ex situ exothermic reaction on the electrode surface and using infrared thermography to measure the resulting temperature profile. Experiments with a moving GDEmore » containing created defects were conducted to demonstrate the applicability of the diagnostic for real-time web-line inspection.« less

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

CATO DM; DAHL MM; PHILO GL

This report documents the results of tests designed to characterize the relationship between temperature and the measured potential of electrodes installed on multi-probe corrosion monitoring systems in waste tanks. This report also documents the results of tests designed to demonstrate the impact of liquid in-leakage into electrode bodies as well as the contamination of primary reference electrodes by diffusion through the electrode tip.

Application of Lattice Boltzmann Methods in Complex Mass Transfer Systems

NASA Astrophysics Data System (ADS)

Sun, Ning

Lattice Boltzmann Method (LBM) is a novel computational fluid dynamics method that can easily handle complex and dynamic boundaries, couple local or interfacial interactions/reactions, and be easily parallelized allowing for simulation of large systems. While most of the current studies in LBM mainly focus on fluid dynamics, however, the inherent power of this method makes it an ideal candidate for the study of mass transfer systems involving complex/dynamic microstructures and local reactions. In this thesis, LBM is introduced to be an alternative computational method for the study of electrochemical energy storage systems (Li-ion batteries (LIBs) and electric double layer capacitors (EDLCs)) and transdermal drug design on mesoscopic scale. Based on traditional LBM, the following in-depth studies have been carried out: (1) For EDLCs, the simulation of diffuse charge dynamics is carried out for both the charge and the discharge processes on 2D systems of complex random electrode geometries (pure random, random spheres and random fibers). Steric effect of concentrated solutions is considered by using modified Poisson-Nernst-Plank (MPNP) equations and compared with regular Poisson-Nernst-Plank (PNP) systems. The effects of electrode microstructures (electrode density, electrode filler morphology, filler size, etc.) on the net charge distribution and charge/discharge time are studied in detail. The influence of applied potential during discharging process is also discussed. (2) For the study of dendrite formation on the anode of LIBs, it is shown that the Lattice Boltzmann model can capture all the experimentally observed features of microstructure evolution at the anode, from smooth to mossy to dendritic. The mechanism of dendrite formation process in mesoscopic scale is discussed in detail and compared with the traditional Sand's time theories. It shows that dendrite formation is closely related to the inhomogeneous reactively at the electrode-electrolyte interface. When the inhomogeneity is small, dendrites form mainly under high current densities, in which the mass transfer is dominated by electromigration; when the inhomogeneity is very large, dendrites may form under both high and low current densities, which is dominated by electromigration in high current density and by surface reactivity in low current density. We show that the critical current density for dendrite formation is sensitive to surface inhomogeneous reactivity and the onset time of dendrite formation is sensitive to the initial roughness of electrode. A new analysis method is introduced, which can predict the formation of dendrites in batteries at a very early stage even before large dendrites form. Charge/discharge cyclic properties of the system are also studied, which shows that electrode roughness will increase during cycles and the break-off of dendritic structures is inevitable once big dendrites form; however, it is possible to minimize the amount of break-off materials by optimizing the rate of discharge. (3) The LBM is also used to simulate intercalation reactions in a Li-Ion battery with graphite as anode and pure Li metal as counter electrode. Both galvanostatic and potentiostatic conditions were studied. The relation between operation parameters (current and potential) and electrode parameters (porosity, thickness and diffusivity) and plating times were discussed. Different equilibrium potentials forms (empirical fitting, fitting of SONY 18650 cell, and staged profiles) were also compared. By modifying the morphology of electrode with a density gradient, it was shown that much better electrode performance can be obtained, which can be helpful for the designing and manufacturing of better batteries. (4) The transdermal drug delivery system is also simulated by using LBM. Two kinds of transdermal structures are discussed: "brick and mortar" structure and a simple homogenized structure. It is demonstrated that the homogenized system is able to obtain similar steady state flux as the "brick and mortar" structure; however, in the early transient region, their flux value can be different. The influence of different system parameters (amount of drug in patch, patch thickness, partition coefficient at patch/ Stratum Corneum (SC) interface, and the diffusion coefficient of drug in each component) is discussed in details. It turns out that in this system, the rate-determine step for mass transfer should be the partition between patch and SC layers and the diffusion in the SC layer. The influence of enhancer is also tested. It is shown that by adding enhancers, the drug flux can be significantly increased. However, the peak time of drug does not necessarily match the peak flux time of enhancer. The peak time of drug could be adjusted (pushed earlier or dragged later) by using different kinds of enhancers, which has higher/smaller diffusivity than drug in the SC layer.

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.

Evaluation of a new mid-scala cochlear implant electrode using microcomputed tomography.

PubMed

Frisch, Christopher D; Carlson, Matthew L; Lane, John I; Driscoll, Colin L W

2015-12-01

To investigate electrode position, depth of insertion, and electrode contact using an electrode array with a mid-scala design following round window (RW) and cochleostomy insertion. Eight fresh-frozen cadaveric bones were implanted; half via a RW approach and half through an anteroinferior cochleostomy using a styleted mid-scala electrode design. Microcomputed tomography was used to acquire oblique coronal and oblique axial reformations. Individual electrode positions along each array, insertional depth, and electrode contact were determined using National Institutes of Health Image J software. All electrodes were inserted without significant resistance. The average angular depth of insertion was 436.5° for the RW group and 422.7° for the cochleostomy group. All electrodes acquired a perimodiolar position in the proximal segment and a lateral wall position at the basal turn, regardless of approach. Electrodes distal to the basal turn demonstrated a variable location, with 78% mid scala. One cochleostomy array fractured through the interscalar partition (ISP), acquiring a scala vestibuli position. The odds ratio for either abutting the modiolus, ISP, lateral wall or floor, or fracturing through the ISP were 2.7 times more likely following a cochleostomy insertion (P = .032). The styleted mid-scala electrode design acquires a proximal perimodiolar position, a lateral wall location, as it traverses the basal turn, and most commonly a mid-scala position in the distal array. Interscalar excursion occurred in one of the cochleostomy insertions. Cochleostomy insertion is more likely to result in ultimate final electrode position adjacent to critical intracochlear structures. NA. © 2015 The American Laryngological, Rhinological and Otological Society, Inc.

Formation and Diffusion of Metal Impurities in Perovskite Solar Cell Material CH 3NH 3PbI 3 : Implications on Solar Cell Degradation and Choice of Electrode

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

Ming, Wenmei; Yang, Dongwen; Li, Tianshu

Solar cells based on methylammonium lead triiodide (MAPbI 3) have shown remarkable progress in recent years and have demonstrated efficiencies greater than 20%. However, the long-term stability of MAPbI 3-based solar cells has yet to be achieved. Besides the well-known chemical and thermal instabilities, significant native ion migration in lead halide perovskites leads to current–voltage hysteresis and photoinduced phase segregation. Recently, it is further revealed that, despite having excellent chemical stability, the Au electrode can cause serious solar cell degradation due to Au diffusion into MAPbI 3. In addition to Au, many other metals have been used as electrodes inmore » MAPbI 3 solar cells. However, how the external metal impurities introduced by electrodes affect the long-term stability of MAPbI 3 solar cells has rarely been studied. A comprehensive study of formation energetics and diffusion dynamics of a number of noble and transition metal impurities (Au, Ag, Cu, Cr, Mo, W, Co, Ni, Pd) in MAPbI 3 based on first-principles calculations is reported herein. The results uncover important general trends of impurity formation and diffusion in MAPbI 3 and provide useful guidance for identifying the optimal metal electrodes that do not introduce electrically active impurity defects in MAPbI 3 while having low resistivities and suitable work functions for carrier extraction.« less

Formation and Diffusion of Metal Impurities in Perovskite Solar Cell Material CH3NH3PbI3: Implications on Solar Cell Degradation and Choice of Electrode.

PubMed

Ming, Wenmei; Yang, Dongwen; Li, Tianshu; Zhang, Lijun; Du, Mao-Hua

2018-02-01

Solar cells based on methylammonium lead triiodide (MAPbI 3 ) have shown remarkable progress in recent years and have demonstrated efficiencies greater than 20%. However, the long-term stability of MAPbI 3 -based solar cells has yet to be achieved. Besides the well-known chemical and thermal instabilities, significant native ion migration in lead halide perovskites leads to current-voltage hysteresis and photoinduced phase segregation. Recently, it is further revealed that, despite having excellent chemical stability, the Au electrode can cause serious solar cell degradation due to Au diffusion into MAPbI 3 . In addition to Au, many other metals have been used as electrodes in MAPbI 3 solar cells. However, how the external metal impurities introduced by electrodes affect the long-term stability of MAPbI 3 solar cells has rarely been studied. A comprehensive study of formation energetics and diffusion dynamics of a number of noble and transition metal impurities (Au, Ag, Cu, Cr, Mo, W, Co, Ni, Pd) in MAPbI 3 based on first-principles calculations is reported herein. The results uncover important general trends of impurity formation and diffusion in MAPbI 3 and provide useful guidance for identifying the optimal metal electrodes that do not introduce electrically active impurity defects in MAPbI 3 while having low resistivities and suitable work functions for carrier extraction.

Formation and Diffusion of Metal Impurities in Perovskite Solar Cell Material CH 3NH 3PbI 3 : Implications on Solar Cell Degradation and Choice of Electrode

DOE PAGES

Ming, Wenmei; Yang, Dongwen; Li, Tianshu; ...

2017-12-27

Solar cells based on methylammonium lead triiodide (MAPbI 3) have shown remarkable progress in recent years and have demonstrated efficiencies greater than 20%. However, the long-term stability of MAPbI 3-based solar cells has yet to be achieved. Besides the well-known chemical and thermal instabilities, significant native ion migration in lead halide perovskites leads to current–voltage hysteresis and photoinduced phase segregation. Recently, it is further revealed that, despite having excellent chemical stability, the Au electrode can cause serious solar cell degradation due to Au diffusion into MAPbI 3. In addition to Au, many other metals have been used as electrodes inmore » MAPbI 3 solar cells. However, how the external metal impurities introduced by electrodes affect the long-term stability of MAPbI 3 solar cells has rarely been studied. A comprehensive study of formation energetics and diffusion dynamics of a number of noble and transition metal impurities (Au, Ag, Cu, Cr, Mo, W, Co, Ni, Pd) in MAPbI 3 based on first-principles calculations is reported herein. The results uncover important general trends of impurity formation and diffusion in MAPbI 3 and provide useful guidance for identifying the optimal metal electrodes that do not introduce electrically active impurity defects in MAPbI 3 while having low resistivities and suitable work functions for carrier extraction.« less

Formation and Diffusion of Metal Impurities in Perovskite Solar Cell Material CH3NH3PbI3: Implications on Solar Cell Degradation and Choice of Electrode

PubMed Central

Ming, Wenmei; Yang, Dongwen; Li, Tianshu

2017-01-01

Abstract Solar cells based on methylammonium lead triiodide (MAPbI3) have shown remarkable progress in recent years and have demonstrated efficiencies greater than 20%. However, the long‐term stability of MAPbI3‐based solar cells has yet to be achieved. Besides the well‐known chemical and thermal instabilities, significant native ion migration in lead halide perovskites leads to current–voltage hysteresis and photoinduced phase segregation. Recently, it is further revealed that, despite having excellent chemical stability, the Au electrode can cause serious solar cell degradation due to Au diffusion into MAPbI3. In addition to Au, many other metals have been used as electrodes in MAPbI3 solar cells. However, how the external metal impurities introduced by electrodes affect the long‐term stability of MAPbI3 solar cells has rarely been studied. A comprehensive study of formation energetics and diffusion dynamics of a number of noble and transition metal impurities (Au, Ag, Cu, Cr, Mo, W, Co, Ni, Pd) in MAPbI3 based on first‐principles calculations is reported herein. The results uncover important general trends of impurity formation and diffusion in MAPbI3 and provide useful guidance for identifying the optimal metal electrodes that do not introduce electrically active impurity defects in MAPbI3 while having low resistivities and suitable work functions for carrier extraction. PMID:29610728

Dose measurement in heterogeneous phantoms with an extrapolation chamber

NASA Astrophysics Data System (ADS)

Deblois, Francois

A hybrid phantom-embedded extrapolation chamber (PEEC) made of Solid Water(TM) and bone-equivalent material was used for determining absolute dose in a bone-equivalent phantom irradiated with clinical radiation beams (cobalt-60 gamma rays; 6 and 18 MV x-rays; and 9 and 15 MeV electrons). The dose was determined with the Spencer-Attix cavity theory, using ionization gradient measurements and an indirect determination of the chamber air-mass through measurements of chamber capacitance. The air gaps used were between 2 and 3 mm and the sensitive air volume of the extrapolation chamber was remotely controlled through the motion of the motorized piston with a precision of +/-0.0025 mm. The collected charge was corrected for ionic recombination and diffusion in the chamber air volume following the standard two-voltage technique. Due to the hybrid chamber design, correction factors accounting for scatter deficit and electrode composition were determined and applied in the dose equation to obtain dose data for the equivalent homogeneous bone phantom. Correction factors for graphite electrodes were calculated with Monte Carlo techniques and the calculated results were verified through relative air cavity dose measurements for three different polarizing electrode materials: graphite, steel, and brass in conjunction with a graphite collecting electrode. Scatter deficit, due mainly to loss of lateral scatter in the hybrid chamber, reduces the dose to the air cavity in the hybrid PEEC in comparison with full bone PEEC from 0.7 to ˜2% depending on beam quality and energy. In megavoltage photon and electron beams, graphite electrodes do not affect the dose measurement in the Solid Water(TM) PEEC but decrease the cavity dose by up to 5% in the bone-equivalent PEEC even for very thin graphite electrodes (<0.0025 cm). The collecting electrode material in comparison with the polarizing electrode material has a larger effect on the electrode correction factor; the thickness of thin electrodes, on the other hand, has a negligible effect on dose determination. The uncalibrated hybrid PEEC is an accurate and absolute device for measuring the dose directly in bone material in conjunction with appropriate correction factors determined with Monte Carlo techniques.

Simultaneous characterization of lateral lipid and prothrombin diffusion coefficients by z-scan fluorescence correlation spectroscopy.

PubMed

Stefl, Martin; Kułakowska, Anna; Hof, Martin

2009-08-05

A new (to our knowledge) robust approach for the determination of lateral diffusion coefficients of weakly bound proteins is applied for the phosphatidylserine specific membrane interaction of bovine prothrombin. It is shown that z-scan fluorescence correlation spectroscopy in combination with pulsed interleaved dual excitation allows simultaneous monitoring of the lateral diffusion of labeled protein and phospholipids. Moreover, from the dependencies of the particle numbers on the axial sample positions at different protein concentrations phosphatidylserine-dependent equilibrium dissociation constants are derived confirming literature values. Increasing the amount of membrane-bound prothrombin retards the lateral protein and lipid diffusion, indicating coupling of both processes. The lateral diffusion coefficients of labeled lipids are considerably larger than the simultaneously determined lateral diffusion coefficients of prothrombin, which contradicts findings reported for the isolated N-terminus of prothrombin.

Charging/discharging stability of a metal hydride battery electrode

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

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

1999-07-01

The metal hydride (MH) alloy powder for the negative electrode of the Ni/MH battery was first pulverized and oxidized by electrochemically charging and discharging for a number of cycles. The plate of the negative electrode of an experimental cell in this study was made from a mixture of a multicomponent AB{sub 5}-based alloy powder, nickel powder, and polytetra fluoroethylene (PTFE). The characteristics of the negative electrode, including discharge capacity, exchange current density, and hydrogen diffusivity, were studied by means of the electrochemical experiments and analysis in an experimental cell. The exchange current density of a Mm{sub 0.95}Ti{sub 0.05}Ni{sub 3.85}Co{sub 0.45}Mn{submore » 0.35}Al{sub 0.35} alloy electrode increases with increasing number of charge/discharge cycles and then remains almost constant after 20 cycles. A microcracking activation, resulting from an increase in reaction surface area and an improvement in the electrode surface activation, increases the hydrogen exchange current densities. Measurement of hydrogen diffusivities for Mm{sub 0.95}Ti{sub 0.05}Ni{sub 3.85}Co{sub 0.45}Mn{sub 0.35}Al{sub 0.35} alloy powder shows that the ratio of D/a{sup 2} (D = hydrogen diffusivity; a = sphere radius) increases with increasing number of cycles but remains constant after 20 cycles.« less

Self-diffusion of electrolyte species in model battery electrodes using Magic Angle Spinning and Pulsed Field Gradient Nuclear Magnetic Resonance

NASA Astrophysics Data System (ADS)

Tambio, Sacris Jeru; Deschamps, Michaël; Sarou-Kanian, Vincent; Etiemble, Aurélien; Douillard, Thierry; Maire, Eric; Lestriez, Bernard

2017-09-01

Lithium-ion batteries are electrochemical storage devices using the electrochemical activity of the lithium ion in relation to intercalation compounds owing to mass transport phenomena through diffusion. Diffusion of the lithium ion in the electrode pores has been poorly understood due to the lack of experimental techniques for measuring its self-diffusion coefficient in porous media. Magic-Angle Spinning, Pulsed Field Gradient, Stimulated-Echo Nuclear Magnetic Resonance (MAS-PFG-STE NMR) was used here for the first time to measure the self-diffusion coefficients of the electrolyte species in the LP30 battery electrolyte (i.e. a 1 M solution of LiPF6 dissolved in 1:1 Ethylene Carbonate - Dimethyl Carbonate) in model composites. These composite electrodes were made of alumina, carbon black and PVdF-HFP. Alumina's magnetic susceptibility is close to the measured magnetic susceptibility of the LP30 electrolyte thereby limiting undesirable internal field gradients. Interestingly, the self-diffusion coefficient of lithium ions decreases with increasing carbon content. FIB-SEM was used to describe the 3D geometry of the samples. The comparison between the reduction of self-diffusion coefficients as measured by PFG-NMR and as geometrically derived from FIB/SEM tortuosity values highlights the contribution of specific interactions at the material/electrolyte interface on the lithium transport properties.

Suppression of Lateral Diffusion and Surface Leakage Currents in nBn Photodetectors Using an Inverted Design

NASA Astrophysics Data System (ADS)

Du, X.; Savich, G. R.; Marozas, B. T.; Wicks, G. W.

2018-02-01

Surface leakage and lateral diffusion currents in InAs-based nBn photodetectors have been investigated. Devices fabricated using a shallow etch processing scheme that etches through the top contact and stops at the barrier exhibited large lateral diffusion current but undetectably low surface leakage. Such large lateral diffusion current significantly increased the dark current, especially in small devices, and causes pixel-to-pixel crosstalk in detector arrays. To eliminate the lateral diffusion current, two different approaches were examined. The conventional solution utilized a deep etch process, which etches through the top contact, barrier, and absorber. This deep etch processing scheme eliminated lateral diffusion, but introduced high surface current along the device mesa sidewalls, increasing the dark current. High device failure rate was also observed in deep-etched nBn structures. An alternative approach to limit lateral diffusion used an inverted nBn structure that has its absorber grown above the barrier. Like the shallow etch process on conventional nBn structures, the inverted nBn devices were fabricated with a processing scheme that only etches the top layer (the absorber, in this case) but avoids etching through the barrier. The results show that inverted nBn devices have the advantage of eliminating the lateral diffusion current without introducing elevated surface current.

Nanoband array electrode as a platform for high sensitivity enzyme-based glucose biosensing.

PubMed

Falk, Magnus; Sultana, Reshma; Swann, Marcus J; Mount, Andrew R; Freeman, Neville J

2016-12-01

We describe a novel glucose biosensor based on a nanoband array electrode design, manufactured using standard semiconductor processing techniques, and bio-modified with glucose oxidase immobilized at the nanoband electrode surface. The nanoband array architecture allows for efficient diffusion of glucose and oxygen to the electrode, resulting in a thousand-fold improvement in sensitivity and wide linear range compared to a conventional electrode. The electrode constitutes a robust and manufacturable sensing platform. Copyright © 2016 Elsevier B.V. All rights reserved.

Particle size effect in porous film electrodes of ligand-modified graphene for enhanced supercapacitor performance

DOE PAGES

Jang, Gyoung Gug; Song, Bo; Moon, Kyoung-sik; ...

2017-04-17

Graphene-based electrodes for high performance supercapacitors are developed by taking advantage of particle size control, large mass loading, and surface functionalization of reduced graphene oxide (rGO) sheets. Two controlled sizes of graphene sheets (100 nm vs. 45 μm average lateral dimensions) were prepared to study two-electrode system performance. The nano-size graphenes led to the formation of mesoporous films, resulting in higher capacitance, better capacitance retension and lower equivalent series resistance (ESR), indicating better surface usability for diffusion and accessibility of electrolyte ions by shortening transport paths (compared with horizontally stacked films from micro-sized graphenes). For studies using an aqueous electrolyte,more » the maximum specific capacitance of nano-rGO film was 302 F/g (at 1 A/g with 4.3 mg/cm 2 of mass loading), which was ~2.4 times higher than micro-rGO film, and achieved a ~67% reduced ESR. With an organic electrolyte, the nano-rGO delivered ~4.2 times higher capacitance (115 F/g at 2 A/g with 4.3 mg/cm 2), 4.0 times lower IR drops, and an order-of-magnitude lower charge-transfer resistance with an energy density of 18.7 Wh/kg. Finally, the results of this work indicate that the size control of graphene sheet particles for film deposit electrodes can be a simple but effective approach to improve supercapacitor performance.« less

Particle size effect in porous film electrodes of ligand-modified graphene for enhanced supercapacitor performance

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

Jang, Gyoung Gug; Song, Bo; Moon, Kyoung-sik

Graphene-based electrodes for high performance supercapacitors are developed by taking advantage of particle size control, large mass loading, and surface functionalization of reduced graphene oxide (rGO) sheets. Two controlled sizes of graphene sheets (100 nm vs. 45 μm average lateral dimensions) were prepared to study two-electrode system performance. The nano-size graphenes led to the formation of mesoporous films, resulting in higher capacitance, better capacitance retension and lower equivalent series resistance (ESR), indicating better surface usability for diffusion and accessibility of electrolyte ions by shortening transport paths (compared with horizontally stacked films from micro-sized graphenes). For studies using an aqueous electrolyte,more » the maximum specific capacitance of nano-rGO film was 302 F/g (at 1 A/g with 4.3 mg/cm 2 of mass loading), which was ~2.4 times higher than micro-rGO film, and achieved a ~67% reduced ESR. With an organic electrolyte, the nano-rGO delivered ~4.2 times higher capacitance (115 F/g at 2 A/g with 4.3 mg/cm 2), 4.0 times lower IR drops, and an order-of-magnitude lower charge-transfer resistance with an energy density of 18.7 Wh/kg. Finally, the results of this work indicate that the size control of graphene sheet particles for film deposit electrodes can be a simple but effective approach to improve supercapacitor performance.« less

Fabrication and characterization of microfabricated on-chip microelectrochemical cell for biosensing applications

NASA Astrophysics Data System (ADS)

Said, N. A. Mohd; Twomey, K.; Herzog, G.; Ogurtsov, V. I.

2017-03-01

The fabrication of on-chip microelectrochemical cell on Si wafer by means of photolithography is described here. The single on-chip microelectrochemical cell device has dimensions of 100 × 380 mm with integrated Pt counter electrode (CE), Ag/AgCl reference electrode (RE) and gold microelectrode array of 500 nm recess depth as the working electrode (WE). Two geometries of electrode array were implemented, band and disc, with fixed diameter/width of 10 µm; and varied centre-to-centre spacing (d) and number of electrodes (N) in the array. The on-chip microelectrochemical cell structure has been designed to facilitate further WE biomodifications. Firstly, the developed microelectrochemical cell does not require packaging hence reducing the production cost and time. Secondly, the working electrode (WE) on the microelectrochemical cell is positioned towards the end of the chip enabling modification of the working electrode surface to be carried out for surface bio-functionalisation without affecting both the RE and CE surface conditions. The developed on-chip microelectrochemical cell was examined with scanning electron microscopy (SEM) and characterised by two electrochemical techniques. Both cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were performed in 1 mM ferrocenecarboxylic acid (FCA) in 0.01 M phosphate buffered saline (PBS) solution at pH7.4. Electrochemical experiments showed that in the case of halving the interspacing distance of the microdisc WE array (50 nm instead of 100 nm), the voltammogram shifted from a steady-state CV (feature of hemispherical diffusion) to an inclined peak-shaped CV (feature of linear diffusion) albeit the arrays had the same surface area. In terms of EIS it was also found that linear diffusion dominates the surface instead of hemispherical diffusion once the interspacing distance was reduced, supporting the fact that closely packed arrays may behave like a macroelectrode

Palladium nanoparticles decorated on reduced graphene oxide rotating disk electrodes toward ultrasensitive hydrazine detection: effects of particle size and hydrodynamic diffusion.

PubMed

Krittayavathananon, Atiweena; Srimuk, Pattarachai; Luanwuthi, Santamon; Sawangphruk, Montree

2014-12-16

Although metal nanoparticle/graphene composites have been widely used as the electrode in electrochemical sensors, two effects, consisting of the particle size of the nanoparticles and the hydrodynamic diffusion of analytes to the electrodes, are not yet fully understood. In this work, palladium nanoparticles/reduced graphene oxide (PdNPs/rGO) composites were synthesized using an in situ polyol method. Palladium(II) ions and graphene oxide were reduced together with a reducing agent, ethylene glycol. By varying the concentration of palladium(II) nitrate, PdNPs with different sizes were decorated on the surface of rGO sheets. The as-fabricated PdNPs/rGO rotating disk electrodes (RDEs) were investigated toward hydrazine detection. Overall, a 3.7 ± 1.4 nm diameter PdNPs/rGO RDE exhibits high performance with a rather low limit of detection of about 7 nM at a rotation speed of 6000 rpm and provides a wide linear range of 0.1-1000 μM with R(2) = 0.995 at 2000 rpm. This electrode is highly selective to hydrazine without interference from uric acid, glucose, ammonia, caffeine, methylamine, ethylenediamine, hydroxylamine, n-butylamine, adenosine, cytosine, guanine, thymine, and l-arginine. The PdNPs/rGO RDEs with larger sizes show lower detection performance. Interestingly, the detection performance of the electrodes is sensitive to the hydrodynamic diffusion of hydrazine. The as-fabricated electrode can detect trace hydrazine in wastewater with high stability, demonstrating its practical use as an electrochemical sensor. These findings may lead to an awareness of the effect of the hydrodynamic diffusion of analyte that has been previously ignored, and the 3.7 ± 1.4 nm PdNPs/rGO RDE may be useful toward trace hydrazine detection, especially in wastewater from related chemical industries.

Advances in Studies of Electrode Kinetics and Mass Transport in AMTEC Cells (abstract)

NASA Technical Reports Server (NTRS)

Williams, R. M.; Jeffries-Nakamura, B.; Ryan, M. A.; Underwood, M. L.; Kisor, A.; O'Connor, D.; Kikkert, S.

1993-01-01

Previous work reported from JPL has included characterization of electrode kinetics and alkali atom transport from electrodes including Mo, W, WRh(sub x), WPt(sub x)(Mn), in sodium AMTEC cells and vapor exposure cells, and Mo in potassium vapor exposure cells. These studies were generally performed in cells with small area electrodes (about 1 to 5 cm(sup 2)), and device geometry had little effect on transport. Alkali diffusion coefficients through these electrodes have been characterized, and approximate surface diffusion coefficients derived in cases of activated transport. A basic model of electrode kinetic at the alkali metal vapor/porous metal electrode/alkali beta'-alumina solid electrolyte three phase boundary has been proposed which accounts for electrochemical reaction rates with a collision frequency near the three phase boundary and tunneling from the porous electrode partially covered with adsorbed alkali metal atoms. The small electrode effect in AMTEC cells has been discussed in several papers, but quantitative investigations have described only the overall effect and the important contribution of electrolyte resistance. The quantitative characterization of transport losses in cells with large area electrodes has been limited to simulations of large area electrode effects, or characterization of transport losses from large area electrodes with significant longitudinal temperature gradients. This paper describes new investigations of electrochemical kinetics and transport, particularily with WPt(sub 3.5) electrodes, including the influence of electrode size on the mass transport loss in the AMTEC cell. These electrodes possess excellent sodium transport properties making verification of device limitations on transport much more readily attained.

Challenging aspects of contemporary cochlear implant electrode array design.

PubMed

Mistrík, Pavel; Jolly, Claude; Sieber, Daniel; Hochmair, Ingeborg

2017-12-01

A design comparison of current perimodiolar and lateral wall electrode arrays of the cochlear implant (CI) is provided. The focus is on functional features such as acoustic frequency coverage and tonotopic mapping, battery consumption and dynamic range. A traumacity of their insertion is also evaluated. Review of up-to-date literature. Perimodiolar electrode arrays are positioned in the basal turn of the cochlea near the modiolus. They are designed to initiate the action potential in the proximity to the neural soma located in spiral ganglion. On the other hand, lateral wall electrode arrays can be inserted deeper inside the cochlea, as they are located along the lateral wall and such insertion trajectory is less traumatic. This class of arrays targets primarily surviving neural peripheral processes. Due to their larger insertion depth, lateral wall arrays can deliver lower acoustic frequencies in manner better corresponding to cochlear tonotopicity. In fact, spiral ganglion sections containing auditory nerve fibres tuned to low acoustic frequencies are located deeper than 1 and half turn inside the cochlea. For this reason, a significant frequency mismatch might be occurring for apical electrodes in perimodiolar arrays, detrimental to speech perception. Tonal languages such as Mandarin might be therefore better treated with lateral wall arrays. On the other hand, closer proximity to target tissue results in lower psychophysical threshold levels for perimodiolar arrays. However, the maximal comfort level is also lower, paradoxically resulting in narrower dynamic range than that of lateral wall arrays. Battery consumption is comparable for both types of arrays. Lateral wall arrays are less likely to cause trauma to cochlear structures. As the current trend in cochlear implantation is the maximal protection of residual acoustic hearing, the lateral wall arrays seem more suitable for hearing preservation CI surgeries. Future development could focus on combining the advantages of both types: perimodiolar location in the basal turn extended to lateral wall location for higher turn locations.

Three-dimensional reduced graphene oxide/polyaniline nanocomposite film prepared by diffusion driven layer-by-layer assembly for high-performance supercapacitors

NASA Astrophysics Data System (ADS)

Hong, Xiaodong; Zhang, Binbin; Murphy, Elizabeth; Zou, Jianli; Kim, Franklin

2017-03-01

As a simple and versatile method, diffusion driven Layer-by-Layer assembly (dd-LbL) is developed to assemble graphene oxide (GO) into three-dimensional (3D) structure. The assembled GO macrostructure can be reduced through a hydrothermal treatment and used as a high volumetric capacitance electrode in supercapacitors. In this report we use rGO framework created from dd-LbL as a scaffold for in situ polymerization of aniline within the pores of the framework to form rGO/polyaniline (rGO/PANI) composite. The rGO/PANI composite affords a robust and porous structure, which facilitates electrolyte diffusion and exhibits excellent electrochemical performance as binder-free electrodes in a sandwich-configuration supercapacitor. Combining electric double layer capacitance and pseudo-capacitance, rGO/PANI electrodes exhibit a specific capacitance of 438.8 F g-1 at discharge rate of 5 mA (mass of electrodes were 10.0 mg, 0.5 A g-1) in 1 mol L-1 H2SO4 electrolyte; furthermore, the generated PANI nanoparticles in rGO template achieve a higher capacitance of 763 F g-1. The rGO/PANI composite electrodes also show an improved recyclability, 76.5% of capacitance retains after recycled 2000 times.

Efficient Conservative Reformulation Schemes for Lithium Intercalation

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

Urisanga, PC; Rife, D; De, S

Porous electrode theory coupled with transport and reaction mechanisms is a widely used technique to model Li-ion batteries employing an appropriate discretization or approximation for solid phase diffusion with electrode particles. One of the major difficulties in simulating Li-ion battery models is the need to account for solid phase diffusion in a second radial dimension r, which increases the computation time/cost to a great extent. Various methods that reduce the computational cost have been introduced to treat this phenomenon, but most of them do not guarantee mass conservation. The aim of this paper is to introduce an inherently mass conservingmore » yet computationally efficient method for solid phase diffusion based on Lobatto III A quadrature. This paper also presents coupling of the new solid phase reformulation scheme with a macro-homogeneous porous electrode theory based pseudo 20 model for Li-ion battery. (C) The Author(s) 2015. Published by ECS. All rights reserved.« less

Characteristics and applications of diffuse discharge of water electrode in air

NASA Astrophysics Data System (ADS)

Wenzheng, LIU; Tahan, WANG; Xiaozhong, CHEN; Chuanlong, MA

2018-01-01

Plasma water treatment technology, which aims to produce strong oxidizing reactive particles that act on the gas-liquid interface by way of discharging, is used to treat the organic pollutants that do not degrade easily in water. This paper presents a diffuse-discharge plasma water treatment method, which is realized by constructing a conical air gap through an uneven medium layer. The proposed method uses water as one electrode, and a dielectric barrier discharge electrode is constructed by using an uneven dielectric. The electric field distribution in the discharge space will be uneven, wherein the long gap electric field will have a smaller intensity, while the short one will have a larger intensity. A diffuse glow discharge is formed in the cavity. With this type of plasma water treatment equipment, a methyl orange solution with a concentration of 10 mg l-1 was treated, and the removal rate was found to reach 88.96%.

A diffuse argon plume generated by a longitudinal slit jet equipped with a quadri-electrode barrier discharge

NASA Astrophysics Data System (ADS)

Li, Xuechen; Chu, Jingdi; Zhang, Qi; Zhang, Panpan; Jia, Pengying; Dong, Lifang

2018-04-01

A diffuse argon plume at atmospheric pressure is generated downstream of a longitudinal slit jet equipped with a dielectric barrier discharge in a quadri-electrode configuration. Results indicate that both the plume length and the spectral line intensities increase with the increase in the peak voltage. With fast photography it is found that there is a clear difference for discharges with different polarities. The positive discharge is composed of nonuniform branching filaments; however, it is fairly uniform for the negative discharge. Due to the charge overflow of the intra-electrode discharge, the streamer mechanism is involved in the plume discharge. In fact, the positive discharge and the negative one correspond to a cathode-directed streamer and an anode-directed streamer, respectively. The formation mechanisms of the branching filaments and the diffuse background are discussed at last.

Lateral diffusion in model membranes is independent of the size of the hydrophobic region of molecules.

PubMed Central

Balcom, B J; Petersen, N O

1993-01-01

We have systematically investigated the probe size and shape dependence of lateral diffusion in model dimyristoyl phosphatidylcholine membranes. Linear hydrophobic polymers, which differ in length by an order of magnitude, were used to explore the effect on the lateral diffusion coefficient of hydrodynamic restrictions in the bilayer interior. The polymers employed are isoprenoid alcohols--citronellol, solanesol, and dolichol. Tracer lateral diffusion coefficients were measured by fluorescence photobleaching recovery. Despite the large difference in lengths, the nitrobenzoxadiazole labelled alcohols all diffuse at the rate of lipid self-diffusion (5.0 x 10(-12) m2 s-1, 29 degrees C) in the liquid crystal phase. Companion measurements in isotropic polymer solution, in gel phase lipid membranes and with nonpolar fluorescent polyaromatic hydrocarbons, show a marked dependence of the lateral diffusion coefficient on the probe molecule size. Our results in the liquid crystal phase are in accord with free area theory which asserts that lateral diffusion in the membrane is restricted by the surface-free area. Probe molecules which are significantly longer than the host phospholipid, seven times longer in the case of dolichol, are still restricted in their lateral motion by the surface properties of the bilayer in the liquid crystal phase. Fluorescence quenching experiments indicate that the nitrobenzoxadiazole label does not reside at the aqueous interface, although it must reside in close proximity according to the diffusion measurements. PMID:8218892

Monte Carlo random walk simulation of electron transport in confined porous TiO{sub 2} as a promising candidate for photo-electrode of nano-crystalline solar cells

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

Javadi, M.; Abdi, Y., E-mail: y.abdi@ut.ac.ir

2015-08-14

Monte Carlo continuous time random walk simulation is used to study the effects of confinement on electron transport, in porous TiO{sub 2}. In this work, we have introduced a columnar structure instead of the thick layer of porous TiO{sub 2} used as anode in conventional dye solar cells. Our simulation results show that electron diffusion coefficient in the proposed columnar structure is significantly higher than the diffusion coefficient in the conventional structure. It is shown that electron diffusion in the columnar structure depends both on the cross section area of the columns and the porosity of the structure. Also, wemore » demonstrate that such enhanced electron diffusion can be realized in the columnar photo-electrodes with a cross sectional area of ∼1 μm{sup 2} and porosity of 55%, by a simple and low cost fabrication process. Our results open up a promising approach to achieve solar cells with higher efficiencies by engineering the photo-electrode structure.« less

Monte Carlo random walk simulation of electron transport in confined porous TiO2 as a promising candidate for photo-electrode of nano-crystalline solar cells

NASA Astrophysics Data System (ADS)

Javadi, M.; Abdi, Y.

2015-08-01

Monte Carlo continuous time random walk simulation is used to study the effects of confinement on electron transport, in porous TiO2. In this work, we have introduced a columnar structure instead of the thick layer of porous TiO2 used as anode in conventional dye solar cells. Our simulation results show that electron diffusion coefficient in the proposed columnar structure is significantly higher than the diffusion coefficient in the conventional structure. It is shown that electron diffusion in the columnar structure depends both on the cross section area of the columns and the porosity of the structure. Also, we demonstrate that such enhanced electron diffusion can be realized in the columnar photo-electrodes with a cross sectional area of ˜1 μm2 and porosity of 55%, by a simple and low cost fabrication process. Our results open up a promising approach to achieve solar cells with higher efficiencies by engineering the photo-electrode structure.

Modeling and simulation of Cu diffusion and drift in porous CMOS backend dielectrics

NASA Astrophysics Data System (ADS)

Ali, R.; Fan, Y.; King, S.; Orlowski, M.

2018-06-01

With the advent of porous dielectrics, Cu drift-diffusion reliability issues in CMOS backend have only been exacerbated. In this regard, a modeling and simulation study of Cu atom/ion drift-diffusion in porous dielectrics is presented to assess the backend reliability and to explore conditions for a reliable Resistive Random Access Memory (RRAM) operation. The numerical computation, using elementary jump frequencies for a random walk in 2D and 3D, is based on an extended adjacency tensor concept. It is shown that Cu diffusion and drift transport are affected as much by the level of porosity as by the pore morphology. Allowance is made for different rates of Cu dissolution into the dielectric and for Cu absorption and transport at and on the inner walls of the pores. Most of the complex phenomena of the drift-diffusion transport in porous media can be understood in terms of local lateral and vertical gradients and the degree of their perturbation caused by the presence of pores in the transport domain. The impact of pore morphology, related to the concept of tortuosity, is discussed in terms of "channeling" and "trapping" effects. The simulations are calibrated to experimental results of porous SiCOH layers of 25 nm thickness, sandwiched between Cu and Pt(W) electrodes with experimental porosity levels of 0%, 8%, 12%, and 25%. We find that porous SICOH is more immune to Cu+ drift at 300 K than non-porous SICOH.

Arbitrary helicity control of circularly polarized light from lateral-type spin-polarized light-emitting diodes at room temperature

NASA Astrophysics Data System (ADS)

Nishizawa, Nozomi; Aoyama, Masaki; Roca, Ronel C.; Nishibayashi, Kazuhiro; Munekata, Hiro

2018-05-01

We demonstrate arbitrary helicity control of circularly polarized light (CPL) emitted at room temperature from the cleaved side facet of a lateral-type spin-polarized light-emitting diode (spin-LED) with two ferromagnetic electrodes in an antiparallel magnetization configuration. Driving alternate currents through the two electrodes results in polarization switching of CPL with frequencies up to 100 kHz. Furthermore, tuning the current density ratio in the two electrodes enables manipulation of the degree of circular polarization. These results demonstrate arbitrary electrical control of polarization with high speed, which is required for the practical use of lateral-type spin-LEDs as monolithic CPL light sources.

Moving characteristics of electrodes for vacuum circuit breaker

NASA Astrophysics Data System (ADS)

Yuan, Shun; Wang, Jimei

1994-05-01

This paper analyzes the effect of the gap of electrodes on the state of vacuum arc by experiment and theory. And the model of vacuum arc is set up. The optimal gap can be deduced from controlling the vacuum arc to be diffusion state, in order to get the optimal moving characteristics of electrodes.

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.

Dual gas-diffusion membrane- and mediatorless dihydrogen/air-breathing biofuel cell operating at room temperature

NASA Astrophysics Data System (ADS)

Xia, Hong-qi; So, Keisei; Kitazumi, Yuki; Shirai, Osamu; Nishikawa, Koji; Higuchi, Yoshiki; Kano, Kenji

2016-12-01

A membraneless direct electron transfer (DET)-type dihydrogen (H2)/air-breathing biofuel cell without any mediator was constructed wherein bilirubin oxidase from Myrothecium verrucaria (BOD) and membrane-bound [NiFe] hydrogenase from Desulfovibrio vulgaris Miyazaki F (MBH) were used as biocatalysts for the cathode and the anode, respectively, and Ketjen black-modified water proof carbon paper (KB/WPCC) was used as an electrode material. The KB/WPCC surface was modified with 2-aminobenzoic acid and p-phenylenediamine, respectively, to face the positively charged electron-accepting site of BOD and the negatively charged electron-donating site of MBH to the electrode surface. A gas-diffusion system was employed for the electrodes to realize high-speed substrate supply. As result, great improvement in the current density of O2 reduction with BOD and H2 reduction with MBH were realized at negatively and postively charged surfaces, respectively. Gas diffusion system also suppressed the oxidative inactivation of MBH at high electrode potentials. Finally, based on the improved bioanode and biocathode, a dual gas-diffusion membrane- and mediatorless H2/air-breathing biofuel cell was constructed. The maximum power density reached 6.1 mW cm-2 (at 0.72 V), and the open circuit voltage was 1.12 V using 1 atm of H2 gas as a fuel at room temperature and under passive and quiescent conditions.

Interfacial strain effects on lithium diffusion pathways in the spinel solid electrolyte Li-doped MgAl2O4

NASA Astrophysics Data System (ADS)

O'Rourke, Conn; Morgan, Benjamin J.

2018-04-01

The (Li,Al)-codoped magnesium spinel (LixMg1 -2 xAl2 +xO4 ) is a solid lithium-ion electrolyte with potential use in all-solid-state lithium-ion batteries. The spinel structure means that interfaces with spinel electrodes, such as LiyMn2O4 and Li4 +3 zTi5O12 , may be lattice matched, with potentially low interfacial resistances. Small lattice parameter differences across a lattice-matched interface are unavoidable, causing residual epitaxial strain. This strain potentially modifies lithium diffusion near the electrolyte-electrode interface, contributing to interfacial resistance. Here, we report a density functional theory study of strain effects on lithium diffusion pathways for (Li,Al)-codoped magnesium spinel, for xLi=0.25 and xLi=0.5 . We have calculated diffusion profiles for the unstrained materials, and for isotropic and biaxial tensile strains of up to 6 % , corresponding to {100 } epitaxial interfaces with LiyMn2O4 and Li4 +3 zTi5O12 . We find that isotropic tensile strain reduces lithium diffusion barriers by as much as 0.32 eV , with typical barriers reduced by ˜0.1 eV. This effect is associated with increased volumes of transitional octahedral sites, and broadly follows qualitative changes in local electrostatic potentials. For biaxial (epitaxial) strain, which more closely approximates strain at a lattice-matched electrolyte-electrode interface, changes in octahedral site volumes and in lithium diffusion barriers are much smaller than under isotropic strain. Typical barriers are reduced by only ˜0.05 eV. Individual effects, however, depend on the pathway considered and the relative strain orientation. These results predict that isotropic strain strongly affects ionic conductivities in (Li,Al)-codoped magnesium spinel electrolytes, and that tensile strain is a potential route to enhanced lithium transport. For a lattice-matched interface with candidate spinel-structured electrodes, however, epitaxial strain has a small, but complex, effect on lithium diffusion barriers.

Effect of Post Treatment For Cu-Cr Source/Drain Electrodes on a-IGZO TFTs.

PubMed

Hu, Shiben; Fang, Zhiqiang; Ning, Honglong; Tao, Ruiqiang; Liu, Xianzhe; Zeng, Yong; Yao, Rihui; Huang, Fuxiang; Li, Zhengcao; Xu, Miao; Wang, Lei; Lan, Linfeng; Peng, Junbiao

2016-07-27

We report a high-performance amorphous Indium-Gallium-Zinc-Oxide (a-IGZO) thin-film transistor (TFT) with new copper-chromium (Cu-Cr) alloy source/drain electrodes. The TFT shows a high mobility of 39.4 cm 2 ·V - 1 ·s - 1 a turn-on voltage of -0.8 V and a low subthreshold swing of 0.47 V/decade. Cu diffusion is suppressed because pre-annealing can protect a-IGZO from damage during the electrode sputtering and reduce the copper diffusion paths by making film denser. Due to the interaction of Cr with a-IGZO, the carrier concentration of a-IGZO, which is responsible for high mobility, rises.

Effect of Post Treatment For Cu-Cr Source/Drain Electrodes on a-IGZO TFTs

PubMed Central

Hu, Shiben; Fang, Zhiqiang; Ning, Honglong; Tao, Ruiqiang; Liu, Xianzhe; Zeng, Yong; Yao, Rihui; Huang, Fuxiang; Li, Zhengcao; Xu, Miao; Wang, Lei; Lan, Linfeng; Peng, Junbiao

2016-01-01

We report a high-performance amorphous Indium-Gallium-Zinc-Oxide (a-IGZO) thin-film transistor (TFT) with new copper-chromium (Cu-Cr) alloy source/drain electrodes. The TFT shows a high mobility of 39.4 cm2·V−1·s−1 a turn-on voltage of −0.8 V and a low subthreshold swing of 0.47 V/decade. Cu diffusion is suppressed because pre-annealing can protect a-IGZO from damage during the electrode sputtering and reduce the copper diffusion paths by making film denser. Due to the interaction of Cr with a-IGZO, the carrier concentration of a-IGZO, which is responsible for high mobility, rises. PMID:28773743

Exploratory laboratory study of lateral turbulent diffusion at the surface of an alluvial channel

USGS Publications Warehouse

Sayre, William W.; Chamberlain, A.R.

1964-01-01

In natural streams turbulent diffusion is one of the principal mechanisms by which liquid and suspended-particulate contaminants are dispersed in the flow. A knowledge of turbulence characteristics is therefore essential in predicting the dispersal rates of contaminants in streams. In this study the theory of diffusion by continuous movements for homogeneous turbulence is applied to lateral diffusion at the surface of an open channel in which there is uniform flow. An exploratory-laboratory investigation was conducted in which the lateral dispersion at the water surface of a sand-Led flume was studied by measuring the lateral spread from a point source of small floating polyethylene articles. The experiment was restricted to a single set of low and channel geometry conditions. The results of the study indicate that with certain restrictions lateral dispersion in alluvial channels may be successfully described by the theory of diffusion by continuous movements. The experiment demonstrates a means for evaluating the lateral diffusion coefficient and also methods for quantitatively estimating fundamental turbulence properties, such as the intensity and the Lagrangian integral scale of turbulence in an alluvial channel. The experimental results show that with increasing distance from the source the coefficient of lateral turbulent diffusion increases initially but tends toward a constant limiting value. This result is in accordance with turbulent diffusion theory. Indications are that the distance downstream from the source required for the diffusion coefficient to reach its limiting value is actually very small when compared to the length scale of most diffusion phenomena in natural streams which are of practical interest.

Oxygen concentration sensor for an internal combustion engine

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

Nakajima, T.; Okada, Y.; Mieno, T.

1988-09-29

This patent describes an oxygen concentration sensor, comprising: an oxygen ion conductive solid electrolyte member forming a gas diffusion restricted region into which a measuring gas is introduced; a pair of electrodes sandwiching the solid electrolyte member; pump current supply means applying a pump voltage to the pair of electrodes through a current detection element to generate a pump current; and a heater element connected to the solid electrolyte member for heating the solid electrolyte member for heating the solid electrolyte member when a heater current is supplied from a heater current source; wherein the oxygen concentration sensor detects anmore » oxygen concentration in the measuring gas in terms of a current value of the pump current supplied through the current detection element and controls oxygen concentration in the gas diffusion restricted region by conducting oxygen ions through the solid electrolyte member in accordance to the flow of the pump current; and wherein the current detection element is connected to the electrode of the pair of electrodes facing the gas diffusion restricted region for insuring that the current value is representative of the pump current and possible leakage current from the heater current.« less

Nonlinear dynamics of capacitive charging and desalination by porous electrodes.

PubMed

Biesheuvel, P M; Bazant, M Z

2010-03-01

The rapid and efficient exchange of ions between porous electrodes and aqueous solutions is important in many applications, such as electrical energy storage by supercapacitors, water desalination and purification by capacitive deionization, and capacitive extraction of renewable energy from a salinity difference. Here, we present a unified mean-field theory for capacitive charging and desalination by ideally polarizable porous electrodes (without Faradaic reactions or specific adsorption of ions) valid in the limit of thin double layers (compared to typical pore dimensions). We illustrate the theory for the case of a dilute, symmetric, binary electrolyte using the Gouy-Chapman-Stern (GCS) model of the double layer, for which simple formulae are available for salt adsorption and capacitive charging of the diffuse part of the double layer. We solve the full GCS mean-field theory numerically for realistic parameters in capacitive deionization, and we derive reduced models for two limiting regimes with different time scales: (i) in the "supercapacitor regime" of small voltages and/or early times, the porous electrode acts like a transmission line, governed by a linear diffusion equation for the electrostatic potential, scaled to the RC time of a single pore, and (ii) in the "desalination regime" of large voltages and long times, the porous electrode slowly absorbs counterions, governed by coupled, nonlinear diffusion equations for the pore-averaged potential and salt concentration.

Nonlinear dynamics of capacitive charging and desalination by porous electrodes

NASA Astrophysics Data System (ADS)

Biesheuvel, P. M.; Bazant, M. Z.

2010-03-01

The rapid and efficient exchange of ions between porous electrodes and aqueous solutions is important in many applications, such as electrical energy storage by supercapacitors, water desalination and purification by capacitive deionization, and capacitive extraction of renewable energy from a salinity difference. Here, we present a unified mean-field theory for capacitive charging and desalination by ideally polarizable porous electrodes (without Faradaic reactions or specific adsorption of ions) valid in the limit of thin double layers (compared to typical pore dimensions). We illustrate the theory for the case of a dilute, symmetric, binary electrolyte using the Gouy-Chapman-Stern (GCS) model of the double layer, for which simple formulae are available for salt adsorption and capacitive charging of the diffuse part of the double layer. We solve the full GCS mean-field theory numerically for realistic parameters in capacitive deionization, and we derive reduced models for two limiting regimes with different time scales: (i) in the “supercapacitor regime” of small voltages and/or early times, the porous electrode acts like a transmission line, governed by a linear diffusion equation for the electrostatic potential, scaled to the RC time of a single pore, and (ii) in the “desalination regime” of large voltages and long times, the porous electrode slowly absorbs counterions, governed by coupled, nonlinear diffusion equations for the pore-averaged potential and salt concentration.

Charge transport through split photoelectrodes in dye-sensitized solar cells

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

Fakharuddin, Azhar; Ahmed, Irfan; Yusoff, Mashitah M.

2014-04-28

Charge transport and recombination are relatively ignored parameters while upscaling dye-sensitized solar cells (DSCs). Enhanced photovoltaic parameters are anticipated by merely widening the devices physical dimensions, viz., thickness and area as evident from the device design adopted in reported large area DSCs. These strip designs lead to ≤50% loss in photocurrent compared to the high efficiency lab scale devices. Herein, we report that the key to achieving higher current density (J{sub SC}) is optimized diffusion volume rather than the increased photoelectrode area because kinetics of the devices is strongly influenced by the varied choices of diffusion pathways upon increasing themore » electrode area. For a given electrode area and thickness, we altered the photoelectrode design by splitting the electrode into multiple fractions to restrict the electron diffusion pathways. We observed a correlation between the device physical dimensions and its charge collection efficiency via current-voltage and impedance spectroscopy measurements. The modified electrode designs showed >50% increased J{sub SC} due to shorter transport time, higher recombination resistance and enhanced charge collection efficiency compared to the conventional ones despite their similar active volume (∼3.36 × 10{sup −4} cm{sup 3}). A detailed charge transport characteristic of the split devices and their comparison with single electrode configuration is described in this article.« less

Lithium manganese oxide spinel electrodes

NASA Astrophysics Data System (ADS)

Darling, Robert Mason

Batteries based oil intercalation eletrodes are currently being considered for a variety of applications including automobiles. This thesis is concerned with the simulation and experimental investigation of one such system: spinel LiyMn2O4. A mathematical model simulating the behavior of an electrochemical cell containing all intercalation electrode is developed and applied to Li yMn2O4 based systems. The influence of the exchange current density oil the propagation of the reaction through the depth of the electrode is examined theoretically. Galvanostatic cycling and relaxation phenomena on open circuit are simulated for different particle-size distributions. The electrode with uniformly sized particles shows the best performance when the current is on, and relaxes towards equilibrium most quickly. The impedance of a porous electrode containing a particle-size distribution at low frequencies is investigated with all analytic solution and a simplified version of the mathematical model. The presence of the particle-size distribution leads to an apparent diffusion coefficient which has all incorrect concentration dependence. A Li/1 M LiClO4 in propylene carbonate (PC)/ LiyMn 2O4 cell is used to investigate the influence of side reactions oil the current-potential behavior of intercalation electrodes. Slow cyclic voltammograms and self-discharge data are combined to estimate the reversible potential of the host material and the kinetic parameters for the side reaction. This information is then used, together with estimates of the solid-state diffusion coefficient and main-reaction exchange current density, in a mathematical model of the system. Predictions from the model compare favorably with continuous cycling results and galvanostatic experiments with periodic current interruptions. The variation with respect to composition of' the diffusion coefficient of lithium in LiyMn2O4 is estimated from incomplete galvanostatic discharges following open-circult periods. The results compared favorably with those available in the literature. Dynamic Monte Carlo simulations were conducted to investigate the concentration dependence of the diffusion coefficient fundamentally. The dynamic Monte Carlo predictions compare favorably with the experimental data.

Toward highly efficient electrocatalyst for Li–O 2 batteries using biphasic N-doping cobalt@graphene multiple-capsule heterostructures

DOE PAGES

Tan, Guoqiang; Chong, Lina; Amine, Rachid; ...

2017-04-12

To promote lithium-oxygen batteries available for practical applications, the development of advanced cathode catalysts with low-cost, high activity and stable structural properties is demanded. Such development is rooted on certain intelligent catalyst-electrode design that fundamentally facilitates electronic and ionic transport, and improves oxygen diffusivity in a porous environment. Here we design a biphasic nitrogen-doped cobalt@graphene multiple-capsule heterostructure, combined with a flexible, stable porous electrode architecture, and apply it as promising cathodes for lithium-oxygen cells. The biphasic nitrogen-doping feature improves the electric conductivity and catalytic activity; the multiple-nanocapsule configuration makes high/uniform electro-active zones possible; furthermore, the colander-like porous electrode facilitates themore » oxygen diffusion, catalytic reaction, and stable deposition of discharge products. Finally, the electrode exhibits much improved electrocatalytic properties associated with unique morphologies of electrochemically grown lithium peroxides.« less

Toward Highly Efficient Electrocatalyst for Li–O 2 Batteries Using Biphasic N-Doping Cobalt@Graphene Multiple-Capsule Heterostructures

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

Tan, Guoqiang; Chong, Lina; Amine, Rachid

For the promotion of lithium oxygen batteries available for :practical applications, the development of advanced cathode catalysts with low-high activity, and stable structural properties is demanded. Such development is rooted on certain intelligent catalyst-electrode design that fundamentally facilitates electronic and ionic transport and improves oxygen diffusivity in a porous environment. Here we design a biphasic nitrogen-doped cobalt@grapbene Multiple-capsule heterostructure, combined with a flexible, stable porous electrode architecture, and apply it as promising cathodes for lithium oxygen cells. 'The biphasic nitrogen-doping feature improves the electric conductivity and catalytic activity; the multiple-nanocapsule configuration makes high/uniform electroactive zones possible; furthermore the colander-like porousmore » electrode facilitates the oxygen diffusion, catalytic reaction,and stable deposition of discharge products. As a result, the electrode exhibits much improved electrocatalytic properties associated with unique morphologies of electrochemically grown lithium peroxides.« less

Toward highly efficient electrocatalyst for Li–O 2 batteries using biphasic N-doping cobalt@graphene multiple-capsule heterostructures

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

Tan, Guoqiang; Chong, Lina; Amine, Rachid

To promote lithium-oxygen batteries available for practical applications, the development of advanced cathode catalysts with low-cost, high activity and stable structural properties is demanded. Such development is rooted on certain intelligent catalyst-electrode design that fundamentally facilitates electronic and ionic transport, and improves oxygen diffusivity in a porous environment. Here we design a biphasic nitrogen-doped cobalt@graphene multiple-capsule heterostructure, combined with a flexible, stable porous electrode architecture, and apply it as promising cathodes for lithium-oxygen cells. The biphasic nitrogen-doping feature improves the electric conductivity and catalytic activity; the multiple-nanocapsule configuration makes high/uniform electro-active zones possible; furthermore, the colander-like porous electrode facilitates themore » oxygen diffusion, catalytic reaction, and stable deposition of discharge products. Finally, the electrode exhibits much improved electrocatalytic properties associated with unique morphologies of electrochemically grown lithium peroxides.« less

Toward Highly Efficient Electrocatalyst for Li-O2 Batteries Using Biphasic N-Doping Cobalt@Graphene Multiple-Capsule Heterostructures.

PubMed

Tan, Guoqiang; Chong, Lina; Amine, Rachid; Lu, Jun; Liu, Cong; Yuan, Yifei; Wen, Jianguo; He, Kun; Bi, Xuanxuan; Guo, Yuanyuan; Wang, Hsien-Hau; Shahbazian-Yassar, Reza; Al Hallaj, Said; Miller, Dean J; Liu, Dijia; Amine, Khalil

2017-05-10

For the promotion of lithium-oxygen batteries available for practical applications, the development of advanced cathode catalysts with low-cost, high activity, and stable structural properties is demanded. Such development is rooted on certain intelligent catalyst-electrode design that fundamentally facilitates electronic and ionic transport and improves oxygen diffusivity in a porous environment. Here we design a biphasic nitrogen-doped cobalt@graphene multiple-capsule heterostructure, combined with a flexible, stable porous electrode architecture, and apply it as promising cathodes for lithium-oxygen cells. The biphasic nitrogen-doping feature improves the electric conductivity and catalytic activity; the multiple-nanocapsule configuration makes high/uniform electroactive zones possible; furthermore, the colander-like porous electrode facilitates the oxygen diffusion, catalytic reaction, and stable deposition of discharge products. As a result, the electrode exhibits much improved electrocatalytic properties associated with unique morphologies of electrochemically grown lithium peroxides.

A MoO2 sheet as a promising electrode material: ultrafast Li-diffusion and astonishing Li-storage capacity

NASA Astrophysics Data System (ADS)

Zhou, Yungang; Geng, Cheng

2017-03-01

The potential of MoO2 crystal as an electrode material is reported, and nanostructural MoO2 systems, including nanoparticles, nanospheres, nanobelts and nanowires, were synthesized and proved to be advanced electrode materials. A two-dimensional (2D) geometric structure represents an extreme of surface-to-volume ratio, and thus is more suitable as an electrode material in general. Stimulated by the recent fabrication of 2D MoO2, we adopted an ab initio molecular dynamics simulation and density functional theory calculation to study the stability and electrochemical properties of a MoO2 sheet. Identified by a phonon dispersion curve and potential energy curve calculations, the MoO2 sheet proved to be dynamically and thermally stable. After lithiation, similar to most promising 2D structures, we found that a Li atom can strongly adsorb on a MoO2 sheet, and the lithiated MoO2 sheet presented excellent metallic properties. Note that, compared with most promising 2D structures, we unexpectedly revealed that the diffusion barrier of the Li atom on the MoO2 sheet was much lower and the storage capacity of the MoO2 sheet was much larger. The calculated energy barrier for the diffusion of Li on the MoO2 sheet was only 75 meV, and, due to multilayer adsorption, the theoretical capacity of the MoO2 sheet can reach up to 2513 mA h g-1. Benefiting from general properties, such as strong Li-binding and excellent conductivity, and unique phenomena, such as ultrafast diffusion capacity and astonishing storage capacity, we highlight a new promising electrode material for the Li-ion battery.

Simulations of Cyclic Voltammetry for Electric Double Layers in Asymmetric Electrolytes: A Generalized Modified Poisson-Nernst-Planck Model

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

Wang, Hainan; Thiele, Alexander; Pilon, Laurent

2013-11-15

This paper presents a generalized modified Poisson–Nernst–Planck (MPNP) model derived from first principles based on excess chemical potential and Langmuir activity coefficient to simulate electric double-layer dynamics in asymmetric electrolytes. The model accounts simultaneously for (1) asymmetric electrolytes with (2) multiple ion species, (3) finite ion sizes, and (4) Stern and diffuse layers along with Ohmic potential drop in the electrode. It was used to simulate cyclic voltammetry (CV) measurements for binary asymmetric electrolytes. The results demonstrated that the current density increased significantly with decreasing ion diameter and/or increasing valency |z i| of either ion species. By contrast, the ionmore » diffusion coefficients affected the CV curves and capacitance only at large scan rates. Dimensional analysis was also performed, and 11 dimensionless numbers were identified to govern the CV measurements of the electric double layer in binary asymmetric electrolytes between two identical planar electrodes of finite thickness. A self-similar behavior was identified for the electric double-layer integral capacitance estimated from CV measurement simulations. Two regimes were identified by comparing the half cycle period τ CV and the “RC time scale” τ RC corresponding to the characteristic time of ions’ electrodiffusion. For τ RC ← τ CV, quasi-equilibrium conditions prevailed and the capacitance was diffusion-independent while for τ RC → τ CV, the capacitance was diffusion-limited. The effect of the electrode was captured by the dimensionless electrode electrical conductivity representing the ratio of characteristic times associated with charge transport in the electrolyte and that in the electrode. The model developed here will be useful for simulating and designing various practical electrochemical, colloidal, and biological systems for a wide range of applications.« less

Probing Electrode Heterogeneity Using Fourier-Transformed Alternating Current Voltammetry: Application to a Dual-Electrode Configuration.

PubMed

Tan, Sze-Yin; Unwin, Patrick R; Macpherson, Julie V; Zhang, Jie; Bond, Alan M

2017-03-07

Quantitative studies of electron transfer processes at electrode/electrolyte interfaces, originally developed for homogeneous liquid mercury or metallic electrodes, are difficult to adapt to the spatially heterogeneous nanostructured electrode materials that are now commonly used in modern electrochemistry. In this study, the impact of surface heterogeneity on Fourier-transformed alternating current voltammetry (FTACV) has been investigated theoretically under the simplest possible conditions where no overlap of diffusion layers occurs and where numerical simulations based on a 1D diffusion model are sufficient to describe the mass transport problem. Experimental data that meet these requirements can be obtained with the aqueous [Ru(NH 3 ) 6 ] 3+/2+ redox process at a dual-electrode system comprised of electrically coupled but well-separated glassy carbon (GC) and boron-doped diamond (BDD) electrodes. Simulated and experimental FTACV data obtained with this electrode configuration, and where distinctly different heterogeneous charge transfer rate constants (k 0 values) apply at the individual GC and BDD electrode surfaces, are in excellent agreement. Principally, because of the far greater dependence of the AC current magnitude on k 0 , it is straightforward with the FTACV method to resolve electrochemical heterogeneities that are ∼1-2 orders of magnitude apart, as applies in the [Ru(NH 3 ) 6 ] 3+/2+ dual-electrode configuration experiments, without prior knowledge of the individual kinetic parameters (k 0 1 and k 0 2 ) or the electrode size ratio (θ 1 :θ 2 ). In direct current voltammetry, a difference in k 0 of >3 orders of magnitude is required to make this distinction.

Rotating disk electrode system for elevated pressures and temperatures.

PubMed

Fleige, M J; Wiberg, G K H; Arenz, M

2015-06-01

We describe the development and test of an elevated pressure and temperature rotating disk electrode (RDE) system that allows measurements under well-defined mass transport conditions. As demonstrated for the oxygen reduction reaction on polycrystalline platinum (Pt) in 0.5M H2SO4, the setup can easily be operated in a pressure range of 1-101 bar oxygen, and temperature of 140 °C. Under such conditions, diffusion limited current densities increase by almost two orders of magnitude as compared to conventional RDE setups allowing, for example, fuel cell catalyst studies under more realistic conditions. Levich plots demonstrate that the mass transport is indeed well-defined, i.e., at low electrode potentials, the measured current densities are fully diffusion controlled, while at higher potentials, a mixed kinetic-diffusion controlled regime is observed. Therefore, the setup opens up a new field for RDE investigations under temperature and current density conditions relevant for low and high temperature proton exchange membrane fuel cells.

Rotating disk electrode system for elevated pressures and temperatures

NASA Astrophysics Data System (ADS)

Fleige, M. J.; Wiberg, G. K. H.; Arenz, M.

2015-06-01

We describe the development and test of an elevated pressure and temperature rotating disk electrode (RDE) system that allows measurements under well-defined mass transport conditions. As demonstrated for the oxygen reduction reaction on polycrystalline platinum (Pt) in 0.5M H2SO4, the setup can easily be operated in a pressure range of 1-101 bar oxygen, and temperature of 140 °C. Under such conditions, diffusion limited current densities increase by almost two orders of magnitude as compared to conventional RDE setups allowing, for example, fuel cell catalyst studies under more realistic conditions. Levich plots demonstrate that the mass transport is indeed well-defined, i.e., at low electrode potentials, the measured current densities are fully diffusion controlled, while at higher potentials, a mixed kinetic-diffusion controlled regime is observed. Therefore, the setup opens up a new field for RDE investigations under temperature and current density conditions relevant for low and high temperature proton exchange membrane fuel cells.

Interdye Hole Transport Accelerates Recombination in Dye Sensitized Mesoporous Films.

PubMed

Moia, Davide; Szumska, Anna; Vaissier, Valérie; Planells, Miquel; Robertson, Neil; O'Regan, Brian C; Nelson, Jenny; Barnes, Piers R F

2016-10-12

Charge recombination between oxidized dyes attached to mesoporous TiO 2 and electrons in the TiO 2 was studied in inert electrolytes using transient absorption spectroscopy. Simultaneously, hole transport within the dye monolayers was monitored by transient absorption anisotropy. The rate of recombination decreased when hole transport was inhibited selectively, either by decreasing the dye surface coverage or by changing the electrolyte environment. From Monte Carlo simulations of electron and hole diffusion in a particle, modeled as a cubic structure, we identify the conditions under which hole lifetime depends on the hole diffusion coefficient for the case of normal (disorder free) diffusion. From simulations of transient absorption and transient absorption anisotropy, we find that the rate and the dispersive character of hole transport in the dye monolayer observed spectroscopically can be explained by incomplete coverage and disorder in the monolayer. We show that dispersive transport in the dye monolayer combined with inhomogeneity in the TiO 2 surface reactivity can contribute to the observed stretched electron-hole recombination dynamics and electron density dependence of hole lifetimes. Our experimental and computational analysis of lateral processes at interfaces can be applied to investigate and optimize charge transport and recombination in solar energy conversion devices using electrodes functionalized with molecular light absorbers and catalysts.

Simultaneous in vivo imaging of diffuse optical reflectance, optoacoustic pressure and ultrasonic scattering (Conference Presentation)

NASA Astrophysics Data System (ADS)

Subochev, Pavel V.; Orlova, Anna G.; Turchin, Ilya V.

2017-03-01

We will present reflection-mode bioimaging system providing complementary optical, photoacsoutic and acoustic measurements by acoustic detector after each laser pulse with 2kHz repetition rate. The photons absorbed within the biological tissue provide optoacoustic (OA) signals, the photons absorbed by the external electrode of a detector provide the measurable diffuse reflectance (DR) from the sample and the probing ultrasonic (US) pulse. To demonstrate the in vivo capabilities of the system we performed complementary DR/OA/US imaging of small laboratory animals and human palm with 3.5mm/50μm/35μm lateral resolution at up to 3 mm diagnostic depth. Functional OA and DR imaging demonstrated the levels of tissue vascularization and blood supply. Structural US imaging was essential for understanding the position of vessels and zones with different perfusion. Before BiOS-2017 we plan to accomplish more in vivo experiments validating the developed triple-modality system as diagnostic tool to detect vascularization as well as mechanisms of vascular changes when monitoring response to therapy.

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

Warren, Oden Lee; Asif, Syed Amanulla Syed; Oh, Yunje

A testing instrument for mechanical testing at nano or micron scale includes a transducer body, and a coupling shaft coupled with a probe tip. A transducer body houses a capacitor. The capacitor includes first and second counter electrodes and a center electrode assembly interposed therebetween. The center electrode assembly is movable with the coupling shaft relative to the first and second counter electrodes, for instance in one or more of dimensions including laterally and normally. The center electrode assembly includes a center plate coupled with the coupling shaft and one or more springs extending from the center plate. Upper andmore » lower plates are coupled with the center plate and cover the center plate and the one or more springs. A shaft support assembly includes one or more support elements coupled along the coupling shaft. The shaft support assembly provides lateral support to the coupling shaft.« less

Electrodeposition of Polymer Nanostructures using Three Diffuse Double Layers: Polymerization beyond the Liquid/Liquid Interfaces

NASA Astrophysics Data System (ADS)

Divya, Velpula; Sangaranarayanan, M. V.

2018-04-01

Nanostructured conducting polymers have received immense attention during the past few decades on account of their phenomenal usefulness in diverse contexts, while the interface between two immiscible liquids is of great interest in chemical and biological applications. Here we propose a novel Electrode(solid)/Electrolyte(aqueous)/Electrolyte(organic) Interfacial assembly for the synthesis of polymeric nanostructures using a novel concept of three diffuse double layers. There exist remarkable differences between the morphologies of the polymers synthesized using the conventional electrode/electrolyte method and that of the new approach. In contrast to the commonly employed electrodeposition at liquid/liquid interfaces, these polymer modified electrodes can be directly employed in diverse applications such as sensors, supercapacitors etc.

Induced polarization: Simulation and inversion of nonlinear mineral electrodics

NASA Astrophysics Data System (ADS)

Agunloye, Olu

1983-02-01

Graph-theoretic representations are used to model nonlinear electrodics, while forward and inverse simulations are based on reaction rate theory. The electrodic responses are presented as distorted elliptical Lissajous shapes obtained from dynamic impedance over a full cycle. Simulations show that asymmetry in reaction energy barrier causes slight asymmetry in the shape of the response ellipse and hardly affects the phase angle of the complex electrode impedance. The charge transfer resistance and the diffusion constraints tend to have opposite effects. The former causes reduction in the phase angle, tending to make the impedance purely resistive. Both of these mechanisms show saturation effects. Charge transfer resistance at its limit forces a thin S-type symmetry on the Lissajous patterns, while with diffusion control the size of the Lissajous patterns begins to reduce after saturation. The fixed layer causes substantial increase in the phase angle and tends to “enlarge” the Lissajous patterns. It is responsible for the hysteresis-like shapes of the Lissajous patterns when superimposed on strong charge transfer resistance. This study shows that it is quite possible to deduce the mechanisms that control the electrodic processes by inverting electrodic parameters from “observed” distorted, nonelliptical Lissajous patterns characteristic of nonlinear electrodics. The results and qualities of the inversion technique are discussed.

Biomolecular detection device

DOEpatents

Huo, Qisheng [Albuquerque, NM; Liu, Jun [Albuquerque, NM

2008-10-21

A device for detecting and measuring the concentration of biomolecules in solution, utilizing a conducting electrode in contact with a solution containing target biomolecules, with a film with controllable pore size distribution characteristics applied to at least one surface of the conducting electrode. The film is functionalized with probe molecules that chemically interact with the target biomolecules at the film surface, blocking indicator molecules present in solution from diffusing from the solution to the electrode, thereby changing the electrochemical response of the electrode.

Solid state oxygen sensor

DOEpatents

Garzon, Fernando H.; Brosha, Eric L.

1997-01-01

A potentiometric oxygen sensor is formed having a logarithmic response to a differential oxygen concentration while operating as a Nernstian-type sensor. Very thin films of mixed conducting oxide materials form electrode services while permitting diffusional oxygen access to the interface between the zirconia electrolyte and the electrode. Diffusion of oxygen through the mixed oxide is not rate-limiting. Metal electrodes are not used so that morphological changes in the electrode structure do not occur during extended operation at elevated temperatures.

Solid state oxygen sensor

DOEpatents

Garzon, F.H.; Brosha, E.L.

1997-12-09

A potentiometric oxygen sensor is formed having a logarithmic response to a differential oxygen concentration while operating as a Nernstian-type sensor. Very thin films of mixed conducting oxide materials form electrode services while permitting diffusional oxygen access to the interface between the zirconia electrolyte and the electrode. Diffusion of oxygen through the mixed oxide is not rate-limiting. Metal electrodes are not used so that morphological changes in the electrode structure do not occur during extended operation at elevated temperatures. 6 figs.

A large-area diffuse air discharge plasma excited by nanosecond pulse under a double hexagon needle-array electrode.

PubMed

Liu, Zhi-Jie; Wang, Wen-Chun; Yang, De-Zheng; Wang, Sen; Zhang, Shuai; Tang, Kai; Jiang, Peng-Chao

2014-01-01

A large-area diffuse air discharge plasma excited by bipolar nanosecond pulse is generated under a double hexagon needle-array electrode at atmospheric pressure. The images of the diffuse discharge, electric characteristics, and the optical emission spectra emitted from the diffuse air discharge plasma are obtained. Based on the waveforms of pulse voltage and current, the power consumption, and the power density of the diffuse air discharge plasma are investigated under different pulse peak voltages. The electron density and the electron temperature of the diffuse plasma are estimated to be approximately 1.42×10(11) cm(-3) and 4.4 eV, respectively. The optical emission spectra are arranged to determine the rotational and vibrational temperatures by comparing experimental with simulated spectra. Meanwhile, the rotational and vibrational temperatures of the diffuse discharge plasma are also discussed under different pulse peak voltages and pulse repetition rates, respectively. In addition, the diffuse air discharge plasma can form an area of about 70×50 mm(2) on the surface of dielectric layer and can be scaled up to the required size. Crown Copyright © 2013. Published by Elsevier B.V. All rights reserved.

Fully Coupled Simulation of Lithium Ion Battery Cell Performance

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

Trembacki, Bradley L.; Murthy, Jayathi Y.; Roberts, Scott Alan

Lithium-ion battery particle-scale (non-porous electrode) simulations applied to resolved electrode geometries predict localized phenomena and can lead to better informed decisions on electrode design and manufacturing. This work develops and implements a fully-coupled finite volume methodology for the simulation of the electrochemical equations in a lithium-ion battery cell. The model implementation is used to investigate 3D battery electrode architectures that offer potential energy density and power density improvements over traditional layer-by-layer particle bed battery geometries. Advancement of micro-scale additive manufacturing techniques has made it possible to fabricate these 3D electrode microarchitectures. A variety of 3D battery electrode geometries are simulatedmore » and compared across various battery discharge rates and length scales in order to quantify performance trends and investigate geometrical factors that improve battery performance. The energy density and power density of the 3D battery microstructures are compared in several ways, including a uniform surface area to volume ratio comparison as well as a comparison requiring a minimum manufacturable feature size. Significant performance improvements over traditional particle bed electrode designs are observed, and electrode microarchitectures derived from minimal surfaces are shown to be superior. A reduced-order volume-averaged porous electrode theory formulation for these unique 3D batteries is also developed, allowing simulations on the full-battery scale. Electrode concentration gradients are modeled using the diffusion length method, and results for plate and cylinder electrode geometries are compared to particle-scale simulation results. Additionally, effective diffusion lengths that minimize error with respect to particle-scale results for gyroid and Schwarz P electrode microstructures are determined.« less

Electrodeposition in microgravity: Ground-based experiments

NASA Technical Reports Server (NTRS)

Riley, C.; Coble, H. D.

1982-01-01

Electrodeposition was studied at one-hundreth g and compared with bench studies at 1 g. The low gravity was achieved during KC-135 aircraft parobolic flights. Flow in a simple cobalt cell (1 M CoSO4) operating under typical commercial conditions (10 to 20 mA/sq cm and 1 V) was monitored with a Schlieren optical system. Natural convection was absent at one-hundreth g. Quantitative comparisons on a cobalt cell with shielded electrodes using interferometry were carried out. Fringe shift differences indicate greater semi-infinite linear diffusion at 1 g than at one-hundreth g for cobalt. Since a shielded electrode operates under diffusion controlled conditions, no differences between 1 g and one-hundreth g would be expected. Similar comparisons on a shielded electrode copper cell were inconclusive. Bench codeposition experiments using polystyrene neutral buoyancy particles coupled with a shielded electrode cobalt cell were begun. Tracking of 12 micron particles showed no measurable difference between thermal/Brownian motion when the cell was operational or nonoperational. Initial experiments on codeposition quality showed a strong dependence upon cathode surface preparation in a shielded electrode configuration.

[Lateral diffusion of saturated phosphatidylcholines in cholesterol-containing bilayers].

PubMed

Filippov, A V; Rudakova, M A; Oradd, G; Lindblom, J

2007-01-01

Lateral diffusion in oriented bilayers of saturated cholesterol-containing phosphatidylcholines, dipalmitoylphosphatidylcholine and dimyrilstoylphosphatidylcholine upon their limiting hydration has been studied by NMR with impulse gradient of magnetic field. For both systems, similar dependences of the coefficient of lateral diffusion on temperature and cholesterol concentration were observed, which agree with the phase diagram showing the presence of regions of ordered and unordered liquid-crystalline phases and a two-phase region. Under similar conditions, the coefficient of lateral diffusion for dipalmytoylphosphatidylcholine has lower values, which is in qualitative agreement with its greater molecular mass. A comparison of data for dipalmytoylphosphatidylcholine with the results obtained earlier for dipalmytoylsphyngomyelin/cholesterol under the same conditions shows, despite a similarity in phase diagrams, greater (two- to threefold) differences in the values of the coefficient of lateral diffusion and a different mode of dependence of the coefficient on cholesterol concentration. A comparison of data for dimyrilstoylphosphatidylcholine with the results obtained previously shows that the values of the coefficient of lateral diffusion and the mode of its dependence on cholesterol concentration coincide in the region of higher concentrations (more than 15 mole %) and differ in the region of lower concentrations (below 15 mole %). The discrepancies may be explained by different contents of water in the systems during the measurements. At a limiting hydration (more than 35%) of water, the coefficient of lateral diffusion decreases with increasing cholesterol concentration. If the content of water is about 25% (as a result of equilibrium hydration from vapors), the coefficient of lateral diffusion of phosphatidylcholine is probably independent of cholesterol concentration. This results from a denser packing of molecules in the bilayer at a lower water concentration, an effect that competes with the ordering effect of cholesterol.

Multifunctional reference electrode

DOEpatents

Redey, Laszlo; Vissers, Donald R.

1983-01-01

A multifunctional, low mass reference electrode of a nickel tube, thermocouple means inside the nickel tube electrically insulated therefrom for measuring the temperature thereof, a housing surrounding the nickel tube, an electrolyte having a fixed sulfide ion activity between the housing and the outer surface of the nickel tube forming the nickel/nickel sulfide/sulfide half-cell. An ion diffusion barrier is associated with the housing in contact with the electrolyte. Also disclosed is a cell using the reference electrode to measure characteristics of a working electrode.

Multifunctional reference electrode

DOEpatents

Redey, L.; Vissers, D.R.

1981-12-30

A multifunctional, low mass reference electrode of a nickel tube, thermocouple means inside the nickel tube electrically insulated therefrom for measuring the temperature thereof, a housing surrounding the nickel tube, an electrolyte having a fixed sulfide ion activity between the housing and the outer surface of the nickel tube forming the nickel/nickel sulfide/sulfide half-cell are described. An ion diffusion barrier is associated with the housing in contact with the electrolyte. Also disclosed is a cell using the reference electrode to measure characteristics of a working electrode.

Elementary reaction modeling of reversible CO/CO2 electrochemical conversion on patterned nickel electrodes

NASA Astrophysics Data System (ADS)

Luo, Yu; Shi, Yixiang; Li, Wenying; Cai, Ningsheng

2018-03-01

CO/CO2 are the major gas reactant/product in the fuel electrode of reversible solid oxide cells (RSOC). This study proposes a two-charge-transfer-step mechanism to describe the reaction and transfer processes of CO-CO2 electrochemical conversion on a patterned Ni electrode of RSOC. An elementary reaction model is developed to couple two charge transfer reactions, C(Ni)+O2-(YSZ) ↔ CO(Ni)+(YSZ) +2e- and CO(Ni)+O2-(YSZ) ↔ CO2(Ni)+(YSZ)+2e-, with adsorption/desorption, surface chemical reactions and surface diffusion. This model well validates in both solid oxide electrolysis cell (SOEC) and solid oxide fuel cell (SOFC) modes by the experimental data from a patterned Ni electrode with 10 μm stripe width at different pCO (0-0.25 atm), pCO2 (0-0.35 atm) and operating temperature (600-700 °C). This model indicates SOEC mode is dominated by charge transfer step C(Ni)+O2-(YSZ)↔CO(Ni)+(YSZ) +2e-, while SOFC mode by CO(Ni)+ O2-(YSZ)↔CO2(Ni)+(YSZ)+2e- on the patterned Ni electrode. The sensitivity analysis shows charge transfer step is the major rate-determining step for RSOC, besides, surface diffusion of CO and CO2 as well as CO2 adsorption also plays a significant role in the electrochemical reaction of SOEC while surface diffusion of CO and CO2 desorption could be co-limiting in SOFC.

Dimensionless numbers and correlating equations for the analysis of the membrane-gas diffusion electrode assembly in polymer electrolyte fuel cells

NASA Astrophysics Data System (ADS)

Gyenge, E. L.

The Quraishi-Fahidy method [Can. J. Chem. Eng. 59 (1981) 563] was employed to derive characteristic dimensionless numbers for the membrane-electrolyte, cathode catalyst layer and gas diffuser, respectively, based on the model presented by Bernardi and Verbrugge for polymer electrolyte fuel cells [AIChE J. 37 (1991) 1151]. Monomial correlations among dimensionless numbers were developed and tested against experimental and mathematical modeling results. Dimensionless numbers comparing the bulk and surface-convective ionic conductivities, the electric and viscous forces and the current density and the fixed surface charges, were employed to describe the membrane ohmic drop and its non-linear dependence on current density due to membrane dehydration. The analysis of the catalyst layer yielded electrode kinetic equivalents of the second Damköhler number and Thiele modulus, influencing the penetration depth of the oxygen reduction front based on the pseudohomogeneous film model. The correlating equations for the catalyst layer could describe in a general analytical form, all the possible electrode polarization scenarios such as electrode kinetic control coupled or not with ionic and/or oxygen mass transport limitation. For the gas diffusion-backing layer correlations are presented in terms of the Nusselt number for mass transfer in electrochemical systems. The dimensionless number-based correlating equations for the membrane electrode assembly (MEA) could provide a practical approach to quantify single-cell polarization results obtained under a variety of experimental conditions and to implement them in models of the fuel cell stack.

Electrochemical Detection of Dopamine via Assisted Ion Transfer at Nanopipet Electrode Using Cyclic Voltammetry.

PubMed

Colombo, Michelle L; McNeil, Swami; Iwai, Nicholas; Chang, Albert; Shen, Mei

2016-01-01

We present here the detection of dopamine (DA) at nanopipet electrodes with radii of hundreds of nanometers ranging from 160 nm to 480 nm. Dibenzo-18-crown-6 (DB18C6) was employed as an ionophore to facilitate DA transfer, resulting in a half-wave transfer potential, E 1/2, DA , of -0.322 (±0.020) V vs. E 1/2, TBA . Well-defined steady-state sigmoidal cyclic voltammograms were observed for the transfer of DA. High resolution scanning electron microscopy was used to measure the size and taper angle of the nanopipet electrodes. The detection is linear with concentration of DA ranging from 0.25 mM to 2 mM; calculated diffusion coefficient at nanopipet electrodes with above mentioned sizes is 4.87 (±0.28) × 10 -10 m 2 /s. The effect of the common interferent ascorbic acid on DA detection with nanopipet electrodes was evaluated, where DA detection still shows linear behavior with well-defined sigmoidal CVs with E 1/2, DA being -0.328 (±0.029) V vs. E 1/2, TBA . The diffusion coefficient for DA transfer in MgCl 2 with the presence of 2 mM AA was measured to be 1.93 (±0.59) × 10 -10 m 2 /s on nanoelectrodes with radii from 161 nm to 263 nm, but the physiological concentration of 0.1 mM AA had no effect on DA's diffusion coefficient.

Diffusion in biofilms respiring on electrodes

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

Renslow, Ryan S.; Babauta, Jerome T.; Majors, Paul D.

2012-11-15

The goal of this study was to measure spatially and temporally resolved effective diffusion coefficients (De) in biofilms respiring on electrodes. Two model electrochemically active biofilms, Geobacter sulfurreducens PCA and Shewanella oneidensis MR-1, were investigated. A novel nuclear magnetic resonance microimaging perfusion probe capable of simultaneous electrochemical and pulsed-field gradient nuclear magnetic resonance (PFG-NMR) techniques was used. PFG-NMR allowed for noninvasive, nondestructive, high spatial resolution in situ De measurements in living biofilms respiring on electrodes. The electrodes were polarized so that they would act as the sole terminal electron acceptor for microbial metabolism. We present our results as both two-dimensionalmore » De heat maps and surface-averaged relative effective diffusion coefficient (Drs) depth profiles. We found that (1) Drs decreases with depth in G. sulfurreducens biofilms, following a sigmoid shape; (2) Drs at a given location decreases with G. sulfurreducens biofilm age; (3) average De and Drs profiles in G. sulfurreducens biofilms are lower than those in S. oneidensis biofilms—the G. sulfurreducens biofilms studied here were on average 10 times denser than the S. oneidensis biofilms; and (4) halting the respiration of a G. sulfurreducens biofilm decreases the De values. Density, reflected by De, plays a major role in the extracellular electron transfer strategies of electrochemically active biofilms.« less

Electrochemical Reduction of CO2 to Organic Acids by a Pd-MWNTs Gas-Diffusion Electrode in Aqueous Medium

PubMed Central

Lu, Guang; Bian, Zhaoyong; Liu, Xin

2013-01-01

Pd-multiwalled carbon nanotubes (Pd-MWNTs) catalysts for the conversion of CO2 to organic acids were prepared by the ethylene glycol reduction and fully characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV) technologies. The amorphous Pd particles with an average size of 5.7 nm were highly dispersed on the surface of carbon nanotubes. Functional groups of the MWNTs played a key role in the palladium deposition. The results indicated that Pd-MWNTs could transform CO2 into organic acid with high catalytic activity and CO2 could take part in the reduction reaction directly. Additionally, the electrochemical reduction of CO2 was investigated by a diaphragm electrolysis device, using a Pd-MWNTs gas-diffusion electrode as a cathode and a Ti/RuO2 net as an anode. The main products in present system were formic acid and acetic acid identified by ion chromatograph. The selectivity of the products could be achieved by reaction conditions changing. The optimum faraday efficiencies of formic and acetic acids formed on the Pd-MWNTs gas-diffusion electrode at 4 V electrode voltages under 1 atm CO2 were 34.5% and 52.3%, respectively. PMID:24453849

Electrochemical synthesis of copper nanoparticles using cuprous oxide as a precursor in choline chloride-urea deep eutectic solvent: nucleation and growth mechanism.

PubMed

Zhang, Q B; Hua, Y X

2014-12-28

The electrochemical nucleation and growth kinetics of copper nanoparticles on a Ni electrode have been studied with cyclic voltammetry and chronoamperometry in the choline chloride (ChCl)-urea based deep eutectic solvent (DES). The copper source was introduced into the solvent by the dissolution of Cu(I) oxide (Cu2O). Cyclic voltammetry indicates that the electroreduction of Cu(I) species in the DES is a diffusion-controlled quasi-reversible process. The analysis of the chronoamperometric transient behavior during electrodeposition suggests that the deposition of copper on the Ni electrode at low temperatures follows a progressive nucleation and three-dimensional growth controlled by diffusion. The effect of temperature on the diffusion coefficient of Cu(I) species that is present in the solvent and electron transfer rate constant obeys the Arrhenius law, according to which the activation energies are estimated to be 49.20 and 21.72 kJ mol(-1), respectively. The initial stage of morphological study demonstrates that both electrode potential and temperature play important roles in controlling the nucleation and growth kinetics of the nanocrystals during the electrodeposition process. Electrode potential is observed to affect mainly the nucleation process, whereas temperature makes a major contribution to the growth process.

Kinetics of intercalation of lithium into NbSe3 and TiS2 cathodes

NASA Technical Reports Server (NTRS)

Ratnakumar, B. V.; Nagasubramanian, G.; Di Stefano, S.; Bankston, C. P.

1992-01-01

Titanium disulfide and niobium triselenide are two well-studied candidate materials for positive electrodes in rechargeable lithium cells. A comparative study of the kinetics of intercalation of lithium in both the cathodes is made here based on various electrochemical techniques, i.e., linear polarization, potentiodynamic polarization, and ac impedance under different experimental conditions such as prismatic or disk configuration of fresh, partially discharged, or cycled electrode. Further, the diffusion coefficients of lithium ions in these cathodes are estimated under these conditions using conventional techniques, i.e., ac impedance, chronocoulometry, chronoamperometry, and current pulse relaxation. Based on the values of the diffusion coefficients, the applicability of these methods for the determination of diffusion coefficients is discussed.

Electrical characterization of HgTe nanowires using conductive atomic force microscopy

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

Gundersen, P.; Department of Physics, Norwegian University of Science and Technology, NO-7491 Trondheim; Kongshaug, K. O.

Self-organized HgTe nanowires grown by molecular beam epitaxy (MBE) have been characterized using conductive atomic force microscopy. As HgTe will degrade or evaporate at normal baking temperatures for electron beam lithography (EBL) resists, an alternative method was developed. Using low temperature optical lithography processes, large Au contacts were deposited on a sample covered with randomly oriented, lateral HgTe nanowires. Nanowires partly covered by the large electrodes were identified with a scanning electron microscope and then localized in the atomic force microscope (AFM). The conductive tip of the AFM was then used as a movable electrode to measure current-voltage curves atmore » several locations on HgTe nanowires. The measurements revealed that polycrystalline nanowires had diffusive electron transport, with resistivities two orders of magnitude larger than that of an MBE-grown HgTe film. The difference can be explained by scattering at the rough surface walls and at the grain boundaries in the wires. The method can be a solution when EBL is not available or requires too high temperature, or when measurements at several positions along a wire are required.« less

Graphene based nanocomposite hybrid electrodes for supercapacitors

NASA Astrophysics Data System (ADS)

Aphale, Ashish N.

There is an unmet need to develop high performance energy storage systems (ESS), capable of storing energy from both renewable and non-renewable sources to meet the current energy crisis and depletion of non-renewable sources. Amongst many available ESS, supercapacitors (ECs) are the most promising because they exhibit a high charge/discharge rate and power density, along with a long cycle life. The possibility of exploring the use of atomically thin carbon allotropes like graphene, carbon nanotubes (CNTs) and electrically conducting polymers (ECPs) such as polypyrrole (PPy) has been studied as a high performance conducting electrodes in supercapacitor application. A novel templated sustainable nanocomposite electrode has been fabricated using cellulose extracted from Cladophora c. aegagropila algae as component of the assembled supercapacitor device which later has been transitioned to a unique template-less freestanding nanocomposite supercapacitor electrode. The specific capacitance of polypyrrole-graphene-cellulose nanocomposite as calculated from cyclic voltammetry curve is 91.5 F g -1 at the scan rate 50 m Vs-1 in the presence of 1M NaCl electrolyte. The open circuit voltage of the device with polypyrrole -graphene-cellulose electrode was found to be around 225 m V and that of the polypyrrole -cellulose device is only 53 m V without the presence of graphene in the nanocomposite electrode. Understanding the fundamentals by fabricating template nanocomposite electrode, it led to fabricate a unique nanocomposite template-less freestanding film which comprises of polypyrrole-graphene-CNT hybrid. Various experiments have been performed using different electrolytes such ascorbic acid, sodium sulfate and sulfuric acid in different scan rates. The specific capacitance of polypyrrole-graphene-CNT nanocomposite with 0.1 wt% of graphene-CNT, as calculated from cyclic voltammetry curve is 450 F g-1 at the scan rate 5 m V s-1. For the first time a nanofibrous membrane has been developed as a separator which acts as an electrolyte reservoir and ionic diffusion membrane. The performance of the fabricated supercapacitor device has been analyzed using a multimeter and compared with a conventional alkaline (1.5 V) battery. Lighting up of 2.2 V light emitting diode has been demonstrated using the fabricated supercapacitor.

Improvements to Zirconia Thick-Film Oxygen Sensors

NASA Astrophysics Data System (ADS)

Maskell, William C.; Brett, Daniel J. L.; Brandon, Nigel P.

2013-06-01

Thick-film zirconia gas sensors are normally screen-printed onto a planar substrate. A sandwich of electrode-electrolyte-electrode is fired at a temperature sufficient to instigate sintering of the zirconia electrolyte. The resulting porous zirconia film acts as both the electrolyte and as the diffusion barrier through which oxygen diffuses. The high sintering temperature results in de-activation of the electrodes so that sensors must be operated at around 800 °C for measurements in the percentage range of oxygen concentration. This work shows that the use of cobalt oxide as a sintering aid allows reduction of the sensor operating temperature by 100-200 °C with clear benefits. Furthermore, an interesting and new technique is presented for the investigation of the influence of dopants and of the through-porosity of ionically-conducting materials.

Calculation method for steady-state pollutant concentration in mixing zones considering variable lateral diffusion coefficient.

PubMed

Wu, Wen; Wu, Zhouhu; Song, Zhiwen

2017-07-01

Prediction of the pollutant mixing zone (PMZ) near the discharge outfall in Huangshaxi shows large error when using the methods based on the constant lateral diffusion assumption. The discrepancy is due to the lack of consideration of the diffusion coefficient variation. The variable lateral diffusion coefficient is proposed to be a function of the longitudinal distance from the outfall. Analytical solution of the two-dimensional advection-diffusion equation of a pollutant is derived and discussed. Formulas to characterize the geometry of the PMZ are derived based on this solution, and a standard curve describing the boundary of the PMZ is obtained by proper choices of the normalization scales. The change of PMZ topology due to the variable diffusion coefficient is then discussed using these formulas. The criterion of assuming the lateral diffusion coefficient to be constant without large error in PMZ geometry is found. It is also demonstrated how to use these analytical formulas in the inverse problems including estimating the lateral diffusion coefficient in rivers by convenient measurements, and determining the maximum allowable discharge load based on the limitations of the geometrical scales of the PMZ. Finally, applications of the obtained formulas to onsite PMZ measurements in Huangshaxi present excellent agreement.

Bounded diffusion impedance characterization of battery electrodes using fractional modeling

NASA Astrophysics Data System (ADS)

Gabano, Jean-Denis; Poinot, Thierry; Huard, Benoît

2017-06-01

This article deals with the ability of fractional modeling to describe the bounded diffusion behavior encountered in modern thin film and nanoparticles lithium battery electrodes. Indeed, the diffusion impedance of such batteries behaves as a half order integrator characterized by the Warburg impedance at high frequencies and becomes a classical integrator described by a capacitor at low frequencies. The transition between these two behaviors depends on the particles geometry. Three of them will be considered in this paper: planar, cylindrical and spherical ones. The fractional representation proposed is a gray box model able to perfectly fit the low and high frequency diffusive impedance behaviors while optimizing the frequency response transition. Identification results are provided using frequential simulation data considering the three electrochemical diffusion models based on the particles geometry. Furthermore, knowing this geometry allows to estimate the diffusion ionic resistance and time constant using the relationships linking these physical parameters to the structural fractional model parameters. Finally, other simulations using Randles impedance models including the charge transfer impedance and the external resistance demonstrate the interest of fractional modeling in order to identify properly not only the charge transfer impedance but also the diffusion physical parameters whatever the particles geometry.

Control of Silver Diffusion in Low-Temperature Co-Fired Diopside Glass-Ceramic Microwave Dielectrics

PubMed Central

Chou, Chen-Chia; Chang, Chun-Yao; Chen, Guang-Yu; Feng, Kuei-Chih; Tsao, Chung-Ya

2017-01-01

Electrode material for low-temperature co-fired diopside glass-ceramic used for microwave dielectrics was investigated in the present work. Diffusion of silver from the electrode to diopside glass-ceramics degrades the performance of the microwave dielectrics. Two approaches were adopted to resolve the problem of silver diffusion. Firstly, silicon-oxide (SiO2) powder was employed and secondly crystalline phases were chosen to modify the sintering behavior and inhibit silver ions diffusion. Nanoscale amorphous SiO2 powder turns to the quartz phase uniformly in dielectric material during the sintering process, and prevents the silver from diffusion. The chosen crystalline phase mixing into the glass-ceramics enhances crystallinity of the material and inhibits silver diffusion as well. The result provides a method to decrease the diffusivity of silver ions by adding the appropriate amount of SiO2 and appropriate crystalline ceramics in diopside glass-ceramic dielectric materials. Finally, we used IEEE 802.11a 5.8 GHz as target specification to manufacture LTCC antenna and the results show that a good broadband antenna was made using CaMgSi2O6 with 4 wt % silicon oxide. PMID:29286330

Method and means for detecting optically transmitted signals and establishing optical interference pattern between electrodes

DOEpatents

Kostenbauder, Adnah G.

1988-01-01

A photodetector for detecting signal pulses transmitted in an optical carrier signal relies on the generation of electron-hole pairs and the diffusion of the generated electrons and holes to the electrodes on the surface of the semiconductor detector body for generating photovoltaic pulses. The detector utilizes the interference of optical waves for generating an electron-hole grating within the semiconductor body, and, by establishing an electron-hole pair maximum at one electrode and a minimum at the other electrode, a detectable voltaic pulse is generated across the electrode.

Method and means for detecting optically transmitted signals and establishing optical interference pattern between electrodes

DOEpatents

Kostenbauder, A.G.

1988-06-28

A photodetector for detecting signal pulses transmitted in an optical carrier signal relies on the generation of electron-hole pairs and the diffusion of the generated electrons and holes to the electrodes on the surface of the semiconductor detector body for generating photovoltaic pulses. The detector utilizes the interference of optical waves for generating an electron-hole grating within the semiconductor body, and, by establishing an electron-hole pair maximum at one electrode and a minimum at the other electrode, a detectable voltaic pulse is generated across the electrode. 4 figs.

The new mid-scala electrode array: a radiologic and histologic study in human temporal bones.

PubMed

Hassepass, Frederike; Bulla, Stefan; Maier, Wolfgang; Laszig, Roland; Arndt, Susan; Beck, Rainer; Traser, Lousia; Aschendorff, Antje

2014-09-01

To analyze the quality of insertion of the newly developed midscala (MS) electrode, which targets a midscalar electrode position to reduce the risk of trauma to the lateral wall and the modiolus. Modern cochlear implant surgery aims for a safe intracochlear placement of electrode arrays with an ongoing debate regarding cochleostomy or round window (RW) insertion and the use of lateral wall or perimodiolar electrode placement. Intracochlear trauma after insertion of different electrodes depends on insertion mode and electrode design and may result in trauma to the delicate structures of the cochlear. We performed a temporal bone (TB) trial with insertion of the MS electrode in n = 20 TB's after a mastoidectomy and posterior tympanotomy. Insertion was performed either via the RW or a cochleostomy. Electrode positioning, length of insertion, and angle of insertion were analyzed with rotational tomography (RT). TBs were histologically analyzed. Results of RT and histology were compared. Scala tympani (ST) insertion could be accomplished reliably by both RW and via a cochleostomy approach. In 20 TBs, 1 scala vestibuli insertion, 1 incomplete (ST), and 1 elevation of basilar membrane were depicted. No trauma was found in 94.7% of all ST insertions. RT allowed determination of the intracochlear electrode position, which was specified by histologic sectioning. The new MS electrode seems to fulfill reliable atraumatic intracochlear placement via RW and cochleostomy approaches. RT is available for evaluation of intracochlear electrode position, serving as a potential quality control instrument in human implantation.

Determination of axial and lateral exciton diffusion length in GaN by electron energy dependent cathodoluminescence

NASA Astrophysics Data System (ADS)

Hocker, Matthias; Maier, Pascal; Jerg, Lisa; Tischer, Ingo; Neusser, Gregor; Kranz, Christine; Pristovsek, Markus; Humphreys, Colin J.; Leute, Robert A. R.; Heinz, Dominik; Rettig, Oliver; Scholz, Ferdinand; Thonke, Klaus

2016-08-01

We demonstrate the application of low-temperature cathodoluminescence (CL) with high lateral, depth, and spectral resolution to determine both the lateral (i.e., perpendicular to the incident primary electron beam) and axial (i.e., parallel to the electron beam) diffusion length of excitons in semiconductor materials. The lateral diffusion length in GaN is investigated by the decrease of the GaN-related luminescence signal when approaching an interface to Ga(In)N based quantum well stripes. The axial diffusion length in GaN is evaluated from a comparison of the results of depth-resolved CL spectroscopy (DRCLS) measurements with predictions from Monte Carlo simulations on the size and shape of the excitation volume. The lateral diffusion length was found to be (95 ± 40) nm for nominally undoped GaN, and the axial exciton diffusion length was determined to be (150 ± 25) nm. The application of the DRCLS method is also presented on a semipolar (11 2 ¯ 2 ) sample, resulting in a value of (70 ± 10) nm in p-type GaN.

Longitudinal Hierarchy Co3O4 Mesocrystals with High-dense Exposure Facets and Anisotropic Interfaces for Direct-Ethanol Fuel Cells.

PubMed

Hassen, Diab; El-Safty, Sherif A; Tsuchiya, Koichi; Chatterjee, Abhijit; Elmarakbi, Ahmed; Shenashen, Mohamed A; Sakai, Masaru

2016-04-14

Novel electrodes are needed for direct ethanol fuel cells with improved quality. Hierarchical engineering can produce catalysts composed of mesocrystals with many exposed active planes and multi-diffused voids. Here we report a simple, one-pot, hydrothermal method for fabricating Co3O4/carbon/substrate electrodes that provides control over the catalyst mesocrystal morphology (i.e., corn tubercle pellets or banana clusters oriented along nanotube domains, or layered lamina or multiple cantilevered sheets). These morphologies afforded catalysts with a high density of exposed active facets, a diverse range of mesopores in the cage interior, a window architecture, and vertical alignment to the substrate, which improved efficiency in an ethanol electrooxidation reaction compared with a conventional platinum/carbon electrode. On the atomic scale, the longitudinally aligned architecture of the Co3O4 mesocrystals resulted in exposed low- and high-index single and interface surfaces that had improved electron transport and diffusion compared with currently used electrodes.

Manganese oxide micro-supercapacitors with ultra-high areal capacitance

NASA Astrophysics Data System (ADS)

Wang, Xu; Myers, Benjamin D.; Yan, Jian; Shekhawat, Gajendra; Dravid, Vinayak; Lee, Pooi See

2013-05-01

A symmetric micro-supercapacitor is constructed by electrochemically depositing manganese oxide onto micro-patterned current collectors. High surface-to-volume ratio of manganese oxide and short diffusion distance between electrodes give an ultra-high areal capacitance of 56.3 mF cm-2 at a current density of 27.2 μA cm-2.A symmetric micro-supercapacitor is constructed by electrochemically depositing manganese oxide onto micro-patterned current collectors. High surface-to-volume ratio of manganese oxide and short diffusion distance between electrodes give an ultra-high areal capacitance of 56.3 mF cm-2 at a current density of 27.2 μA cm-2. Electronic supplementary information (ESI) available: Experimental procedures; optical images of micro-supercapacitors; areal capacitances of samples M-0.3C, M-0.6C and M-0.9C; illustration of interdigital finger electrodes; Nyquist plot of Co(OH)2 deposited on micro-electrodes. See DOI: 10.1039/c3nr00210a

Longitudinal Hierarchy Co3O4 Mesocrystals with High-dense Exposure Facets and Anisotropic Interfaces for Direct-Ethanol Fuel Cells

NASA Astrophysics Data System (ADS)

Hassen, Diab; El-Safty, Sherif A.; Tsuchiya, Koichi; Chatterjee, Abhijit; Elmarakbi, Ahmed; Shenashen, Mohamed. A.; Sakai, Masaru

2016-04-01

Novel electrodes are needed for direct ethanol fuel cells with improved quality. Hierarchical engineering can produce catalysts composed of mesocrystals with many exposed active planes and multi-diffused voids. Here we report a simple, one-pot, hydrothermal method for fabricating Co3O4/carbon/substrate electrodes that provides control over the catalyst mesocrystal morphology (i.e., corn tubercle pellets or banana clusters oriented along nanotube domains, or layered lamina or multiple cantilevered sheets). These morphologies afforded catalysts with a high density of exposed active facets, a diverse range of mesopores in the cage interior, a window architecture, and vertical alignment to the substrate, which improved efficiency in an ethanol electrooxidation reaction compared with a conventional platinum/carbon electrode. On the atomic scale, the longitudinally aligned architecture of the Co3O4 mesocrystals resulted in exposed low- and high-index single and interface surfaces that had improved electron transport and diffusion compared with currently used electrodes.

ZIF-8 Cooperating in TiN/Ti/Si Nanorods as Efficient Anodes in Micro-Lithium-Ion-Batteries.

PubMed

Yu, Yingjian; Yue, Chuang; Lin, Xionggui; Sun, Shibo; Gu, Jinping; He, Xu; Zhang, Chuanhui; Lin, Wei; Lin, Donghai; Liao, Xinli; Xu, Binbin; Wu, Suntao; Zheng, Mingsen; Li, Jing; Kang, Junyong; Lin, Liwei

2016-02-17

Zeolite imidazolate framework-8 (ZIF-8) nanoparticles embedded in TiN/Ti/Si nanorod (NR) arrays without pyrolysis have shown increased energy storage capacity as anodes for lithium ion batteries (LIBs). A high capacity of 1650 μAh cm(-2) has been achieved in this ZIF-8 composited multilayered electrode, which is ∼100 times higher than the plain electrodes made of only silicon NR. According to the electrochemical impedance spectroscopy (EIS) and (1)H nuclear magnetic resonance (NMR) characterizations, the improved diffusion of lithium ions in ZIF-8 and boosted electron/Li(+) transfer by the ZIF-8/TiN/Ti multilayer coating are proposed to be responsible for the enhanced energy storage ability. The first-principles calculations further indicate the favorable accessibility of lithium with appropriate size to diffuse in the open pores of ZIF-8. This work broadens the application of ZIF-8 to silicon-based LIBs electrodes without the pyrolysis and provides design guidelines for other metal-organic frameworks/Si composite electrodes.

Thin-layer voltammetry of soluble species on screen-printed electrodes: proof of concept.

PubMed

Botasini, S; Martí, A C; Méndez, E

2016-10-17

Thin-layer diffusion conditions were accomplished on screen-printed electrodes by placing a controlled-weight onto the cast solution and allowing for its natural spreading. The restricted diffusive conditions were assessed by cyclic voltammetry at low voltage scan rates and electrochemical impedance spectroscopy. The relationship between the weight exerted over the drop and the thin-layer thickness achieved was determined, in such a way that the simple experimental set-up designed for this work could be developed into a commercial device with variable control of the thin-layer conditions. The experimental results obtained resemble those reported for the voltammetric features of electroactive soluble species employing electrodes modified with carbon nanotubes or graphene layers, suggesting that the attainment of the benefits reported for these nanomaterials could be done simply by forcing the solution to spread over the screen-printed electrodic system to form a thin layer solution. The advantages of thin-layer voltammetry in the kinetic characterization of quasi-reversible and irreversible processes are highlighted.

Longitudinal Hierarchy Co3O4 Mesocrystals with High-dense Exposure Facets and Anisotropic Interfaces for Direct-Ethanol Fuel Cells

PubMed Central

Hassen, Diab; El-Safty, Sherif A.; Tsuchiya, Koichi; Chatterjee, Abhijit; Elmarakbi, Ahmed; Shenashen, Mohamed. A.; Sakai, Masaru

2016-01-01

Novel electrodes are needed for direct ethanol fuel cells with improved quality. Hierarchical engineering can produce catalysts composed of mesocrystals with many exposed active planes and multi-diffused voids. Here we report a simple, one-pot, hydrothermal method for fabricating Co3O4/carbon/substrate electrodes that provides control over the catalyst mesocrystal morphology (i.e., corn tubercle pellets or banana clusters oriented along nanotube domains, or layered lamina or multiple cantilevered sheets). These morphologies afforded catalysts with a high density of exposed active facets, a diverse range of mesopores in the cage interior, a window architecture, and vertical alignment to the substrate, which improved efficiency in an ethanol electrooxidation reaction compared with a conventional platinum/carbon electrode. On the atomic scale, the longitudinally aligned architecture of the Co3O4 mesocrystals resulted in exposed low- and high-index single and interface surfaces that had improved electron transport and diffusion compared with currently used electrodes. PMID:27075551

Microfluidic electrochemical device and process for chemical imaging and electrochemical analysis at the electrode-liquid interface in-situ

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

Yu, Xiao-Ying; Liu, Bingwen; Yang, Li

2016-03-01

A microfluidic electrochemical device and process are detailed that provide chemical imaging and electrochemical analysis under vacuum at the surface of the electrode-sample or electrode-liquid interface in-situ. The electrochemical device allows investigation of various surface layers including diffuse layers at selected depths populated with, e.g., adsorbed molecules in which chemical transformation in electrolyte solutions occurs.

Comparing Macroscale and Microscale Simulations of Porous Battery Electrodes

DOE PAGES

Higa, Kenneth; Wu, Shao-Ling; Parkinson, Dilworth Y.; ...

2017-06-22

This article describes a vertically-integrated exploration of NMC electrode rate limitations, combining experiments with corresponding macroscale (macro-homogeneous) and microscale models. Parameters common to both models were obtained from experiments or based on published results. Positive electrode tortuosity was the sole fitting parameter used in the macroscale model, while the microscale model used no fitting parameters, instead relying on microstructural domains generated from X-ray microtomography of pristine electrode material held under compression while immersed in electrolyte solution (additionally providing novel observations of electrode wetting). Macroscale simulations showed that the capacity decrease observed at higher rates resulted primarily from solution-phase diffusion resistance.more » This ability to provide such qualitative insights at low computational costs is a strength of macroscale models, made possible by neglecting electrode spatial details. To explore the consequences of such simplification, the corresponding, computationally-expensive microscale model was constructed. This was found to have limitations preventing quantitatively accurate predictions, for reasons that are discussed in the hope of guiding future work. Nevertheless, the microscale simulation results complement those of the macroscale model by providing a reality-check based on microstructural information; in particular, this novel comparison of the two approaches suggests a reexamination of salt diffusivity measurements.« less

Reduced order modeling of mechanical degradation induced performance decay in lithium-ion battery porous electrodes

DOE PAGES

Barai, Pallab; Smith, Kandler; Chen, Chien -Fan; ...

2015-06-17

In this paper, a one-dimensional computational framework is developed that can solve for the evolution of voltage and current in a lithium-ion battery electrode under different operating conditions. A reduced order model is specifically constructed to predict the growth of mechanical degradation within the active particles of the carbon anode as a function of particle size and C-rate. Using an effective diffusivity relation, the impact of microcracks on the diffusivity of the active particles has been captured. Reduction in capacity due to formation of microcracks within the negative electrode under different operating conditions (constant current discharge and constant current constantmore » voltage charge) has been investigated. At the beginning of constant current discharge, mechanical damage to electrode particles predominantly occurs near the separator. As the reaction front shifts, mechanical damage spreads across the thickness of the negative electrode and becomes relatively uniform under multiple discharge/charge cycles. Mechanical degradation under different drive cycle conditions has been explored. It is observed that electrodes with larger particle sizes are prone to capacity fade due to microcrack formation. Finally, under drive cycle conditions, small particles close to the separator and large particles close to the current collector can help in reducing the capacity fade due to mechanical degradation.« less

Hydrogen oxidation mechanisms on Ni/yttria stabilized zirconia anodes: Separation of reaction pathways by geometry variation of pattern electrodes

NASA Astrophysics Data System (ADS)

Doppler, M. C.; Fleig, J.; Bram, M.; Opitz, A. K.

2018-03-01

Nickel/yttria stabilized zirconia (YSZ) electrodes are affecting the overall performance of solid oxide fuel cells (SOFCs) in general and strongly contribute to the cell resistance in case of novel metal supported SOFCs in particular. The electrochemical fuel conversion mechanisms in these electrodes are, however, still only partly understood. In this study, micro-structured Ni thin film electrodes on YSZ with 15 different geometries are utilized to investigate reaction pathways for the hydrogen electro-oxidation at Ni/YSZ anodes. From electrodes with constant area but varying triple phase boundary (TPB) length a contribution to the electro-catalytic activity is found that does not depend on the TPB length. This additional activity could clearly be attributed to a yet unknown reaction pathway scaling with the electrode area. It is shown that this area related pathway has significantly different electrochemical behavior compared to the TPB pathway regarding its thermal activation, sulfur poisoning behavior, and H2/H2O partial pressure dependence. Moreover, possible reaction mechanisms of this reaction pathway are discussed, identifying either a pathway based on hydrogen diffusion through Ni with water release at the TPB or a path with oxygen diffusion through Ni to be a very likely explanation for the experimental results.

Hybrid capacitors utilizing halogen-based redox reactions at interface between carbon positive electrode and aqueous electrolytes

NASA Astrophysics Data System (ADS)

Yamazaki, Shigeaki; Ito, Tatsuya; Murakumo, Yuka; Naitou, Masashi; Shimooka, Toshiharu; Yamagata, Masaki; Ishikawa, Masashi

2016-09-01

We propose novel hybrid capacitors (HCs) with electrolyte-involved redox reactions of bromide or iodide species by pretreatment of an activated carbon positive electrode. The treatment is simple; impregnation of pores at an activated carbon fiber cloth (ACFC) as a positive electrode with bromine- or iodine-containing water before cell assembly. The treated positive electrode is applied to a HC cell with a non-treated negative electrode of ACFC and its electrochemical performance is investigated by galvanostatic cycling and leakage current tests. Few studies on such "electrolytic" charge storage systems have provided acceptable capacitor performance because of inevitable self-discharge caused by diffusion of charged species form an electrode to the other one through an electrolyte. Nevertheless, our electrolyte-redox-based HCs show excellent performance without undesirable diffusion of charged species. Moreover, the present HC utilizing a bromide redox system fulfills a practical cell voltage of 1.8 V in spite of an aqueous electrolyte system. This high voltage provides excellent energy density, which is 5 times higher than that in a conventional aqueous electric double-layer capacitor (EDLC), and 1.2 times higher even than that in a 2.7 V-class non-aqueous EDLC, while keeping high charge-discharge rate capability.

Uniform implantation of CNTs on total activated carbon surfaces: a smart engineering protocol for commercial supercapacitor applications

NASA Astrophysics Data System (ADS)

Jiang, Jian; Li, Linpo; Liu, Yani; Liu, Siyuan; Xu, Maowen; Zhu, Jianhui

2017-04-01

The main obstacles to building better supercapacitors are still trade-offs between energy and power parameters. To promote commercial supercapacitor behaviors, proper optimization toward electrode configurations/architectures may be a feasible and effective way. We herein propose a smart and reliable electrode engineering protocol, by in situ implantation of carbon nanotubes (CNTs) on total activated carbon (AC) surfaces via a mild chemical vapor deposition process at ˜550 °C, using nickel nitrate hydroxide (NNH) thin films and waste ethanol solvents as the catalyst and carbon sources, respectively. The direct and conformal growth of NNH layers onto carbonaceous scaffold guarantees the later uniform implantation of long and high-quality CNTs on total AC outer surfaces. Such fluffy and entangled CNTs preserve ionic diffusion channels, well connect neighboring ACs and function as superhighways for electrons transfer, endowing electrodes with outstanding capacitive behaviors including large output capacitances of ˜230 F g-1 in 1 M Na2SO4 neutral solution and ˜502.5 F g-1 in 6 M KOH using Ni valence state variation, and very negligible capacity decay in long-term cycles. Furthermore, a full symmetric supercapacitor device of CNTs@ACs//CNTs@ACs has been constructed, capable of delivering both high specific energy and power densities (maximum values reaching up to ˜97.2 Wh kg-1 and ˜10.84 kW kg-1), which holds great potential in competing with current mainstream supercapacitors.

Uniform implantation of CNTs on total activated carbon surfaces: a smart engineering protocol for commercial supercapacitor applications.

PubMed

Jiang, Jian; Li, Linpo; Liu, Yani; Liu, Siyuan; Xu, Maowen; Zhu, Jianhui

2017-04-07

The main obstacles to building better supercapacitors are still trade-offs between energy and power parameters. To promote commercial supercapacitor behaviors, proper optimization toward electrode configurations/architectures may be a feasible and effective way. We herein propose a smart and reliable electrode engineering protocol, by in situ implantation of carbon nanotubes (CNTs) on total activated carbon (AC) surfaces via a mild chemical vapor deposition process at ∼550 °C, using nickel nitrate hydroxide (NNH) thin films and waste ethanol solvents as the catalyst and carbon sources, respectively. The direct and conformal growth of NNH layers onto carbonaceous scaffold guarantees the later uniform implantation of long and high-quality CNTs on total AC outer surfaces. Such fluffy and entangled CNTs preserve ionic diffusion channels, well connect neighboring ACs and function as superhighways for electrons transfer, endowing electrodes with outstanding capacitive behaviors including large output capacitances of ∼230 F g -1 in 1 M Na 2 SO 4 neutral solution and ∼502.5 F g -1 in 6 M KOH using Ni valence state variation, and very negligible capacity decay in long-term cycles. Furthermore, a full symmetric supercapacitor device of CNTs@ACs//CNTs@ACs has been constructed, capable of delivering both high specific energy and power densities (maximum values reaching up to ∼97.2 Wh kg -1 and ∼10.84 kW kg -1 ), which holds great potential in competing with current mainstream supercapacitors.

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.

Lateral diffusion study of the Pt-Al system using the NAC nuclear microprobe.

NASA Astrophysics Data System (ADS)

de Waal, H.; Pretorius, R.

1999-10-01

In this study a nuclear microprobe (NMP) was used to analyse phase formation during reaction in Pt-Al lateral diffusion couples. Phase identification was done by Rutherford backscattering spectroscopy. These results were compared with phase formation during conventional thin film Pt-Al interactions. The co-existence of multiple phases in lateral diffusion couples is discussed with reference to the effective heat of formation (EHF) model.

Amyotrophic Lateral Sclerosis (ALS)

MedlinePlus

... Pacing System, which uses implanted electrodes and a battery pack to cause the diaphragm (breathing muscle) to ... Pacing System, which uses implanted electrodes and a battery pack to cause the diaphragm (breathing muscle) to ...

Laryngeal electromyography: electrode guidance based on 3-dimensional magnetic resonance tomography images of the larynx.

PubMed

Storck, Claudio; Gehrer, Raphael; Hofer, Michael; Neumayer, Bernhard; Stollberger, Rudolf; Schumacher, Ralf; Gugatschka, Markus; Friedrich, Gerhard; Wolfensberger, Markus

2012-01-01

Laryngeal electromyography (LEMG) is an important tool for the assessment of laryngeal nerve and muscle functioning. The purpose of the study was to determine electrode insertion angle and insertion depth for the various laryngeal muscles. Twenty-three cadaver larynges were examined with magnetic resonance tomography (MRT) and Materialize Interactive Medical Image Control System (Leuven, Belgium) 3-dimensional (3D) imaging software. Geometrical analysis was used to calculate the electrode insertion angles. All laryngeal muscles could be identified and 3D visualized on MRT scans. Although the insertion angles were the same in male and female larynges, the insertion depth was significantly larger in male than in female larynges (P<0.05). Of particular clinical importance is the fact that the electrode has to be directed lateral and upward for the thyroarytenoid muscle but lateral and downward for the lateral cricoarytenoid muscle (insertion point=midline lower border of the thyroid). This is the first study that analyzes electrode insertion angles and insertion depths for each laryngeal muscle using 3D imaging. We hope that the information gained from this study will help clinicians performing LEMG to localize the individual laryngeal muscles. Copyright © 2012 The Voice Foundation. Published by Mosby, Inc. All rights reserved.

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

Dees, D. W.; Kawauchi, S.; Abraham, D. P.

Galvanostatic Intermittent Titration Technique (GITT) experiments were conducted to determine the lithium diffusion coefficient of LiNi{sub 0.8}Co{sub 0.15}Al{sub 0.05}O{sub 2}, used as the active material in a lithium-ion battery porous composite positive electrode. An electrochemical model, based on concentrated solution porous electrode theory, was developed to analyze the GITT experimental results and compare to the original GITT analytical theory. The GITT experimental studies on the oxide active material were conducted between 3.5 and 4.5 V vs. lithium, with the maximum lithium diffusion coefficient value being 10{sup -10} cm{sup 2} s{sup -1} at 3.85 V. The lithium diffusion coefficient values obtainedmore » from this study agree favorably with the values obtained from an earlier electrochemical impedance spectroscopy study.« less

Sensors for measurement of moisture diffusion in power cables with oil-impregnated paper

NASA Astrophysics Data System (ADS)

Thomas, Z. M.; Zahn, M.; Yang, W.

2007-07-01

Some old power cables use oil-impregnated paper as the insulation material, which is enclosed by a layer of lead sheath. As cracks can form on the sheath of aged cables, the oil-impregnated paper can be exposed to the environmental conditions, and ambient moisture can diffuse into the paper through the cracks, causing a reduced breakdown voltage. To understand this diffusion phenomenon, multi-wavelength dielectrometry sensors have been used to measure permittivity and conductivity, aiming to obtain information on the moisture content. Different electrode-grouping strategies have been suggested to obtain more detailed information. Effectively, an electrode-grouping approach forms a type of electrical capacitance tomography sensor. This paper presents different sensor designs together with a capacitance measuring circuit. Some analytical results are also presented.

Ligand binding affinity and changes in the lateral diffusion of receptor for advanced glycation endproducts (RAGE).

PubMed

Syed, Aleem; Zhu, Qiaochu; Smith, Emily A

2016-12-01

The effect of ligand on the lateral diffusion of receptor for advanced glycation endproducts (RAGE), a receptor involved in numerous pathological conditions, remains unknown. Single particle tracking experiments that use quantum dots specifically bound to hemagglutinin (HA)-tagged RAGE (HA-RAGE) are reported to elucidate the effect of ligand binding on HA-RAGE diffusion in GM07373 cell membranes. The ligand used in these studies is methylglyoxal modified-bovine serum albumin (MGO-BSA) containing advanced glycation end products modifications. The binding affinity between soluble RAGE and MGO-BSA increases by 1.8 to 9.7-fold as the percent primary amine modification increases from 24 to 74% and with increasing negative charge on the MGO-BSA. Ligand incubation affects the HA-RAGE diffusion coefficient, the radius of confinement, and duration of confinement. There is, however, no correlation between MGO-BSA ligand binding affinity with soluble RAGE and the extent of the changes in HA-RAGE lateral diffusion. The ligand induced changes to HA-RAGE lateral diffusion do not occur when cholesterol is depleted from the cell membrane, indicating the mechanism for ligand-induced changes to HA-RAGE diffusion is cholesterol dependent. The results presented here serve as a first step in unraveling how ligand influences RAGE lateral diffusion. Copyright © 2016. Published by Elsevier B.V.

Insights into electrode/electrolyte interfacial processes and the effect of nanostructured cobalt oxides loading on graphene-based hybrids by scanning electrochemical microscopy

NASA Astrophysics Data System (ADS)

Gupta, Sanju; Carrizosa, Sara B.

2016-12-01

Nanostructured cobalt oxide polymorphs (CoO and Co3O4) deposited via electrodeposition allowed optimal loading on supercapacitive graphene nanosheets producing a set of graphene-based hybrids namely, CoO/GO, CoO/ErGO, Co3O4/GO, Co3O4/rGO, and Co3O4/ErGO, as pseudocapacitive electrochemical electrodes. We gained fundamental insights into the complex physicochemical interfacial processes at electrode surfaces and electrode/electrolyte (or solid/liquid) interfaces by scanning electrochemical microscopy operating in the feedback probe approach and imaging modes while monitoring and mapping the redox probe (re)activity behavior. We determined the various experimental descriptors including diffusion coefficient, electron transfer rate, and electroactive site distribution on electrodes. We emphasize the interplay of (1) heterogeneous basal and edge plane active sites, (2) graphene surface functional moieties (conducting/semiconducting), and (3) crystalline spinel cobalt oxides (semiconducting/insulating) coated graphene, reinforcing the available electron density of states in the vicinity of the Fermi level contributing to higher electroactivity, faster interfacial diffusion, and shorter distances for electron transfer, facilitated through molecular and chemical bridges obtained by electrodeposition as compared with the physical deposition.

Apparatus for inspecting fuel elements

DOEpatents

Oakley, David J.; Groves, Oliver J.; Kaiser, Bruce J.

1986-01-01

Disclosed is an alpha monitor usable in an automated nuclear fuel pin loading and processing unit. Fuel pins or other elongated pins are fed laterally into the alpha monitor in a singular fashion and are translated by a first roller assembly into a weld flare machining and decontamination substation not forming a part of the invention. Pins return and are lifted upwardly and transferred across to a combined pin lifting and electrode operating means which lifts the pins upwardly into a clamshell electrode assembly which is spread open by a combined pin lifting and electrode operating means. Once inserted the clamshell type electrode arrangement closes around the fuel pins so that inspection can occur. Fuel pins are inspected by charging electrodes to a negative potential and measuring the change in charge occurring when positively charged alpha particles strike the negatively charged electrodes. After inspection, the fuel pins are lowered by the pin lifting and electrode operating means into a second roller assembly which longitudinally conveys approved pins from the airtight enclosure in which the alpha monitor is mounted. If the fuel pins are rejected then they are moved laterally by a second transfer means and onto another system for further processing.

Apparatus for inspecting fuel elements

DOEpatents

Kaiser, B.J.; Oakley, D.J.; Groves, O.J.

1984-12-21

This disclosure describes an alpha monitor usable in an automated nuclear fuel pin loading and processing unit. Fuel pins or other elongated pins are fed laterally into the alpha monitor in a singular fashion and are translated by a first roller assembly into a weld flare machining and decontamination substation not forming a part of the invention. Pins return and are lifted upwardly and transferred across to a combined pin lifting and electrode operating means which lifts the pins upwardly into a clamshell electrode assembly which is spread open by a combined pin lifting and electrode operating means. Once inserted the clamshell type electrode arrangement closes around the fuel pins so that inspection can occur. Fuel pins are inspected by charging electrodes to a negative potential and measuring the change in charge occurring when positively charged alpha particles strike the negatively charged electrodes. After inspection, the fuel pins are lowered by the pin lifting and electrode operating means into a second roller assembly which longitudinally conveys approved pins from the airtight enclosure in which the alpha monitor is mounted. If the fuel pins are rejected then they are moved laterally by a second transfer means and onto another system for further processing.

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

A Novel of Multi-wall Carbon Nanotubes/Chitosan Electrochemical Sensor for Determination of Cupric ion

NASA Astrophysics Data System (ADS)

Tan, Funeng; Li, Lei

2018-03-01

A multi-wall carbon nanotubes/Chitosan electrochemical sensor had been fabricated by dropping CHS/MWNT solution directly onto the GC surface. The sensor was charactered by cyclic voltammetry and AC impedance with K3Fe(CN)6 as a electrochemical probe; Cyclic voltammograms(CV) and electrochemical impedance spectroscopy(EIS) indicated that the active area and electrochemical behavior of the sensor increased and improved significantly after the electrode was modified by carbon nanotubes dispersed by the chitosan. The sensor showed good electrocatalytic activity of K3Fe(CN)6. Also, from the cyclic voltammograms, we can see the process was diffusion controlled on the bare electrode and kinetics and diffusion controlled on the modified electrode. Finally Cu2+ responsed sensitively at the sensor which supplied a new method for the detection of Cu2+.

Lifetime of Major Histocompatibility Complex Class-I Membrane Clusters Is Controlled by the Actin Cytoskeleton

PubMed Central

Lavi, Yael; Gov, Nir; Edidin, Michael; Gheber, Levi A.

2012-01-01

Lateral heterogeneity of cell membranes has been demonstrated in numerous studies showing anomalous diffusion of membrane proteins; it has been explained by models and experiments suggesting dynamic barriers to free diffusion, that temporarily confine membrane proteins into microscopic patches. This picture, however, comes short of explaining a steady-state patchy distribution of proteins, in face of the transient opening of the barriers. In our previous work we directly imaged persistent clusters of MHC-I, a type I transmembrane protein, and proposed a model of a dynamic equilibrium between proteins newly delivered to the cell surface by vesicle traffic, temporary confinement by dynamic barriers to lateral diffusion, and dispersion of the clusters by diffusion over the dynamic barriers. Our model predicted that the clusters are dynamic, appearing when an exocytic vesicle fuses with the plasma membrane and dispersing with a typical lifetime that depends on lateral diffusion and the dynamics of barriers. In a subsequent work, we showed this to be the case. Here we test another prediction of the model, and show that changing the stability of actin barriers to lateral diffusion changes cluster lifetimes. We also develop a model for the distribution of cluster lifetimes, consistent with the function of barriers to lateral diffusion in maintaining MHC-I clusters. PMID:22500754

Lateral spin valves with two-different Heusler-alloy electrodes on the same platform

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

Oki, S.; Yamada, S.; Tanikawa, K.

2013-11-18

Using room-temperature molecular beam epitaxy on Si(111), we demonstrate Heusler-alloy bilayers consisting of L2{sub 1}-Co{sub 2}FeSi (CFS) and D0{sub 3}-Fe{sub 3}Si (FS). By fabricating lateral spin valves with L2{sub 1}-CFS and D0{sub 3}-FS electrodes, we can see ideal spin signals even though we use one L2{sub 1}-CFS as a spin injector and another D0{sub 3}-FS as a spin detector. The difference in the spin absorption between L2{sub 1}-CFS and D0{sub 3}-FS can also be examined, and we find that the spin resistance of D0{sub 3}-FS is larger than that of L2{sub 1}-CFS. This work will be useful for understanding spinmore » transport in lateral spin-valve devices with different Heusler-alloy electrodes.« less

Controlled morphology and optical properties of n-type porous silicon: effect of magnetic field and electrode-assisted LEF.

PubMed

Antunez, Edgar E; Campos, Jose; Basurto, Miguel A; Agarwal, Vivechana

2014-01-01

Fabrication of photoluminescent n-type porous silicon (nPS), using electrode-assisted lateral electric field accompanied with a perpendicular magnetic field, is reported. The results have been compared with the porous structures fabricated by means of conventional anodization and electrode-assisted lateral electric field without magnetic field. The lateral electric field (LEF) applied across the silicon substrate leads to the formation of structural gradient in terms of density, dimension, and depth of the etched pores. Apart from the pore shape tunability, the simultaneous application of LEF and magnetic field (MF) contributes to a reduction of the dimension of the pores and promotes relatively more defined pore tips as well as a decreased side-branching in the pore walls of the macroporous structure. Additionally, when using magnetic field-assisted etching, within a certain range of LEF, an enhancement of the photoluminescence (PL) response was obtained.

Controlled morphology and optical properties of n-type porous silicon: effect of magnetic field and electrode-assisted LEF

PubMed Central

2014-01-01

Fabrication of photoluminescent n-type porous silicon (nPS), using electrode-assisted lateral electric field accompanied with a perpendicular magnetic field, is reported. The results have been compared with the porous structures fabricated by means of conventional anodization and electrode-assisted lateral electric field without magnetic field. The lateral electric field (LEF) applied across the silicon substrate leads to the formation of structural gradient in terms of density, dimension, and depth of the etched pores. Apart from the pore shape tunability, the simultaneous application of LEF and magnetic field (MF) contributes to a reduction of the dimension of the pores and promotes relatively more defined pore tips as well as a decreased side-branching in the pore walls of the macroporous structure. Additionally, when using magnetic field-assisted etching, within a certain range of LEF, an enhancement of the photoluminescence (PL) response was obtained. PMID:25313298

A study of Na(x)Pt3O4 as an O2 electrode bifunctional electrocatalyst

NASA Technical Reports Server (NTRS)

Fielder, William L.; Singer, Joseph

1991-01-01

The present study suggests that polytetrafluoroethylene (PTFE) bonded Na(X)Pt3O4 gas porous diffusion electrodes may be a viable candidate for bifunctional O2 reduction and evolution activity. The electrodes exhibited Tafel slopes of about 0.06 V/decade for both O2 reduction an evolution. For O2 reduction, the 0.06 slope doubled to 0.12 V/decade at larger current densities. Preliminary stability testing at 24 C suggest that the Na(x)Pt3O4 electrodes were relatively stable at reducing and oxidizing potentials typically encountered at the O2 electrodes in a regenerative fuel cell.

The limits of low-temperature performance of Li-ion cells

NASA Technical Reports Server (NTRS)

Huang, C.; Sakamoto, J.; Wolfenstine, J.; Surampudi, S.

2000-01-01

The results of electrode and electrolyte studies reveal that the poor low-temperature (<-30 degrees C) performance of Li-ion cells is mainly caused by the carbon electrodes and not the organic electrolytes and solid electrolyte interphase, as previously suggested. It is suggested that the main causes for the poor performance in the carbon electrodes are (i) the low value and concentration depedence of the Li diffusivity and (ii) limited Li capacity.

Detection efficiency vs. cathode and anode separation in cylindrical vacuum photodiodes used for measuring x-rays from plasma focus device.

PubMed

Borthakur, T K; Talukdar, N; Neog, N K; Rao, C V S; Shyam, A

2011-10-01

A qualitative study on the performance of cylindrical vacuum photodiodes (VPDs) for x-ray detection in plasma focus device has been carried out. Various parameters of VPD such as electrode's diameter, electrode's separation, and its sensitivity are experimentally tested in plasma focus environment. For the first time it is found experimentally that the electrode-separation in the lateral direction of the two coaxial electrodes of cylindrical VPD also plays an important role to increase the efficiency of the detector. The efficiency is found to be highest for the detector with smaller cathode-anode lateral gap (1.5 mm) with smaller photo cathode diameter (10 mm). A comparison between our VPD with PIN (BPX-65) diode as an x-ray detector has also been made.

Electrode performance parameters for a radioisotope-powered AMTEC for space power applications

NASA Technical Reports Server (NTRS)

Underwood, M. L.; O'Connor, D.; Williams, R. M.; Jeffries-Nakamura, B.; Ryan, M. A.; Bankston, C. P.

1992-01-01

The alkali metal thermoelastic converter (AMTEC) is a device for the direct conversion of heat to electricity. Recently a design of an AMTEC using a radioisotope heat source was described, but the optimum condenser temperature was hotter than the temperatures used in the laboratory to develop the electrode performance model. Now laboratory experiments have confirmed the dependence of two model parameters over a broader range of condenser and electrode temperatures for two candidate electrode compositions. One parameter, the electrochemical exchange current density at the reaction interface, is independent of the condenser temperature, and depends only upon the collision rate of sodium at the reaction zone. The second parameter, a morphological parameter, which measures the mass transport resistance through the electrode, is independent of condenser and electrode temperatures for molybdenum electrodes. For rhodium-tungsten electrodes, however, this parameter increases for decreasing electrode temperature, indicating an activated mass transport mechanism such as surface diffusion.

Frequency response of electrochemical cells

NASA Technical Reports Server (NTRS)

Thomas, Daniel L.

1989-01-01

Impedance concepts can be applied to the analysis of battery electrodes, yielding information about the structure of the electrode and the processes occurring in the electrode. Structural parameters such as the specific area (surface area per gram of electrode) can be estimated. Electrode variables such as surface overpotential, ohmic losses, and diffusion limitations may be studied. Nickel and cadmium electrodes were studied by measuring the ac impedance as a function of frequency, and the specific areas that were determined were well within the range of specific areas determined from BET measurements. Impedance spectra were measured for the nickel and cadmium electrodes, and for a 20 A-hr NiCd battery as functions of the state of charge. More work is needed to determine the feasibility of using frequency response as a nondestructive testing technique for batteries.

Effects of discrete-electrode arrangement on traveling-wave electroosmotic pumping

NASA Astrophysics Data System (ADS)

Liu, Weiyu; Shao, Jinyou; Ren, Yukun; Wu, Yupan; Wang, Chunhui; Ding, Haitao; Jiang, Hongyuan; Ding, Yucheng

2016-09-01

Traveling-wave electroosmotic (TWEO) pumping arises from the action of an imposed traveling-wave (TW) electric field on its own induced charge in the diffuse double layer, which is formed on top of an electrode array immersed in electrolyte solutions. Such a traveling field can be merely realized in practice by a discrete electrode array upon which the corresponding voltages of correct phase are imposed. By employing the theory of linear and weakly nonlinear double-layer charging dynamics, a physical model incorporating both the nonlinear surface capacitance of diffuse layer and Faradaic current injection is developed herein in order to quantify the changes in TWEO pumping performance from a single-mode TW to discrete electrode configuration. Benefiting from the linear analysis, we investigate the influence of using discrete electrode array to create the TW signal on the resulting fluid motion, and several approaches are suggested to improve the pumping performance. In the nonlinear regime, our full numerical analysis considering the intervening isolation spacing indicates that a practical four-phase discrete electrode configuration of equal electrode and gap width exhibits stronger nonlinearity than expected from the idealized pump applied with a single-mode TW in terms of voltage-dependence of the ideal pumping frequency and peak flow rate, though it has a much lower pumping performance. For model validation, pumping of electrolytes by TWEO is achieved over a confocal spiral four-phase electrode array covered by an insulating microchannel; measurement of flow velocity indicates the modified nonlinear theory considering moderate Faradaic conductance is indeed a more accurate physical description of TWEO. These results offer useful guidelines for designing high-performance TWEO microfluidic pumps with discrete electrode array.

Electrochemical Behavior of Sulfur in Aqueous Alkaline Solutions

NASA Astrophysics Data System (ADS)

Mamyrbekova, Aigul; Mamitova, A. D.; Mamyrbekova, Aizhan

2018-03-01

The kinetics and mechanism of the electrode oxidation-reduction of sulfur on an electrically conductive sulfur-graphite electrode in an alkaline solution was studied by the potentiodynamic method. To examine the mechanism of electrode processes occurring during AC polarization on a sulfur-graphite electrode, the cyclic polarization in both directions and anodic polarization curves were recorded. The kinetic parameters: charge transfer coefficients (α), diffusion coefficients ( D), heterogeneous rate constants of electrode process ( k s), and effective activation energies of the process ( E a) were calculated from the results of polarization measurements. An analysis of the results and calculated kinetic parameters of electrode processes showed that discharge ionization of sulfur in alkaline solutions occurs as a sequence of two stages and is a quasireversible process.

Spin and charge transport across cobalt/graphene interfaces

NASA Astrophysics Data System (ADS)

Chshiev, Mairbek; Kalitsov, Alan; Mryasov, Oleg

We report ballistic calculations of in-plane and out-of-plane spin and charge transport through graphene attached to the hcp-Co electrodes. Our calculations are based on the Keldysh non-equilibrium Green Function formalism and the tight binding Hamiltonian model tailored to treat both lateral and vertical device configurations. We present results for (i) vertical device that consists of a one-side fluorinated C4F graphene sandwiched between two hcp Co electrodes and (ii) lateral device consisting of pristine graphene/C4F graphene bilayer with two top hcp-Co electrodes Our calculations predict large magnetoresistance with small resistance-area product and significant deviation from sinusoidal behavior of spin transfer torque for the vertical device configuration.

Porous Electrode Studies.

DTIC Science & Technology

1980-07-01

the reac- tion modes of the Ag/AgCl, AgO/Ag 2O/Ag, and Zn/ ZnO electrodes and to testing various theories that predict electrode behavior. v LOCKHEED...of sudden passivation was related to a simul- taneous precipitation of flocculent ZnO , and this passivation was removed by addi- tion of fresh...vation occurred more slowly by covering with a thin, adherent film, and that a dis- solution, diffusion, deposition mode prevailed in the formation of ZnO

Space water electrolysis: Space Station through advance missions

NASA Technical Reports Server (NTRS)

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

1991-01-01

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

A top-down approach for fabricating free-standing bio-carbon supercapacitor electrodes with a hierarchical structure.

PubMed

Li, Yingzhi; Zhang, Qinghua; Zhang, Junxian; Jin, Lei; Zhao, Xin; Xu, Ting

2015-09-23

Biomass has delicate hierarchical structures, which inspired us to develop a cost-effective route to prepare electrode materials with rational nanostructures for use in high-performance storage devices. Here, we demonstrate a novel top-down approach for fabricating bio-carbon materials with stable structures and excellent diffusion pathways; this approach is based on carbonization with controlled chemical activation. The developed free-standing bio-carbon electrode exhibits a high specific capacitance of 204 F g(-1) at 1 A g(-1); good rate capability, as indicated by the residual initial capacitance of 85.5% at 10 A g(-1); and a long cycle life. These performance characteristics are attributed to the outstanding hierarchical structures of the electrode material. Appropriate carbonization conditions enable the bio-carbon materials to inherit the inherent hierarchical texture of the original biomass, thereby facilitating effective channels for fast ion transfer. The macropores and mesopores that result from chemical activation significantly increase the specific surface area and also play the role of temporary ion-buffering reservoirs, further shortening the ionic diffusion distance.

Meso-pores carbon nano-tubes (CNTs) tissues-perfluorocarbons (PFCs) hybrid air-electrodes for Li-O2 battery

NASA Astrophysics Data System (ADS)

Balaish, Moran; Ein-Eli, Yair

2018-03-01

Adding immiscible perfluorocarbons (PFCs), possessing superior oxygen solubility and diffusivity, to a free-standing (metal-free and binder-free) CNTs air-electrode tissues with a meso-pore structure, fully maximized the advantages of PFCs as oxygenated-species' channels-providers. The discharge behavior of hybrid PFCs-CNT Li-O2 systems demonstrated a drastic increase in cell capacity at high current density (0.2 mA cm-2), where oxygen transport limitations are best illustrated. The results of this research revealed several key factors affecting PFCs-Li-O2 systems. The incorporation of PFCs with higher superoxide solubility and oxygen diffusivity, but more importantly higher PFCs/electrolyte miscibility, in a meso-pore air-electrode enabled better exploitation of PFCs potential. Consequently, the utilization of the air-electrode' surface area was enhanced via the formation of artificial three phase reaction zones with additional oxygen transportation routes, leading to uniform and intimate Li2O2 deposit at areas further away from the oxygen reservoir. Associated mechanisms are discussed along with insights into an improved Li-O2 battery system.

Immobilization of nanobeads on a surface to control the size, shape and distribution of pores in electrochemically generated sol-gel films.

PubMed

Ciabocco, Michela; Berrettoni, Mario; Zamponi, Silvia; Cox, James A

2015-07-01

Electrochemically assisted deposition of an ormosil film at a potential where hydrogen ion is generated as the catalyst yields insulating films on electrodes. When the base electrode is modified with 20-nm poly(styrene sulfonate), PSS, beads bound to the surface with 3-aminopropyltriethoxysilane (APTES) and using (CH 3 ) 3 SiOCH 3 as the precursor, the resulting film of organically modified silica (ormosil) has cylindrical channels that reflect both the diameter of the PSS and the distribution of the APTES-PSS on the electrode. At an electrode modified by a 20-min immersion in 0.5 mmol dm -3 APTES followed by a 30-s immersion in PSS, a 20-min electrolysis at 1.5 V in acidified (CH 3 ) 3 SiOCH 3 resulted in an ormosil film with 20-nm pores separated by 100 nm. Cyclic voltammetry of Ru(CN) 6 4- at scan rates above 5 mVs -1 yielded currents controlled primarily by linear diffusion. Below 5 mVs -1 , convection rather than the expected factor, radial diffusion, apparently limited the current.

Electrochemistry in an acoustically levitated drop.

PubMed

Chainani, Edward T; Ngo, Khanh T; Scheeline, Alexander

2013-02-19

Levitated drops show potential as microreactors, especially when radicals are present as reactants or products. Solid/liquid interfaces are absent or minimized, avoiding adsorption and interfacial reaction of conventional microfluidics. We report amperometric detection in an acoustically levitated drop with simultaneous ballistic addition of reactant. A gold microelectrode sensor was fabricated with a lithographic process; active electrode area was defined by a photosensitive polyimide mask. The microdisk gold working electrode of radius 19 μm was characterized using ferrocenemethanol in aqueous buffer. Using cyclic voltammetry, the electrochemically active surface area was estimated by combining a recessed microdisk electrode model with the Randles-Sevcik equation. Computer-controlled ballistic introduction of reactant droplets into the levitated drop was developed. Chronoamperometric measurements of ferrocyanide added ballistically demonstrate electrochemical monitoring using the microfabricated electrode in a levitated drop. Although concentration increases with time due to drop evaporation, the extent of concentration is predictable with a linear evaporation model. Comparison of diffusion-limited currents in pendant and levitated drops show that convection arising from acoustic levitation causes an enhancement of diffusion-limited current on the order of 16%.

Enhanced performance of polybenzimidazole-based high temperature proton exchange membrane fuel cell with gas diffusion electrodes prepared by automatic catalyst spraying under irradiation technique

NASA Astrophysics Data System (ADS)

Su, Huaneng; Pasupathi, Sivakumar; Bladergroen, Bernard Jan; Linkov, Vladimir; Pollet, Bruno G.

2013-11-01

Gas diffusion electrodes (GDEs) prepared by a novel automatic catalyst spraying under irradiation (ACSUI) technique are investigated for improving the performance of phosphoric acid (PA)-doped polybenzimidazole (PBI) high temperature proton exchange membrane fuel cell (PEMFC). The physical properties of the GDEs are characterized by pore size distribution and scanning electron microscopy (SEM). The electrochemical properties of the membrane electrode assembly (MEA) with the GDEs are evaluated and analyzed by polarization curve, cyclic voltammetry (CV) and electrochemistry impedance spectroscopy (EIS). Effects of PTFE binder content, PA impregnation and heat treatment on the GDEs are investigated to determine the optimum performance of the single cell. At ambient pressure and 160 °C, the maximum power density can reach 0.61 W cm-2, and the current density at 0.6 V is up to 0.38 A cm-2, with H2/air and a platinum loading of 0.5 mg cm-2 on both electrodes. The MEA with the GDEs shows good stability for fuel cell operating in a short term durability test.

Gas diffusion electrode setup for catalyst testing in concentrated phosphoric acid at elevated temperatures

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

Wiberg, Gustav K. H., E-mail: gustav.wiberg@gmail.com, E-mail: m.arenz@chem.ku.dk; Fleige, Michael; Arenz, Matthias, E-mail: gustav.wiberg@gmail.com, E-mail: m.arenz@chem.ku.dk

2015-02-15

We present a detailed description of the construction and testing of an electrochemical cell setup allowing the investigation of a gas diffusion electrode containing carbon supported high surface area catalysts. The setup is designed for measurements in concentrated phosphoric acid at elevated temperature, i.e., very close to the actual conditions in high temperature proton exchange membrane fuel cells (HT-PEMFCs). The cell consists of a stainless steel flow field and a PEEK plastic cell body comprising the electrochemical cell, which exhibits a three electrode configuration. The cell body and flow field are braced using a KF-25 vacuum flange clamp, which allowsmore » an easy assembly of the setup. As demonstrated, the setup can be used to investigate temperature dependent electrochemical processes on high surface area type electrocatalysts, but it also enables quick screening tests of HT-PEMFC catalysts under realistic conditions.« less

The platinum microelectrode/Nafion interface - An electrochemical impedance spectroscopic analysis of oxygen reduction kinetics and Nafion characteristics

NASA Technical Reports Server (NTRS)

Parthasarathy, Arvind; Dave, Bhasker; Srinivasan, Supramaniam; Appleby, John A.; Martin, Charles R.

1992-01-01

The objectives of this study were to use electrochemical impedance spectroscopy (EIS) to study the oxygen-reduction reaction under lower humidification conditions than previously studied. The EIS technique permits the discrimination of electrode kinetics of oxygen reduction, mass transport of O2 in the membrane, and the electrical characteristics of the membrane. Electrode-kinetic parameters for the oxygen-reduction reaction, corrosion current densities for Pt, and double-layer capacitances were calculated. The production of water due to electrochemical reduction of oxygen greatly influenced the EIS response and the electrode kinetics at the Pt/Nafion interface. From the finite-length Warburg behavior, a measure of the diffusion coefficient of oxygen in Nafion and diffusion-layer thickness was obtained. An analysis of the EIS data in the high-frequency domain yielded membrane and interfacial characteristics such as ionic conductivity of the membrane, membrane grain-boundary capacitance and resistance, and uncompensated resistance.

Gas diffusion electrode setup for catalyst testing in concentrated phosphoric acid at elevated temperatures

NASA Astrophysics Data System (ADS)

Wiberg, Gustav K. H.; Fleige, Michael; Arenz, Matthias

2015-02-01

We present a detailed description of the construction and testing of an electrochemical cell setup allowing the investigation of a gas diffusion electrode containing carbon supported high surface area catalysts. The setup is designed for measurements in concentrated phosphoric acid at elevated temperature, i.e., very close to the actual conditions in high temperature proton exchange membrane fuel cells (HT-PEMFCs). The cell consists of a stainless steel flow field and a PEEK plastic cell body comprising the electrochemical cell, which exhibits a three electrode configuration. The cell body and flow field are braced using a KF-25 vacuum flange clamp, which allows an easy assembly of the setup. As demonstrated, the setup can be used to investigate temperature dependent electrochemical processes on high surface area type electrocatalysts, but it also enables quick screening tests of HT-PEMFC catalysts under realistic conditions.

Oxidized Ni/Au Transparent Electrode in Efficient CH3 NH3 PbI3 Perovskite/Fullerene Planar Heterojunction Hybrid Solar Cells.

PubMed

Lai, Wei-Chih; Lin, Kun-Wei; Wang, Yuan-Ting; Chiang, Tsung-Yu; Chen, Peter; Guo, Tzung-Fang

2016-05-01

The successful application of a Ni/Au transparent electrode for fabricating efficient perovskite-based solar cells is demonstrated. Through interdiffusion of the Ni/Au bilayer, Au forms an interconnected metallic network structure as the transparent electrode. Ni diffuses to the bilayer surface and oxidizes into NiOx becoming an appropriate electrode interlayer. These ITO- and PSS-free devices have potential applications in the design of future cost-effective, low-weight, and stable solar cells. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Virtual Electrochemical Strain Microscopy of Polycrystalline LiCoO2 Films

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

Chung, Ding-wen; Balke, Nina; Kalinin, Sergei V

2011-01-01

A recently developed technique, electrochemical strain microscopy (ESM), utilizes the strong coupling between ionic current and anisotropic volumetric chemical expansion of lithium-ion electrode materials to dynamically probe the sub-one-hundred? nm inter-facial kinetic intercalation properties. A numerical technique based on the finite element method was developed to analyze the underlying physics that govern the ESM signal generation and establish relations to battery performance. The performed analysis demonstrates that the diffusion path within a thin film is tortuous and the extent of lithium diffusion into the electrode is dependent on the SPM-tip-imposed overpotential frequency. The detected surface actuation gives rise to themore » development of an electromechanical hysteresis loop whose shape is dependent on grain size and overpotential frequency. Shape and tilting angle of the loop are classified into low and high frequency regimes, separated by a transition frequency which is also a function of lithium diffusivity and grain size, f{sub T} = D//{sup 2}. Research shows that the crystallographic orientation of the surface actuated grain has a significant impact on the shape of the loop. The polycrystalline crystallographic orientation of the grains induces a diffusion path network in the electrode which impacts on the mechanical reliability of the battery. Simulations demonstrate that continuous battery cycling results in a cumulative capacity loss as a result of the hysteric non-reversible lithium intercalation. Furthermore, results suggest that ESM has the capability to infer the local out-of-plane lithium diffusivity and the out-of-plane contribution to Vegard tensor.« less

Virtual Electrochemical Strain Microscopy of Polycrystalline LiCoO2 Films

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

Chung, Ding-Wen; Balke, Nina; Kalinin, Sergei V.

2011-08-03

A recently developed technique, electrochemical strain microscopy (ESM), utilizes the strong coupling between ionic current and anisotropic volumetric chemical expansion of lithium-ion electrode materials to dynamically probe the sub-one-hundred? nm inter-facial kinetic intercalation properties. A numerical technique based on the finite element method was developed to analyze the underlying physics that govern the ESM signal generation and establish relations to battery performance. The performed analysis demonstrates that the diffusion path within a thin film is tortuous and the extent of lithium diffusion into the electrode is dependent on the SPM-tip-imposed overpotential frequency. The detected surface actuation gives rise to themore » development of an electromechanical hysteresis loop whose shape is dependent on grain size and overpotential frequency. Shape and tilting angle of the loop are classified into low and high frequency regimes, separated by a transition frequency which is also a function of lithium diffusivity and grain size, f T = D/l₂. Research shows that the crystallographic orientation of the surface actuated grain has a significant impact on the shape of the loop. The polycrystalline crystallographic orientation of the grains induces a diffusion path network in the electrode which impacts on the mechanical reliability of the battery. Simulations demonstrate that continuous battery cycling results in a cumulative capacity loss as a result of the hysteric non-reversible lithium intercalation. Furthermore, results suggest that ESM has the capability to infer the local out-of-plane lithium diffusivity and the out-of-plane contribution to Vegard tensor.« less

Magnetic modulation of inverse spin Hall effect in lateral spin-valves

NASA Astrophysics Data System (ADS)

Andrianov, T.; Vedyaev, A.; Dieny, B.

2018-05-01

We analytically investigated the spin-dependent transport properties in a lateral spin-valve device comprising pinned ferromagnetic electrodes allowing the injection of a spin current in a spin conducting channel where spin orbit scattering takes place. This produces an inverse spin Hall (ISHE) voltage across the thickness of the spin conducting channel. It is shown that by adding an extra soft ferromagnetic electrode with rotatable magnetization along the spin conducting channel, the ISHE generated voltage can be magnetically modulated by changing the magnetization orientation of this additional electrode. The dependence of the ISHE voltage on the direction of magnetization of the ferromagnetic electrode with rotatable magnetization was calculated in various configurations. Our results suggest that such structures could be considered as magnetic field sensors in situations where the total thickness of the sensor is constrained such as in hard disk drive readers.

Three-Dimensional Electrodes for High-Performance Bioelectrochemical Systems

PubMed Central

Yu, Yang-Yang; Zhai, Dan-Dan; Si, Rong-Wei; Sun, Jian-Zhong; Liu, Xiang; Yong, Yang-Chun

2017-01-01

Bioelectrochemical systems (BES) are groups of bioelectrochemical technologies and platforms that could facilitate versatile environmental and biological applications. The performance of BES is mainly determined by the key process of electron transfer at the bacteria and electrode interface, which is known as extracellular electron transfer (EET). Thus, developing novel electrodes to encourage bacteria attachment and enhance EET efficiency is of great significance. Recently, three-dimensional (3D) electrodes, which provide large specific area for bacteria attachment and macroporous structures for substrate diffusion, have emerged as a promising electrode for high-performance BES. Herein, a comprehensive review of versatile methodology developed for 3D electrode fabrication is presented. This review article is organized based on the categorization of 3D electrode fabrication strategy and BES performance comparison. In particular, the advantages and shortcomings of these 3D electrodes are presented and their future development is discussed. PMID:28054970

Examining the validity of Stoney-equation for in-situ stress measurements in thin film electrodes using a large-deformation finite-element procedure

NASA Astrophysics Data System (ADS)

Wen, Jici; Wei, Yujie; Cheng, Yang-Tse

2018-05-01

During the lithiation and delithiation of a thin film electrode, stress in the electrode is deduced from the curvature change of the film using the Stoney equation. The accuracy of such a measurement is conditioned on the assumptions that (a) the mechanical properties of the electrode remain unchanged during lithiation and (b) small deformation holds. Here, we demonstrate that the change in elastic properties can influence the measurement of the stress in thin film electrodes. We consider the coupling between diffusion and deformation during lithiation and delithiation of thin film electrodes and implement the constitutive behavior in a finite-deformation finite element procedure. We demonstrate that both the variation in elastic properties in thin film electrodes and finite-deformation during lithiation and delithiation would challenge the applicability of the Stoney-equation for in-situ stress measurements of thin film electrodes.

Electrochemical determination of hydroquinone using hydrophobic ionic liquid-type carbon paste electrodes

PubMed Central

2010-01-01

Three types of carbon paste electrodes (CPEs) with different liquid binders were fabricated, and their electrochemical behavior was characterized via a potassium hexacyanoferrate(II) probe. 1-Octyl-3-methylimidazolium hexafluorophosphate ionic liquid (IL) as a hydrophobic conductive pasting binder showed better electrochemical performance compared with the commonly employed binder. The IL-contained CPEs demonstrated excellent electroactivity for oxidation of hydroquinone. A diffusion control mechanism was confirmed and the diffusion coefficient (D) of 5.05 × 10-4 cm2 s-1 was obtained. The hydrophobic IL-CPE is promising for the determination of hydroquinone in terms of high sensitivity, easy operation, and good durability. PMID:20977733

Electrochemical fuel cell generator having an internal and leak tight hydrocarbon fuel reformer

DOEpatents

Dederer, J.T.; Hager, C.A.

1998-03-31

An electrochemical fuel cell generator configuration is made having a generator section which contains a plurality of axially elongated fuel cells, each cell containing a fuel electrode, air electrode, and solid oxide electrolyte between the electrodes, in which axially elongated dividers separate portions of the fuel cells from each other, and where at least one divider also reforms a reformable fuel gas mixture prior to electricity generation reactions, the at least one reformer-divider is hollow having a closed end and an open end entrance for a reformable fuel mixture to pass to the closed end of the divider and then reverse flow and pass back along the hollowed walls to be reformed, and then finally to pass as reformed fuel out of the open end of the divider to contact the fuel cells, and further where the reformer-divider is a composite structure having a gas diffusion barrier of metallic foil surrounding the external walls of the reformer-divider except at the entrance to prevent diffusion of the reformable gas mixture through the divider, and further housed in an outer insulating jacket except at the entrance to prevent short-circuiting of the fuel cells by the gas diffusion barrier. 10 figs.

Electrochemical fuel cell generator having an internal and leak tight hydrocarbon fuel reformer

DOEpatents

Dederer, Jeffrey T.; Hager, Charles A.

1998-01-01

An electrochemical fuel cell generator configuration is made having a generator section which contains a plurality of axially elongated fuel cells, each cell containing a fuel electrode, air electrode, and solid oxide electrolyte between the electrodes, in which axially elongated dividers separate portions of the fuel cells from each other, and where at least one divider also reforms a reformable fuel gas mixture prior to electricity generation reactions, the at least one reformer-divider is hollow having a closed end and an open end entrance for a reformable fuel mixture to pass to the closed end of the divider and then reverse flow and pass back along the hollowed walls to be reformed, and then finally to pass as reformed fuel out of the open end of the divider to contact the fuel cells, and further where the reformer-divider is a composite structure having a gas diffusion barrier of metallic foil surrounding the external walls of the reformer-divider except at the entrance to prevent diffusion of the reformable gas mixture through the divider, and further housed in an outer insulating jacket except at the entrance to prevent short-circuiting of the fuel cells by the gas diffusion barrier.

Postmortem diffusion MRI of the human brainstem and thalamus for deep brain stimulator electrode localization

PubMed Central

Calabrese, Evan; Hickey, Patrick; Hulette, Christine; Zhang, Jingxian; Parente, Beth; Lad, Shivanand P.; Johnson, G. Allan

2015-01-01

Deep brain stimulation (DBS) is an established surgical therapy for medically refractory tremor disorders including essential tremor (ET) and is currently under investigation for use in a variety of other neurologic and psychiatric disorders. There is growing evidence that the anti-tremor effects of DBS for ET are directly related to modulation of the dentatorubrothalamic tract (DRT), a white matter pathway that connects the cerebellum, red nucleus, and ventral intermediate nucleus of the thalamus. Emerging white matter targets for DBS, like the DRT, will require improved 3D reference maps of deep brain anatomy and structural connectivity for accurate electrode targeting. High-resolution diffusion MRI of postmortem brain specimens can provide detailed volumetric images of important deep brain nuclei and 3D reconstructions of white matter pathways with probabilistic tractography techniques. We present a high spatial and angular resolution diffusion MRI template of the postmortem human brainstem and thalamus with 3D reconstructions of the nuclei and white matter tracts involved in ET circuitry. We demonstrate accurate registration of these data to in vivo, clinical images from patients receiving DBS therapy, and correlate electrode proximity to tractography of the DRT with improvement of ET symptoms. PMID:26043869

Analysis of charge transport in gels containing polyoxometallates using methods of different sensitivity to migration.

PubMed

Caban, Karolina; Lewera, Adam; Zukowska, Grazyna Z; Kulesza, Pawel J; Stojek, Zbigniew; Jeffrey, Kenneth R

2006-08-04

Two methods have been used for examination of transport of charge in gels soaked with DMF and containing dissolved polyoxometallates. The first method is based on the analysis of both Cottrellian and steady-state currents and therefore is capable of giving the concentration of the electroactive redox centres and their transport (diffusion-type) coefficient. The second method provides the real diffusion coefficients, i.e. transport coefficients free of migrational influence, for both the substrate and the product of the electrode reaction. Several gels based on poly(methyl methacrylate), with charged (addition of 1-acrylamido-2-methyl-2-propanesulphonic acid to the polymerization mixture) and uncharged chains, have been used in the investigation. The ratio obtained for the diffusion coefficient (second method) and transport coefficient (first method) was smaller for the gels containing charged polymer chains than for the gels with uncharged chains. In part these changes could be explained by the contribution of migration to the transport of polyoxomatallates in the gels. However, the impact of the changes in the polymer-channel capacity at the electrode surface while the electrode process proceeds was also considered. These structural changes should affect differently the methods based on different time domains.

Improved lifetime high voltage switch electrode

NASA Astrophysics Data System (ADS)

Halverson, W.

1985-06-01

In this Phase 1 Small Business Innovation Research (SBIR) program, preliminary tests of ion implantation to increase the lifetime of spark switch electrodes have indicated that a 185 keV carbon ion implant into a tungsten-copper composite has reduced electrode erosion by a factor of two to four. Apparently, the thin layer of tungsten carbide (WC) has better thermal properties than pure tungsten; the WC may have penetrated into the unimplanted body of the electrode by liquid and/or solid phase diffusion during erosion testing. These encouraging results should provide the basis for a Phase 2 SBIR program to investigate further the physical and chemical effects of ion implantation on spark gap electrodes and to optimize the technique for applications.

Innovation Becoming Trajectories: Leveraging Lateral and Vertical Moves for Collaborative Diffusion of Twenty-First Century Learning Practices

ERIC Educational Resources Information Center

Hung, David; Toh, Yancy; Jamaludin, Azilawati; So, Hyo-Jeong

2017-01-01

This paper argues for innovation diffusion as a "becoming" process in the context of lateral and vertical moves. The context of these innovations involves technology-mediated innovations and their diffusion trajectories in the Singapore education system. Embedded in a centralized-decentralized dialectics, this paper traces particular…

Role of Au(NPs) in the enhanced response of Au(NPs)-decorated MWCNT electrochemical biosensor

PubMed Central

Mehmood, Shahid; Ciancio, Regina; Carlino, Elvio; Bhatti, Arshad S

2018-01-01

Background The combination of Au-metallic-NPs and CNTs are a new class of hybrid nanomaterials for the development of electrochemical biosensor. Concentration of Au(nanoparticles [NPs]) in the electrochemical biosensor is crucial for the efficient charge transfer between the Au-NPs-MWCNTs modified electrode and electrolytic solution. Methods In this work, the charge transfer kinetics in the glassy carbon electrode (GCE) modified with Au(NPs)–multiwalled carbon nanotube (MWCNT) nanohybrid with varied concentrations of Au(NPs) in the range 40–100 nM was studied using electrochemical impedance spectroscopy (EIS). Field emission scanning electron microscopy and transmission electron microscopy confirmed the attachment of Au(NPs) on the surface of MWCNTs. Results The cyclic voltammetry and EIS results showed that the charge transfer mechanism was diffusion controlled and the rate of charge transfer was dependent on the concentration of Au(NPs) in the nanohybrid. The formation of spherical diffusion zone, which was dependent on the concentration of Au(NPs) in nanohybrids, was attributed to result in 3 times the increase in the charge transfer rate ks, 5 times increase in mass transfer, and 5% (9%) increase in Ipa (Ipc) observed in cyclic voltammetry in 80 nM Au(NP) nanohybrid-modified GCE from MWCNT-modified GCE. The work was extended to probe the effect of charge transfer rates at various concentrations of Au(NPs) in the nanohybrid-modified electrodes in the presence of Escherichia coli. The cyclic voltammetry results clearly showed the best results for 80 nM Au(NPs) in nanohybrid electrode. Conclusion The present study suggested that the formation of spherical diffusion zone in nanohybrid-modified electrodes is critical for the enhanced electrochemical biosensing applications. PMID:29713161

Carbon nanotube yarns for deep brain stimulation electrode.

PubMed

Jiang, Changqing; Li, Luming; Hao, Hongwei

2011-12-01

A new form of deep brain stimulation (DBS) electrode was proposed that was made of carbon nanotube yarns (CNTYs). Electrode interface properties were examined using cyclic voltammetry (CV) and electrochemical impedance spectrum (EIS). The CNTY electrode interface exhibited large charge storage capacity (CSC) of 12.3 mC/cm(2) which increased to 98.6 mC/cm(2) after acid treatment, compared with 5.0 mC/cm(2) of Pt-Ir. Impedance spectrum of both untreated and treated CNTY electrodes showed that finite diffusion process occurred at the interface due to their porous structure and charge was delivered through capacitive mechanism. To evaluate stability electrical stimulus was exerted for up to 72 h and CV and EIS results of CNTY electrodes revealed little alteration. Therefore CNTY could make a good electrode material for DBS.

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

Huo, Ya Ruth, E-mail: ruth.huo@gmail.com; Pillai, Krishna, E-mail: panthera6444@yahoo.com.au; Akhter, Javed, E-mail: s8603151@unsw.edu.au

BackgroundThe dual-electrode bipolar-RFA (B-RFA) is increasingly used to ablate large liver tumours (3–7 cm). However, the challenging aspect of B-RFA is the placement of the two electrodes around the tumour. Realignment often requires the electrodes to be extracted and reinserted.AimThe aim of this study is to examine “Edgeboost”, a novel technique to increase the lateral ablation dimension without requiring any realignment of the electrodes.Methods and MaterialsAn egg-white model and an ex vivo calf liver model were used compare the standard bipolar mode ablation to Edgeboost-1 (reaching full impedance in bipolar mode initially, then cycling in unipolar mode between left and rightmore » probes) and Edgeboost-2 (similar to Edgeboost-1 but not reaching full impedance initially in bipolar mode in order to minimize charring and, thus, to increase total ablation time).ResultsA significantly larger outer lateral ablation dimension to the probe was achieved with Edgeboost-1 compared to the standard method in the liver model (1.14 cm, SD: 0.16 vs. 0.44 cm, SD: 0.24, p = 0.04). Edgeboost-2 achieved the largest outer lateral ablation dimension of 1.75 cm (SD: 0.35). A similar association was seen in the egg model. Edgeboost-2 almost doubled the mass ablated with standard bipolar alone (mass ratio: 1:1.94 in egg white and 1:1.84 in liver).ConclusionThis study demonstrates that the novel “Edgeboost” technique can increase the outer lateral ablation dimension without requiring the two inserted electrodes to be reinserted. This would be beneficial for interventionists who use the dual B-RFA.« less

Synthesis, spectroscopic and electrochemical performance of pasted β-nickel hydroxide electrode in alkaline electrolyte

NASA Astrophysics Data System (ADS)

Shruthi, B.; Bheema Raju, V.; Madhu, B. J.

2015-01-01

β-Nickel hydroxide (β-Ni(OH)2) was successfully synthesized using precipitation method. The structure and property of the β-Ni(OH)2 were characterized by X-ray diffraction (XRD), Fourier Transform infra-red (FT-IR), Raman spectra and thermal gravimetric-differential thermal analysis (TG-DTA). The results of the FTIR spectroscopy and TG-DTA studies indicate that the β-Ni(OH)2 contains water molecules and anions. The microstructural and composition studies have been performed using Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray (EDX) analysis. A pasted-type electrode is prepared using β-Ni(OH)2 powder as the active material on a nickel sheet as a current collector. Cyclic voltammetry (CV) and Electrochemical impedance spectroscopy (EIS) studies were performed to evaluate the electrochemical performance of the β-Ni(OH)2 electrode in 6 M KOH electrolyte. CV curves showed a pair of strong redox peaks as a result of the Faradaic redox reactions of β-Ni(OH)2. The proton diffusion coefficient (D) for the present β-Ni(OH)2 electrode material is found to be 1.44 × 10-12 cm2 s-1. Further, electrochemical impedance studies confirmed that the β-Ni(OH)2 electrode reaction processes are diffusion controlled.

Synthesis, spectroscopic and electrochemical performance of pasted β-nickel hydroxide electrode in alkaline electrolyte.

PubMed

Shruthi, B; Bheema Raju, V; Madhu, B J

2015-01-25

β-Nickel hydroxide (β-Ni(OH)2) was successfully synthesized using precipitation method. The structure and property of the β-Ni(OH)2 were characterized by X-ray diffraction (XRD), Fourier Transform infra-red (FT-IR), Raman spectra and thermal gravimetric-differential thermal analysis (TG-DTA). The results of the FTIR spectroscopy and TG-DTA studies indicate that the β-Ni(OH)2 contains water molecules and anions. The microstructural and composition studies have been performed using Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray (EDX) analysis. A pasted-type electrode is prepared using β-Ni(OH)2 powder as the active material on a nickel sheet as a current collector. Cyclic voltammetry (CV) and Electrochemical impedance spectroscopy (EIS) studies were performed to evaluate the electrochemical performance of the β-Ni(OH)2 electrode in 6M KOH electrolyte. CV curves showed a pair of strong redox peaks as a result of the Faradaic redox reactions of β-Ni(OH)2. The proton diffusion coefficient (D) for the present β-Ni(OH)2 electrode material is found to be 1.44×10(-12) cm(2) s(-1). Further, electrochemical impedance studies confirmed that the β-Ni(OH)2 electrode reaction processes are diffusion controlled. Copyright © 2014 Elsevier B.V. All rights reserved.

High Energy Conversion Efficiency with 3-D Micro-Patterned Photoanode for Enhancement Diffusivity and Modification of Photon Distribution in Dye-Sensitized Solar Cells.

PubMed

Yun, Min Ju; Sim, Yeon Hyang; Cha, Seung I; Seo, Seon Hee; Lee, Dong Y

2017-11-08

Dye sensitize solar cells (DSSCs) have been considered as the promising alternatives silicon based solar cell with their characteristics including high efficiency under weak illumination and insensitive power output to incident angle. Therefore, many researches have been studied to improve the energy conversion efficiency of DSSCs. However the efficiency of DSSCs are still trapped at the around 10%. In this study, micro-scale hexagonal shape patterned photoanode have proposed to modify light distribution of photon. In the patterned electrode, the appearance efficiency have been obtained from 7.1% to 7.8% considered active area and the efficiency of 12.7% have been obtained based on the photoanode area. Enhancing diffusion of electrons and modification of photon distribution utilizing the morphology of the electrode are major factors to improving the performance of patterned electrode. Also, finite element method analyses of photon distributions were conducted to estimate morphological effect that influence on the photon distribution and current density. From our proposed study, it is expecting that patterned electrode is one of the solution to overcome the stagnant efficiency and one of the optimized geometry of electrode to modify photon distribution. Process of inter-patterning in photoanode has been minimized.

Fabrication Method for Laboratory-Scale High-Performance Membrane Electrode Assemblies for Fuel Cells.

PubMed

Sassin, Megan B; Garsany, Yannick; Gould, Benjamin D; Swider-Lyons, Karen E

2017-01-03

Custom catalyst-coated membranes (CCMs) and membrane electrode assemblies (MEAs) are necessary for the evaluation of advanced electrocatalysts, gas diffusion media (GDM), ionomers, polymer electrolyte membranes (PEMs), and electrode structures designed for use in next-generation fuel cells, electrolyzers, or flow batteries. This Feature provides a reliable and reproducible fabrication protocol for laboratory scale (10 cm 2 ) fuel cells based on ultrasonic spray deposition of a standard Pt/carbon electrocatalyst directly onto a perfluorosulfonic acid PEM.

Enabling fast charging – A battery technology gap assessment

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

Ahmed, Shabbir; Bloom, Ira; Jansen, Andrew N.

The battery technology literature is reviewed, with an emphasis on key elements that limit extreme fast charging. Key gaps in existing elements of the technology are presented as well as developmental needs. Among these needs are advanced models and methods to detect and prevent lithium plating; new positive-electrode materials which are less prone to stress-induced failure; better electrode designs to accommodate very rapid diffusion in and out of the electrode; and thermal management and pack designs to accommodate the higher operating voltage.

Enabling fast charging – A battery technology gap assessment

DOE PAGES

Ahmed, Shabbir; Bloom, Ira; Jansen, Andrew N.; ...

2017-10-23

The battery technology literature is reviewed, with an emphasis on key elements that limit extreme fast charging. Key gaps in existing elements of the technology are presented as well as developmental needs. Among these needs are advanced models and methods to detect and prevent lithium plating; new positive-electrode materials which are less prone to stress-induced failure; better electrode designs to accommodate very rapid diffusion in and out of the electrode; and thermal management and pack designs to accommodate the higher operating voltage.

Capacitive radio frequency discharges with a single ring-shaped narrow trench of various depths to enhance the plasma density and lateral uniformity

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

Ohtsu, Y., E-mail: ohtsuy@cc.saga-u.ac.jp; Matsumoto, N.; Schulze, J.

2016-03-15

Spatial structures of the electron density and temperature in ring-shaped hollow cathode capacitive rf plasma with a single narrow trench of 2 mm width have been investigated at various trench depths of D = 5, 8, 10, 12, and 15 mm. It is found that the plasma density is increased in the presence of the trench and that the radial profile of the plasma density has a peak around the narrow hollow trench near the cathode. The density becomes uniform further away from the cathode at all trench depths, whereas the electron temperature distribution remains almost uniform. The measured radial profiles of the plasmamore » density are in good agreement with a theoretical diffusion model for all the trench depths, which explains the local density increase by a local enhancement of the electron heating. Under the conditions investigated, the trench of 10 mm depth is found to result in the highest plasma density at various axial and radial positions. The results show that the radial uniformity of the plasma density at various axial positions can be improved by using structured electrodes of distinct depths rather than planar electrodes.« less

Sodium transport modes in AMTEC electrodes

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

Williams, R.M.; Homer, M.L.; Lara, L.

1998-07-01

Transport of alkali metal atoms through porous cathodes of alkali metal thermal-to-electric converter (AMTEC) cells is responsible for significant, reducible losses in the electrical performance of these cells. Sodium transport has been characterized in a variety of AMTEC electrodes and several different transport modes clearly exist. Free molecular flow is the dominant transport mechanism in clean porous molybdenum and tungsten electrodes, and contributes to sodium transport in all porous electrodes, including WPt{sub 2}, WRh{sub 3}, and TiN. Molybdenum and tungsten electrodes containing phases such as Na{sub 2}MoO{sub 4} and Na{sub 2}WO{sub 4} exhibit very efficient sodium ion transport through themore » electrode in the ionic conducting phase. These electrodes also show reversible electrochemical reactions in which sodium ions and electrons are inserted or removed from into phases such as Na{sub 2}MoO{sub 4} and Na{sub 2}Mo{sub 3}O{sub 6} which are present in the electrode WPt{sub 2} and WRh{sub 3} electrodes typically exhibit both free molecular flow transport as well as an enhanced thermally activated transport mode which is probably surface and/or grain boundary diffusion of sodium in the alloy electrode. Data for large area WPt{sub 2} electrodes within a cylindrical heat shield are reported in this paper. Sodium transport away from these electrodes is effected by both the electrode's properties and the exterior environment which inhibits sodium gas flow to the condenser. Liquid alloy electrodes have been examined and have fairly efficient transport properties by liquid phase diffusion, but have generally not been considered advantageous for development. Titanium nitride, TiN, electrodes used in AMTEC cells, and similar electronically conducting refractory compounds such as TiB{sub 2} and NbN are always physically porous to some degree as formed by sputter deposition or screen printing, and these compounds sinter quite slowly. Hence free molecular flow is always a significant sodium transport mode in these electrodes. However, the sodium transport rate computed from the physical morphology of the electrodes is not as efficient as actual sodium transport in TiN electrodes, implicating an enhanced transport mode, which remains operational at lower AMTEC operating temperatures. Some TiN electrodes also have been found to exhibit electrochemical reactions involving electrode phases which persist in sodium exposure test cells at 1223K, as reported in this paper.« less

Synthesis of a novel magnetic Fe3O4/γ-Al2O3 hybrid composite using electrode-alternation technique for the removal of an azo dye

NASA Astrophysics Data System (ADS)

Jung, Kyung-Won; Choi, Brian Hyun; Ahn, Kyu-Hong; Lee, Sang-Hyup

2017-11-01

A novel magnetic adsorbent of Fe3O4/γ-Al2O3 hybrid composite (denoted as M-Fe/Al-H) was developed electrochemically via a sequential application of iron and aluminum electrodes in a one-pot fashion, which called here as electrode-alternation technique, followed by pyrolysis. Physical and chemical properties of the prepared adsorbents were characterized and their feasibility towards the removal of di-anionic azo dye Acid Black 1 (AB1) was assessed. Textural and structural characterization revealed that the prepared M-Fe/Al-H possesses superior properties than those of M-Fe (sole usage of iron electrode), which may improve the adsorption capacity. Kinetics revealed that the adsorption equilibrium was reached within 12 h with approximately 90% of the equilibrium adsorption capacity within the first 3 h. Comprehensive analysis using the pseudo-second order and intraparticle diffusion models indicated that the dominant mechanism of the reaction is film diffusion with intraparticle diffusion being the rate determining step. The adsorption equilibrium isotherm data were best represented by the Sips isotherm model, which found to be approximately 1501, 1786, and 1959 mg/g at 283, 293, and 303 K, respectively. The exceptional performance as well as its ease of separation allows M-Fe/Al-H to be a promising candidate as an effective for azo dye removal from various aqueous medium.

First-principles investigation of aluminum intercalation and diffusion in TiO2 materials: Anatase versus rutile

NASA Astrophysics Data System (ADS)

Tang, Weiqiang; Xuan, Jin; Wang, Huizhi; Zhao, Shuangliang; Liu, Honglai

2018-04-01

Aluminum-ion batteries, emerging as a promising post-lithium battery solution, have been a subject of increasing research interest. Yet, most existing aluminum-ion research has focused on electrode materials development and synthesis. There has been a lack of fundamental understanding of the electrode processes and thus theoretical guidelines for electrode materials selection and design. In this study, by using density functional theory, we for the first time report a first-principles investigation on the thermodynamic and kinetic properties of aluminum intercalation into two common TiO2 polymorphs, i.e., anatase and rutile. After examining the aluminum intercalation sites, intercalation voltages, storage capacities and aluminum diffusion paths in both cases, we demonstrate that the stable aluminum intercalation site locates at the center of the O6 octahedral for TiO2 rutile and off center for TiO2 anatase. The maximum achievable Al/Ti ratios for rutile and anatase are 0.34375 and 0.36111, respectively. Although rutile is found to have an aluminum storage capacity slightly higher than anatase, the theoretical specific energy of rutile can reach 20.90 Wh kg-1, nearly twice as high as anatase (9.84 Wh kg-1). Moreover, the diffusion coefficient of aluminum ions in rutile is 10-9 cm2 s-1, significantly higher than that in anatase (10-20 cm2 s-1). In this regard, TiO2 rutile appears to be a better candidate than anatase as an electrode material for aluminum-ion batteries.

The influence of acid diffusion on the performance of lead-acid cells

NASA Astrophysics Data System (ADS)

Kappus, W.; Bohmann, J.

1983-11-01

A model for the discharge performance of the lead-acid cell is proposed. Diffusion of acid into the porous electrodes, which is connected with diffusio Curves of diffusional polarizations as a function of the discharge time are presented. Calculated discharge capacities show the influence of various pa

Lateral eddy diffusivity estimates from simulated and observed drifter trajectories: a case study for the Agulhas Current system

NASA Astrophysics Data System (ADS)

Rühs, Siren; Zhurbas, Victor; Durgadoo, Jonathan V.; Biastoch, Arne

2017-04-01

The Lagrangian description of fluid motion by sets of individual particle trajectories is extensively used to characterize connectivity between distinct oceanic locations. One important factor influencing the connectivity is the average rate of particle dispersal, generally quantified as Lagrangian diffusivity. In addition to Lagrangian observing programs, Lagrangian analyses are performed by advecting particles with the simulated flow field of ocean general circulation models (OGCMs). However, depending on the spatio-temporal model resolution, not all scale-dependent processes are explicitly resolved in the simulated velocity fields. Consequently, the dispersal of advective Lagrangian trajectories has been assumed not to be sufficiently diffusive compared to observed particle spreading. In this study we present a detailed analysis of the spatially variable lateral eddy diffusivity characteristics of advective drifter trajectories simulated with realistically forced OGCMs and compare them with estimates based on observed drifter trajectories. The extended Agulhas Current system around South Africa, known for its intricate mesoscale dynamics, serves as a test case. We show that a state-of-the-art eddy-resolving OGCM indeed features theoretically derived dispersion characteristics for diffusive regimes and realistically represents Lagrangian eddy diffusivity characteristics obtained from observed surface drifter trajectories. The estimates for the maximum and asymptotic lateral single-particle eddy diffusivities obtained from the observed and simulated drifter trajectories show a good agreement in their spatial pattern and magnitude. We further assess the sensitivity of the simulated lateral eddy diffusivity estimates to the temporal and lateral OGCM output resolution and examine the impact of the different eddy diffusivity characteristics on the Lagrangian connectivity between the Indian Ocean and the South Atlantic.

Lateral diffusion of proteins in the periplasm of Escherichia coli.

PubMed Central

Brass, J M; Higgins, C F; Foley, M; Rugman, P A; Birmingham, J; Garland, P B

1986-01-01

We have introduced biologically active, fluorescently labeled maltose-binding protein into the periplasmic space of Escherichia coli and measured its lateral diffusion coefficient by the fluorescence photobleaching recovery method. Diffusion of this protein in the periplasm was found to be surprisingly low (lateral diffusion coefficient, 0.9 X 10(-10) cm2 s-1), about 1,000-fold lower than would be expected for diffusion in aqueous medium and almost 100-fold lower than for an equivalent-size protein in the cytoplasm. Galactose-binding protein, myoglobin, and cytochrome c were also introduced into the periplasm and had diffusion coefficients identical to that determined for the maltose-binding protein. For all proteins nearly 100% recovery of fluorescence was obtained after photobleaching, indicating that the periplasm is a single contiguous compartment surrounding the cell. These data have considerable implications for periplasmic structure and for the role of periplasmic proteins in transport and chemotaxis. Images PMID:3005237

Spatial and temporal dynamics of receptor for advanced glycation endproducts, integrins, and actin cytoskeleton as probed with fluorescence-based imaging techniques

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

Syed, Aleem

Systematic spatial and temporal fluctuations are a fundamental part of any biological process. For example, lateral diffusion of membrane proteins is one of the key mechanisms in their cellular function. Lateral diffusion governs how membrane proteins interact with intracellular, transmembrane, and extracellular components to achieve their function. Herein, fluorescence-based techniques are used to elucidate the dynamics of receptor for advanced glycation end-products (RAGE) and integrin membrane proteins. RAGE is a transmembrane protein that is being used as a biomarker for various diseases. RAGE dependent signaling in numerous pathological conditions is well studied. However, RAGE lateral diffusion in the cell membranemore » is poorly understood. For this purpose, effect of cholesterol, cytoskeleton dynamics, and presence of ligand on RAGE lateral diffusion is investigated.« less

Integrated field emission array for ion desorption

DOEpatents

Resnick, Paul J; Hertz, Kristin L.; Holland, Christopher; Chichester, David

2016-08-23

An integrated field emission array for ion desorption includes an electrically conductive substrate; a dielectric layer lying over the electrically conductive substrate comprising a plurality of laterally separated cavities extending through the dielectric layer; a like plurality of conically-shaped emitter tips on posts, each emitter tip/post disposed concentrically within a laterally separated cavity and electrically contacting the substrate; and a gate electrode structure lying over the dielectric layer, including a like plurality of circular gate apertures, each gate aperture disposed concentrically above an emitter tip/post to provide a like plurality of annular gate electrodes and wherein the lower edge of each annular gate electrode proximate the like emitter tip/post is rounded. Also disclosed herein are methods for fabricating an integrated field emission array.

Integrated field emission array for ion desorption

DOEpatents

Resnick, Paul J; Hertz, Kristin L; Holland, Christopher; Chichester, David; Schwoebel, Paul

2013-09-17

An integrated field emission array for ion desorption includes an electrically conductive substrate; a dielectric layer lying over the electrically conductive substrate comprising a plurality of laterally separated cavities extending through the dielectric layer; a like plurality of conically-shaped emitter tips on posts, each emitter tip/post disposed concentrically within a laterally separated cavity and electrically contacting the substrate; and a gate electrode structure lying over the dielectric layer, including a like plurality of circular gate apertures, each gate aperture disposed concentrically above an emitter tip/post to provide a like plurality of annular gate electrodes and wherein the lower edge of each annular gate electrode proximate the like emitter tip/post is rounded. Also disclosed herein are methods for fabricating an integrated field emission array.

Analysis and experimental study on formation conditions of large-scale barrier-free diffuse atmospheric pressure air plasmas in repetitive pulse mode

NASA Astrophysics Data System (ADS)

Li, Lee; Liu, Lun; Liu, Yun-Long; Bin, Yu; Ge, Ya-Feng; Lin, Fo-Chang

2014-01-01

Atmospheric air diffuse plasmas have enormous application potential in various fields of science and technology. Without dielectric barrier, generating large-scale air diffuse plasmas is always a challenging issue. This paper discusses and analyses the formation mechanism of cold homogenous plasma. It is proposed that generating stable diffuse atmospheric plasmas in open air should meet the three conditions: high transient power with low average power, excitation in low average E-field with locally high E-field region, and multiple overlapping electron avalanches. Accordingly, an experimental configuration of generating large-scale barrier-free diffuse air plasmas is designed. Based on runaway electron theory, a low duty-ratio, high voltage repetitive nanosecond pulse generator is chosen as a discharge excitation source. Using the wire-electrodes with small curvature radius, the gaps with highly non-uniform E-field are structured. Experimental results show that the volume-scaleable, barrier-free, homogeneous air non-thermal plasmas have been obtained between the gap spacing with the copper-wire electrodes. The area of air cold plasmas has been up to hundreds of square centimeters. The proposed formation conditions of large-scale barrier-free diffuse air plasmas are proved to be reasonable and feasible.

Early detection of Candida albicans biofilms at porous electrodes.

PubMed

Congdon, Robert B; Feldberg, Alexander S; Ben-Yakar, Natalie; McGee, Dennis; Ober, Christopher; Sammakia, Bahgat; Sadik, Omowunmi A

2013-02-15

We describe the development of an electrochemical sensor for early detection of biofilm using Candida albicans. The electrochemical sensor used the ability of biofilms to accept electrons from redox mediators relative to the number of metabolically active cells present. Cyclic voltammetry and differential pulse voltammetry techniques were used to monitor the redox reaction of K(3)Fe(CN)(6) at porous reticulated vitreous carbon (RVC) (238.7 cm(2)) working electrodes versus Ag/AgCl reference. A shift in the peak potential occurred after 12 h of film growth, which is attributed to the presence of C. albicans. Moreover, the intensity of the ferricyanide reduction peak first increased as C. albicans deposited onto the porous electrodes at various growth times. The peak current subsequently decreased at extended periods of growth of 48 h. The reduction in peak current was attributed to the biofilm reaching its maximum growth thickness, which correlated with the maximum number of metabolically active cells. The observed diffusion coefficients for the bare RVC and biofilm-coated electrodes were 2.2 × 10(-3) and 7.0 × 10(-6) cm(2)/s, respectively. The increase in diffusivity from the bare electrode to the biofilm-coated electrode indicated some enhancement of electron transfer mediated by the biofilm to the porous electrode. Verification of the growth of biofilm was achieved using scanning electron microcopy and laser scanning confocal imaging microscopy. Validation with conventional plating techniques confirmed that the correlation (R(2) = 0.9392) could be achieved between the electrochemical sensors data and colony-forming units. Copyright © 2012 Elsevier Inc. All rights reserved.

Nano-fabricated perpendicular magnetic anisotropy electrodes for lateral spin valves and observation of Nernst-Ettingshausen related signals

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

Chejanovsky, N.; Sharoni, A., E-mail: amos.sharoni@biu.ac.il

2014-08-21

Lateral spin valves (LSVs) are efficient structures for characterizing spin currents in spintronics devices. Most LSVs are based on ferromagnetic (FM) electrodes for spin-injection and detection. While there are advantages for using perpendicular magnetic anisotropy (PMA) FM, e.g., stability to nano-scaling, these have almost not been studied. This is mainly due to difficulties in fabricating PMA FMs in a lateral geometry. We present here an efficient method, based on ion-milling through an AlN mask, for fabrication of LSVs with multi-layered PMA FMs such as Co/Pd and Co/Ni. We demonstrate, using standard permalloy FMs, that the method enables efficient spin injection.more » We show the multi-layer electrodes retain their PMA properties as well as spin injection and detection in PMA LSVs. In addition, we find a large asymmetric voltage signal which increases with current. We attribute this to a Nernst-Ettingshausen effect caused by local Joule heating and the perpendicular magnetic easy axis.« less

Electrode performance parameters for a radioisotope-powered AMTEC for space power applications

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

Underwood, M.L.; O'Connor, D.; Williams, R.M.

1992-08-01

The alkali metal thermoelastic converter (AMTEC) is a device for the direct conversion of heat to electricity. Recently a design of an AMTEC using a radioisotope heat source was described, but the optimum condenser temperature was hotter than the temperatures used in the laboratory to develop the electrode performance model. Now laboratory experiments have confirmed the dependence of two model parameters over a broader range of condenser and electrode temperatures for two candidate electrode compositions. One parameter, the electrochemical exchange current density at the reaction interface, is independent of the condenser temperature, and depends only upon the collision rate ofmore » sodium at the reaction zone. The second parameter, a morphological parameter, which measures the mass transport resistance through the electrode, is independent of condenser and electrode temperatures for molybdenum electrodes. For rhodium-tungsten electrodes, however, this parameter increases for decreasing electrode temperature, indicating an activated mass transport mechanism such as surface diffusion. 21 refs.« less

Development of High Interruption Capability Vacuum Circuit Breaker -Technology of Vacuum Arc Control-

NASA Astrophysics Data System (ADS)

Niwa, Yoshimitsu; Kaneko, Eiji

Vacuum circuit breakers (VCB) have been widely used for power distribution systems. Vacuum Interrupters, which are the current interruption unit, have been increased its interruption capability with the development of vacuum arc control technology by magnetic field. There are three major type electrodes: disk shaped electrodes, radial magnetic field electrodes, axial magnetic field (AMF) electrodes. In the disk shaped electrode, the vacuum arc between the electrodes is not controlled. In the AMF electrode, the vacuum arc is diffused and stabilized by an axial magnetic field, which is parallel to the arc current. In the last type of electrodes, the vacuum arc column is rotated by magnetic force generated by the current flowing in the electrodes. The interruption current and the voltage of one break VCB is increased to 100 kA, 144 kV respectively. This paper describes basic configurations and functions of VCB, vacuum arc control technology in vacuum interrupters, recent researches and applications of VCB.

Intracochlear administration of steroids with a catheter during human cochlear implantation: a safety and feasibility study.

PubMed

Prenzler, Nils K; Salcher, Rolf; Timm, Max; Gaertner, Lutz; Lenarz, Thomas; Warnecke, Athanasia

2018-05-14

Suppression of foreign body reaction, improvement of electrode-nerve interaction, and preservation of residual hearing are essential research topics in cochlear implantation. Intracochlear pharmaco- or cell-based therapies can open new horizons in this field. Local drug delivery strategies are desirable as higher local concentrations of agents can be realized and side effects can be minimized compared to systemic administrations. When administered locally at accessible, basal parts of the cochlea, drugs reach apical regions later and in much lower concentrations due to poor diffusion patterns in cochlear fluids. Therefore, new devices are needed to warrant rapid distribution of agents into all parts of the cochlea. Five patients received a deep intracochlear injection of triamcinolone with a specifically designed cochlear catheter during cochlear implantation right before inserting a cochlear implant electrode. As a measure for formation of fibrous tissue around the electrode, electrical impedances were measured in the operation room and over 4 months thereafter. No adverse events were observed peri- and postoperatively. The handling of the device was easy. Severe damage to the microstructure of the cochlea was excluded as far as possible by cone beam computed tomography and vestibular testing. A delayed rise of the impedances was seen in the catheter group compared to controls over all regions of the cochlea. A statistical significance, however, was only obtained at the midregion of the cochlea. Consequently, the cochlear catheter is a safe and feasible device for local drug delivery of pharmaceutical agents into deeper regions of the cochlea.

Computational modeling of mediator oxidation by oxygen in an amperometric glucose biosensor.

PubMed

Simelevičius, Dainius; Petrauskas, Karolis; Baronas, Romas; Razumienė, Julija

2014-02-07

In this paper, an amperometric glucose biosensor is modeled numerically. The model is based on non-stationary reaction-diffusion type equations. The model consists of four layers. An enzyme layer lies directly on a working electrode surface. The enzyme layer is attached to an electrode by a polyvinyl alcohol (PVA) coated terylene membrane. This membrane is modeled as a PVA layer and a terylene layer, which have different diffusivities. The fourth layer of the model is the diffusion layer, which is modeled using the Nernst approach. The system of partial differential equations is solved numerically using the finite difference technique. The operation of the biosensor was analyzed computationally with special emphasis on the biosensor response sensitivity to oxygen when the experiment was carried out in aerobic conditions. Particularly, numerical experiments show that the overall biosensor response sensitivity to oxygen is insignificant. The simulation results qualitatively explain and confirm the experimentally observed biosensor behavior.

Computational Modeling of Mediator Oxidation by Oxygen in an Amperometric Glucose Biosensor

PubMed Central

Šimelevičius, Dainius; Petrauskas, Karolis; Baronas, Romas; Julija, Razumienė

2014-01-01

In this paper, an amperometric glucose biosensor is modeled numerically. The model is based on non-stationary reaction-diffusion type equations. The model consists of four layers. An enzyme layer lies directly on a working electrode surface. The enzyme layer is attached to an electrode by a polyvinyl alcohol (PVA) coated terylene membrane. This membrane is modeled as a PVA layer and a terylene layer, which have different diffusivities. The fourth layer of the model is the diffusion layer, which is modeled using the Nernst approach. The system of partial differential equations is solved numerically using the finite difference technique. The operation of the biosensor was analyzed computationally with special emphasis on the biosensor response sensitivity to oxygen when the experiment was carried out in aerobic conditions. Particularly, numerical experiments show that the overall biosensor response sensitivity to oxygen is insignificant. The simulation results qualitatively explain and confirm the experimentally observed biosensor behavior. PMID:24514882

Fuel cell assembly unit for promoting fluid service and electrical conductivity

DOEpatents

Jones, Daniel O.

1999-01-01

Fluid service and/or electrical conductivity for a fuel cell assembly is promoted. Open-faced flow channel(s) are formed in a flow field plate face, and extend in the flow field plate face between entry and exit fluid manifolds. A resilient gas diffusion layer is located between the flow field plate face and a membrane electrode assembly, fluidly serviced with the open-faced flow channel(s). The resilient gas diffusion layer is restrained against entering the open-faced flow channel(s) under a compressive force applied to the fuel cell assembly. In particular, a first side of a support member abuts the flow field plate face, and a second side of the support member abuts the resilient gas diffusion layer. The support member is formed with a plurality of openings extending between the first and second sides of the support member. In addition, a clamping pressure is maintained for an interface between the resilient gas diffusion layer and a portion of the membrane electrode assembly. Preferably, the support member is spikeless and/or substantially flat. Further, the support member is formed with an electrical path for conducting current between the resilient gas diffusion layer and position(s) on the flow field plate face.

Light and Life in Baltimore—and Beyond

PubMed Central

Edidin, Michael

2015-01-01

Baltimore has been the home of numerous biophysical studies using light to probe cells. One such study, quantitative measurement of lateral diffusion of rhodopsin, set the standard for experiments in which recovery after photobleaching is used to measure lateral diffusion. Development of this method from specialized microscopes to commercial scanning confocal microscopes has led to widespread use of the technique to measure lateral diffusion of membrane proteins and lipids, and as well diffusion and binding interactions in cell organelles and cytoplasm. Perturbation of equilibrium distributions by photobleaching has also been developed into a robust method to image molecular proximity in terms of fluorescence resonance energy transfer between donor and acceptor fluorophores. PMID:25650914

Lateral mobility of plasma membrane proteins in dividing eggs of the loach (Misgurnus fossilis): Regional differences and changes during the cell cycle.

PubMed

Bozhkova, V P; Budayova, M; Kvasnicka, P; Cigankova, N; Chorvat, D

1994-12-01

Regional differences in lateral diffusion rates of fluorescence-labeled proteins have been studied in the plasma membrane of dividing eggs of the loach (Misgurnus fossilis) by fluorescence recovery after photobleaching (FRAP). Apparent animal-vegetal differences in fluorescence intensity, lateral diffusion coefficients, and fractions of mobile proteins have been found, with all these quantities being higher in the animal pole region than in the yolk region. Cyclic changes in protein diffusion coefficients and mobile fractions during the first few cell cycles have also been recorded. Soon after the end of a cleavage, the diffusion coefficient reaches its minimal value and increases rapidly before the next cleavage.

Lateral carrier diffusion and current gain in terahertz InGaAs/InP double-heterojunction bipolar transistors

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

Chiang, Han-Wei; Rode, Johann C.; Choudhary, Prateek

2014-01-21

The DC current gain in In{sub 0.53}Ga{sub 0.47}As/InP double-heterojunction bipolar transistors is computed based on a drift-diffusion model, and is compared with experimental data. Even in the absence of other scaling effects, lateral diffusion of electrons to the base Ohmic contacts causes a rapid reduction in DC current gain as the emitter junction width and emitter-base contact spacing are reduced. The simulation and experimental data are compared in order to examine the effect of carrier lateral diffusion on current gain. The impact on current gain due to device scaling and approaches to increase current gain are discussed.

Thermal imaging measurement of lateral diffusivity and non-invasive material defect detection

DOEpatents

Sun, Jiangang; Deemer, Chris

2003-01-01

A system and method for determining lateral thermal diffusivity of a material sample using a heat pulse; a sample oriented within an orthogonal coordinate system; an infrared camera; and a computer that has a digital frame grabber, and data acquisition and processing software. The mathematical model used within the data processing software is capable of determining the lateral thermal diffusivity of a sample of finite boundaries. The system and method may also be used as a nondestructive method for detecting and locating cracks within the material sample.

Investigations of HID Lamp Electrodes under HF Operation

NASA Astrophysics Data System (ADS)

Reinelt, Jens; Langenscheidt, Oliver; Westermeier, Michael; Mentel, Juergen; Awakowicz, Peter

2007-10-01

Low pressure lamps are operated many years at high frequencies to improve the efficiency of these lamps and drivers. For high pressure discharge lamps this operation mode has not been installed yet. Generally it can be assumed that there are changes in the electrode physics which may lead to an undesired lamp behavior if HID lamps are operated at a high frequency. To gain insights into these fundamental changes the so called Bochum Model Lamp is used. It is an easy system which allows a fundamental research on HID electrode behavior and the near electrode region without the occurrence of acoustic resonances. For the investigation phase resolved photography, pyrometry and spectrometry is used. The presented results describe changes in the electrode temperature and changes in the kind of arc attachment on the electrodes (diffuse and spot mode) depending on frequency. Also measurements of the Electrode-Sheath-Voltage (ESV), depending on frequency, are presented.

Engineering the Interfaces of Superadsorbing Graphene-Based Electrodes with Gas and Electrolyte to Boost Gas Evolution and Activation Reactions.

PubMed

Zhang, Jun-Jun; Lv, Li-Bing; Zhao, Tian-Jian; Lin, Yun-Xiao; Yu, Qiu-Ying; Su, Juan; Hirano, Shin-Ichi; Li, Xin-Hao; Chen, Jie-Sheng

2018-05-30

Electrochemical gas evolution and activation reactions are complicated processes, involving not only active electrocatalysts but also the interaction among solid electrodes, electrolyte, and gas-phase products and reactants. In this study, multiphase interfaces of superadsorbing graphene-based electrodes were controlled without changing the active centers to significantly facilitate mass diffusion kinetics for superior performance. The achieved in-depth understanding of how to regulate the interfacial properties to promote the electrochemical performance could provide valuable clues for electrode manufacture and for the design of more active electrocatalysts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical and kinetic studies of ultrafast laser structured LiFePO4 electrodes

NASA Astrophysics Data System (ADS)

Mangang, M.; Gotcu-Freis, P.; Seifert, H. J.; Pfleging, W.

2015-03-01

Due to a growing demand of cost-efficient lithium-ion batteries with an increased energy and power density as well as an increased life-time, the focus is set on intercalation cathode materials like LiFePO4. It has a high practical capacity, is environmentally friendly and has low material costs. However, its low electrical conductivity and low ionic diffusivity are major drawbacks for its use in electrochemical storage devices or electric vehicles. By adding conductive agents, the electrical conductivity can be enhanced. By increasing the surface of the cathode material which is in direct contact with the liquid electrolyte the lithium-ion diffusion kinetics can be improved. A new approach to increase the surface of the active material without changing the active particle packing density or the weight proportion of carbon black is the laser-assisted generation of 3D surface structures in electrode materials. In this work, ultrafast laser radiation was used to create a defined surface structure in LiFePO4 electrodes. It was shown that by using ultrashort laser pulses instead of nanosecond laser pulses, the ablation efficiency could be significantly increased. Furthermore, melting and debris formation were reduced. To investigate the diffusion kinetics, electrochemical methods such as cyclic voltammetry and galvanostatic intermittent titration technique were applied. It could be shown that due to a laser generated 3D structure, the lithium-ion diffusion kinetic, the capacity retention and cell life-time can be significantly improved.

Limitations of the commonly used simplified laterally uniform optical fiber probe-tissue interface in Monte Carlo simulations of diffuse reflectance

PubMed Central

Naglič, Peter; Pernuš, Franjo; Likar, Boštjan; Bürmen, Miran

2015-01-01

Light propagation models often simplify the interface between the optical fiber probe tip and tissue to a laterally uniform boundary with mismatched refractive indices. Such simplification neglects the precise optical properties of the commonly used probe tip materials, e.g. stainless steel or black epoxy. In this paper, we investigate the limitations of the laterally uniform probe-tissue interface in Monte Carlo simulations of diffuse reflectance. In comparison to a realistic probe-tissue interface that accounts for the layout and properties of the probe tip materials, the simplified laterally uniform interface is shown to introduce significant errors into the simulated diffuse reflectance. PMID:26504647

Membrane Orientation and Lateral Diffusion of BODIPY-Cholesterol as a Function of Probe Structure

PubMed Central

Solanko, Lukasz M.; Honigmann, Alf; Midtiby, Henrik Skov; Lund, Frederik W.; Brewer, Jonathan R.; Dekaris, Vjekoslav; Bittman, Robert; Eggeling, Christian; Wüstner, Daniel

2013-01-01

Cholesterol tagged with the BODIPY fluorophore via the central difluoroboron moiety of the dye (B-Chol) is a promising probe for studying intracellular cholesterol dynamics. We synthesized a new BODIPY-cholesterol probe (B-P-Chol) with the fluorophore attached via one of its pyrrole rings to carbon-24 of cholesterol (B-P-Chol). Using two-photon fluorescence polarimetry in giant unilamellar vesicles and in the plasma membrane (PM) of living intact and actin-disrupted cells, we show that the BODIPY-groups in B-Chol and B-P-Chol are oriented perpendicular and almost parallel to the bilayer normal, respectively. B-Chol is in all three membrane systems much stronger oriented than B-P-Chol. Interestingly, we found that the lateral diffusion in the PM was two times slower for B-Chol than for B-P-Chol, although we found no difference in lateral diffusion in model membranes. Stimulated emission depletion microscopy, performed for the first time, to our knowledge, with fluorescent sterols, revealed that the difference in lateral diffusion of the BODIPY-cholesterol probes was not caused by anomalous subdiffusion, because diffusion of both analogs in the PM was free but not hindered. Our combined measurements show that the position and orientation of the BODIPY moiety in cholesterol analogs have a severe influence on lateral diffusion specifically in the PM of living cells. PMID:24209853

Remote fluorescence imaging of dynamic concentration profiles with micrometer resolution using a coherent optical fiber bundle.

PubMed

Amatore, Christian; Chovin, Arnaud; Garrigue, Patrick; Servant, Laurent; Sojic, Neso; Szunerits, Sabine; Thouin, Laurent

2004-12-15

Dynamic concentration profiles within the diffusion layer of an electrode were imaged in situ using fluorescence detection through a multichannel imaging fiber. In this work, a coherent optical fiber bundle is positioned orthogonal to the surface of an electrode and is used to report spatial and temporal micrometric changes in the fluorescence intensity of an initial fluorescent species. The fluorescence signal is directly related to the local concentration of a redox fluorescent reagent, which is electrochemically modulated by the electrode. Fluorescence images are collected through the optical fiber bundle during the oxidation of tris(2,2'-bipyridine)ruthenium(II) to ruthenium(III) at a diffusion-limited rate and allow the concentration profiles of Ru(II) reagent to be monitored in situ as a function of time. Tris(2,2'-bipyridine)ruthenium(II) is excited at 485 nm and emits fluorescence at 605 nm, whereas the Ru(III) oxidation state is not fluorescent. Our experiments emphasize the influence of two parameters on the micrometer spatial resolution: the numerical aperture of optical fibers within the bundle and the Ru(II) bulk concentration. The extent of the volume probed by each individual fiber of the bundle is discussed qualitatively in terms of a primary inner-filter effect and refractive index gradient. Experimentally measured fluorescence intensity profiles were found to be in very good agreement with concentration profiles predicted upon considering planar diffusion and thus validate the concept of this new application of imaging fibers. The originality of this remote approach is to provide a global view of the entire diffusion layer at a given time through one single image and to allow the time expansion of the diffusion layer to be followed quantitatively in real time.

Interictal spike detection comparing subdural and depth electrodes during electrocorticography.

PubMed

Privitera, M D; Quinlan, J G; Yeh, H S

1990-11-01

We compared the ability of subdural and depth electrodes to detect and localize interictal epileptiform discharges (IEDs) in the temporal lobe. Sixteen patients had simultaneous intraoperative recordings with depth and subdural electrodes while undergoing anterior temporal lobe resections under local anesthesia for medically intractable seizures. IEDs that were focal (detected at just 1 or 2 electrode contacts) typically registered at the nearest contact, regardless of type. IEDs that were regional (engaging more than 2 electrode contacts) typically appeared simultaneously at both electrode types. Neither method was better able to indicate whether an IED was mesial or lateral, posterior or anterior. Subdural and depth electrodes seem to provide complementary information on the location of IEDs within the temporal lobe.

A Strange Case of Downward Displacement of a Deep Brain Stimulation Electrode 10 Years Following Implantation: The Gliding Movement of Snakes Theory.

PubMed

Iacopino, Domenico Gerardo; Maugeri, Rosario; Giugno, Antonella; Giller, Cole A

2015-08-01

Despite the best efforts to ensure stereotactic precision, deep brain stimulation (DBS) electrodes can wander from their intended position after implantation. We report a case of downward electrode migration 10 years following successful implantation in a patient with Parkinson disease. A 53-year-old man with Parkinson disease underwent bilateral implantation of DBS electrodes connected to a subclavicular 2-channel pulse generator. The generator was replaced 7 years later, and a computed tomography (CT) scan confirmed the correct position of both leads. The patient developed a gradual worsening affecting his right side 3 years later, 10 years after the original implantation. A CT scan revealed displacement of the left electrode inferiorly into the pons. The new CT scans and the CT scans obtained immediately after the implantation were merged within a stereotactic planning workstation (Brainlab). Comparing the CT scans, the distal end of the electrode was in the same position, the proximal tip being significantly more inferior. The size and configuration of the coiled portions of the electrode had not changed. At implantation, the length was 27.7 cm; after 10 years, the length was 30.6 cm. These data suggests that the electrode had been stretched into its new position rather than pushed. Clinicians evaluating patients with a delayed worsening should be aware of this rare event. Copyright © 2015 Elsevier Inc. All rights reserved.

Localizing and tracking electrodes using stereovision in epilepsy cases

NASA Astrophysics Data System (ADS)

Fan, Xiaoyao; Ji, Songbai; Roberts, David W.; Paulsen, Keith D.

2015-03-01

In epilepsy cases, subdural electrodes are often implanted to acquire intracranial EEG (iEEG) for seizure localization and resection planning. However, the electrodes may shift significantly between implantation and resection, during the time that the patient is monitored for iEEG recording. As a result, the accuracy of surgical planning based on electrode locations at the time of resection can be compromised. Previous studies have only quantified the electrode shift with respect to the skull, but not with respect to the cortical surface, because tracking cortical shift between surgeries is challenging. In this study, we use an intraoperative stereovision (iSV) system to visualize and localize the cortical surface as well as electrodes, record three-dimensional (3D) locations of the electrodes in MR space at the time of implantation and resection, respectively, and quantify the raw displacements, i.e., with respect to the skull. Furthermore, we track the cortical surface and quantify the shift between surgeries using an optical flow (OF) based motion-tracking algorithm. Finally, we compute the electrode shift with respect to the cortical surface by subtracting the cortical shift from raw measured displacements. We illustrate the method using one patient example. In this particular patient case, the results show that the electrodes not only shifted significantly with respect to the skull (8.79 +/- 3.00 mm in the lateral direction, ranging from 2.88 mm to 12.87 mm), but also with respect to the cortical surface (7.20 +/- 3.58 mm), whereas the cortical surface did not shift significantly in the lateral direction between surgeries (2.23 +/- 0.76 mm).

Enhanced electrochemical nanoring electrode for analysis of cytosol in single cells.

PubMed

Zhuang, Lihong; Zuo, Huanzhen; Wu, Zengqiang; Wang, Yu; Fang, Danjun; Jiang, Dechen

2014-12-02

A microelectrode array has been applied for single cell analysis with relatively high throughput; however, the cells were typically cultured on the microelectrodes under cell-size microwell traps leading to the difficulty in the functionalization of an electrode surface for higher detection sensitivity. Here, nanoring electrodes embedded under the microwell traps were fabricated to achieve the isolation of the electrode surface and the cell support, and thus, the electrode surface can be modified to obtain enhanced electrochemical sensitivity for single cell analysis. Moreover, the nanometer-sized electrode permitted a faster diffusion of analyte to the surface for additional improvement in the sensitivity, which was evidenced by the electrochemical characterization and the simulation. To demonstrate the concept of the functionalized nanoring electrode for single cell analysis, the electrode surface was deposited with prussian blue to detect intracellular hydrogen peroxide at a single cell. Hundreds of picoamperes were observed on our functionalized nanoring electrode exhibiting the enhanced electrochemical sensitivity. The success in the achievement of a functionalized nanoring electrode will benefit the development of high throughput single cell electrochemical analysis.

Capillary reference half-cell

DOEpatents

Hall, Stephen H.

1996-01-01

The present invention is a reference half-cell electrode wherein intermingling of test fluid with reference fluid does not affect the performance of the reference half-cell over a long time. This intermingling reference half-cell may be used as a single or double junction submersible or surface reference electrode. The intermingling reference half-cell relies on a capillary tube having a first end open to reference fluid and a second end open to test fluid wherein the small diameter of the capillary tube limits free motion of fluid within the capillary to diffusion. The electrode is placed near the first end of the capillary in contact with the reference fluid. The method of operation of the present invention begins with filling the capillary tube with a reference solution. After closing the first end of the capillary, the capillary tube may be fully submerged or partially submerged with the second open end inserted into test fluid. Since the electrode is placed near the first end of the capillary, and since the test fluid may intermingle with the reference fluid through the second open end only by diffusion, this intermingling capillary reference half-cell provides a stable voltage potential for long time periods.

Capillary reference half-cell

DOEpatents

Hall, S.H.

1996-02-13

The present invention is a reference half-cell electrode wherein intermingling of test fluid with reference fluid does not affect the performance of the reference half-cell over a long time. This intermingling reference half-cell may be used as a single or double junction submersible or surface reference electrode. The intermingling reference half-cell relies on a capillary tube having a first end open to reference fluid and a second end open to test fluid wherein the small diameter of the capillary tube limits free motion of fluid within the capillary to diffusion. The electrode is placed near the first end of the capillary in contact with the reference fluid. The method of operation of the present invention begins with filling the capillary tube with a reference solution. After closing the first end of the capillary, the capillary tube may be fully submerged or partially submerged with the second open end inserted into test fluid. Since the electrode is placed near the first end of the capillary, and since the test fluid may intermingle with the reference fluid through the second open end only by diffusion, this intermingling capillary reference half-cell provides a stable voltage potential for long time periods. 11 figs.

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

NASA Astrophysics Data System (ADS)

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

2014-10-01

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

Fullerene-C60-modified electrode as a sensitive voltammetric sensor for detection of nandrolone--an anabolic steroid used in doping.

PubMed

Goyal, Rajendra N; Gupta, Vinod K; Bachheti, Neeta

2007-07-30

The electrochemical behaviour of nandrolone is investigated by cyclic, differential pulse and square-wave voltammetry in phosphate buffer system at fullerene-C60-modified electrode. The modified electrode shows an excellent electrocatalytic activity towards the oxidation of nandrolone resulting in a marked lowering in the peak potential and considerable improvement of the peak current as compared to the electrochemical activity at the bare glassy carbon electrode. The oxidation process is shown to be irreversible and diffusion-controlled. A linear range of 50 microM to 0.1 nM is obtained along with a detection limit and sensitivity of 0.42 nM and 0.358 nA nM(-1), respectively, in square-wave voltammetric technique. A diffusion coefficient of 4.13x10(-8) cm2 s(-1) was found for nandrolone using chronoamperometry. The effect of interferents, stability and reproducibility of the proposed method were also studied. The described method was successfully employed for the determination of nandrolone in human serum and urine samples. A cross-validation of observed results by GC-MS indicates that the results are in good agreement with each other.

Postmortem diffusion MRI of the human brainstem and thalamus for deep brain stimulator electrode localization.

PubMed

Calabrese, Evan; Hickey, Patrick; Hulette, Christine; Zhang, Jingxian; Parente, Beth; Lad, Shivanand P; Johnson, G Allan

2015-08-01

Deep brain stimulation (DBS) is an established surgical therapy for medically refractory tremor disorders including essential tremor (ET) and is currently under investigation for use in a variety of other neurologic and psychiatric disorders. There is growing evidence that the anti-tremor effects of DBS for ET are directly related to modulation of the dentatorubrothalamic tract (DRT), a white matter pathway that connects the cerebellum, red nucleus, and ventral intermediate nucleus of the thalamus. Emerging white matter targets for DBS, like the DRT, will require improved three-dimensional (3D) reference maps of deep brain anatomy and structural connectivity for accurate electrode targeting. High-resolution diffusion MRI of postmortem brain specimens can provide detailed volumetric images of important deep brain nuclei and 3D reconstructions of white matter pathways with probabilistic tractography techniques. We present a high spatial and angular resolution diffusion MRI template of the postmortem human brainstem and thalamus with 3D reconstructions of the nuclei and white matter tracts involved in ET circuitry. We demonstrate registration of these data to in vivo, clinical images from patients receiving DBS therapy, and correlate electrode proximity to tractography of the DRT with improvement of ET symptoms. © 2015 Wiley Periodicals, Inc.

Cyclic steady states in diffusion-induced plasticity with applications to lithium-ion batteries

NASA Astrophysics Data System (ADS)

Peigney, Michaël

2018-02-01

Electrode materials in lithium-ion batteries offer an example of medium in which stress and plastic flow are generated by the diffusion of guest atoms. In such a medium, deformation and diffusion are strongly coupled processes. For designing electrodes with improved lifetime and electro-mechanical efficiency, it is crucial to understand how plasticity and diffusion evolve over consecutive charging-recharging cycles. With such questions in mind, this paper provides general results for the large-time behavior of media coupling plasticity with diffusion when submitted to cyclic chemo-mechanical loadings. Under suitable assumptions, we show that the stress, the plastic strain rate, the chemical potential and the flux of guest atoms converge to a cyclic steady state which is largely independent of the initial state. A special emphasis is laid on the special case of elastic shakedown, which corresponds to the situation where the plastic strain stops evolving after a sufficiently large number of cycles. Elastic shakedown is expected to be beneficial for the fatigue behavior and - in the case of lithium-ion batteries - for the electro-chemical efficiency. We provide a characterization of the chemo-mechanical loadings for which elastic shakedown occurs. Building on that characterization, we suggest a general method for designing structures in such fashion that they operate in the elastic shakedown regime, whatever the initial state is. An attractive feature of the proposed method is that incremental analysis of the fully coupled plasticity-diffusion problem is avoided. The results obtained are applied to the model problem of a battery electrode cylinder particle under cyclic charging. Closed-form expressions are obtained for the set of charging rates and charging amplitudes for which elastic shakedown occurs, as well as for the corresponding cyclic steady states of stress, lithium concentration and chemical potential. Some results for a spherical particle are also presented.

Light and life in Baltimore--and beyond.

PubMed

Edidin, Michael

2015-02-03

Baltimore has been the home of numerous biophysical studies using light to probe cells. One such study, quantitative measurement of lateral diffusion of rhodopsin, set the standard for experiments in which recovery after photobleaching is used to measure lateral diffusion. Development of this method from specialized microscopes to commercial scanning confocal microscopes has led to widespread use of the technique to measure lateral diffusion of membrane proteins and lipids, and as well diffusion and binding interactions in cell organelles and cytoplasm. Perturbation of equilibrium distributions by photobleaching has also been developed into a robust method to image molecular proximity in terms of fluorescence resonance energy transfer between donor and acceptor fluorophores. Copyright © 2015 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Defibrillation efficacy of different electrode placements in a human thorax model.

PubMed

de Jongh, A L; Entcheva, E G; Replogle, J A; Booker, R S; Kenknight, B H; Claydon, F J

1999-01-01

The objective of this study was to measure the defibrillation threshold (DFT) associated with different electrode placements using a three-dimensional anatomically realistic finite element model of the human thorax. Coil electrodes (Endotak DSP, model 125, Guidant/CPI) were placed in the RV apex along the lateral wall (RV), withdrawn 10 mm away from the RV apex along the lateral wall (RVprox), in the RV apex along the anterior septum (RVseptal), and in the SVC. An active pulse generator (can) was placed in the subcutaneous prepectoral space. Five electrode configurations were studied: RV-->SVC, RVprox-->SVC, RVSEPTAL-->SVC, RV-->Can, and RV-->SVC + Can. DFTs are defined as the energy required to produce a potential gradient of at least 5 V/cm in 95% of the ventricular myocardium. DFTs for RV-->SVC, RVprox-->SVC, RVseptal-->SVC, RV-->Can, and RV-->SVC + Can were 10, 16, 7, 9, and 6 J, respectively. The DFTs measured at each configuration fell within one standard deviation of the mean DFTs reported in clinical studies using the Endotak leads. The relative changes in DFT among electrode configurations also compared favorably. This computer model allows measurements of DFT or other defibrillation parameters with several different electrode configurations saving time and cost of clinical studies.

Enabling fast charging - A battery technology gap assessment

NASA Astrophysics Data System (ADS)

Ahmed, Shabbir; Bloom, Ira; Jansen, Andrew N.; Tanim, Tanvir; Dufek, Eric J.; Pesaran, Ahmad; Burnham, Andrew; Carlson, Richard B.; Dias, Fernando; Hardy, Keith; Keyser, Matthew; Kreuzer, Cory; Markel, Anthony; Meintz, Andrew; Michelbacher, Christopher; Mohanpurkar, Manish; Nelson, Paul A.; Robertson, David C.; Scoffield, Don; Shirk, Matthew; Stephens, Thomas; Vijayagopal, Ram; Zhang, Jiucai

2017-11-01

The battery technology literature is reviewed, with an emphasis on key elements that limit extreme fast charging. Key gaps in existing elements of the technology are presented as well as developmental needs. Among these needs are advanced models and methods to detect and prevent lithium plating; new positive-electrode materials which are less prone to stress-induced failure; better electrode designs to accommodate very rapid diffusion in and out of the electrode; measure temperature distributions during fast charge to enable/validate models; and develop thermal management and pack designs to accommodate the higher operating voltage.

Current collector for AMTEC

NASA Technical Reports Server (NTRS)

Williams, Roger M. (Inventor)

1989-01-01

An electrode having higher power output is formed of an open mesh current collector such as expanded nickel covering an electrode film applied to a tube of beta-alumina solid electrolyte (BASE). A plurality of cross-members such as spaced, parallel loops of molybdenum metal wire surround the BASE tube. The loops are electrically connected by a bus wire. As the AMTEC cell is heated, the grid of expanded nickel expands more than the BASE tube and the surrounding loop of wire and become diffusion welded to the electrode film and to the wire loops.

Nonsaturable microdryer

DOEpatents

Hirschfeld, Tomas B.

1985-01-01

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

Nonsaturable microdryer

DOEpatents

Hirschfeld, T.B.

1984-05-23

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

Arrays of Very Small Voltammetric Electrodes Based on Reticulated Vitreous Carbon.

DTIC Science & Technology

1983-10-14

1H D-fli34 73ifARRAYS OF VERY SMALL YOLTAMMETRIC ELECTRODES BA5ED ON i/i RETICULATED VITREOUS CARBON (U) STATE UNIV OF NEW YORK I AT BUFFALO AMHERST N...PEIOiUD COVI[R9 1^. Arrays of Very Small Voltametric Electrodes 0 Based on Reticulated Vitreous Carbon - S. PRFROG OG. REPORT NUM A 7. AUTNOR) 0...Cofigi nueu eav’e,o *ee i necesaery and Iden lly by block number) L.Uj Reticulated vitreous carbon ; microelectrodes; nonlinear diffusion; vol tammetry

Rational material design for ultrafast rechargeable lithium-ion batteries.

PubMed

Tang, Yuxin; Zhang, Yanyan; Li, Wenlong; Ma, Bing; Chen, Xiaodong

2015-10-07

Rechargeable lithium-ion batteries (LIBs) are important electrochemical energy storage devices for consumer electronics and emerging electrical/hybrid vehicles. However, one of the formidable challenges is to develop ultrafast charging LIBs with the rate capability at least one order of magnitude (>10 C) higher than that of the currently commercialized LIBs. This tutorial review presents the state-of-the-art developments in ultrafast charging LIBs by the rational design of materials. First of all, fundamental electrochemistry and related ionic/electronic conduction theories identify that the rate capability of LIBs is kinetically limited by the sluggish solid-state diffusion process in electrode materials. Then, several aspects of the intrinsic materials, materials engineering and processing, and electrode materials architecture design towards maximizing both ionic and electronic conductivity in the electrode with a short diffusion length are deliberated. Finally, the future trends and perspectives for the ultrafast rechargeable LIBs are discussed. Continuous rapid progress in this area is essential and urgent to endow LIBs with ultrafast charging capability to meet huge demands in the near future.

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.

Fabrication and Characterization of a Nanocoax-Based Electrochemical Sensor

NASA Astrophysics Data System (ADS)

Rizal, Binod; Archibald, Michelle M.; Naughton, Jeffrey R.; Connolly, Timothy; Shepard, Stephen C.; Burns, Michael J.; Chiles, Thomas C.; Naughton, Michael J.

2014-03-01

We used an imprint lithography process to fabricate three dimensional electrochemical sensors comprising arrays of vertically-oriented coaxial electrodes, with the coax cores and shields serving as working and counter electrodes, respectively, and with nanoscale separation gaps.[2] Arrays of devices with different electrode gaps (coax annuli) were prepared, yielding increasing sensitivity with decreasing annulus thickness. A coax-based sensor with a 100 nm annulus was found to have sensitivity 100 times greater than that of a conventional planar sensor control, which had millimeter-scale electrode gap spacing. We suggest that this enhancement is due to an increase in the diffusion of molecules between electrodes, which improves the current per unit surface area compared to the planar device. Supported by NIH (National Cancer Institute and the National Institute of Allergy and Infectious Diseases).

NEUTRON MEASURING METHOD AND APPARATUS

DOEpatents

Seaborg, G.T.; Friedlander, G.; Gofman, J.W.

1958-07-29

A fast neutron fission detecting apparatus is described consisting of a source of fast neutrons, an ion chamber containing air, two electrodes within the ion chamber in confronting spaced relationship, a high voltage potential placed across the electrodes, a shield placed about the source, and a suitable pulse annplifier and recording system in the electrode circuit to record the impulse due to fissions in a sannple material. The sample material is coated onto the active surface of the disc electrode and shielding means of a material having high neutron capture capabilities for thermal neutrons are provided in the vicinity of the electrodes and about the ion chamber so as to absorb slow neutrons of thermal energy to effectively prevent their diffusing back to the sample and causing an error in the measurement of fast neutron fissions.

Optimized programming algorithm for cylindrical and directional deep brain stimulation electrodes.

PubMed

Anderson, Daria Nesterovich; Osting, Braxton; Vorwerk, Johannes; Dorval, Alan D; Butson, Christopher R

2018-04-01

Deep brain stimulation (DBS) is a growing treatment option for movement and psychiatric disorders. As DBS technology moves toward directional leads with increased numbers of smaller electrode contacts, trial-and-error methods of manual DBS programming are becoming too time-consuming for clinical feasibility. We propose an algorithm to automate DBS programming in near real-time for a wide range of DBS lead designs. Magnetic resonance imaging and diffusion tensor imaging are used to build finite element models that include anisotropic conductivity. The algorithm maximizes activation of target tissue and utilizes the Hessian matrix of the electric potential to approximate activation of neurons in all directions. We demonstrate our algorithm's ability in an example programming case that targets the subthalamic nucleus (STN) for the treatment of Parkinson's disease for three lead designs: the Medtronic 3389 (four cylindrical contacts), the direct STNAcute (two cylindrical contacts, six directional contacts), and the Medtronic-Sapiens lead (40 directional contacts). The optimization algorithm returns patient-specific contact configurations in near real-time-less than 10 s for even the most complex leads. When the lead was placed centrally in the target STN, the directional leads were able to activate over 50% of the region, whereas the Medtronic 3389 could activate only 40%. When the lead was placed 2 mm lateral to the target, the directional leads performed as well as they did in the central position, but the Medtronic 3389 activated only 2.9% of the STN. This DBS programming algorithm can be applied to cylindrical electrodes as well as novel directional leads that are too complex with modern technology to be manually programmed. This algorithm may reduce clinical programming time and encourage the use of directional leads, since they activate a larger volume of the target area than cylindrical electrodes in central and off-target lead placements.

Membrane orientation and lateral diffusion of BODIPY-cholesterol as a function of probe structure.

PubMed

Solanko, Lukasz M; Honigmann, Alf; Midtiby, Henrik Skov; Lund, Frederik W; Brewer, Jonathan R; Dekaris, Vjekoslav; Bittman, Robert; Eggeling, Christian; Wüstner, Daniel

2013-11-05

Cholesterol tagged with the BODIPY fluorophore via the central difluoroboron moiety of the dye (B-Chol) is a promising probe for studying intracellular cholesterol dynamics. We synthesized a new BODIPY-cholesterol probe (B-P-Chol) with the fluorophore attached via one of its pyrrole rings to carbon-24 of cholesterol (B-P-Chol). Using two-photon fluorescence polarimetry in giant unilamellar vesicles and in the plasma membrane (PM) of living intact and actin-disrupted cells, we show that the BODIPY-groups in B-Chol and B-P-Chol are oriented perpendicular and almost parallel to the bilayer normal, respectively. B-Chol is in all three membrane systems much stronger oriented than B-P-Chol. Interestingly, we found that the lateral diffusion in the PM was two times slower for B-Chol than for B-P-Chol, although we found no difference in lateral diffusion in model membranes. Stimulated emission depletion microscopy, performed for the first time, to our knowledge, with fluorescent sterols, revealed that the difference in lateral diffusion of the BODIPY-cholesterol probes was not caused by anomalous subdiffusion, because diffusion of both analogs in the PM was free but not hindered. Our combined measurements show that the position and orientation of the BODIPY moiety in cholesterol analogs have a severe influence on lateral diffusion specifically in the PM of living cells. Copyright © 2013 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Diffusion tensor imaging analysis of sequential spreading of disease in amyotrophic lateral sclerosis confirms patterns of TDP-43 pathology.

PubMed

Kassubek, Jan; Müller, Hans-Peter; Del Tredici, Kelly; Brettschneider, Johannes; Pinkhardt, Elmar H; Lulé, Dorothée; Böhm, Sarah; Braak, Heiko; Ludolph, Albert C

2014-06-01

Diffusion tensor imaging can identify amyotrophic lateral sclerosis-associated patterns of brain alterations at the group level. Recently, a neuropathological staging system for amyotrophic lateral sclerosis has shown that amyotrophic lateral sclerosis may disseminate in a sequential regional pattern during four disease stages. The objective of the present study was to apply a new methodological diffusion tensor imaging-based approach to automatically analyse in vivo the fibre tracts that are prone to be involved at each neuropathological stage of amyotrophic lateral sclerosis. Two data samples, consisting of 130 diffusion tensor imaging data sets acquired at 1.5 T from 78 patients with amyotrophic lateral sclerosis and 52 control subjects; and 55 diffusion-tensor imaging data sets at 3.0 T from 33 patients with amyotrophic lateral sclerosis and 22 control subjects, were analysed by a tract of interest-based fibre tracking approach to analyse five tracts that become involved during the course of amyotrophic lateral sclerosis: the corticospinal tract (stage 1); the corticorubral and the corticopontine tracts (stage 2); the corticostriatal pathway (stage 3); the proximal portion of the perforant path (stage 4); and two reference pathways. The statistical analyses of tracts of interest showed differences between patients with amyotrophic lateral sclerosis and control subjects for all tracts. The significance level of the comparisons at the group level was lower, the higher the disease stage with corresponding involved fibre tracts. Both the clinical phenotype as assessed by the amyotrophic lateral sclerosis functional rating scale-revised and disease duration correlated significantly with the resulting staging scheme. In summary, the tract of interest-based technique allowed for individual analysis of predefined tract structures, thus making it possible to image in vivo the disease stages in amyotrophic lateral sclerosis. This approach can be used not only for individual clinical work-up purposes, but enlarges the spectrum of potential non-invasive surrogate markers as a neuroimaging-based read-out for amyotrophic lateral sclerosis studies within a clinical context. © The Author (2014). Published by Oxford University Press on behalf of the Guarantors of Brain. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Methods and apparatus for using gas and liquid phase cathodic depolarizers

NASA Technical Reports Server (NTRS)

Murphy, Oliver J. (Inventor); Hitchens, G. Duncan (Inventor)

1998-01-01

The invention provides methods for using gas and liquid phase cathodic depolarizers in an electrochemical cell having a cation exchange membrane in intimate contact with the anode and cathode. The electrochemical conversion of cathodic depolarizers at the cathode lowers the cell potential necessary to achieve a desired electrochemical conversion, such as ozone evolution, at the anode. When gaseous cathodic depolarizers, such as oxygen, are used, a gas diffusion cathode having the cation exchange membrane bonded thereto is preferred. When liquid phase cathodic depolarizers are used, the cathode may be a flow-by electrode, flow-through electrode, packed-bed electrode or a fluidized-bed electrode in intimate contact with the cation exchange membrane.

Lateral fluid flow fractionation using dielectrophoresis (LFFF-DEP) for size-independent, label-free isolation of circulating tumor cells.

PubMed

Waheed, Waqas; Alazzam, Anas; Mathew, Bobby; Christoforou, Nicolas; Abu-Nada, Eiyad

2018-06-15

This short communication introduces a continuous-flow, dielectrophoresis-based lateral fluid flow fractionation microdevice for detection/isolation of circulating tumor cells in the presence of other haematological cells. The device utilizes two sets of planar interdigitated transducer electrodes micropatterned on top of a glass wafer using standard microfabrication techniques. A microchannel with a single inlet and two outlets, realized in polydimethylsiloxane, is bonded on the glass substrate. The two sets of electrodes slightly protrude into the microchannel. Both of the electrode sets are energized with signals at different frequencies and different operating voltages ensuring that the cancer cells experience positive dielectrophoretic force from one set of the electrodes and negative dielectrophoretic force from the other array. Normal cells experience unequal negative dielectrophoretic forces from opposing sets of electrodes. The resultant dielectrophoretic forces on cancer and normal cells push them to flow towards their designed outlets. Successful isolation of green fluorescent protein-labelled MDA-MB-231 breast cancer cells from regular blood cells, both suspended in a sucrose/dextrose medium, is reported in this work. Copyright © 2018 Elsevier B.V. All rights reserved.

Lateral Membrane Diffusion Modulated by a Minimal Actin Cortex

PubMed Central

Heinemann, Fabian; Vogel, Sven K.; Schwille, Petra

2013-01-01

Diffusion of lipids and proteins within the cell membrane is essential for numerous membrane-dependent processes including signaling and molecular interactions. It is assumed that the membrane-associated cytoskeleton modulates lateral diffusion. Here, we use a minimal actin cortex to directly study proposed effects of an actin meshwork on the diffusion in a well-defined system. The lateral diffusion of a lipid and a protein probe at varying densities of membrane-bound actin was characterized by fluorescence correlation spectroscopy (FCS). A clear correlation of actin density and reduction in mobility was observed for both the lipid and the protein probe. At high actin densities, the effect on the protein probe was ∼3.5-fold stronger compared to the lipid. Moreover, addition of myosin filaments, which contract the actin mesh, allowed switching between fast and slow diffusion in the minimal system. Spot variation FCS was in accordance with a model of fast microscopic diffusion and slower macroscopic diffusion. Complementing Monte Carlo simulations support the analysis of the experimental FCS data. Our results suggest a stronger interaction of the actin mesh with the larger protein probe compared to the lipid. This might point toward a mechanism where cortical actin controls membrane diffusion in a strong size-dependent manner. PMID:23561523

A hydrogen fuel cell for rapid, enzyme-catalysed organic synthesis with continuous monitoring.

PubMed

Wan, Lei; Megarity, Clare F; Siritanaratkul, Bhavin; Armstrong, Fraser A

2018-01-23

A one-pot fuel cell for specific, enzyme-catalysed organic synthesis, with continuous monitoring of rate and reaction progress, combines an electrode catalysing rapid, reversible and diffusion-controlled interconversion of NADP + and NADPH with a Pt electrode catalysing 2H + /H 2 interconversion. This Communication demonstrates its performance and characteristics using the reductive amination of 2-oxoglutarate as a test system.

Core-shell fuel cell electrodes

DOEpatents

Adzic, Radoslav; Bliznakov, Stoyan; Vukmirovic, Miomir

2017-07-25

Embodiments of the disclosure relate to electrocatalysts. The electrocatalyst may include at least one gas-diffusion layer having a first side and a second side, and particle cores adhered to at least one of the first and second sides of the at least one gas-diffusion layer. The particle cores includes surfaces adhered to the at least one of the first and second sides of the at least one gas-diffusion layer and surfaces not in contact with the at least one gas-diffusion layer. Furthermore, a thin layer of catalytically atoms may be adhered to the surfaces of the particle cores not in contact with the at least one gas-diffusion layer.

A Rayleighian approach for modeling kinetics of ionic transport in polymeric media

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

Kumar, Rajeev

2017-02-14

Here, we report a theoretical approach for analyzing impedance of ionic liquids (ILs) and charged polymers such as polymerized ionic liquids (PolyILs) within linear response. The approach is based on the Rayleigh dissipation function formalism, which provides a computational framework for a systematic study of various factors, including polymer dynamics, in affecting the impedance. We present an analytical expression for the impedance within linear response by constructing a one-dimensional model for ionic transport in ILs/PolyILs. This expression is used to extract mutual diffusion constants, the length scale of mutual diffusion, and thicknesses of a low-dielectric layer on the electrodes frommore » the broadband dielectric spectroscopy (BDS) measurements done for an IL and three PolyILs. Also, static dielectric permittivities of the IL and the PolyILs are determined. The extracted mutual diffusion constants are compared with the self diffusion constants of ions measured using pulse field gradient (PFG) fluorine nuclear magnetic resonance (NMR). For the first time, excellent agreements between the diffusivities extracted from the Electrode Polarization spectra (EPS) of IL/PolyILs and those measured using the PFG-NMR are found, which allows the use of the EPS and the PFG-NMR techniques in a complimentary manner for a general understanding of the ionic transport.« less

Effects of proton irradiation on structural and electrochemical charge storage properties of TiO 2 nanotube electrodes for lithium-ion batteries

DOE PAGES

Smith, Kassiopeia A.; Savva, Andreas I.; Deng, Changjian; ...

2017-03-23

The effects of proton irradiation on nanostructured metal oxides have been investigated. Recent studies suggest that the presence of structural defects (e.g. vacancies and interstitials) in metal oxides may enhance the material's electrochemical charge storage capacity. A new approach to introduce defects in electrode materials is to use ion irradiation as it can produce a supersaturation of point defects in the target material. In this work we report the effect of low-energy proton irradiation on amorphous TiO 2 nanotube electrodes at both room temperature and high temperature (250 °C). Upon room temperature irradiation the nanotubes demonstrate an irradiation-induced phase transformationmore » to a mixture of amorphous, anatase, and rutile domains while showing a 35% reduction in capacity compared to anatase TiO 2. On the other hand, the high temperature proton irradiation induced a disordered rutile phase within the nanotubes as characterized by Raman spectroscopy and transmission electron microscopy, which displays an improved capacity by 20% at ~240 mA h g –1 as well as improved rate capability compared to an unirradiated anatase sample. Voltammetric sweep data were used to determine the contributions from diffusion-limited intercalation and capacitive processes and it was found that the electrodes after irradiation had more contributions from diffusion in lithium charge storage. Finally, our work suggests that tailoring the defect generation through ion irradiation within metal oxide electrodes could present a new avenue for designing advanced electrode materials.« less

Effects of proton irradiation on structural and electrochemical charge storage properties of TiO 2 nanotube electrodes for lithium-ion batteries

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

Smith, Kassiopeia A.; Savva, Andreas I.; Deng, Changjian

The effects of proton irradiation on nanostructured metal oxides have been investigated. Recent studies suggest that the presence of structural defects (e.g. vacancies and interstitials) in metal oxides may enhance the material's electrochemical charge storage capacity. A new approach to introduce defects in electrode materials is to use ion irradiation as it can produce a supersaturation of point defects in the target material. In this work we report the effect of low-energy proton irradiation on amorphous TiO 2 nanotube electrodes at both room temperature and high temperature (250 °C). Upon room temperature irradiation the nanotubes demonstrate an irradiation-induced phase transformationmore » to a mixture of amorphous, anatase, and rutile domains while showing a 35% reduction in capacity compared to anatase TiO 2. On the other hand, the high temperature proton irradiation induced a disordered rutile phase within the nanotubes as characterized by Raman spectroscopy and transmission electron microscopy, which displays an improved capacity by 20% at ~240 mA h g –1 as well as improved rate capability compared to an unirradiated anatase sample. Voltammetric sweep data were used to determine the contributions from diffusion-limited intercalation and capacitive processes and it was found that the electrodes after irradiation had more contributions from diffusion in lithium charge storage. Finally, our work suggests that tailoring the defect generation through ion irradiation within metal oxide electrodes could present a new avenue for designing advanced electrode materials.« less

Crossbar nanoarchitectonics of the crosslinked self-assembled monolayer

PubMed Central

2014-01-01

A bottom-up approach was devised to build a crossbar device using the crosslinked SAM of the 5,5′-bis (mercaptomethyl)-2,2′-bipyridine-Ni2+ (BPD- Ni2+) on a gold surface. To avoid metal diffusion through the organic film, the author used (i) nanoscale bottom electrodes to reduce the probability of defects on the bottom electrodes and (ii) molecular crosslinked technology to avoid metal diffusion through the SAMs. The properties of the crosslinked self-assembled monolayer were determined by XPS. I-V characteristics of the device show thermally activated hopping transport. The implementation of this type of architecture will open up new vistas for a new class of devices for transport, storage, and computing. PMID:24994952

Centerband-only-detection-of-exchange (31)P nuclear magnetic resonance and phospholipid lateral diffusion: theory, simulation and experiment.

PubMed

Lai, Angel; Saleem, Qasim; Macdonald, Peter M

2015-10-14

Centerband-only-detection-of-exchange (CODEX) (31)P NMR lateral diffusion measurements were performed on dimyristoylphosphatidylcholine (DMPC) assembled into large unilamellar spherical vesicles. Optimization of sample and NMR acquisition conditions provided significant sensitivity enhancements relative to an earlier first report (Q. Saleem, A. Lai, H. Morales, and P. M. Macdonald, Chem. Phys. Lipids, 2012, 165, 721). An analytical description was developed that permitted the extraction of lateral diffusion coefficients from CODEX data, based on a Gaussian-diffusion-on-a-sphere model (A. Ghosh, J. Samuel, and S. Sinha, Europhys. Lett., 2012, 98, 30003-p1) as relevant to CODEX (31)P NMR measurements on a population of spherical unilamellar phospholipid bilayer vesicles displaying a distribution of vesicle radii.

Nucleation and growth kinetics of electrodeposited sulfate-doped polypyrrole: determination of the diffusion coefficient of SO(4)(2-) in the polymeric membrane.

PubMed

Licona-Sánchez, T de J; Alvarez-Romero, G A; Mendoza-Huizar, L H; Galán-Vidal, C A; Palomar-Pardavé, M; Romero-Romo, M; Herrera-Hernández, H; Uruchurtu, J; Juárez-García, J M

2010-08-05

A kinetic study for the electrosynthesis of polypyrrole (Ppy) doped with SO(4)(2-) ions is presented. Ppy films were electrochemically polymerized onto a graphite-epoxy resin electrode. Experimental current density transients (j-t) were obtained for three different potentiometric behaviors: anionic, cationic, and a combination. Theoretical models were used to fit the experimental j-t data to determine the nucleation and growth processes controlling the polymer synthesis. It was encountered that, in all cases, pyrrole electropolimerization involves two concomitant processes, namely, a Ppy diffusion limited multiple 3D nucleation and growth and pyrrole electro-oxidation on the growing surface of the Ppy nuclei. SEM analysis of the electrodes surfaces reveals that Ppy deposition occurred over most of the electrode surface by multiple nucleation of hemispheres, as the theoretical model used for the analysis of the current transients required. Hemispherical particles formed the polymeric film displaying different sizes. The order for the particle size was as follows: anionic > anionic-cationic > cationic. These results are congruent with those obtained by theoretical analysis of the corresponding current transients. Analysis of the impedance measurements recorded on the anionic Ppy film, immersed in an aqueous solution with different sulfate ion concentrations evidenced that SO(4)(2-) ions diffuse through the Ppy film provoking a decrease of its electrical resistance and an increase of its dielectric constant. From the Warburg impedance coefficient, the sulfate coefficient of diffusion in the Ppy film was 1.38 x 10(-9) cm(2) s(-1).

Natural cellulose fiber as substrate for supercapacitor.

PubMed

Gui, Zhe; Zhu, Hongli; Gillette, Eleanor; Han, Xiaogang; Rubloff, Gary W; Hu, Liangbing; Lee, Sang Bok

2013-07-23

Cellulose fibers with porous structure and electrolyte absorption properties are considered to be a good potential substrate for the deposition of energy material for energy storage devices. Unlike traditional substrates, such as gold or stainless steel, paper prepared from cellulose fibers in this study not only functions as a substrate with large surface area but also acts as an interior electrolyte reservoir, where electrolyte can be absorbed much in the cellulose fibers and is ready to diffuse into an energy storage material. We demonstrated the value of this internal electrolyte reservoir by comparing a series of hierarchical hybrid supercapacitor electrodes based on homemade cellulose paper or polyester textile integrated with carbon nanotubes (CNTs) by simple solution dip and electrodeposited with MnO2. Atomic layer deposition of Al2O3 onto the fiber surface was used to limit electrolyte absorption into the fibers for comparison. Configurations designed with different numbers of ion diffusion pathways were compared to show that cellulose fibers in paper can act as a good interior electrolyte reservoir and provide an effective pathway for ion transport facilitation. Further optimization using an additional CNT coating resulted in an electrode of paper/CNTs/MnO2/CNTs, which has dual ion diffusion and electron transfer pathways and demonstrated superior supercapacitive performance. This paper highlights the merits of the mesoporous cellulose fibers as substrates for supercapacitor electrodes, in which the water-swelling effect of the cellulose fibers can absorb electrolyte, and the mesoporous internal structure of the fibers can provide channels for ions to diffuse to the electrochemical energy storage materials.

Effects of epitaxial structure and processing on electrical characteristics of InAs-based nBn infrared detectors

NASA Astrophysics Data System (ADS)

Du, X.; Savich, G. R.; Marozas, B. T.; Wicks, G. W.

2017-02-01

The conventional processing of the III-V nBn photodetectors defines mesa devices by etching the contact n-layer and stopping immediately above the barrier, i.e., a shallow etch. This processing enables great suppression of surface leakage currents without having to explore surface passivation techniques. However, devices that are made with this processing scheme are subject to lateral diffusion currents. To address the lateral diffusion current, we compare the effects of different processing approaches and epitaxial structures of nBn detectors. The conventional solution for eliminating lateral diffusion current, a deep etch through the barrier and the absorber, creates increased dark currents and an increased device failure rate. To avoid deep etch processing, a new device structure is proposed, the inverted-nBn structure. By comparing with the conventional nBn structure, the results show that the lateral diffusion current is effectively eliminated in the inverted-nBn structure without elevating the dark currents.

Binder-free Si nanoparticle electrode with 3D porous structure prepared by electrophoretic deposition for lithium-ion batteries.

PubMed

Yang, Yang; Chen, Dingqiong; Liu, Bo; Zhao, Jinbao

2015-04-15

A binder-free silicon (Si) based electrode for lithium-ion battery was fabricated in an organic solvent through one-step electrophoretic deposition (EPD). The nanosized Si and acetylene black (AB) particles were bonded tightly together to form a homogeneous co-deposited film with 3D porous structure through the EPD process. The 3D porous structure provides buffer spaces to alleviate the mechanical stress due to silicon volume change during the cycling and improves lithium-ion conductivity by shortening ion diffusion length and better ion conducting pathway. The electrode prepared with 5 s deposition duration shows the best cycling performance among electrodes fabricated by EPD method, and thus, it was selected to be compared with the silicon electrode prepared by the conventional method. Our results demonstrate that the Si nanoparticle electrode prepared through EPD exhibits smaller cycling capacity decay rate and better rate capability than the electrode prepared by the conventional method.

Removal of unburned carbon from coal fly ash using a pneumatic triboelectrostatic separator.

PubMed

Kim, J K; Cho, H C; Kim, S C

2001-01-01

A pneumatic triboelectrostatic beneficiation system of fly ash was studied using a continuous, bench-scale electroseparator composed of two vertical electrode plates and an ejector-tribocharger. Tests were conducted to evaluate the charge density and the separation efficiency at various operating conditions. It was found that the higher charge densities were obtained at (1) the air flow rate of 1.75 m3/min. (2) the feed rate of less than 50 kg/h. and (3) the relative humidity of less than 30% with use of a stainless ejector tribocharger. With these optimum conditions, the clean ash of less than LOI 3% was recovered with a yield over 75% when operated at the diffuser slit gap of 4mm, the diffuser outlet velocity of 16.1-18.6 m/s, and the distance of 15 cm between diffuser slit and splitter. The optimum feed rate was found to be 740 kg/h per m2 of electrode surface area, which can be used as a scale-up factor of electroseparator.

Potentiometric analytical microsystem based on the integration of a gas-diffusion step for on-line ammonium determination in water recycling processes in manned space missions.

PubMed

Calvo-López, Antonio; Ymbern, Oriol; Puyol, Mar; Casalta, Joan Manel; Alonso-Chamarro, Julián

2015-05-18

The design, construction and evaluation of a versatile cyclic olefin copolymer (COC)-based continuous flow potentiometric microanalyzer to monitor the presence of ammonium ion in recycling water processes for future manned space missions is presented. The microsystem integrates microfluidics, a gas-diffusion module and a detection system in a single substrate. The gas-diffusion module was integrated by a hydrophobic polyvinylidene fluoride (PVDF) membrane. The potentiometric detection system is based on an all-solid state ammonium selective electrode and a screen-printed Ag/AgCl reference electrode. The analytical features provided by the analytical microsystem after the optimization process were a linear range from 0.15 to 500 mg L(-1) and a detection limit of 0.07 ± 0.01 mg L(-1). Nevertheless, the operational features can be easily adapted to other applications through the modification of the hydrodynamic variables of the microfluidic platform. Copyright © 2014 Elsevier B.V. All rights reserved.

Regulation of electron transfer processes affects phototrophic mat structure and activity

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

Ha, Phuc T.; Renslow, Ryan S.; Atci, Erhan

Phototrophic microbial mats are among the most diverse ecosystems in nature. These systems undergo daily cycles in redox potential caused by variations in light energy input and metabolic interactions among the microbial species. In this work, solid electrodes with controlled potentials were placed under mats to study the electron transfer processes between the electrode and the microbial mat. The phototrophic microbial mat was harvested from Hot Lake, a hypersaline, epsomitic lake located near Oroville (Washington, USA). We operated two reactors: graphite electrodes were polarized at potentials of -700 mV Ag/AgCl [cathodic (CAT) mat system] and +300 mV Ag/AgCl [anodic (AN)more » mat system] and the electron transfer rates between the electrode and mat were monitored. We observed a diel cycle of electron transfer rates for both AN and CAT mat systems. Interestingly, the CAT mats generated the highest reducing current at the same time points that the AN mats showed the highest oxidizing current. To characterize the physicochemical factors influencing electron transfer processes, we measured depth profiles of dissolved oxygen (DO) and sulfide in the mats using microelectrodes. We further demonstrated that the mat-to-electrode and electrode-to-mat electron transfer rates were light- and temperature-dependent. Using nuclear magnetic resonance (NMR) imaging, we determined that the electrode potential regulated the diffusivity and porosity of the microbial mats. Both porosity and diffusivity were higher in the CAT mats than in the AN mats. We also used NMR spectroscopy for high-resolution quantitative metabolite analysis and found that the CAT mats had significantly higher concentrations of osmoprotectants such as betaine and trehalose. Subsequently, we performed amplicon sequencing across the V4 region of the 16S rRNA gene of incubated mats to understand the impact of electrode potential on microbial community structure. In conclusion, these data suggested that variation in the electrochemical conditions under which mats were generated significantly impacted the relative abundances of mat members and mat metabolism.« less

Regulation of electron transfer processes affects phototrophic mat structure and activity

DOE PAGES

Ha, Phuc T.; Renslow, Ryan S.; Atci, Erhan; ...

2015-09-03

Phototrophic microbial mats are among the most diverse ecosystems in nature. These systems undergo daily cycles in redox potential caused by variations in light energy input and metabolic interactions among the microbial species. In this work, solid electrodes with controlled potentials were placed under mats to study the electron transfer processes between the electrode and the microbial mat. The phototrophic microbial mat was harvested from Hot Lake, a hypersaline, epsomitic lake located near Oroville (Washington, USA). We operated two reactors: graphite electrodes were polarized at potentials of -700 mV Ag/AgCl [cathodic (CAT) mat system] and +300 mV Ag/AgCl [anodic (AN)more » mat system] and the electron transfer rates between the electrode and mat were monitored. We observed a diel cycle of electron transfer rates for both AN and CAT mat systems. Interestingly, the CAT mats generated the highest reducing current at the same time points that the AN mats showed the highest oxidizing current. To characterize the physicochemical factors influencing electron transfer processes, we measured depth profiles of dissolved oxygen (DO) and sulfide in the mats using microelectrodes. We further demonstrated that the mat-to-electrode and electrode-to-mat electron transfer rates were light- and temperature-dependent. Using nuclear magnetic resonance (NMR) imaging, we determined that the electrode potential regulated the diffusivity and porosity of the microbial mats. Both porosity and diffusivity were higher in the CAT mats than in the AN mats. We also used NMR spectroscopy for high-resolution quantitative metabolite analysis and found that the CAT mats had significantly higher concentrations of osmoprotectants such as betaine and trehalose. Subsequently, we performed amplicon sequencing across the V4 region of the 16S rRNA gene of incubated mats to understand the impact of electrode potential on microbial community structure. In conclusion, these data suggested that variation in the electrochemical conditions under which mats were generated significantly impacted the relative abundances of mat members and mat metabolism.« less

The effects of bilateral stimulation of the subthalamic nucleus on heart rate variability in patients with Parkinson's disease.

PubMed

Liu, Kang-Du; Shan, Din-E; Kuo, Terry B J; Yang, Cheryl C H

2013-07-01

The beneficial effects of subthalamic nucleus deep brain stimulation (STN-DBS) on motor symptoms and quality of life in Parkinson's disease (PD) are well known, but little is known of the effects on autonomic function. Diffusion of current during stimulation of the STN may simultaneously involve the motor and nonmotor, limbic and associative areas of the STN. The aims of this study were to examine whether STN stimulation affects functions of the autonomic nervous system and, if so, to correlate the effects with the active contacts of electrodes in the STN. Eight PD patients with good motor control and quality of sleep after STN-DBS surgery were recruited. All patients had two days of recordings with portable polysomnography (PSG) (first night with stimulation "on" and second night "off"). From the PSG data, the first sleep cycle of each recording night was defined. Heart rate variability (HRV) was analyzed between the same uninterrupted periods of the two sleep nights. In addition, the optimal electrode positions were defined from postoperative MRI studies, and the coordinates of active contacts were confirmed. HRV spectral analysis showed that only low-frequency (LF)/high-frequency (HF) power was significantly activated in the stimulation "on" groups (P = 0.011). There was a significant negative correlation between power change of LF/HF and electrode position lateral to the midcommissural point (ρ = 0.857, P = 0.007) These results demonstrate that STN-DBS can enhance sympathetic regulation; the autonomic response may be due to electrical signals being distributed to limbic components of the STN or descending sympathetic pathways in the zona incerta.

Electrochemical Impedance Imaging via the Distribution of Diffusion Times

NASA Astrophysics Data System (ADS)

Song, Juhyun; Bazant, Martin Z.

2018-03-01

We develop a mathematical framework to analyze electrochemical impedance spectra in terms of a distribution of diffusion times (DDT) for a parallel array of random finite-length Warburg (diffusion) or Gerischer (reaction-diffusion) circuit elements. A robust DDT inversion method is presented based on complex nonlinear least squares regression with Tikhonov regularization and illustrated for three cases of nanostructured electrodes for energy conversion: (i) a carbon nanotube supercapacitor, (ii) a silicon nanowire Li-ion battery, and (iii) a porous-carbon vanadium flow battery. The results demonstrate the feasibility of nondestructive "impedance imaging" to infer microstructural statistics of random, heterogeneous materials.

Design of Supercapacitor Electrodes Using Molecular Dynamics Simulations

NASA Astrophysics Data System (ADS)

Bo, Zheng; Li, Changwen; Yang, Huachao; Ostrikov, Kostya; Yan, Jianhua; Cen, Kefa

2018-06-01

Electric double-layer capacitors (EDLCs) are advanced electrochemical devices for energy storage and have attracted strong interest due to their outstanding properties. Rational optimization of electrode-electrolyte interactions is of vital importance to enhance device performance for practical applications. Molecular dynamics (MD) simulations could provide theoretical guidelines for the optimal design of electrodes and the improvement of capacitive performances, e.g., energy density and power density. Here we discuss recent MD simulation studies on energy storage performance of electrode materials containing porous to nanostructures. The energy storage properties are related to the electrode structures, including electrode geometry and electrode modifications. Altering electrode geometry, i.e., pore size and surface topography, can influence EDL capacitance. We critically examine different types of electrode modifications, such as altering the arrangement of carbon atoms, doping heteroatoms and defects, which can change the quantum capacitance. The enhancement of power density can be achieved by the intensified ion dynamics and shortened ion pathway. Rational control of the electrode morphology helps improve the ion dynamics by decreasing the ion diffusion pathway. Tuning the surface properties (e.g., the affinity between the electrode and the ions) can affect the ion-packing phenomena. Our critical analysis helps enhance the energy and power densities of EDLCs by modulating the corresponding electrode structures and surface properties.[Figure not available: see fulltext.

Dynamics of electrical double layer formation in room-temperature ionic liquids under constant-current charging conditions

NASA Astrophysics Data System (ADS)

Jiang, Xikai; Huang, Jingsong; Zhao, Hui; Sumpter, Bobby G.; Qiao, Rui

2014-07-01

We report detailed simulation results on the formation dynamics of an electrical double layer (EDL) inside an electrochemical cell featuring room-temperature ionic liquids (RTILs) enclosed between two planar electrodes. Under relatively small charging currents, the evolution of cell potential from molecular dynamics (MD) simulations during charging can be suitably predicted by the Landau-Ginzburg-type continuum model proposed recently (Bazant et al 2011 Phys. Rev. Lett. 106 046102). Under very large charging currents, the cell potential from MD simulations shows pronounced oscillation during the initial stage of charging, a feature not captured by the continuum model. Such oscillation originates from the sequential growth of the ionic space charge layers near the electrode surface. This allows the evolution of EDLs in RTILs with time, an atomistic process difficult to visualize experimentally, to be studied by analyzing the cell potential under constant-current charging conditions. While the continuum model cannot predict the potential oscillation under such far-from-equilibrium charging conditions, it can nevertheless qualitatively capture the growth of cell potential during the later stage of charging. Improving the continuum model by introducing frequency-dependent dielectric constant and density-dependent ion diffusion coefficients may help to further extend the applicability of the model. The evolution of ion density profiles is also compared between the MD and the continuum model, showing good agreement.

Dynamics of electrical double layer formation in room-temperature ionic liquids under constant-current charging conditions.

PubMed

Jiang, Xikai; Huang, Jingsong; Zhao, Hui; Sumpter, Bobby G; Qiao, Rui

2014-07-16

We report detailed simulation results on the formation dynamics of an electrical double layer (EDL) inside an electrochemical cell featuring room-temperature ionic liquids (RTILs) enclosed between two planar electrodes. Under relatively small charging currents, the evolution of cell potential from molecular dynamics (MD) simulations during charging can be suitably predicted by the Landau-Ginzburg-type continuum model proposed recently (Bazant et al 2011 Phys. Rev. Lett. 106 046102). Under very large charging currents, the cell potential from MD simulations shows pronounced oscillation during the initial stage of charging, a feature not captured by the continuum model. Such oscillation originates from the sequential growth of the ionic space charge layers near the electrode surface. This allows the evolution of EDLs in RTILs with time, an atomistic process difficult to visualize experimentally, to be studied by analyzing the cell potential under constant-current charging conditions. While the continuum model cannot predict the potential oscillation under such far-from-equilibrium charging conditions, it can nevertheless qualitatively capture the growth of cell potential during the later stage of charging. Improving the continuum model by introducing frequency-dependent dielectric constant and density-dependent ion diffusion coefficients may help to further extend the applicability of the model. The evolution of ion density profiles is also compared between the MD and the continuum model, showing good agreement.

Nanoeletromechanical switch and logic circuits formed therefrom

DOEpatents

Nordquist, Christopher D [Albuquerque, NM; Czaplewski, David A [Albuquerque, NM

2010-05-18

A nanoelectromechanical (NEM) switch is formed on a substrate with a source electrode containing a suspended electrically-conductive beam which is anchored to the substrate at each end. This beam, which can be formed of ruthenium, bows laterally in response to a voltage applied between a pair of gate electrodes and the source electrode to form an electrical connection between the source electrode and a drain electrode located near a midpoint of the beam. Another pair of gate electrodes and another drain electrode can be located on an opposite side of the beam to allow for switching in an opposite direction. The NEM switch can be used to form digital logic circuits including NAND gates, NOR gates, programmable logic gates, and SRAM and DRAM memory cells which can be used in place of conventional CMOS circuits, or in combination therewith.

Modeling Diffusion Induced Stresses for Lithium-Ion Battery Materials

NASA Astrophysics Data System (ADS)

Chiu Huang, Cheng-Kai

Advancing lithium-ion battery technology is of paramount importance for satisfying the energy storage needs in the U.S., especially for the application in the electric vehicle industry. To provide a better acceleration for electric vehicles, a fast and repeatable discharging rate is required. However, particle fractures and capacity loss have been reported under high current rate (C-rate) during charging/discharging and after a period of cycling. During charging and discharging, lithium ions extract from and intercalate into electrode materials accompanied with the volume change and phase transition between Li-rich phase and Li-poor phase. It is suggested that the diffusion-induced-stress is one of the main reasons causing capacity loss due to the mechanical degradation of electrode particles. Therefore, there is a fundamental need to provide a mechanistic understanding by considering the structure-mechanics-property interactions in lithium-ion battery materials. Among many cathode materials, the olivine-based lithium-iron-phosphate (LiFePO4) with an orthorhombic crystal structure is one of the promising cathode materials for the application in electric vehicles. In this research we first use a multiphysic approach to investigate the stress evolution, especially on the phase boundary during lithiation in single LiFePO4 particles. A diffusion-controlled finite element model accompanied with the experimentally observed phase boundary propagation is developed via a finite element package, ANSYS, in which lithium ion concentration-dependent anisotropic material properties and volume misfits are incorporated. The stress components on the phase boundary are used to explain the Mode I, Mode II, and Mode III fracture propensities in LiFePO4 particles. The elastic strain energy evolution is also discussed to explain why a layer-by-layer lithium insertion mechanism (i.e. first-order phase transformation) is energetically preferred. Another importation issue is how current rate (C-rate) during charging/discharging affects diffusion induced stresses inside electrode materials. For the experimental part we first conduct charging/discharging under different C-rates to observe the voltage responses for commercial LiFePO4 batteries. Then Time-of-Flight Secondary Ion Mass Spectrometry technique is applied to measure the lithium ion intensities in different C-rate charged/discharged samples. These experimental results could be used to support that a more significant voltage fluctuation under high C-rates is due to different lithium insertion mechanisms, rather than the amount of lithium ions intercalated into electrode materials. Thus the investigation of C-rate-dependent stress evolution is required for the development of a more durable lithium ion battery. In this dissertation, we extend the single particle finite element model to investigate the C-rate-dependent diffusion induced stresses in a multi-particle system. Concentration dependent anisotropic material properties, C-rate-dependent volume misfits and concentration dependent Li-ion diffusivity are incorporated in the model. The concentration gradients, diffusion induced stresses, and strain energies under different C-rates are discussed in this study. Particle fractures have been observed in many experimental results, in this study we further discuss the effect of the crack surface orientation on the lithium concentration profile and stress level in cathode materials. The results of this dissertation provide a better understanding of diffusion induced stresses in electrode materials and contribute to our fundamental knowledge of interplay between lithium intercalations, stress evolutions, particle fractures and the capacity fade in lithium-ion batteries.

Series interconnected photovoltaic cells and method for making same

DOEpatents

Albright, S.P.; Chamberlin, R.R.; Thompson, R.A.

1995-01-31

A novel photovoltaic module and method for constructing the same are disclosed. The module includes a plurality of photovoltaic cells formed on a substrate and laterally separated by interconnection regions. Each cell includes a bottom electrode, a photoactive layer and a top electrode layer. Adjacent cells are connected in electrical series by way of a conductive-buffer line. The buffer line is also useful in protecting the bottom electrode against severing during downstream layer cutting processes. 11 figs.

Controlled Growth of Polypyrrole on Microelectrodes

NASA Astrophysics Data System (ADS)

Kannan, Bhuvaneswari; Williams, David E.; Travas-Sejdic, Jandranka

2009-07-01

Electrochemical growth of a conducting polymer generally leads to a microstructure which is an irregular assembly of irregular spheres, generally taken to be indicative of a diffusion-limited aggregation in which oligomers generated at or near the electrode aggregate into particles that in turn aggregate onto the electrode. We have explored the possibilities for controlling this growth mode by using short current pulses to form the polymer. We illustrate the alteration in growth morphology achievable by the use of different pulse sequences. In particular, we show the possibility to grow isolated dendrites (`nanowires') of conducting polymer on an electrode surface.

Numerical simulation of the dielectrophoretic concentration of DNA particles and the effect of AC electroosmosis

NASA Astrophysics Data System (ADS)

Loucaides, N. G.; Georghiou, G. E.; Charalambous, C. D.

2007-04-01

The dielectrophoretic concentration of DNA particles suspended in a solution is investigated in a system of parallel electrodes, where the particles are attracted to the edges of the electrodes by positive dielectrophoresis. The AC electroosmotic motion of the fluid is also considered, as well as the diffusion of the particles, using the solution of the Smoluchowski equation. The results examine the effect of AC electroosmosis in steady state dielectrophoretic concentration of particles, by demonstrating that AC electroosmosis significantly reduces the dielectrophoretic concentration at the edges and moves the particles towards the electrode centres.

Enabling fast charging – A battery technology gap assessment

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

Ahmed, Shabbir; Bloom, Ira; Jansen, Andrew N.

The battery technology literature is reviewed, with an emphasis on key elements that limit extreme fast charging. Key gaps in existing elements of the technology are presented as well as developmental needs. Among these needs are advanced models and methods to detect and prevent lithium plating; new positive-electrode materials which are less prone to stress-induced failure; better electrode designs to accommodate very rapid diffusion in and out of the electrode; measure temperature distributions during fast charge to enable/validate models; and develop thermal management and pack designs to accommodate the higher operating voltage.

Enabling fast charging – A battery technology gap assessment

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

Ahmed, Shabbir; Bloom, Ira; Jansen, Andrew N.

The battery technology literature is reviewed, with an emphasis on key elements that limit extreme fast charging. Key gaps in existing elements of the technology are presented as well as developmental needs. Among these needs are advanced models and methods to detect and prevent lithium plating; new positive-electrode materials which are less prone to stress-induced failure; better electrode designs to accommodate very rapid diffusion in and out of the electrode; measure temperature distributions during fast charge to enable / validate models; and develop thermal management and pack designs to accommodate the higher operating voltage.

A field induced guide-antiguide modulator of GaAs-AlGaAs

NASA Technical Reports Server (NTRS)

Huang, T. C.; Chung, Y.; Young, D. B.; Dagli, N.; Coldren, L. A.

1991-01-01

A guide-antiguide modulator of GaAs-AlGaAs using the electric-field-induced waveguide concept was demonstrated. The device was formed with a central waveguide electrode sandwiched between two antiguide electrodes on the surface of a p-i-n multiple quantum well (MQW). Switching between lateral guiding and antiguiding was accomplished by reverse biasing either the central electrode or the adjacent electrodes to increase the index beneath these respective regions. The on-off ratio was measured to be 20:1 with a propagation loss of the on-state of about 5 dB/mm.

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

NASA Technical Reports Server (NTRS)

Prakash, Jai; Tryk, Donald; Yeager, Ernest

1990-01-01

The lead ruthenate pyrochlore Pb2Ru2O6.5, in both high- and low-area forms, has been characterized using thermogravimetric analysis, X-ray photoelectron spectroscopy, X-ray diffraction, cyclic voltammetry, and O2 reduction and generation kinetic-mechanistic studies. Mechanisms are proposed. Compounds in which part of the Ru is substituted with Ir have also been prepared. They exhibit somewhat better performance for O2 reduction in porous, gas-fed electrodes than the unsubstituted compound. The anodic corrosion resistance of pyrochlore-based porous electrodes was improved by using two different anionically conducting polymer overlayers, which slow down the diffusion of ruthenate and plumbate out of the electrode. The O2 generation performance was improved with both types of electrodes. With a hydrogel overlayer, the O2 reduction performance was also improved.

Layer-by-layer assembly of MXene and carbon nanotubes on electrospun polymer films for flexible energy storage.

PubMed

Zhou, Zehang; Panatdasirisuk, Weerapha; Mathis, Tyler S; Anasori, Babak; Lu, Canhui; Zhang, Xinxing; Liao, Zhiwei; Gogotsi, Yury; Yang, Shu

2018-03-29

Free-standing, highly flexible and foldable supercapacitor electrodes were fabricated through the spray-coating assisted layer-by-layer assembly of Ti3C2Tx (MXene) nanoflakes together with multi-walled carbon nanotubes (MWCNTs) on electrospun polycaprolactone (PCL) fiber networks. The open structure of the PCL network and the use of MWCNTs as spacers not only limit the restacking of Ti3C2Tx flakes but also increase the accessible surface of the active materials, facilitating fast diffusion of electrolyte ions within the electrode. Composite electrodes have areal capacitance (30-50 mF cm-2) comparable to other templated electrodes reported in the literature, but showed significantly improved rate performance (14-16% capacitance retention at a scan rate of 100 V s-1). Furthermore, the composite electrodes are flexible and foldable, demonstrating good tolerance against repeated mechanical deformation, including twisting and folding. Therefore, these tens of micron thick fiber electrodes will be attractive for applications in energy storage, electroanalytical chemistry, brain electrodes, electrocatalysis and other fields, where flexible freestanding electrodes with an open and accessible surface are highly desired.

Improvement of High-Temperature Stability of Al₂O₃/Pt/ZnO/Al₂O₃ Film Electrode for SAW Devices by Using Al₂O₃ Barrier Layer.

PubMed

Liu, Xingpeng; Peng, Bin; Zhang, Wanli; Zhu, Jun; Liu, Xingzhao; Wei, Meng

2017-12-01

In order to develop film electrodes for the surface acoustic wave (SAW) devices operating in harsh high-temperature environments, novel Al₂O₃/Pt/ZnO/Al₂O₃ multilayered film electrodes were prepared by laser molecular beam epitaxy (LMBE) at 150 °C. The first Al₂O₃ layer was used as a barrier layer to prevent the diffusion of Ga, La, and Si atoms from the La₃Ga₅SiO 14 (LGS) substrate to the film electrode and thus improved the crystalline quality of ZnO and Pt films. It was found that the resistance of the Al₂O₃/Pt/ZnO/Al₂O₃ electrode did not vary up to a temperature of 1150 °C, suggesting a high reliability of electrode under harsh high-temperature environments. The mechanism of the stable resistance of the Al₂O₃/Pt/ZnO/Al₂O₃ film electrodes at high temperature was investigated by analyzing its microstructure. The proposed Al₂O₃/Pt/ZnO/Al₂O₃ film electrode has great potential for application in high-temperature SAW devices.

Carbon Quantum Dot Surface-Engineered VO2 Interwoven Nanowires: A Flexible Cathode Material for Lithium and Sodium Ion Batteries.

PubMed

Balogun, Muhammad-Sadeeq; Luo, Yang; Lyu, Feiyi; Wang, Fuxin; Yang, Hao; Li, Haibo; Liang, Chaolun; Huang, Miao; Huang, Yongchao; Tong, Yexiang

2016-04-20

The use of electrode materials in their powdery form requires binders and conductive additives for the fabrication of the cells, which leads to unsatisfactory energy storage performance. Recently, a new strategy to design flexible, binder-, and additive-free three-dimensional electrodes with nanoscale surface engineering has been exploited in boosting the storage performance of electrode materials. In this paper, we design a new type of free-standing carbon quantum dot coated VO2 interwoven nanowires through a simple fabrication process and demonstrate its potential to be used as cathode material for lithium and sodium ion batteries. The versatile carbon quantum dots that are vastly flexible for surface engineering serve the function of protecting the nanowire surface and play an important role in the diffusion of electrons. Also, the three-dimensional carbon cloth coated with VO2 interwoven nanowires assisted in the diffusion of ions through the inner and the outer surface. With this unique architecture, the carbon quantum dot nanosurface engineered VO2 electrode exhibited capacities of 420 and 328 mAh g(-1) at current density rate of 0.3 C for lithium and sodium storage, respectively. This work serves as a milestone for the potential replacement of lithium ion batteries and next generation postbatteries.

Advancing from Rules of Thumb: Quantifying the Effects of Small Density Changes in Mass Transport to Electrodes. Understanding Natural Convection.

PubMed

Ngamchuea, Kamonwad; Eloul, Shaltiel; Tschulik, Kristina; Compton, Richard G

2015-07-21

Understanding mass transport is prerequisite to all quantitative analysis of electrochemical experiments. While the contribution of diffusion is well understood, the influence of density gradient-driven natural convection on the mass transport in electrochemical systems is not. To date, it has been assumed to be relevant only for high concentrations of redox-active species and at long experimental time scales. If unjustified, this assumption risks misinterpretation of analytical data obtained from scanning electrochemical microscopy (SECM) and generator-collector experiments, as well as analytical sensors utilizing macroelectrodes/microelectrode arrays. It also affects the results expected from electrodeposition. On the basis of numerical simulation, herein it is demonstrated that even at less than 10 mM concentrations and short experimental times of tens of seconds, density gradient-driven natural convection significantly affects mass transport. This is evident from in-depth numerical simulation for the oxidation of hexacyanoferrate (II) at various electrode sizes and electrode orientations. In each case, the induced convection and its influence on the diffusion layer established near the electrode are illustrated by maps of the velocity fields and concentration distributions evolving with time. The effects of natural convection on mass transport and chronoamperometric currents are thus quantified and discussed for the different cases studied.

Opposing Effects of cAMP and T259 Phosphorylation on Plasma Membrane Diffusion of the Water Channel Aquaporin-5 in Madin-Darby Canine Kidney Cells

PubMed Central

Koffman, Jennifer S.; Arnspang, Eva C.; Marlar, Saw; Nejsum, Lene N.

2015-01-01

Aquaporin-5 (AQP5) facilitates passive water transport in glandular epithelia in response to secretory stimuli via intracellular pathways involving calcium release, cAMP and protein kinase A (PKA). In epithelial plasma membranes, AQP5 may be acutely regulated to facilitate water transport in response to physiological stimuli by changes in protein modifications, interactions with proteins and lipids, nanoscale membrane domain organization, and turnover rates. Such regulatory mechanisms could potentially be associated with alteration of diffusion behavior, possibly resulting in a change in the plasma membrane diffusion coefficient of AQP5. We aimed to test the short-term regulatory effects of the above pathways, by measuring lateral diffusion of AQP5 and an AQP5 phospho-mutant, T259A, using k-space Image Correlation Spectroscopy of quantum dot- and EGFP-labeled AQP5. Elevated cAMP and PKA inhibition significantly decreased lateral diffusion of AQP5, whereas T259A mutation showed opposing effects; slowing diffusion without stimulation and increasing diffusion to basal levels after cAMP elevation. Thus, lateral diffusion of AQP5 is significantly regulated by cAMP, PKA, and T259 phosphorylation, which could be important for regulating water flow in glandular secretions. PMID:26218429

A core–shell electrode for dynamically and statically stable Li–S battery chemistry

DOE PAGES

Chung, Sheng-Heng; Chang, Chi-Hao; Manthiram, Arumugam

2016-08-17

Sulfur is an appealing cathode material for establishing advanced lithium batteries as it offers a high theoretical capacity of 1675 mA h g -1 at low material and operating costs. However, the lithium–sulfur (Li–S) electrochemical cells face several formidable challenges arising from both the materials chemistry (e.g., low electrochemical utilization of sulfur and severe polysulfide diffusion) and battery chemistry (e.g., dynamic and static instability and low sulfur loadings). Here in this study, we present the design of a core–shell cathode with a pure sulfur core shielded within a conductive shell-shaped electrode. The new electrode configuration allows Li–S cells to loadmore » with a high amount of sulfur (sulfur loadings of up to 30 mg cm -2 and sulfur content approaching 70 wt%). The core–shell cathodes demonstrate a superior dynamic and static electrochemical stability in Li–S cells. The high-loading cathodes exhibit (i) a high sulfur utilization of up to 97% at C/20–C/2 rates and (ii) a low self-discharge during long-term cell storage for a three-month rest period and at different cell-storage conditions. Finally, a polysulfide-trap cell configuration is designed to evidence the eliminations of polysulfide diffusion and to investigate the relationship between the electrode configuration and electrochemical characteristics. Finally, the comprehensive analytical results based on the high-loading cathodes suggest that (i) the core–shell cathode is a promising solution for designing highly reversible Li–S cells and (ii) the polysulfide-trap cell configuration is a viable approach to qualitatively evaluating the presence or absence of polysulfide diffusion.« less

Predicting efficiency of solar cells based on transparent conducting electrodes

NASA Astrophysics Data System (ADS)

Kumar, Ankush

2017-01-01

Efficiency of a solar cell is directly correlated with the performance of its transparent conducting electrodes (TCEs) which dictates its two core processes, viz., absorption and collection efficiencies. Emerging designs of a TCE involve active networks of carbon nanotubes, silver nanowires and various template-based techniques providing diverse structures; here, voids are transparent for optical transmittance while the conducting network acts as a charge collector. However, it is still not well understood as to which kind of network structure leads to an optimum solar cell performance; therefore, mostly an arbitrary network is chosen as a solar cell electrode. Herein, we propose a new generic approach for understanding the role of TCEs in determining the solar cell efficiency based on analysis of shadowing and recombination losses. A random network of wires encloses void regions of different sizes and shapes which permit light transmission; two terms, void fraction and equivalent radius, are defined to represent the TCE transmittance and wire spacings, respectively. The approach has been applied to various literature examples and their solar cell performance has been compared. To obtain high-efficiency solar cells, optimum density of the wires and their aspect ratio as well as active layer thickness are calculated. Our findings show that a TCE well suitable for one solar cell may not be suitable for another. For high diffusion length based solar cells, the void fraction of the network should be low while for low diffusion length based solar cells, the equivalent radius should be lower. The network with less wire spacing compared to the diffusion length behaves similar to continuous film based TCEs (such as indium tin oxide). The present work will be useful for architectural as well as material engineering of transparent electrodes for improvisation of solar cell performance.

Highly transparent, low-haze, hybrid cellulose nanopaper as electrodes for flexible electronics.

PubMed

Xu, Xuezhu; Zhou, Jian; Jiang, Long; Lubineau, Gilles; Ng, Tienkhee; Ooi, Boon S; Liao, Hsien-Yu; Shen, Chao; Chen, Long; Zhu, J Y

2016-06-16

Paper is an excellent candidate to replace plastics as a substrate for flexible electronics due to its low cost, renewability and flexibility. Cellulose nanopaper (CNP), a new type of paper made of nanosized cellulose fibers, is a promising substrate material for transparent and flexible electrodes due to its potentially high transparency and high mechanical strength. Although CNP substrates can achieve high transparency, they are still characterized by high diffuse transmittance and small direct transmittance, resulting in high optical haze of the substrates. In this study, we proposed a simple methodology for large-scale production of high-transparency, low-haze CNP comprising both long cellulose nanofibrils (CNFs) and short cellulose nanocrystals (CNCs). By varying the CNC/CNF ratio in the hybrid CNP, we could tailor its total transmittance, direct transmittance and diffuse transmittance. By increasing the CNC content, the optical haze of the hybrid CNP could be decreased and its transparency could be increased. The direct transmittance and optical haze of the CNP were 75.1% and 10.0%, respectively, greatly improved from the values of previously reported CNP (31.1% and 62.0%, respectively). Transparent, flexible electrodes were fabricated by coating the hybrid CNP with silver nanowires (AgNWs). The electrodes showed a low sheet resistance (minimum 1.2 Ω sq(-1)) and a high total transmittance (maximum of 82.5%). The electrodes were used to make a light emitting diode (LED) assembly to demonstrate their potential use in flexible displays.

Synthesis and characterisation of Co-Co(OH)2 composite anode material on Cu current collector for energy storage devices

NASA Astrophysics Data System (ADS)

Yavuz, Abdulcabbar; Yakup Hacıibrahimoğlu, M.; Bedir, Metin

2017-04-01

A Co-Co(OH)2 modified electrode on inexpensive Cu substrate was synthesized at room temperature and demonstrated to be a promising anode material for energy storage devices. A modified Co film was obtained potentiostatically and was then potentiodynamically treated with KOH solution to form Co(OH)2. Co-Co(OH)2 coatings were obtained and were dominated by Co(OH)2 at the oxidized side, whereas Co dominant Co-Co(OH)2 occurred at the reduced side (-1.1 V). As OH- ions were able to diffuse into (out of) the film during oxidation (reduction) and did not react with the Cu current collector, the Co-Co(OH)2 electrode can be used as an anode material in energy storage devices. Although the specific capacitance of the electrodes varied depending on thickness, the redox reaction between the modified electrode and KOH electrolyte remained the same consisting of a surface-controlled and diffusion-controlled mechanism which had a desirable fast charge and discharge property. Capacity values remained constant after 250 cycles as the film evolved. Overall capacity retention was 84% for the film after 450 scans. A specific capacitance of 549 F g-1 was obtained for the Co-Co(OH)2 composite electrode in 6 M KOH at a scan rate of 5 mV s-1 and 73% of capacitance was retained when the scan rate was increased to 100 mV s-1.

Electrochemical behaviour of vanadium(V)/vanadium(IV) redox couple at graphite electrodes

NASA Astrophysics Data System (ADS)

Zhong, S.; Skyllas-Kazacos, M.

The electrochemical behaviour of the V(V)/V(IV) couple has been studied at a graphite disc electrode in sulfuric acid using both cyclic and rotating-disc voltammetry. The results from the latter technique have revealed that the cathodic and anodic characteristics of this redox couple are quite different. The diffusion coefficient for V(IV), 2.14×10-6 cm2 s-1, is independent of the vanadium concentration. For V(IV) oxidation, the electrode kinetic parameters i0 and α have values of 2.47×10-4 A cm-2 and 0.71, respectively. The exchange current density, i0, for the V(V)/V(IV) reaction has been obtained at both graphite felt and reticulated vitreous carbon electrodes.

Temperature field analysis for PZT pyroelectric cells for thermal energy harvesting.

PubMed

Hsiao, Chun-Ching; Ciou, Jing-Chih; Siao, An-Shen; Lee, Chi-Yuan

2011-01-01

This paper proposes the idea of etching PZT to improve the temperature variation rate of a thicker PZT sheet in order to enhance the energy conversion efficiency when used as pyroelectric cells. A partially covered electrode was proven to display a higher output response than a fully covered electrode did. A mesh top electrode monitored the temperature variation rate and the electrode area. The mesh electrode width affected the distribution of the temperature variation rate in a thinner pyroelectric material. However, a pyroelectric cell with a thicker pyroelectric material was beneficial in generating electricity pyroelectrically. The PZT sheet was further etched to produce deeper cavities and a smaller electrode width to induce lateral temperature gradients on the sidewalls of cavities under homogeneous heat irradiation, enhancing the temperature variation rate.

Temperature Field Analysis for PZT Pyroelectric Cells for Thermal Energy Harvesting

PubMed Central

Hsiao, Chun-Ching; Ciou, Jing-Chih; Siao, An-Shen; Lee, Chi-Yuan

2011-01-01

This paper proposes the idea of etching PZT to improve the temperature variation rate of a thicker PZT sheet in order to enhance the energy conversion efficiency when used as pyroelectric cells. A partially covered electrode was proven to display a higher output response than a fully covered electrode did. A mesh top electrode monitored the temperature variation rate and the electrode area. The mesh electrode width affected the distribution of the temperature variation rate in a thinner pyroelectric material. However, a pyroelectric cell with a thicker pyroelectric material was beneficial in generating electricity pyroelectrically. The PZT sheet was further etched to produce deeper cavities and a smaller electrode width to induce lateral temperature gradients on the sidewalls of cavities under homogeneous heat irradiation, enhancing the temperature variation rate. PMID:22346652

Electrocatalytic Dechlorination Of A PCB Congener At A Palladized Granular Graphite-Packed Electrode: Reaction Equilibrium And Mechanism

EPA Science Inventory

Our previous study on the electrocatalytic dechlorination of 2-chlorobiphenyl at a Pd-loaded granular graphite-packed electrode demonstrated that the process did not follow the first order kinetics. The rate constant varied with the applied potential at the beginning, but later b...

76 FR 67411 - Small Diameter Graphite Electrodes From the People's Republic of China: Extension of Time Limit...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-11-01

... DEPARTMENT OF COMMERCE International Trade Administration [A-570-929] Small Diameter Graphite... diameter graphite electrodes from the People's Republic of China (PRC) for the period February 1, 2010... Graphite, Co. The preliminary results of the review are currently due no later than October 31, 2011...

Source reconstruction via the spatiotemporal Kalman filter and LORETA from EEG time series with 32 or fewer electrodes.

PubMed

Hamid, Laith; Al Farawn, Ali; Merlet, Isabelle; Japaridze, Natia; Heute, Ulrich; Stephani, Ulrich; Galka, Andreas; Wendling, Fabrice; Siniatchkin, Michael

2017-07-01

The clinical routine of non-invasive electroencephalography (EEG) is usually performed with 8-40 electrodes, especially in long-term monitoring, infants or emergency care. There is a need in clinical and scientific brain imaging to develop inverse solution methods that can reconstruct brain sources from these low-density EEG recordings. In this proof-of-principle paper we investigate the performance of the spatiotemporal Kalman filter (STKF) in EEG source reconstruction with 9-, 19- and 32- electrodes. We used simulated EEG data of epileptic spikes generated from lateral frontal and lateral temporal brain sources using state-of-the-art neuronal population models. For validation of source reconstruction, we compared STKF results to the location of the simulated source and to the results of low-resolution brain electromagnetic tomography (LORETA) standard inverse solution. STKF consistently showed less localization bias compared to LORETA, especially when the number of electrodes was decreased. The results encourage further research into the application of the STKF in source reconstruction of brain activity from low-density EEG recordings.

Static and Dynamic Effects of Lateral Carrier Diffusion in Semiconductor Lasers

NASA Technical Reports Server (NTRS)

Li, Jian-Zhong; Cheung, Samson H.; Ning, C. Z.; Biegel, Bryan A. (Technical Monitor)

2002-01-01

Electron and hole diffusions in the plane of semiconductor quantum wells play an important part in the static and dynamic operations of semiconductor lasers. It is well known that the value of diffusion coefficients affects the threshold pumping current of a semiconductor laser. At the same time, the strength of carrier diffusion process is expected to affect the modulation bandwidth of an AC-modulated laser. It is important not only to investigate the combined DC and AC effects due to carrier diffusion, but also to separate the AC effects from that of the combined effects in order to provide design insights for high speed modulation. In this presentation, we apply a hydrodynamic model developed by the present authors recently from the semiconductor Bloch equations. The model allows microscopic calculation of the lateral carrier diffusion coefficient, which is a nonlinear function of the carrier density and plasma temperature. We first studied combined AC and DC effects of lateral carrier diffusion by studying the bandwidth dependence on diffusion coefficient at a given DC current under small signal modulation. The results show an increase of modulation bandwidth with decrease in the diffusion coefficient. We simultaneously studied the effects of nonlinearity in the diffusion coefficient. To clearly identify how much of the bandwidth increase is a result of decrease in the threshold pumping current for smaller diffusion coefficient, thus an effective increase of DC pumping, we study the bandwidth dependence on diffusion coefficient at a given relative pumping. A detailed comparison of the two cases will be presented.

In General, the Total Voltammetric Current from a Mixture of Redox-Active Substances will Not be the Sum of the Currents that Each Substance would Produce Independently at the Same Concentration as in the Mixture

NASA Technical Reports Server (NTRS)

Leventis, Nicholas; Oh, Woon Su; Gao, Xue-Rong; Rawashdeh, Abdel Monem M.

2003-01-01

At the potential range where both decamethylferrocene (dMeFc) and ferrocene (Fc) are oxidized with rates controlled by linear diffusion, electrogenerated Fc(+) radicals diffusing outwards from the electrode react quantitatively (K23 C=5.8 x 10(exp 8) with dMeFc diffusing towards the electrode and produce Fc and dMeFc. That reaction replaces dMeFc with Fc, whose diffusion coefficient is higher than that of dMeFc(+), and the total mass-transfer limited current from the mixture is increased by approximately 10%. Analogous observations are made when mass-transfer is controlled by convective-diffusion as in RDE voltammetry. Similar results have been obtained with another, and for all practical purposes randomly selected pair of redox-active substances, [Co(bipy)3](2+) and N - methylphenothiazine (MePTZ); reaction of MePTZ(+) with [Co(bipy)3](2+) replaces the latter with MePTZ, which diffuses faster and the current increases by approximately 20%. The experimental voltammograms have been simulated numerically and the role of (a) the rate constant of the homogeneous reaction; (b) the relative concentrations; and, (c) the diffusion coefficients of all species involved have been studied in detail. Importantly, it was also identified that within any given redox system the dependence of the mass-transfer limited current on the bulk concentrations of the redox-active species is expected to be non-linear. These findings are discussed in terms of their electroanalytical implications.

General Model of Hindered Diffusion.

PubMed

Eloul, Shaltiel; Compton, Richard G

2016-11-03

The diffusion of a particle from bulk solution is slowed as it moves close to an adsorbing surface. A general model is reported that is easily applied by theoreticians and experimentalists. Specifically, it is shown here that in general and regardless of the space size, the magnitude of the effect of hindered diffusion on the flux is a property of the diffusion layer thickness. We explain and approximate the effect. Predictions of concentration profiles show that a "hindered diffusion layer" is formed near the adsorbing surface within the diffusion layer, observed even when the particle radius is just a 0.1% of the diffusion layer thickness. In particular, we focus on modern electrochemistry processes involving with impact of particles with either ultrasmall electrodes or particles in convective systems. The concept of the "hindered diffusion layer" is generally important for example in recent biophysical models of particles diffusion to small targets.

Laterally configured resistive switching device based on transition-metal nano-gap electrode on Gd oxide

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

Kawakita, Masatoshi; Okabe, Kyota; Kimura, Takashi

2016-01-11

We have developed a fabrication process for a laterally configured resistive switching device based on a Gd oxide. A nano-gap electrode connected by a Gd oxide with the ideal interfaces has been created by adapting the electro-migration method in a metal/GdO{sub x} bilayer system. Bipolar set and reset operations have been clearly observed in the Pt/GdO{sub x} system similarly in the vertical device based on GdO{sub x}. Interestingly, we were able to observe a clear bipolar switching also in a ferromagnetic CoFeB nano-gap electrode with better stability compared to the Pt/GdO{sub x} device. The superior performance of the CoFeB/GdO{sub x}more » device implies the importance of the spin on the resistive switching.« less

A Primary Study of Indirect ECG Monitor Embedded in a Bed for Home Health Care

NASA Astrophysics Data System (ADS)

Ueno, Akinori; Shiogai, Yuuki; Ishiyama, Yoji

A system for monitoring electrocardiogram (ECG) through clothes inserted between the measuring electrodes and the body surface of a subject when lying on a mattress has been proposed. The principle of the system is based on capacitive coupling involving the electrode, the clothes, and the skin. Validation of the system revealed the following: (1) In spite of the gain attenuation in the pass band of the system, distortion of the detected signal was subtle even when clothes thicker than 1mm were inserted, (2) The system was able to yield a stable ECG from a subject particularly during sound sleep, (3) The system succeeded in detecting ECG after changing the posture into any of supine, right lateral, or left lateral positions by adopting a newly devised electrode configuration. Therefore, the proposed system appears promising for application to bedding as a non-invasive and awareness-free system for ECG monitoring during sleep.

Lateral diffusion and signaling of receptor for advanced glycation end-products (RAGE): a receptor involved in chronic inflammation.

PubMed

Syed, Aleem; Zhu, Qiaochu; Smith, Emily A

2018-01-01

Membrane diffusion is one of the key mechanisms in the cellular function of receptors. The signaling of receptors for advanced glycation end-products (RAGE) has been extensively studied in the context of several pathological conditions, however, very little is known about RAGE diffusion. To fill this gap, RAGE lateral diffusion is probed in native, cholesterol-depleted, and cytoskeleton-altered cellular conditions. In native GM07373 cellular conditions, RAGE has a 90% mobile fraction and an average diffusion coefficient of 0.3 μm 2 /s. When depolymerization of the actin cytoskeleton is inhibited with the small molecule jasplakinolide (Jsp), the RAGE mobile fraction and diffusion coefficient decrease by 22 and 37%, respectively. In contrast, depolymerizing the filamentous actin cytoskeleton using the small molecule cytochalasin D (CD) does not alter the RAGE diffusion properties. There is a 70 and 50% decrease in phosphorylation of extracellular signal-regulated kinase (p-ERK) when the actin cytoskeleton is disrupted by CD or Jsp, respectively, in RAGE-expressing GM07373 cells. Disrupting the actin cytoskeleton in GM07373 cells that do not express detectable amounts of RAGE results in no change in p-ERK. Cholesterol depletion results in no statistically significant change in the diffusion properties of RAGE or p-ERK. This work presents a strong link between the actin cytoskeleton and RAGE diffusion and downstream signaling, and serves to further our understanding of the factors influencing RAGE lateral diffusion.

Diffuse charge and Faradaic reactions in porous electrodes

NASA Astrophysics Data System (ADS)

Biesheuvel, P. M.; Fu, Yeqing; Bazant, Martin Z.

2011-06-01

Porous electrodes instead of flat electrodes are widely used in electrochemical systems to boost storage capacities for ions and electrons, to improve the transport of mass and charge, and to enhance reaction rates. Existing porous electrode theories make a number of simplifying assumptions: (i) The charge-transfer rate is assumed to depend only on the local electrostatic potential difference between the electrode matrix and the pore solution, without considering the structure of the double layer (DL) formed in between; (ii) the charge-transfer rate is generally equated with the salt-transfer rate not only at the nanoscale of the matrix-pore interface, but also at the macroscopic scale of transport through the electrode pores. In this paper, we extend porous electrode theory by including the generalized Frumkin-Butler-Volmer model of Faradaic reaction kinetics, which postulates charge transfer across the molecular Stern layer located in between the electron-conducting matrix phase and the plane of closest approach for the ions in the diffuse part of the DL. This is an elegant and purely local description of the charge-transfer rate, which self-consistently determines the surface charge and does not require consideration of reference electrodes or comparison with a global equilibrium. For the description of the DLs, we consider the two natural limits: (i) the classical Gouy-Chapman-Stern model for thin DLs compared to the macroscopic pore dimensions, e.g., for high-porosity metallic foams (macropores >50 nm) and (ii) a modified Donnan model for strongly overlapping DLs, e.g., for porous activated carbon particles (micropores <2 nm). Our theory is valid for electrolytes where both ions are mobile, and it accounts for voltage and concentration differences not only on the macroscopic scale of the full electrode, but also on the local scale of the DL. The model is simple enough to allow us to derive analytical approximations for the steady-state and early transients. We also present numerical solutions to validate the analysis and to illustrate the evolution of ion densities, pore potential, surface charge, and reaction rates in response to an applied voltage.

Strategies for "wiring" redox-active proteins to electrodes and applications in biosensors, biofuel cells, and nanotechnology.

PubMed

Nöll, Tanja; Nöll, Gilbert

2011-07-01

In this tutorial review the basic approaches to establish electrochemical communication between redox-active proteins and electrodes are elucidated and examples for applications in electrochemical biosensors, biofuel cells and nanotechnology are presented. The early stage of protein electrochemistry is described giving a short overview over electron transfer (ET) between electrodes and proteins, followed by a brief introduction into experimental procedures for studying proteins at electrodes and possible applications arising thereof. The article starts with discussing the electrochemistry of cytochrome c, the first redox-active protein, for which direct reversible ET was obtained, under diffusion controlled conditions and after adsorption to electrodes. Next, examples for the electrochemical study of redox enzymes adsorbed on electrodes and modes of immobilization are discussed. Shortly the experimental approach for investigating redox-active proteins adsorbed on electrodes is outlined. Possible applications of redox enzymes in electrochemical biosensors and biofuel cells working by direct ET (DET) and mediated ET (MET) are presented. Furthermore, the reconstitution of redox active proteins at electrodes using molecular wire-like units in order to "wire" the proteins to the electrode surface and possible applications in nanotechnology are discussed.

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

Branch, Shirmir D.; Lines, Amanda M.; Lynch, John

The electrochemical and spectroelectrochemical applications of an optically transparent thin film electrode chip are investigated. The working electrode is composed of indium tin oxide (ITO); the counter and quasi-reference electrodes are composed of platinum. The stability of the platinum quasi-reference electrode is modified by coating it with a planar, solid state Ag/AgCl layer. The Ag/AgCl reference is characterized with scanning electron microscopy and energy-dispersive X-ray spectroscopy. Open circuit potential measurements indicate that the potential of the planar Ag/AgCl electrode varies a maximum of 20 mV over four days. Cyclic voltammetry measurements show that the electrode chip is comparable to amore » standard electrochemical cell. Randles-Sevcik analysis of 10 mM K3[Fe(CN)6] in 0.1 M KCl using the electrode chip shows a diffusion coefficient of 1.59 × 10-6 cm2/s, in comparison to the standard electrochemical cell value of 2.38 × 10-6 cm2/s. By using the electrode chip in an optically transparent thin layer electrode (OTTLE), the spectroelectrochemical modulation of [Ru(bpy)3]2+ florescence was demonstrated, achieving a detection limit of 36 nM.« less

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.

Scaling Relations for Intercalation Induced Damage in Electrodes

DOE PAGES

Chen, Chien-Fan; Barai, Pallab; Smith, Kandler; ...

2016-04-02

Mechanical degradation, owing to intercalation induced stress and microcrack formation, is a key contributor to the electrode performance decay in lithium-ion batteries (LIBs). The stress generation and formation of microcracks are caused by the solid state diffusion of lithium in the active particles. Here in this work, scaling relations are constructed for diffusion induced damage in intercalation electrodes based on an extensive set of numerical experiments with a particle-level description of microcrack formation under disparate operating and cycling conditions, such as temperature, particle size, C-rate, and drive cycle. The microcrack formation and evolution in active particles is simulated based onmore » a stochastic methodology. A reduced order scaling law is constructed based on an extensive set of data from the numerical experiments. The scaling relations include combinatorial constructs of concentration gradient, cumulative strain energy, and microcrack formation. Lastly, the reduced order relations are further employed to study the influence of mechanical degradation on cell performance and validated against the high order model for the case of damage evolution during variable current vehicle drive cycle profiles.« less

Electrical Nanocontact Between Bismuth Nanowire Edges and Electrodes

NASA Astrophysics Data System (ADS)

Murata, Masayuki; Nakamura, Daiki; Hasegawa, Yasuhiro; Komine, Takashi; Uematsu, Daisuke; Nakamura, Shinichiro; Taguchi, Takashi

2010-09-01

Three methods for attaching electrodes to a bismuth nanowire sample were investigated. In the first and second methods, thin layers of titanium and copper were deposited by ion plating under vacuum onto the edge surface of individual bismuth nanowire samples that were encapsulated in a quartz template. Good electrical contact between the electrodes and the nanowire was achieved using silver epoxy and conventional solder on the thin-film layers in the first and second methods, respectively. In the third method, a low-melting-point solder was utilized and was also successful in achieving good electrical contact in air atmosphere. The connection methods showed no difference in terms of resistivity temperature dependence or Seebeck coefficient. The third method has an advantage in that nanocontact is easily achieved; however, diffusion of the solder into the nanowire allows contamination near the melting point of the solder. In the first and second methods, the thin-film layer enabled electrical contact to be more safely achieved than the direct contact used in the third method, because the thin-film layer prevented diffusion of binder components.

Tungsten as a Chemically-Stable Electrode Material on Ga-Containing Piezoelectric Substrates Langasite and Catangasite for High-Temperature SAW Devices

PubMed Central

Rane, Gayatri K.; Seifert, Marietta; Menzel, Siegfried; Gemming, Thomas; Eckert, Jürgen

2016-01-01

Thin films of tungsten on piezoelectric substrates La3Ga5SiO14 (LGS) and Ca3TaGa3Si2O14 (CTGS) have been investigated as a potential new electrode material for interdigital transducers for surface acoustic wave-based sensor devices operating at high temperatures up to 800 °C under vacuum conditions. Although LGS is considered to be suitable for high-temperature applications, it undergoes chemical and structural transformation upon vacuum annealing due to diffusion of gallium and oxygen. This can alter the device properties depending on the electrode nature, the annealing temperature, and the duration of the application. Our studies present evidence for the chemical stability of W on these substrates against the diffusion of Ga/O from the substrate into the film, even upon annealing up to 800 °C under vacuum conditions using Auger electron spectroscopy and energy-dispersive X-ray spectroscopy, along with local studies using transmission electron microscopy. Additionally, the use of CTGS as a more stable substrate for such applications is indicated. PMID:28787898

Effect of ion migration in electro-generated chemiluminescence depending on the luminophore types and operating conditions† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc03996d

PubMed Central

Shin, Sangbaie; Park, Yun Sung; Cho, Sunghwan; You, Insang; Kang, In Seok

2018-01-01

Electro-generated chemiluminescence (ECL) has attracted increasing attention as a new platform for light-emitting devices; in particular, the use of mechanically stretchable ECL gels opens up the opportunity to achieve deformable displays. The movements of radical ions under an external electric field include short-range diffusion near the electrodes and long-distance migration between the electrodes. So far, only the diffusion of radical ions has been considered as the operating principle behind ECL. In this study, electrochemical and optical analysis was performed systematically to investigate the role of ion migration in ECL devices. This study reveals that long-distance migration of radical ions can be a key variable in ECL at low frequencies and that this effect depends on the type of ion species and the operating conditions (e.g. voltage and frequency). We also report that the emissions from the two electrodes are not identical, and the emission behaviors are different in the optimal operating conditions for the red, green, and blue ECL emissions. PMID:29732124

Phase Boundary Propagation in Li-Alloying Battery Electrodes Revealed by Liquid-Cell Transmission Electron Microscopy

DOE PAGES

Leenheer, Andrew J.; Jungjohann, Katherine L.; Zavadil, Kevin R.; ...

2016-05-31

Battery cycle life is directly influenced by the microstructural changes occurring in the electrodes during charge and discharge cycles. In this study, we image in situ the nanoscale phase evolution in negative electrode materials for Li-ion batteries using a fully enclosed liquid cell in a transmission electron microscope (TEM) to reveal early degradation that is not evident in the charge–discharge curves. To compare the electrochemical phase transformation behavior between three model materials, thin films of amorphous Si, crystalline Al, and crystalline Au were lithiated and delithiated at controlled rates while immersed in a commercial liquid electrolyte. This method allowed formore » the direct observation of lithiation mechanisms in nanoscale negative electrodes, revealing that a simplistic model of a surface-to-interior lithiation front is insufficient. For the crystalline films, a lithiation front spread laterally from a few initial nucleation points, with continued grain nucleation along the growing interface. The intermediate lithiated phases were identified using electron diffraction, and high-resolution postmortem imaging revealed the details of the final microstructure. Lastly, our results show that electrochemically induced solid–solid phase transformations can lead to highly concentrated stresses at the laterally propagating phase boundary which should be considered for future designs of nanostructured electrodes for Li-ion batteries.« less

Notch-mediated lateral inhibition regulates proneural wave propagation when combined with EGF-mediated reaction diffusion

PubMed Central

Sato, Makoto; Yasugi, Tetsuo; Minami, Yoshiaki; Miura, Takashi; Nagayama, Masaharu

2016-01-01

Notch-mediated lateral inhibition regulates binary cell fate choice, resulting in salt and pepper patterns during various developmental processes. However, how Notch signaling behaves in combination with other signaling systems remains elusive. The wave of differentiation in the Drosophila visual center or “proneural wave” accompanies Notch activity that is propagated without the formation of a salt and pepper pattern, implying that Notch does not form a feedback loop of lateral inhibition during this process. However, mathematical modeling and genetic analysis clearly showed that Notch-mediated lateral inhibition is implemented within the proneural wave. Because partial reduction in EGF signaling causes the formation of the salt and pepper pattern, it is most likely that EGF diffusion cancels salt and pepper pattern formation in silico and in vivo. Moreover, the combination of Notch-mediated lateral inhibition and EGF-mediated reaction diffusion enables a function of Notch signaling that regulates propagation of the wave of differentiation. PMID:27535937

Clinical investigation of the Nucleus Slim Modiolar Electrode.

PubMed

Aschendorff, Antje; Briggs, Robert; Brademann, Goetz; Helbig, Silke; Hornung, Joachim; Lenarz, Thomas; Marx, Mathieu; Ramos, Angel; Stöver, Timo; Escudé, Bernard; James, Chris J

2017-01-01

The Nucleus CI532 cochlear implant incorporates a new precurved electrode array, i.e., the Slim Modiolar electrode (SME), which is designed to bring electrode contacts close to the medial wall of the cochlea while avoiding trauma due to scalar dislocation or contact with the lateral wall during insertion. The primary aim of this prospective study was to determine the final position of the electrode array in clinical cases as evaluated using flat-panel volume computed tomography. Forty-five adult candidates for unilateral cochlear implantation were recruited from 8 centers. Eleven surgeons attended a temporal bone workshop and received further training with a transparent plastic cochlear model just prior to the first surgery. Feedback on the surgical approach and use of the SME was collected via a questionnaire for each case. Computed tomography of the temporal bone was performed postoperatively using flat-panel digital volume tomography or cone beam systems. The primary measure was the final scalar position of the SME (completely in scala tympani or not). Secondly, medial-lateral position and insertion depth were evaluated. Forty-four subjects received a CI532. The SME was located completely in scala tympani for all subjects. Pure round window (44% of the cases), extended round window (22%), and inferior and/or anterior cochleostomy (34%) approaches were successful across surgeons and cases. The SME was generally positioned close to the modiolus. Overinsertion of the array past the first marker tended to push the basal contacts towards the lateral wall and served only to increase the insertion depth of the first electrode contact without increasing the insertion depth of the most apical electrode. Complications were limited to tip fold-overs encountered in 2 subjects; both were attributed to surgical error, with both reimplanted successfully. The new Nucleus CI532 cochlear implant with SME achieved the design goal of producing little or no trauma as indicated by consistent scala tympani placement. Surgeons should be carefully trained to use the new deployment method such that tip fold-overs and over insertion may be avoided. © 2017 S. Karger AG, Basel.

Limiting diffusion current at rotating disk electrode with dense particle layer.

PubMed

Weroński, P; Nosek, M; Batys, P

2013-09-28

Exploiting the concept of diffusion permeability of multilayer gel membrane and porous multilayer we have derived a simple analytical equation for the limiting diffusion current at rotating disk electrode (RDE) covered by a thin layer with variable tortuosity and porosity, under the assumption of negligible convection in the porous film. The variation of limiting diffusion current with the porosity and tortuosity of the film can be described in terms of the equivalent thickness of stagnant solution layer, i.e., the average ratio of squared tortuosity to porosity. In case of monolayer of monodisperse spherical particles, the equivalent layer thickness is an algebraic function of the surface coverage. Thus, by means of cyclic voltammetry of RDE with a deposited particle monolayer we can determine the monolayer surface coverage. The effect of particle layer adsorbed on the surface of RDE increases non-linearly with surface coverage. We have tested our theoretical results experimentally by means of cyclic voltammetry measurements of limiting diffusion current at the glassy carbon RDE covered with a monolayer of 3 μm silica particles. The theoretical and experimental results are in a good agreement at the surface coverage higher than 0.7. This result suggests that convection in a monolayer of 3 μm monodisperse spherical particles is negligibly small, in the context of the coverage determination, in the range of very dense particle layers.

An ion-selective electrode method for determination of chlorine in geological materials

USGS Publications Warehouse

Aruscavage, P. J.; Campbell, E.Y.

1983-01-01

A method is presented for the determination of chlorine in geological materials, in which a chloride-selective ion electrode is used after decomposition of the sample with hydrofluoric acid and separation of chlorine in a gas-diffusion cell. Data are presented for 30 geological standard materials. The relative standard deviation of the method is estimated to be better than 8% for amounts of chloride of 10 ??g and greater. ?? 1983.

Swiss roll nanomembranes with controlled proton diffusion as redox micro-supercapacitors.

PubMed

Ji, Hengxing; Mei, Yongfeng; Schmidt, Oliver G

2010-06-14

We demonstrate a redox Swiss roll micro-supercapacitor by rolling up a multilayered nanomembrane with an electrochemical active layer at either the outer or inner surface for different proton diffusion behaviors. The Swiss roll micro-supercapacitor could achieve high performance (e.g. capacity and life time) in a microscale power source and is helpful for studying charge transfer at the electrolyte/electrode interface.

Suppression of alpha-induced lateral surface events in the COBRA experiment using CdZnTe detectors with an instrumented guard-ring electrode

NASA Astrophysics Data System (ADS)

Arling, J.-H.; Gerhardt, M.; Gößling, C.; Gehre, D.; Klingenberg, R.; Kröninger, K.; Nitsch, C.; Quante, T.; Rohatsch, K.; Tebrügge, J.; Temminghoff, R.; Theinert, R.; Zatschler, S.; Zuber, K.

2017-11-01

The COBRA collaboration searches for neutrinoless double beta-decay (0νββ-decay) using CdZnTe semiconductor detectors with a coplanar-grid readout and a surrounding guard-ring structure. The operation of the COBRA demonstrator at the Gran Sasso underground laboratory (LNGS) indicates that alpha-induced lateral surface events are the dominant source of background events. By instrumenting the guard-ring electrode it is possible to suppress this type of background. In laboratory measurements this method achieved a suppression factor of alpha-induced lateral surface events of 5300+2660-1380, while retaining (85.3 ±0.1%) of gamma events occurring in the entire detector volume. This suppression is superior to the pulse-shape analysis methods used so far in COBRA by three orders of magnitude.

Porous carbon derived from aniline-modified fungus for symmetrical supercapacitor electrodes

DOE PAGES

Wang, Keliang; Xu, Ming; Wang, Xiaomin; ...

2017-01-23

N incorporated carbon materials are proven to be efficient EDLCs electrode materials. In this work, aniline modified fungus served as a raw material, and N-doped porous activated carbon is prepared via an efficient KOH activation method. A porous network with a high specific surface area of 2339 m 2g -1 is displayed by the prepared carbon material, resulting in a high accessible surface area and low ion diffusion resistance which is desirable for EDLC electrode materials. In assembled EDLCs, the N–AC based electrode exhibits a specific capacitance of 218 F g -1 at a current density of 0.1 A gmore » -1. Besides, excellent stability is displayed after 5000 continuous cycles at different current densities ranging from 0.1 to 10 A g -1. Thus, the present work reveals a promising candidate for electrode materials of EDLCs.« less

Toward greener lithium-ion batteries: Aqueous binder-based LiNi0.4Co0.2Mn0.4O2 cathode material with superior electrochemical performance

NASA Astrophysics Data System (ADS)

Chen, Zhen; Kim, Guk-Tae; Chao, Dongliang; Loeffler, Nicholas; Copley, Mark; Lin, Jianyi; Shen, Zexiang; Passerini, Stefano

2017-12-01

This work reports the performance of LiNi0.4Co0.2Mn0.4O2 electrodes employing sodium carboxymethyl cellulose as the binder (CMC/NCM). Compared with conventional organic PVDF-based electrodes, the CMC/NCM electrodes display very uniform distribution of NCM and carbon particles together with strong adhesion among the particles and with the current collector, leading to significantly mitigated crack formation and delamination of the electrode upon repeated delithiation/lithiation processes. Additionally, these electrodes offer enhanced Li+ diffusion kinetics, reduced polarization, therefore, excellent high C-rate capability, and extremely stable cycling performance even at elevated temperature (60 °C). Benefiting from the features of low cost, environmentally friendliness, and easy disposability-recyclability, the water-soluble CMC is a promising binder for practical application in energy storage systems.

Semi-empirical master curve concept describing the rate capability of lithium insertion electrodes

NASA Astrophysics Data System (ADS)

Heubner, C.; Seeba, J.; Liebmann, T.; Nickol, A.; Börner, S.; Fritsch, M.; Nikolowski, K.; Wolter, M.; Schneider, M.; Michaelis, A.

2018-03-01

A simple semi-empirical master curve concept, describing the rate capability of porous insertion electrodes for lithium-ion batteries, is proposed. The model is based on the evaluation of the time constants of lithium diffusion in the liquid electrolyte and the solid active material. This theoretical approach is successfully verified by comprehensive experimental investigations of the rate capability of a large number of porous insertion electrodes with various active materials and design parameters. It turns out, that the rate capability of all investigated electrodes follows a simple master curve governed by the time constant of the rate limiting process. We demonstrate that the master curve concept can be used to determine optimum design criteria meeting specific requirements in terms of maximum gravimetric capacity for a desired rate capability. The model further reveals practical limits of the electrode design, attesting the empirically well-known and inevitable tradeoff between energy and power density.

Microchannel-electrode alignment and separation parameters comparison in microchip capillary electrophoresis by scanning electrochemical microscopy.

PubMed

Wang, Kang; Xia, Xing-Hua

2006-03-31

The end of separation channel in a microchip was electrochemically mapped using the feedback imaging mode of scanning electrochemical microscopy (SECM). This method provides a convenient way for microchannel-electrode alignment in microchip capillary electrophoresis. Influence of electrode-to-channel positions on separation parameters in this capillary electrophoresis-electrochemical detection (CE-ED) was then investigated. For the trapezoid shaped microchannel, detection in the central area resulted in the best apparent separation efficiency and peak shape. In the electrode-to-channel distance ranging from 65 to 15mum, the limiting peak currents of dopamine increased with the decrease of the detection distance due to the limited diffusion and convection of the sample band. Results showed that radial position and axial distance of the detection electrode to microchannel was important for the improvement of separation parameters in CE amperometric detection.

MnO2 nanotubes assembled on conductive graphene/polyester composite fabric as a three-dimensional porous textile electrode for flexible electrochemical capacitors.

PubMed

Jin, Chun; Jin, Li-Na; Guo, Mei-Xia; Liu, Ping; Zhang, Jia-Nan; Bian, Shao-Wei

2017-12-15

A three-dimensional (3D) electrode material was successfully synthesized through a facile ZnO-assisted hydrothermal process in which vertical MnO 2 nanotube arrays were in situ grown on the conductive graphene/polyester composite fabric. The morphology and structure of MnO 2 nanotubes/graphene/polyester textile electrode were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The 3D electrode structure facilitates to achieve the maximum number of active sites for the pesudocapacitance redox reaction, fast electrolyte ion transportation and short ion diffusion path. The electrochemical measurements showed that the electrode possesses good capacitance capacity which reached 498F/g at a scan rate of 2mV/s in Na 2 SO 4 electrolyte solution. The electrode also showed stable electrochemical performances under the conditions of long-term cycling, and mechanical bending and twisting. Copyright © 2017 Elsevier Inc. All rights reserved.

Microstructure of room temperature ionic liquids at stepped graphite electrodes

DOE PAGES

Feng, Guang; Li, Song; Zhao, Wei; ...

2015-07-14

Molecular dynamics simulations of room temperature ionic liquid (RTIL) [emim][TFSI] at stepped graphite electrodes were performed to investigate the influence of the thickness of the electrode surface step on the microstructure of interfacial RTILs. A strong correlation was observed between the interfacial RTIL structure and the step thickness in electrode surface as well as the ion size. Specifically, when the step thickness is commensurate with ion size, the interfacial layering of cation/anion is more evident; whereas, the layering tends to be less defined when the step thickness is close to the half of ion size. Furthermore, two-dimensional microstructure of ionmore » layers exhibits different patterns and alignments of counter-ion/co-ion lattice at neutral and charged electrodes. As the cation/anion layering could impose considerable effects on ion diffusion, the detailed information of interfacial RTILs at stepped graphite presented here would help to understand the molecular mechanism of RTIL-electrode interfaces in supercapacitors.« less

Electrochemical Impedance Imaging via the Distribution of Diffusion Times.

PubMed

Song, Juhyun; Bazant, Martin Z

2018-03-16

We develop a mathematical framework to analyze electrochemical impedance spectra in terms of a distribution of diffusion times (DDT) for a parallel array of random finite-length Warburg (diffusion) or Gerischer (reaction-diffusion) circuit elements. A robust DDT inversion method is presented based on complex nonlinear least squares regression with Tikhonov regularization and illustrated for three cases of nanostructured electrodes for energy conversion: (i) a carbon nanotube supercapacitor, (ii) a silicon nanowire Li-ion battery, and (iii) a porous-carbon vanadium flow battery. The results demonstrate the feasibility of nondestructive "impedance imaging" to infer microstructural statistics of random, heterogeneous materials.

Macroscopic Modeling of a One-Dimensional Electrochemical Cell using the Poisson-Nernst-Planck Equations

NASA Astrophysics Data System (ADS)

Yan, David

This thesis presents the one-dimensional equations, numerical method and simulations of a model to characterize the dynamical operation of an electrochemical cell. This model extends the current state-of-the art in that it accounts, in a primitive way, for the physics of the electrolyte/electrode interface and incorporates diffuse-charge dynamics, temperature coupling, surface coverage, and polarization phenomena. The one-dimensional equations account for a system with one or two mobile ions of opposite charge, and the electrode reaction we consider (when one is needed) is a one-electron electrodeposition reaction. Though the modeled system is far from representing a realistic electrochemical device, our results show a range of dynamics and behaviors which have not been observed previously, and explore the numerical challenges required when adding more complexity to a model. Furthermore, the basic transport equations (which are developed in three spatial dimensions) can in future accomodate the inclusion of additional physics, and coupling to more complex boundary conditions that incorporate two-dimensional surface phenomena and multi-rate reactions. In the model, the Poisson-Nernst-Planck equations are used to model diffusion and electromigration in an electrolyte, and the generalized Frumkin-Butler-Volmer equation is used to model reaction kinetics at electrodes. An energy balance equation is derived and coupled to the diffusion-migration equation. The model also includes dielectric polarization effects by introducing different values of the dielectric permittivity in different regions of the bulk, as well as accounting for surface coverage effects due to adsorption, and finite size "crowding", or steric effects. Advection effects are not modeled but could in future be incorporated. In order to solve the coupled PDE's, we use a variable step size second order scheme in time and finite differencing in space. Numerical tests are performed on a simplified system and the scheme's stability and convergence properties are discussed. While evaluating different methods for discretizing the coupled flux boundary condition, we discover a thresholding behaviour in the adaptive time stepper, and perform additional tests to investigate it. Finally, a method based on ghost points is chosen for its favorable numerical properties compared to the alternatives. With this method, we are able to run simulations with a large range of parameters, including any value of the nondimensionalized Debye length epsilon. The numerical code is first used to run simulations to explore the effects of polarization, surface coverage, and temperature. The code is also used to perform frequency sweeps of input signals in order to mimic impedance spectroscopy experiments. Finally, in Chapter 5, we use our model to apply ramped voltages to electrochemical systems, and show theoretical and simulated current-voltage curves for liquid and solid thin films, cells with blocking (polarized) electrodes, and electrolytes with background charge. Linear sweep and cyclic voltammetry techniques are important tools for electrochemists and have a variety of applications in engineering. Voltammetry has classically been treated with the Randles-Sevcik equation, which assumes an electroneutral supported electrolyte. No general theory of linear-sweep voltammetry is available, however, for unsupported electrolytes and for other situations where diffuse charge effects play a role. We show theoretical and simulated current-voltage curves for liquid and solid thin films, cells with blocking electrodes, and membranes with fixed background charge. The analysis focuses on the coupling of Faradaic reactions and diffuse charge dynamics, but capacitive charging of the double layers is also studied, for early time transients at reactive electrodes and for non-reactive blocking electrodes. The final chapter highlights the role of diffuse charge in the context of voltammetry, and illustrates which regimes can be approximated using simple analytical expressions and which require more careful consideration.

Lipid diffusion in alcoholic environment.

PubMed

Rifici, Simona; Corsaro, Carmelo; Crupi, Cristina; Nibali, Valeria Conti; Branca, Caterina; D'Angelo, Giovanna; Wanderlingh, Ulderico

2014-08-07

We have studied the effects of a high concentration of butanol and octanol on the phase behavior and on the lateral mobility of 1,2-palmitoyl-sn-glycero-3-phosphocholine (DPPC) by means of differential scanning calorimetry and pulsed-gradient stimulated-echo (PGSTE) NMR spectroscopy. A lowering of the lipid transition from the gel to the liquid-crystalline state for the membrane-alcohol systems has been observed. NMR measurements reveal three distinct diffusions in the DPPC-alcohol systems, characterized by a high, intermediate, and slow diffusivity, ascribed to the water, the alcohol, and the lipid, respectively. The lipid diffusion process is promoted in the liquid phase while it is hindered in the interdigitated phase due to the presence of alcohols. Furthermore, in the interdigitated phase, lipid lateral diffusion coefficients show a slight temperature dependence. To the best of our knowledge, this is the first time that lateral diffusion coefficients on alcohol with so a long chain, and at low temperatures, are reported. By the Arrhenius plots of the temperature dependence of the diffusion coefficients, we have evaluated the apparent activation energy in both the liquid and in the interdigitated phase. The presence of alcohol increases this value in both phases. An explanation in terms of a free volume model that takes into account also for energy factors is proposed.

Proton dynamics of phosphoric acid in HT-PEFCs: Towards "operando" experiments

NASA Astrophysics Data System (ADS)

Khaneft, Marina; Shuai, Liu; Lin, Yu; Janßen, Holger; Lüke, Wiebke; Zorn, Reiner; Ivanova, Oxana; Radulescu, Aurel; Holderer, Olaf; Lehnert, Werner

2018-05-01

High Temperature Polymer Electrolyte Fuel Cells (HT-PEFCs) have been studied with quasielastic neutron scattering, which gives access to the proton diffusion in the fuel cell on local length- and timescales. So far, the different components such as the proton conducting membrane and the electrode layers have been studied separately. Here we show that also operating fuel cells can be investigated and the proton diffusion can be measured under real working conditions. The proton diffusion during power production is compared to that "at rest" but at elevated temperatures.

Synthesis and characterization of nanostructured electrodes for solid state ionic devices

NASA Astrophysics Data System (ADS)

Zhang, Yuelan

Solid-state electrochemical energy conversion and storage technologies such as fuel cells and lithium ion batteries will influence the way we use energy and the environment we live in. The demands for advanced power sources with high energy efficiency, minimum environmental impact, and low cost have been the impetus for the development of a new generation of batteries and fuel cells. Currently, lithium ion battery technology's greatest disadvantages are long-term cycling stability and high charge/discharge rate capabilities. On the other hand, fuel cell technology's greatest disadvantage is cost. It is found that these problems could be attenuated by the incorporation of nano-structured materials. But, we are still far away from possessing a solid scientific understanding of what goes on at the nanoscale inside these solid state ionic devices, and what is the relationship between nano-structures and their electrochemical properties, especially between the microstructure and electrode polarization and degradation. Electrode polarization represents a voltage loss in an electrochemical energy conversion process. Such understanding is critical for further progress in solid state ionic devices. This thesis focused on the design, fabrication, and characterization of nanostructured porous electrodes with desired composition and microstructure to minimize electrode polarization losses in the application of fuel cells and lithium ion batteries. Various chemical methods such as sol-gel, hydrothermal, surfactant, colloidal and polymer template-assisted processes have been applied in this work. And various characterization techniques have been used to explore the understanding of the microscopic features with electrochemical interfacial properties of the electrodes. Solid-state diffusion often limits the utilization and rate capability of electrode materials in a lithium-ion battery, especially at high charge/discharge rates. When the fluxes of Li+ insertion or extraction exceeds the diffusion-limited rate of Li+ transport within the bulk phase of an electrode, concentration polarization occurs. Further, large volume changes associated with Li+ insertion or extraction could induce stresses in bulk electrodes, potentially leading to mechanical failure. Porous electrodes with high surface-to-volume ratio would increase the electrochemical reaction surface and suppress the mechanical stress. But porous electrodes also increase the tortuosity of mass transport within solid electrodes. Interconnected porous materials would decrease the percolation threshold for porous electrodes. In this work, electrodes with unique architecture for lithium ion batteries have been fabricated to improve the cycleability, rate capability and capacity retention. Spinel LiMn2O4 with interconnected macropores was created using a glycine-nitrate combustion process. Both microstructure and phase crystallinity were optimized by adjusting the fuel/oxidant ratio. This macroporous LiMn2O4 positive electrode exhibited better capacity retention and rate capability than those with larger particle size prepared by solid state reaction. Detailed electrode kinetic studies indicated that the macroporous microstructure promoted lithium diffusion and the overall reaction process was not controlled by lithium diffusion. Nanostructured tin oxide thin films with columnar grains less than 20 nm were deposited on Au/Si substrate using a combustion CVD method. The microstructure was highly porous and open, and thus was easily accessible to liquid electrolyte. In addition, the microstructure with vertical and radial connectivity of active materials led to decreased tortuosity for mass transport within solid electrodes. Nanoparticles accommodated the large volume change during cycling. These thin film electrodes exhibited highly reversible specific capacity and good capacity retention. It is about 93% after 80 cycles at a charge/discharge rate of 0.3 mA/cm2. When discharged at 0.9 mA/cm2, the obtained capacity retention was about 64% of the capacity at 0.3 mA/cm2. Cathodic interfacial polarization represents the predominant loss in a low-temperature SOFC. In this thesis, several porous nanocomposite electrodes of mixed ionic and electronic conductors (MIEC) with high surface areas were designed and fabricated to improve to minimize the polarization resistance. For the first time, regular, homogeneous and dual porous MIEC electrodes were successfully fabricated using breath figure templating, which is self-assembly of the water droplets in polymer solution. The homogeneous macropores promoted rapid mass transport by decreasing the tortuosity. Further, mesoporous microstructure provided more surface areas for gas adsorption and more TPBs for the electrochemical reactions. The interfacial polarization resistances were 0.94 and 0.39 Ocm 2 at 700 and 750°C, respectively. Furthermore, electrodes consisting of strontium doped lanthanum manganite (LSM) and gadolinium doped ceria (GDC) were developed with a modified sol-gel process for honeycomb SOFCs based on stabilized zirconia electrolytes. The sol gel derived cathodes with fine grain size and large specific surface area, showed much lower interfacial polarization resistances than those prepared by other processing methods. And this process developed strong bonding between the electrode and electrolyte even at low temperatures. The interfacial polarization resistances were 0.65 and 0.16 Ocm 2 at 650 and 750°C, respectively. The mesoscopic regime of overlapping space charge effects had a positive effect on the electrode kinetics. Ceria is a very important catalytic material for fuel reforming in SOFCs and CO poisoning in PEM fuel cells. Especially, the design of a new generation SOFC requires the in-situ reforming of hydrocarbon fuels. In this work, nanostructured ceria was developed via a controlled hydrothermal process in a mixed water-ethanol medium. The microstructure, formation mechanism, and their surface catalytic properties were investigated.

Electrochemical lateral flow immunosensor for detection and quantification of dengue NS1 protein.

PubMed

Sinawang, Prima Dewi; Rai, Varun; Ionescu, Rodica E; Marks, Robert S

2016-03-15

An Electrochemical Lateral Flow Immunosensor (ELFI) is developed combining screen-printed gold electrodes (SPGE) enabling quantification together with the convenience of a lateral flow test strip. A cellulose glassy fiber paper conjugate pad retains the marker immunoelectroactive nanobeads which will bind to the target analyte of interest. The specific immunorecognition event continues to occur along the lateral flow bed until reaching the SPGE-capture antibodies at the end of the cellulosic lateral flow strip. The rationale of the immunoassay consists in the analyte antigen NS1 protein being captured selectively and specifically by the dengue NS1 antibody conjugated onto the immunonanobeads thus forming an immunocomplex. With the aid of a running buffer, the immunocomplexes flow and reach the immuno-conjugated electrode surface and form specific sandwich-type detection due to specific, molecular recognition, while unbound beads move along past the electrodes. The successful sandwich immunocomplex formation is then recorded electrochemically. Specific detection of NS1 is translated into an electrochemical signal contributed by a redox label present on the bead-immobilized detection dengue NS1 antibody while a proportional increase of faradic current is observed with increase in analyte NS1 protein concentration. The first generation ELFI prototype is simply assembled in a cassette and successfully demonstrates wide linear range over a concentration range of 1-25 ng/mL with an ultrasensitive detection limit of 0.5 ng/mL for the qualitative and quantitative detection of analyte dengue NS1 protein. Copyright © 2015 Elsevier B.V. All rights reserved.

Development of a sorption rate technique for single zeolite crystals using an electrodynamic balance

NASA Astrophysics Data System (ADS)

Welegala, Mark Joseph

Conventional means for evaluating intracrystalline diffusion in zeolites are complicated by extracrystalline mass transport resistances, crystallite size distribution, sorption heat effects, and finite instrument response times. A potentially direct means of overcoming these problems is to study sorption uptake on a single crystal suspended within a flowing gas stream in an electrodynamic balance (EDB). The objectives of this research were to design, build and investigate the viability of using such a device for obtaining diffusion coefficients from simple sorbate/zeolite systems, by computing the sorption uptake curve from the levitation voltage as a function of time. The initial electronic cell design was strongly influenced by flow mixing considerations. Accordingly, the conventional bihyperboloid electrode configuration was discarded in favor of novel four-ring (4R), and later two-ring/two-screen (2R/2S) designs with cylindrical interior geometries. A detailed numerical model based on the Method of Discrete Charges (MDC) was developed and used to aid in the design and operational understanding of these cells. Several 2R/2S designs were built and tested, including teflon/mica composite and ceramic cells capable of withstanding up to 750oF, for in situ activation of the zeolites. The diffusion of carbon dioxide in zeolite A was selected for testing due to the large differential weight change (10-20%) which occurs at ambient conditions and the availability of reliable experimental diffusion results (Yucel and Ruthven, 1980a). In addition to the carbon dioxide sorbate, water on zeolite 4A and a system relatively immune to atmospheric contamination, CO2 on activated carbon were also studied. Laboratory 4A crystals of up to 45 μm were grown using Charnell's method. These large solid particles were captured using a dry charging technique, and held during elevated temperature dehydration. Preliminary experimentation introduced externally dried crystals to the cell chamber in 0.5-3 minutes. Only minimal desorption results with carbon dioxide and later, adsorption for water vapor, were obtained. Further experiments revealed that crystal contamination from laboratory air can be considerable in less than one minute, thereby preadsorbing airborne water vapor. The experimental methodology was changed to include in situ heating. Subsequent attempts to circumvent laser heating of the particle had limited success. Particle loss, (due to excessive charge loss) and cell material degradation limited the process to null point temperatures of approximately 260oC, which is insufficient for complete zeolite dehydration. Early, it was demonstrated that gas compositions could be switched while flowing without losing the particle. However, the resulting concentration transient imposes an ultimate limitation on the technique for application to rapidly diffusing systems. Also, the fact that the technique is gravimetric requires that the diffusing species must be appreciably adsorbed at ambient conditions. Thus the single crystal sorption apparatus based on the electrodynamic containment device would appear to have use primarily for strongly adsorbed and slowly diffusing species. (Abstract shortened by UMI.)

An electrocorticographic electrode array for simultaneous recording from medial, lateral, and intrasulcal surface of the cortex in macaque monkeys.

PubMed

Fukushima, Makoto; Saunders, Richard C; Mullarkey, Matthew; Doyle, Alexandra M; Mishkin, Mortimer; Fujii, Naotaka

2014-08-15

Electrocorticography (ECoG) permits recording electrical field potentials with high spatiotemporal resolution over a large part of the cerebral cortex. Application of chronically implanted ECoG arrays in animal models provides an opportunity to investigate global spatiotemporal neural patterns and functional connectivity systematically under various experimental conditions. Although ECoG is conventionally used to cover the gyral cortical surface, recent studies have shown the feasibility of intrasulcal ECoG recordings in macaque monkeys. Here we developed a new ECoG array to record neural activity simultaneously from much of the medial and lateral cortical surface of a single hemisphere, together with the supratemporal plane (STP) of the lateral sulcus in macaque monkeys. The ECoG array consisted of 256 electrodes for bipolar recording at 128 sites. We successfully implanted the ECoG array in the left hemisphere of three rhesus monkeys. The electrodes in the auditory and visual cortex detected robust event related potentials to auditory and visual stimuli, respectively. Bipolar recording from adjacent electrode pairs effectively eliminated chewing artifacts evident in monopolar recording, demonstrating the advantage of using the ECoG array under conditions that generate significant movement artifacts. Compared with bipolar ECoG arrays previously developed for macaque monkeys, this array significantly expands the number of cortical target areas in gyral and intralsulcal cortex. This new ECoG array provides an opportunity to investigate global network interactions among gyral and intrasulcal cortical areas. Published by Elsevier B.V.

Micellar Polymer Encapsulation of Enzymes.

PubMed

Besic, Sabina; Minteer, Shelley D

2017-01-01

Although enzymes are highly efficient and selective catalysts, there have been problems incorporating them into fuel cells. Early enzyme-based fuel cells contained enzymes in solution rather than immobilized on the electrode surface. One problem utilizing an enzyme in solution is an issue of transport associated with long diffusion lengths between the site of bioelectrocatalysis and the electrode. This issue drastically decreases the theoretical overall power output due to the poor electron conductivity. On the other hand, enzymes immobilized at the electrode surface have eliminated the issue of poor electron conduction due to close proximity of electron transfer between electrode and the biocatalyst. Another problem is inefficient and short term stability of catalytic activity within the enzyme that is suspended in free flowing solution. Enzymes in solutions are only stable for hours to days, whereas immobilized enzymes can be stable for weeks to months and now even years. Over the last decade, there has been substantial research on immobilizing enzymes at electrode surfaces for biofuel cell and sensor applications. The most commonly used techniques are sandwich or wired. Sandwich techniques are powerful and successful for enzyme immobilization; however, the enzymes optimal activity is not retained due to the physical distress applied by the polymer limiting its applications as well as the non-uniform distribution of the enzyme and the diffusion of analyte through the polymer is slowed significantly. Wired techniques have shown to extend the lifetime of an enzyme at the electrode surface; however, this technique is very hard to master due to specific covalent bonding of enzyme and polymer which changes the three-dimensional configuration of enzyme and with that decreases the optimal catalytic activity. This chapter details encapsulation techniques where an enzyme will be immobilized within the pores/pockets of the hydrophobically modified micellar polymers such as Nafion ® and chitosan. This strategy has been shown to safely immobilize enzymes at electrode surfaces with storage and continuous operation lifetime of more than 2 years.

Operando XRD studies as a tool for determination of transport parameters of mobile ions in electrode materials

NASA Astrophysics Data System (ADS)

Kondracki, Łukasz; Kulka, Andrzej; Świerczek, Konrad; Ziąbka, Magdalena; Molenda, Janina

2017-11-01

In this work a detailed operando XRD investigations of structural properties of LixMn2O4 manganese spinel are shown to be a complementary, successful method of determination of diffusion coefficient D and surface exchange coefficient k in the working electrode. Kinetics of lithium ions transport are estimated on the basis of rate of structural changes of the cathode material during a relaxation stage after a high current charge, i.e. during structural relaxation of the material. The presented approach seems to be applicable as a complementary method of determination of transport coefficients for all intercalation-type electrode materials.

Increased Accuracy of Ligand Sensing by Receptor Internalization and Lateral Receptor Diffusion

NASA Astrophysics Data System (ADS)

Aquino, Gerardo; Endres, Robert

2010-03-01

Many types of cells can sense external ligand concentrations with cell-surface receptors at extremely high accuracy. Interestingly, ligand-bound receptors are often internalized, a process also known as receptor-mediated endocytosis. While internalization is involved in a vast number of important functions for the life of a cell, it was recently also suggested to increase the accuracy of sensing ligand as overcounting of the same ligand molecules is reduced. A similar role may be played by receptor diffusion om the cell membrane. Fast, lateral receptor diffusion is known to be relevant in neurotransmission initiated by release of neurotransmitter glutamate in the synaptic cleft between neurons. By binding ligand and removal by diffusion from the region of release of the neurotransmitter, diffusing receptors can be reasonably expected to reduce the local overcounting of the same ligand molecules in the region of signaling. By extending simple ligand-receptor models to out-of-equilibrium thermodynamics, we show that both receptor internalization and lateral diffusion increase the accuracy with which cells can measure ligand concentrations in the external environment. We confirm this with our model and give quantitative predictions for experimental parameters values. We give quantitative predictions, which compare favorably to experimental data of real receptors.

Degradation Mechanisms of Electrochemically Cycled Graphite Anodes in Lithium-ion Cells

NASA Astrophysics Data System (ADS)

Bhattacharya, Sandeep

This research is aimed at developing advanced characterization methods for studying the surface and subsurface damage in Li-ion battery anodes made of polycrystalline graphite and identifying the degradation mechanisms that cause loss of electrochemical capacity. Understanding microstructural aspects of the graphite electrode degradation mechanisms during charging and discharging of Li-ion batteries is of key importance in order to design durable anodes with high capacity. An in-situ system was constructed using an electrochemical cell with an observation window, a large depth-of-field digital microscope and a micro-Raman spectrometer. It was revealed that electrode damage by removal of the surface graphite fragments of 5-10 mum size is the most intense during the first cycle that led to a drastic capacity drop. Once a solid electrolyte interphase (SEI) layer covered the electrode surface, the rate of graphite particle loss decreased. Yet, a gradual loss of capacity continued by the formation of interlayer cracks adjacent to SEI/graphite interfaces. Deposition of co-intercalation compounds, LiC6, Li2CO3 and Li2O, near the crack tips caused partial closure of propagating graphite cracks during cycling and reduced the crack growth rate. Bridging of crack faces by delaminated graphite layers also retarded crack propagation. The microstructure of the SEI layer, formed by electrochemical reduction of the ethylene carbonate based electrolyte, consisted of ˜5-20 nm sized crystalline domains (containing Li2CO3, Li2O 2 and nano-sized graphite fragments) dispersed in an amorphous matrix. During the SEI formation, two regimes of Li-ion diffusion were identified at the electrode/electrolyte interface depending on the applied voltage scan rate (dV/dt). A low Li-ion diffusion coefficient ( DLi+) at dV/dt < 0.05 mVs-1 produced a tubular SEI that uniformly covered the graphite surface and prevented damage at 25°C. At 60°C, a high D Li+ formed a Li2CO3-enriched SEI and ensued a 28% increase in the battery capacity at 25°C. On correlating the microscopic information to the electrochemical performance, novel Li2CO3-coated electrodes were fabricated that were durable. The SEI formed on pre-treated electrodes reduced the strain in the graphite lattice from 0.4% (for uncoated electrodes) to 0.1%, facilitated Li-ion diffusion and hence improved the capacity retention of Li-ion batteries during long-term cycling.

DTI-based response-driven modeling of mTLE laterality.

PubMed

Nazem-Zadeh, Mohammad-Reza; Elisevich, Kost; Air, Ellen L; Schwalb, Jason M; Divine, George; Kaur, Manpreet; Wasade, Vibhangini S; Mahmoudi, Fariborz; Shokri, Saeed; Bagher-Ebadian, Hassan; Soltanian-Zadeh, Hamid

2016-01-01

To develop lateralization models for distinguishing between unilateral and bilateral mesial temporal lobe epilepsy (mTLE) and determining laterality in cases of unilateral mTLE. mTLE is the most common form of medically refractory focal epilepsy. Many mTLE patients fail to demonstrate an unambiguous unilateral ictal onset. Intracranial EEG (icEEG) monitoring can be performed to establish whether the ictal origin is unilateral or truly bilateral with independent bitemporal ictal origin. However, because of the expense and risk of intracranial electrode placement, much research has been done to determine if the need for icEEG can be obviated with noninvasive neuroimaging methods, such as diffusion tensor imaging (DTI). Fractional anisotropy (FA) was used to quantify microstructural changes reflected in the diffusivity properties of the corpus callosum, cingulum, and fornix, in a retrospective cohort of 31 patients confirmed to have unilateral (n = 24) or bilateral (n = 7) mTLE. All unilateral mTLE patients underwent resection with an Engel class I outcome. Eleven were reported to have hippocampal sclerosis on pathological analysis; nine had undergone prior icEEG. The bilateral mTLE patients had undergone icEEG demonstrating independent epileptiform activity in both right and left hemispheres. Twenty-three nonepileptic subjects were included as controls. In cases of right mTLE, FA showed significant differences from control in all callosal subregions, in both left and right superior cingulate subregions, and in forniceal crura. Comparison of right and left mTLE cases showed significant differences in FA of callosal genu, rostral body, and splenium and the right posteroinferior and superior cingulate subregions. In cases of left mTLE, FA showed significant differences from control only in the callosal isthmus. Significant differences in FA were identified when cases of right mTLE were compared with bilateral mTLE cases in the rostral and midbody callosal subregions and isthmus. Based on 11 FA measurements in the cingulate, callosal and forniceal subregions, a response-driven lateralization model successfully differentiated all cases (n = 54) into groups of unilateral right (n = 12), unilateral left (n = 12), and bilateral mTLE (n = 7), and nonepileptic control (23). The proposed response-driven DTI biomarker is intended to lessen diagnostic ambiguity of laterality in cases of mTLE and help optimize selection of surgical candidates. Application of this model shows promise in reducing the need for invasive icEEG in prospective cases.

Kinetics of CO/CO2 and H2/H2O reactions at Ni-based and ceria-based solid-oxide-cell electrodes.

PubMed

Graves, Christopher; Chatzichristodoulou, Christodoulos; Mogensen, Mogens B

2015-01-01

The solid oxide electrochemical cell (SOC) is an energy conversion technology that can be operated reversibly, to efficiently convert chemical fuels to electricity (fuel cell mode) as well as to store electricity as chemical fuels (electrolysis mode). The SOC fuel-electrode carries out the electrochemical reactions CO2 + 2e(-) ↔ CO + O(2-) and H2O + 2e(-) ↔ H2 + O(2-), for which the electrocatalytic activities of different electrodes differ considerably. The relative activities in CO/CO2 and H2/H2O and the nature of the differences are not well studied, even for the most common fuel-electrode material, a composite of nickel and yttria/scandia stabilized zirconia (Ni-SZ). Ni-SZ is known to be more active for H2/H2O than for CO/CO2 reactions, but the reported relative activity varies widely. Here we compare AC impedance and DC current-overpotential data measured in the two gas environments for several different electrodes comprised of Ni-SZ, Gd-doped CeO2 (CGO), and CGO nanoparticles coating Nb-doped SrTiO3 backbones (CGOn/STN). 2D model and 3D porous electrode geometries are employed to investigate the influence of microstructure, gas diffusion and impurities.Comparing model and porous Ni-SZ electrodes, the ratio of electrode polarization resistance in CO/CO2vs. H2/H2O decreases from 33 to 2. Experiments and modelling suggest that the ratio decreases due to a lower concentration of impurities blocking the three phase boundary and due to the nature of the reaction zone extension into the porous electrode thickness. Besides showing higher activity for H2/H2O reactions than CO/CO2 reactions, the Ni/SZ interface is more active for oxidation than reduction. On the other hand, we find the opposite behaviour in both cases for CGOn/STN model electrodes, reporting for the first time a higher electrocatalytic activity of CGO nanoparticles for CO/CO2 than for H2/H2O reactions in the absence of gas diffusion limitations. We propose that enhanced surface reduction at the CGOn/gas two phase boundary in CO/CO2 and in cathodic polarization can explain why the highest reaction rate is obtained for CO2 electrolysis. Large differences observed between model electrode kinetics and porous electrode kinetics are discussed.

Materials science and integration bases for fabrication of (BaxSr1-x)TiO3 thin film capacitors with layered Cu-based electrodes

NASA Astrophysics Data System (ADS)

Fan, W.; Kabius, B.; Hiller, J. M.; Saha, S.; Carlisle, J. A.; Auciello, O.; Chang, R. P. H.; Ramesh, R.

2003-11-01

The synthesis and fundamental material properties of layered TiAl/Cu/Ta electrodes were investigated to achieve the integration of Cu electrodes with high-dielectric constant (κ) oxide thin films for application to the fabrication of high-frequency devices. The Ta layer is an excellent diffusion barrier to inhibit deleterious Cu diffusion into the Si substrate, while the TiAl layer provides an excellent barrier against oxygen diffusion into the Cu layer to inhibit Cu oxidation during the growth of the high-κ layer in an oxygen atmosphere. Polycrystalline (BaxSr1-x)TiO3 (BST) thin films were grown on the Cu-based bottom electrode by rf magnetron sputtering at temperatures in the range 400-600 °C in oxygen, to investigate the performance of BST/Cu-based capacitors. Characterization of the Cu-based layered structure using surface analytical methods showed that two amorphous oxide layers were formed on both sides of the TiAl barrier, such that the oxide layer on the free surface of the TiAl layer correlates with TiAlOx, while the oxide layer at the TiAl/Cu interface is an Al2O3-rich layer. This double amorphous barrier layer structure effectively prevents oxygen penetration towards the underlying Cu and Ta layers. The TiAlOx interfacial layer, which has a relatively low dielectric constant compared with BST, reduced the total capacitance of the BST thin film capacitors. In addition, the layered electrode-oxide interface roughening observed during the growth of BST films at high temperature, due to copper grain growth, resulted in large dielectric loss on the fabricated BST capacitors. These problems were solved by growing the BST layer at 450 °C followed by a rapid thermal annealing at 700 °C. This process significantly reduced the thickness of the TiAlOx layer and interface roughness resulting in BST capacitors exhibiting properties suitable for the fabrication of high-performance high-frequency devices. In summary, relatively high dielectric constant (280), low dielectric loss (0.007), and low leakage current (<2×10-8 A/cm2 at 100 kV/cm) were achieved for BST thin film capacitors with Cu-based electrodes.

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.

Novel surface diffusion characteristics for a robust pentacene derivative on Au(1 1 1) surfaces

NASA Astrophysics Data System (ADS)

Miller, Ryan A.; Larson, Amanda; Pohl, Karsten

2017-06-01

Molecular dynamics simulations have been performed in both the ab initio and classical mechanics frameworks of 5,6,7-trithiapentacene-13-one (TTPO) molecules on flat Au(1 1 1) surfaces. Results show new surface diffusion characteristics including a strong preference for the molecule to align its long axis parallel to the sixfold Au(1 1 1) symmetry directions and subsequently diffuse along these close-packed directions, and a calculated activation energy for diffusion of 0.142 eV, about four times larger than that for pure pentacene on Au. The temperature-dependent diffusion coefficients were calculated to help quantify the molecular mobility during the experimentally observed process of forming self-assembled monolayers on gold electrodes.

Investigating axial diffusion in cylindrical pores using confocal single-particle fluorescence correlation spectroscopy.

PubMed

Chen, Fang; Neupane, Bhanu; Li, Peiyuan; Su, Wei; Wang, Gufeng

2016-08-01

We explored the feasibility of using confocal fluorescence correlation spectroscopy to study small nanoparticle diffusion in hundred-nanometer-sized cylindrical pores. By modeling single particle diffusion in tube-like confined three-dimensional space aligned parallel to the confocal optical axis, we showed that two diffusion dynamics can be observed in both original intensity traces and the autocorrelation functions (ACFs): the confined two-dimensional lateral diffusion and the unconfined one-dimensional (1D) axial diffusion. The separation of the axial and confined lateral diffusion dynamics provides an opportunity to study diffusions in different dimensions separately. We further experimentally studied 45 nm carboxylated polystyrene particles diffusing in 300 nm alumina pores. The experimental data showed consistency with the simulation. To extract the accurate axial diffusion coefficient, we found that a 1D diffusion model with a Lorentzian axial collection profile needs to be used to analyze the experimental ACFs. The diffusion of the 45 nm nanoparticles in polyethyleneglycol-passivated 300 nm pores slowed down by a factor of ∼2, which can be satisfactorily explained by hydrodynamic frictions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A fracture mechanics study of the phase separating planar electrodes: Phase field modeling and analytical results

NASA Astrophysics Data System (ADS)

Haftbaradaran, H.; Maddahian, A.; Mossaiby, F.

2017-05-01

It is well known that phase separation could severely intensify mechanical degradation and expedite capacity fading in lithium-ion battery electrodes during electrochemical cycling. Experiments have frequently revealed that such degradation effects could be substantially mitigated via reducing the electrode feature size to the nanoscale. The purpose of this work is to present a fracture mechanics study of the phase separating planar electrodes. To this end, a phase field model is utilized to predict how phase separation affects evolution of the solute distribution and stress profile in a planar electrode. Behavior of the preexisting flaws in the electrode in response to the diffusion induced stresses is then examined via computing the time dependent stress intensity factor arising at the tip of flaws during both the insertion and extraction half-cycles. Further, adopting a sharp-interphase approximation of the system, a critical electrode thickness is derived below which the phase separating electrode becomes flaw tolerant. Numerical results of the phase field model are also compared against analytical predictions of the sharp-interphase model. The results are further discussed with reference to the available experiments in the literature. Finally, some of the limitations of the model are cautioned.

Recent advances in metal oxide-based electrode architecture design for electrochemical energy storage.

PubMed

Jiang, Jian; Li, Yuanyuan; Liu, Jinping; Huang, Xintang; Yuan, Changzhou; Lou, Xiong Wen David

2012-10-02

Metal oxide nanostructures are promising electrode materials for lithium-ion batteries and supercapacitors because of their high specific capacity/capacitance, typically 2-3 times higher than that of the carbon/graphite-based materials. However, their cycling stability and rate performance still can not meet the requirements of practical applications. It is therefore urgent to improve their overall device performance, which depends on not only the development of advanced electrode materials but also in a large part "how to design superior electrode architectures". In the article, we will review recent advances in strategies for advanced metal oxide-based hybrid nanostructure design, with the focus on the binder-free film/array electrodes. These binder-free electrodes, with the integration of unique merits of each component, can provide larger electrochemically active surface area, faster electron transport and superior ion diffusion, thus leading to substantially improved cycling and rate performance. Several recently emerged concepts of using ordered nanostructure arrays, synergetic core-shell structures, nanostructured current collectors, and flexible paper/textile electrodes will be highlighted, pointing out advantages and challenges where appropriate. Some future electrode design trends and directions are also discussed. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fabrication of hollow nanorod electrodes based on RuO2//Fe2O3 for an asymmetric supercapacitor.

PubMed

Wang, Qiufan; Liang, Xiao; Ma, Yun; Zhang, Daohong

2018-06-12

In this work, hollow RuO2 nanotube arrays were successfully grown on carbon cloth by using a facile two-step method to fabricate a binder-free electrode. The well-aligned electrode displays excellent electrochemical performance. By using RuO2 hollow nanotube arrays as the positive electrode and Fe2O3 as the negative electrode, a flexible solid-state asymmetric supercapacitor (ASC) has been fabricated which exhibited excellent electrochemical performance, such as a high capacitance of 4.9 F cm-3, a high energy density of 1.5 mW h cm-3 and a high power density of 9.1 mW cm-3. In addition, the two-electrode SC shows high cycling stability with 97% capacitance retention after 5000 charge-discharge cycles. These excellent electrochemical performances are ascribed to the unique hollow structural design of electrodes, which can shorten the ion diffusion length, provide a fast ion transport channel, and offer a large electrode/electrolyte interface for the charge-transfer reaction. The structural design and the synthesis approach are general and can be extended to synthesizing a broad range of materials systems.

Association and Diffusion of Li(+) in Carboxymethylcellulose Solutions for Environmentally Friendly Li-ion Batteries.

PubMed

Casalegno, Mosè; Castiglione, Franca; Passarello, Marco; Mele, Andrea; Passerini, Stefano; Raos, Guido

2016-07-21

Carboxymethylcellulose (CMC) has been proposed as a polymeric binder for electrodes in environmentally friendly Li-ion batteries. Its physical properties and interaction with Li(+) ions in water are interesting not only from the point of view of electrode preparation-processability in water is one of the main reasons for its environmental friendliness-but also for its possible application in aqueous Li-ion batteries. We combine molecular dynamics simulations and variable-time pulsed field gradient spin-echo (PFGSE) NMR spectroscopy to investigate Li(+) transport in CMC-based solutions. Both the simulations and experimental results show that, at concentrations at which Li-CMC has a gel-like consistency, the Li(+) diffusion coefficient is still very close to that in water. These Li(+) ions interact preferentially with the carboxylate groups of CMC, giving rise to a rich variety of coordination patterns. However, the diffusion of Li(+) in these systems is essentially unrestricted, with a fast, nanosecond-scale exchange of the ions between CMC and the aqueous environment. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Two-dimensional lithium diffusion behavior and probable hybrid phase transformation kinetics in olivine lithium iron phosphate

DOE PAGES

Hong, Liang; Li, Linsen; Chen-Wiegart, Yuchen-Karen; ...

2017-10-30

Olivine lithium iron phosphate is a technologically important electrode material for lithium-ion batteries and a model system for studying electrochemically driven phase transformations. Despite extensive studies, many aspects of the phase transformation and lithium transport in this material are still not well understood. Here we combine operando hard X-ray spectroscopic imaging and phase-field modeling to elucidate the delithiation dynamics of single-crystal lithium iron phosphate microrods with long-axis along the [010] direction. Lithium diffusivity is found to be two-dimensional in microsized particles containing ~3%lithium-iron anti-site defects. Our study provides direct evidence for the previously predicted surface reaction-limited phase-boundary migration mechanism andmore » the potential operation of a hybrid mode of phase growth, in which phase-boundary movement is controlled by surface reaction or lithium diffusion in different crystallographic directions. These findings uncover the rich phase-transformation behaviors in lithium iron phosphate and intercalation com-pounds in general and can help guide the design of better electrodes.« less

Stretched-to-compressed-exponential crossover observed in the electrical degradation kinetics of some spinel-metallic screen-printed structures

NASA Astrophysics Data System (ADS)

Balitska, V.; Shpotyuk, O.; Brunner, M.; Hadzaman, I.

2018-02-01

Thermally-induced (170 °C) degradation-relaxation kinetics is examined in screen-printed structures composed of spinel Cu0.1Ni0.1Co1.6Mn1.2O4 ceramics with conductive Ag or Ag-Pd layered electrodes. Structural inhomogeneities due to Ag and Ag-Pd diffusants in spinel phase environment play a decisive role in non-exponential kinetics of negative relative resistance drift. If Ag migration in spinel is inhibited by Pd addition due to Ag-Pd alloy, the kinetics attains stretched exponential behavior with ∼0.58 exponent, typical for one-stage diffusion in structurally-dispersive media. Under deep Ag penetration into spinel ceramics, as for thick films with Ag-layered electrodes, the degradation kinetics drastically changes, attaining features of two-step diffusing process governed by compressed-exponential dependence with power index of ∼1.68. Crossover from stretched- to compressed-exponential kinetics in spinel-metallic structures is mapped on free energy landscape of non-barrier multi-well system under strong perturbation from equilibrium, showing transition with a character downhill scenario resulting in faster than exponential decaying.

Two-dimensional lithium diffusion behavior and probable hybrid phase transformation kinetics in olivine lithium iron phosphate

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

Hong, Liang; Li, Linsen; Chen-Wiegart, Yuchen-Karen

Olivine lithium iron phosphate is a technologically important electrode material for lithium-ion batteries and a model system for studying electrochemically driven phase transformations. Despite extensive studies, many aspects of the phase transformation and lithium transport in this material are still not well understood. Here we combine operando hard X-ray spectroscopic imaging and phase-field modeling to elucidate the delithiation dynamics of single-crystal lithium iron phosphate microrods with long-axis along the [010] direction. Lithium diffusivity is found to be two-dimensional in microsized particles containing ~3%lithium-iron anti-site defects. Our study provides direct evidence for the previously predicted surface reaction-limited phase-boundary migration mechanism andmore » the potential operation of a hybrid mode of phase growth, in which phase-boundary movement is controlled by surface reaction or lithium diffusion in different crystallographic directions. These findings uncover the rich phase-transformation behaviors in lithium iron phosphate and intercalation com-pounds in general and can help guide the design of better electrodes.« less

Two-dimensional lithium diffusion behavior and probable hybrid phase transformation kinetics in olivine lithium iron phosphate

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

Hong, Liang; Chen-Wiegart, Yu-Chen K.

2017-10-30

Olivine lithium iron phosphate is a technologically important electrode material for lithium-ion batteries and a model system for studying electrochemically driven phase transformations. Despite extensive studies, many aspects of the phase transformation and lithium transport in this material are still not well understood. Here we combine operando hard X-ray spectroscopic imaging and phase-field modeling to elucidate the delithiation dynamics of single-crystal lithium iron phosphate microrods with long-axis along the [010] direction. Lithium diffusivity is found to be two-dimensional in microsized particles containing ~3%lithium-iron anti-site defects. Our study provides direct evidence for the previously predicted surface reaction-limited phase-boundary migration mechanism andmore » the potential operation of a hybrid mode of phase growth, in which phase-boundary movement is controlled by surface reaction or lithium diffusion in different crystallographic directions. These findings uncover the rich phase-transformation behaviors in lithium iron phosphate and intercalation com-pounds in general and can help guide the design of better electrodes.« less

Tests of a Lightweight 200 kW MHD Channel and Diffuser.

DTIC Science & Technology

1980-03-01

used for measuring differential electrode voltages. The difference electrode voltage was determined by subtracting voltages that were picked up in...transients, instantaneous accelerations as high as 75 g were recorded. The acceleration peaks during steady-state firing were normally in the 15 g...normally in the range of 0.01 g2/Hz except for narrow peaks at 2-3 kHz which reach 0.05 - 0.1 g /Hz. The highest spectrum measured was accelerometer

Materials and fabrication of electrode scaffolds for deposition of MnO2 and their true performance in supercapacitors

NASA Astrophysics Data System (ADS)

Cao, Jianyun; Li, Xiaohong; Wang, Yaming; Walsh, Frank C.; Ouyang, Jia-Hu; Jia, Dechang; Zhou, Yu

2015-10-01

MnO2 is a promising electrode material for high energy supercapacitors because of its large pseudo-capacitance. However, MnO2 suffers from low electronic conductivity and poor cation diffusivity, which results in poor utilization and limited rate performance of traditional MnO2 powder electrodes, obtained by pressing a mixed paste of MnO2 powder, conductive additive and polymer binder onto metallic current collectors. Developing binder-free MnO2 electrodes by loading nanoscale MnO2 deposits on pre-fabricated device-ready electrode scaffolds is an effective way to achieve both high power and energy performance. These electrode scaffolds, with interconnected skeletons and pore structures, will not only provide mechanical support and electron collection as traditional current collectors but also fast ion transfer tunnels, leading to high MnO2 utilization and rate performance. This review covers design strategies, materials and fabrication methods for the electrode scaffolds. Rational evaluation of the true performance of these electrodes is carried out, which clarifies that some of the electrodes with as-claimed exceptional performances lack potential in practical applications due to poor mass loading of MnO2 and large dead volume of inert scaffold materials/void spaces in the electrode structure. Possible ways to meet this challenge and bring MnO2 electrodes from laboratory studies to real-world applications are considered.

Electrochemical formation of a Pt/Zn alloy and its use as a catalyst for oxygen reduction reaction in fuel cells.

PubMed

Sode, Aya; Li, Winton; Yang, Yanguo; Wong, Phillip C; Gyenge, Elod; Mitchell, Keith A R; Bizzotto, Dan

2006-05-04

The characterization of an electrochemically created Pt/Zn alloy by Auger electron spectroscopy is presented indicating the formation of the alloy, the oxidation of the alloy, and the room temperature diffusion of the Zn into the Pt regions. The Pt/Zn alloy is stable up to 1.2 V/RHE and can only be removed with the oxidation of the base Pt metal either electrochemically or in aqua regia. The Pt/Zn alloy was tested for its effectiveness toward oxygen reduction. Kinetics of the oxygen reduction reaction (ORR) were measured using a rotating disk electrode (RDE), and a 30 mV anodic shift in the potential of ORR was found when comparing the Pt/Zn alloy to Pt. The Tafel slope was slightly smaller than that measured for the pure Pt electrode. A simple procedure for electrochemically modifying a Pt-containing gas diffusion electrode (GDE) with Zn was developed. The Zn-treated GDE was pressed with an untreated GDE anode, and the created membrane electrode assembly was tested. Fuel cell testing under two operating conditions (similar anode and cathode inlet pressures, and a larger cathode inlet pressure) indicated that the 30 mV shift observed on the RDE was also evident in the fuel cell tests. The high stability of the Pt/Zn alloy in acidic environments has a potential benefit for fuel cell applications.

In situ TEM probing of crystallization form-dependent sodiation behavior in ZnO nanowires for sodium-ion batteries

DOE PAGES

Xu, Feng; Li, Zhengrui; Wu, Lijun; ...

2016-09-13

Development of sodium-ion battery (SIB) electrode materials currently lags behind electrodes in commercial lithium-ion batteries (LIBs). However, in the long term, development of SIB components is a valuable goal. Their similar, but not identical, chemistries require careful identification of the underlying sodiation mechanism in SIBs. Here in this study, we utilize in situ transmission electron microscopy to explore quite different sodiation behaviors even in similar electrode materials through real-time visualization of microstructure and phase evolution. Upon electrochemical sodiation, single-crystalline ZnO nanowires (sc-ZNWs) are found to undergo a step-by-step electrochemical displacement reaction, forming crystalline NaZn 13 nanograins dispersed in a Namore » 2O matrix. This process is characterized by a slowly propagating reaction front and the formation of heterogeneous interfaces inside the ZNWs due to non-uniform sodiation amorphization. In contrast, poly-crystalline ZNWs (pc-ZNWs) exhibited an ultrafast sodiation process, which can partly be ascribed to the availability of unobstructed ionic transport pathways among ZnO nanograins. Thus the reaction front and heterogeneous interfaces disappear. The in situ TEM results, supported by calculation of the ion diffusion coefficient, provide breakthrough insights into the dependence of ion diffusion kinetics on crystallization form. This points toward a goal of optimizing the microstructure of electrode materials in order to develop high performance SIBs.« less

Hydrogen atom kinetics in capacitively coupled plasmas

NASA Astrophysics Data System (ADS)

Nunomura, Shota; Katayama, Hirotaka; Yoshida, Isao

2017-05-01

Hydrogen (H) atom kinetics has been investigated in capacitively coupled very high frequency (VHF) discharges at powers of 16-780 mW cm-2 and H2 gas pressures of 0.1-2 Torr. The H atom density has been measured using vacuum ultra violet absorption spectroscopy (VUVAS) with a micro-discharge hollow cathode lamp as a VUV light source. The measurements have been performed in two different electrode configurations of discharges: conventional parallel-plate diode and triode with an intermediate mesh electrode. We find that in the triode configuration, the H atom density is strongly reduced across the mesh electrode. The H atom density varies from ˜1012 cm-3 to ˜1010 cm-3 by crossing the mesh with 0.2 mm in thickness and 36% in aperture ratio. The fluid model simulations for VHF discharge plasmas have been performed to study the H atom generation, diffusion and recombination kinetics. The simulations suggest that H atoms are generated in the bulk plasma, by the electron impact dissociation (e + H2 \\to e + 2H) and the ion-molecule reaction (H2 + + H2 \\to {{{H}}}3+ + H). The diffusion of H atoms is strongly limited by a mesh electrode, and thus the mesh geometry influences the spatial distribution of the H atoms. The loss of H atoms is dominated by the surface recombination.

Analysis of oxidation of self-baking electrodes (Soederberg electrodes) by means of three-dimensional model

NASA Astrophysics Data System (ADS)

Pashnin, S. V.

2017-10-01

The paper presents the methodology and results of the development of the temperature dependence of the oxidation speed of the self-baking electrode (Soederberg Electrodes) in the ore-thermal furnaces. For the study of oxidation, the working ends of the self-baking electrodes, which were taken out from the ore-thermal furnaces after their scabbings, were used. The temperature of the electrode surface by its height was calculated with the help of the mathematical model of heat work of self-baking electrode. The comparison of electrode surface temperatures with the speed of oxidation of the electrode allowed one to obtain the temperature dependency of the oxidation of the lateral electrode surface. Comparison of the experimental data, obtained in the laboratory by various authors, showed their qualitative coincidence with results of calculations of the oxidation rate presented in this article. With the help of the mathematical model of temperatures fields of electrode, the calculations of the sizes of the cracks, appearing after burnout ribs, were performed. Calculations showed that the sizes of the cracks after the ribs burnout, calculated by means of the obtained temperature dependence, coincide with the experimental data with sufficient accuracy.

Fabrication of a Biologically-Implantable, Multiplexed, Multielectrode Array of JFETS for Cortical Implantation.

DTIC Science & Technology

1984-12-01

which could be implanted at the surface of the brain. Electrodes of microfine dimensions I-1 . ..6...to check the operation of the diffusion furnace oxidation tube by comparing measured thicknesses of the oxide against calculated values. Oxide Growth...faster rate than that of Eq ), (11-2). Initial adjustments made prior to using the diffusion furnace included: (1) profiling the oxidation tube to

Li-Ion Cell Development for Low Temperature Applications

NASA Technical Reports Server (NTRS)

Huang, C.-K.; Sakamoto, J. S.; Surampudi, S.; Wolfenstine, J.

2000-01-01

JPL is involved in the development of rechargeable Li-ion cells for future Mars Exploration Missions. The specific objectives are to improve the Li-ion cell cycle life performance and rate capability at low temperature (<<-20 C) in order to enhance survivability of the Mars lander and rover batteries. Poor Li-ion rate capability at low temperature has been attributed to: (1) the electrolytes becoming viscous or freezing and/or (2) reduced electrode capacity that results from decreased Li diffusivity. Our efforts focus on increasing the rate capability at low temperature for Li-ion cells. In order to improve the rate capability we evaluated the following: (1) cathode performance at low temperatures, (2) electrode active material particle size on low temperature performance and (3) Li diffusivity at room temperature and low temperatures. In this paper, we will discuss the results of our study.

Magnetically Diffused Radial Electric-Arc Air Heater Employing Water-Cooled Copper Electrodes

NASA Technical Reports Server (NTRS)

Mayo, R. F.; Davis, D. D., Jr.

1962-01-01

A magnetically rotated electric-arc air heater has been developed that is novel in that an intense magnetic field of the order of 10,000 to 25,000 gauss is employed. This field is supplied by a coil that is connected in series with the arc. Experimentation with this heater has shown that the presence of an intense magnetic field transverse to the arc results in diffusion of the arc and that the arc has a positive effective resistance. With the field coil in series with the arc, highly stable arc operation is obtained from a battery power supply. External ballast is not required to stabilize the arc when it is operating at maximum power level. The electrode erosion rate is so low that the airstream contamination is no more than 0.07 percent and may be substantially less.

Flexible Hybrid Battery/Pseudocapacitor

NASA Technical Reports Server (NTRS)

Tucker, Dennis S.; Paley, Steven

2015-01-01

Batteries keep devices working by utilizing high energy density, however, they can run down and take tens of minutes to hours to recharge. For rapid power delivery and recharging, high-power density devices, i.e., supercapacitors, are used. The electrochemical processes which occur in batteries and supercapacitors give rise to different charge-storage properties. In lithium ion (Li+) batteries, the insertion of Li+, which enables redox reactions in bulk electrode materials, is diffusion controlled and can be slow. Supercapacitor devices, also known as electrical double-layer capacitors (EDLCs) store charge by adsorption of electrolyte ions onto the surface of electrode materials. No redox reactions are necessary, so the response to changes in potential without diffusion limitations is rapid and leads to high power. However, the charge in EDLCs is confined to the surface, so the energy density is lower than that of batteries.

Spatial-temporal evolution of self-organized loop-patterns on a water surface and a diffuse discharge in the gap

NASA Astrophysics Data System (ADS)

Li, Xuechen; Geng, Jinling; Jia, Pengying; Zhang, Panpan; Zhang, Qi; Li, Yaru

2017-11-01

Excited by an alternating current voltage, a patterned discharge and a diffuse discharge are generated in a needle to liquid configuration. Using an intensified charge-coupled device (ICCD), temporal evolution of the discharge between the two electrodes is investigated for the diffuse mode and the patterned mode, respectively. For the diffuse mode, the positive discharge is in a glow regime, and the negative discharge is in a Townsend discharge regime. For the patterned mode, the discharge always belongs to the Townsend discharge regime. Moreover, in the patterned mode, various patterns including the single loop, single loop with the surrounding corona, triple loops, and concentric loops with a central spot are observed on the water surface with the increasing positive peak-value of the applied voltage (Upp). Temporally resolved images of the loop-patterns are captured on the water surface. From the electrical measurements and the ICCD imaging, it is found that the loop pattern emerges after the discharge bridges the two electrodes. Then, it begins to evolve and finally degenerates with the decrease in the discharge current. The pattern does not disappear until the discharge quenches. Formation of the loop-patterns is attributed to the role of negative ions.

Time-resolved mapping of water diffusion coefficients in a working soft actuator device.

PubMed

Naji, Leila; Chudek, John A; Baker, Richard T

2008-08-14

Diffusion-weighted imaging was employed to spatially map the distribution of the diffusion coefficient of water, D, in bare, water-soaked, Li(+)-exchanged, cast Nafion and in an ionic polymer-metal composite (IPMC) soft actuator element, prepared from this bare Nafion by impregnation with Pt electrodes. D was evaluated in two orthogonal directions: along one of the long dimensions of the sample (Dx) and through its thickness (Dz). D-maps of the IPMC element were obtained both in the absence of an applied potential and in situ during the application of a 3 V dc potential across the thickness of the sample. In the bare Nafion, D-maps showed uniform values of both Dx and Dz of about 6 x 10 (-10) m(2) s(-1). In the IPMC two effects were observed: (i) D at the electroded surfaces of the IPMC was higher than at the center of the sample; (ii) this difference was much greater in Dz than in Dx . Both effects were explained by the influence of the impregnated Pt electrodes on polymer structure. The D-maps in the electrochemical measurements showed high values of D (up to 8 x 10(-10) m(2) s(-1)) at the cathode and low values (from 1 x 10(-10) m(2) s(-1)) at the anode. This was explained in terms of the effect on the Nafion nanostructure of the forced electro-migration of Li(H2O)x(+) species toward the cathode.

"Squishy capacitor" model for electrical double layers and the stability of charged interfaces.

PubMed

Partenskii, Michael B; Jordan, Peter C

2009-07-01

Negative capacitance (NC), predicted by various electrical double layer (EDL) theories, is critically reviewed. Physically possible for individual components of the EDL, the compact or diffuse layer, it is strictly prohibited for the whole EDL or for an electrochemical cell with two electrodes. However, NC is allowed for the artificial conditions of sigma control, where an EDL is described by the equilibrium electric response of electrolyte to a field of fixed, and typically uniform, surface charge-density distributions, sigma. The contradiction is only apparent; in fact local sigma cannot be set independently, but is established by the equilibrium response to physically controllable variables, i.e., applied voltage phi (phi control) or total surface charge q (q control). NC predictions in studies based on sigma control signify potential instabilities and phase transitions for physically realizable conditions. Building on our previous study of phi control [M. B. Partenskii and P. C. Jordan, Phys. Rev. E 77, 061117 (2008)], here we analyze critical behavior under q control, clarifying the basic picture using an exactly solvable "squishy capacitor" toy model. We find that phi can change discontinuously in the presence of a lateral transition, specify stability conditions for an electrochemical cell, analyze the origin of the EDL's critical point in terms of compact and diffuse serial contributions, and discuss perspectives and challenges for theoretical studies not limited by sigma control.

On the diffusion of ferrocenemethanol in room-temperature ionic liquids: an electrochemical study.

PubMed

Lovelock, Kevin R J; Ejigu, Andinet; Loh, Sook Fun; Men, Shuang; Licence, Peter; Walsh, Darren A

2011-06-07

The electrochemical behaviour of ferrocenemethanol (FcMeOH) has been studied in a range of room-temperature ionic liquids (RTILs) using cyclic voltammetry, chronoamperomery and scanning electrochemical microscopy (SECM). The diffusion coefficient of FcMeOH, measured using chronoamperometry, decreased with increasing RTIL viscosity. Analysis of the mass transport properties of the RTILs revealed that the Stokes-Einstein equation did not apply to our data. The "correlation length" was estimated from diffusion coefficient data and corresponded well to the average size of holes (voids) in the liquid, suggesting that a model in which the diffusing species jumps between holes in the liquid is appropriate in these liquids. Cyclic voltammetry at ultramicroelectrodes demonstrated that the ability to record steady-state voltammograms during ferrocenemethanol oxidation depended on the voltammetric scan rate, the electrode dimensions and the RTIL viscosity. Similarly, the ability to record steady-state SECM feedback approach curves depended on the RTIL viscosity, the SECM tip radius and the tip approach speed. Using 1.3 μm Pt SECM tips, steady-state SECM feedback approach curves were obtained in RTILs, provided that the tip approach speed was low enough to maintain steady-state diffusion at the SECM tip. In the case where tip-induced convection contributed significantly to the SECM tip current, this effect could be accounted for theoretically using mass transport equations that include diffusive and convective terms. Finally, the rate of heterogeneous electron transfer across the electrode/RTIL interface during ferrocenemethanol oxidation was estimated using SECM, and k(0) was at least 0.1 cm s(-1) in one of the least viscous RTILs studied.

Series interconnected photovoltaic cells and method for making same

DOEpatents

Albright, Scot P.; Chamberlin, Rhodes R.; Thompson, Roger A.

1995-01-01

A novel photovoltaic module (10) and method for constructing the same are disclosed. The module (10) includes a plurality of photovoltaic cells (12) formed on a substrate (14) and laterally separated by interconnection regions (15). Each cell (12) includes a bottom electrode (16), a photoactive layer (18) and a top electrode layer (20). Adjacent cells (12) are connected in electrical series by way of a conductive-buffer line (22). The buffer line (22) is also useful in protecting the bottom electrode (16) against severing during downstream layer cutting processes.

Quantitating Changes in Jitter and Spike Number Using Concentric Needle Electrodes in Amyotrophic Lateral Sclerosis Patients

PubMed Central

Liu, Ming-Sheng; Niu, Jing-Wen; Li, Yi; Guan, Yu-Zhou; Cui, Li-Ying

2016-01-01

Background: Single-fiber electromyography (SFEMG) has been suggested as a quantitative method for supporting chronic partial denervation in amyotrophic lateral sclerosis (ALS) by the revised EI Escorial criteria. Although concentric needle (CN) electrodes have been used to assess jitter in myasthenia gravis patients and healthy controls, there are few reports using CN electrodes to assess motor unit instability and denervation in neurogenic diseases. The aim of this study was to determine whether quantitative changes in jitter and spike number using CN electrodes could be used for ALS studies. Methods: Twenty-seven healthy controls and 23 ALS patients were studied using both CN and single-fiber needle (SFN) electrodes on the extensor digitorum communis muscle with an SFEMG program. The SFN-jitter and SFN-fiber density data were measured using SFN electrodes. The CN-jitter and spike number were measured using CN electrodes. Results: The mean CN-jitter was significantly increased in ALS patients (47.3 ± 17.0 μs) than in healthy controls (27.4 ± 3.3 μs) (P < 0.001). Besides, the mean spike number was significantly increased in ALS patients (2.5 ± 0.5) than in healthy controls (1.7 ± 0.3) (P < 0.001). The sensitivity and specificity in the diagnosis of ALS were 82.6% and 92.6% for CN-jitter (cut-off value: 32 μs), and 91.3% and 96.3% for the spike number (cut-off value: 2.0), respectively. There was no significant difference between the SFN-jitter and CN-jitter in ALS patients; meanwhile, there was no significant difference between the SFN-jitter and CN-jitter in healthy controls. Conclusion: CN-jitter and spike number could be used to quantitatively evaluate changes due to denervation-reinnervation in ALS. PMID:27098787

Negative differential resistance observation in complex convoluted fullerene junctions

NASA Astrophysics Data System (ADS)

Kaur, Milanpreet; Sawhney, Ravinder Singh; Engles, Derick

2018-04-01

In this work, we simulated the smallest fullerene molecule, C20 in a two-probe device model with gold electrodes. The gold electrodes comprised of (011) miller planes were carved to construct the novel geometry based four unique shapes, which were strung to fullerene molecules through mechanically controlled break junction techniques. The organized devices were later scrutinized using non-equilibrium Green's function based on the density functional theory to calculate their molecular orbitals, energy levels, charge transfers, and electrical parameters. After intense scrutiny, we concluded that five-edged and six-edged devices have the lowest and highest current-conductance values, which result from their electrode-dominating and electrode-subsidiary effects, respectively. However, an interesting observation was that the three-edged and four-edged electrodes functioned as semi-metallic in nature, allowing the C20 molecule to demonstrate its performance with the complementary effect of these electrodes in the electron conduction process of a two-probe device.

MEG Coherence and DTI Connectivity in mTLE

PubMed Central

Nazem-Zadeh, Mohammad-Reza; Bowyer, Susan M.; Moran, John E.; Davoodi-Bojd, Esmaeil; Zillgitt, Andrew; Weiland, Barbara J.; Bagher-Ebadian, Hassan; Mahmoudi, Fariborz; Elisevich, Kost; Soltanian-Zadeh, Hamid

2017-01-01

Purpose Magnetoencephalography (MEG) is a noninvasive imaging method for localization of focal epileptiform activity in patients with epilepsy. Diffusion tensor imaging (DTI) is a noninvasive imaging method for measuring the diffusion properties of the underlying white matter tracts through which epileptiform activity is propagated. This study investigates the relationship between the cerebral functional abnormalities quantified by MEG coherence and structural abnormalities quantified by DTI in mesial temporal lobe epilepsy (mTLE). Methods Resting state MEG data was analyzed using MEG coherence source imaging (MEG-CSI) method to determine the coherence in 54 anatomical sites in 17 adult mTLE patients with surgical resection and Engel class I outcome, and 17 age- and gender- matched controls. DTI tractography identified the fiber tracts passing through these same anatomical sites of the same subjects. Then, DTI nodal degree and laterality index were calculated and compared with the corresponding MEG coherence and laterality index. Results MEG coherence laterality, after Bonferroni adjustment, showed significant differences for right versus left mTLE in insular cortex and both lateral orbitofrontal and superior temporal gyri (p<0.017). Likewise, DTI nodal degree laterality, after Bonferroni adjustment, showed significant differences for right versus left mTLE in gyrus rectus, insular cortex, precuneus and superior temporal gyrus (p<0.017). In insular cortex, MEG coherence laterality correlated with DTI nodal degree laterality (R2 = 0.46; p = 0.003) in the cases of mTLE. None of these anatomical sites showed statistically significant differences in coherence laterality between right and left sides of the controls. Coherence laterality was in agreement with the declared side of epileptogenicity in insular cortex (in 82% of patients) and both lateral orbitofrontal (88%) and superior temporal gyri (88%). Nodal degree laterality was also in agreement with the declared side of epileptogenicity in gyrus rectus (in 88% of patients), insular cortex (71%), precuneus (82%) and superior temporal gyrus (94%). Combining all significant laterality indices improved the lateralization accuracy to 94% and 100% for the coherence and nodal degree laterality indices, respectively. Conclusion The associated variations in diffusion properties of fiber tracts quantified by DTI and coherence measures quantified by MEG with respect to epileptogenicity possibly reflect the chronic microstructural cerebral changes associated with functional interictal activity. The proposed methodology for using MEG and DTI to investigate diffusion abnormalities related to focal epileptogenicity and propagation may provide a further means of noninvasive lateralization. PMID:27060092

[Two cases of mesial temporal lobe epilepsy associated with old intracerebral hemorrhage in the lateral temporal lobe without "dual pathology"].

PubMed

Morioka, T; Nishio, S; Hisada, K; Muraishi, M; Ishibashi, H; Mamiya, K; Ohfu, M; Fukui, M

1998-05-01

Two cases of intractable temporal lobe epilepsy associated with old intracerebral hemorrhage in the lateral temporal lobe were reported. Although preoperative magnetic resonance imaging (MRI) failed to reveal hippocampal atrophy with T2 hyperintensity, electrocorticographic (ECoG) recording with chronic invasive subdural electrodes indicated the mesial temporal lobe to be an ictal onset zone. After anterior temporal lobectomy involving the lesion and hippocampectomy, the patients became seizure-free. Hippocampal sclerosis, namely "dual pathology", was not noted on histological examination. Careful ECoG recording with chronic subdural electrodes is mandatory even when the preoperative MRI does not demonstrate the radiological hippocampal sclerosis.

Effects of body position on lung density estimated from EIT data

NASA Astrophysics Data System (ADS)

Noshiro, Makoto; Ebihara, Kei; Sato, Ena; Nebuya, Satoru; Brown, Brian H.

2010-04-01

Normal subjects took the sitting, supine, prone, right lateral and left lateral positions during the measurement procedure. One minute epochs of EIT data were collected at the levels of the 3rd, 4th, 5th and 6th intercostal spaces in each position during normal tidal breathing. Lung density was then determined from the EIT data using the method proposed by Brown5. Lung density at the electrode level of the 6th intercostal space was different from that at almost any other levels in both male and female subjects, and lung density at the electrode levels of the 4th and 5th intercostal spaces in male subjects did not depend upon position.

Lateral carrier diffusion in InGaAs/GaAs coupled quantum dot-quantum well system

NASA Astrophysics Data System (ADS)

Pieczarka, M.; Syperek, M.; Biegańska, D.; Gilfert, C.; Pavelescu, E. M.; Reithmaier, J. P.; Misiewicz, J.; Sek, G.

2017-05-01

The lateral carrier diffusion process is investigated in coupled InGaAs/GaAs quantum dot-quantum well (QD-QW) structures by means of spatially resolved photoluminescence spectroscopy at low temperature. Under non-resonant photo-excitation above the GaAs bandgap, the lateral carrier transport reflected in the distorted electron-hole pair emission profiles is found to be mainly governed by high energy carriers created within the 3D density of states of GaAs. In contrast, for the case of resonant excitation tuned to the QW-like ground state of the QD-QW system, the emission profiles remain unaffected by the excess kinetic energy of carriers and local phonon heating within the pump spot. The lateral diffusion lengths are determined and present certain dependency on the coupling strength between QW and QDs. While for a strongly coupled structure the diffusion length is found to be around 0.8 μm and monotonically increases up to 1.4 μm with the excitation power density, in weakly coupled structures, it is determined to ca. 1.6 μm and remained virtually independent of the pumping power density.

Lateral diffusion of inositol 1,4,5-trisphosphate receptor type 1 in Purkinje cells is regulated by calcium and actin filaments.

PubMed

Fukatsu, Kazumi; Bannai, Hiroko; Inoue, Takafumi; Mikoshiba, Katsuhiko

2010-09-01

Inositol 1,4,5-trisphosphate receptor type 1 (IP(3) R1) is an intracellular Ca(2+) release channel that plays crucial roles in the functions of Purkinje cells. The dynamics of IP(3) R1 on the endoplasmic reticulum membrane and the distribution of IP(3) R1 in neurons are thought to be important for the spatial regulation of Ca(2+) release. In this study, we analyzed the lateral diffusion of IP(3) R1 in Purkinje cells in cerebellar slice cultures using fluorescence recovery after photobleaching. In the dendrites of Purkinje cells, IP(3) R1 showed lateral diffusion with an effective diffusion constant of approximately 0.30 μm(2) /s, and the diffusion of IP(3) R1 was negatively regulated by actin filaments. We found that actin filaments were also involved in the regulation of IP(3) R1 diffusion in the spine of Purkinje cells. Glutamate or quisqualic acid stimulation, which activates glutamate receptors and leads to a Ca(2+) transient in Purkinje cells, decreased the diffusion of IP(3) R1 and increased the density of actin in spines. These findings indicate that the neuronal activity-dependent augmentation of actin contributes to the stabilization of IP(3) R1 in spines. © 2010 The Authors. Journal Compilation © 2010 International Society for Neurochemistry.

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.

Fractal analysis of lateral movement in biomembranes.

PubMed

Gmachowski, Lech

2018-04-01

Lateral movement of a molecule in a biomembrane containing small compartments (0.23-μm diameter) and large ones (0.75 μm) is analyzed using a fractal description of its walk. The early time dependence of the mean square displacement varies from linear due to the contribution of ballistic motion. In small compartments, walking molecules do not have sufficient time or space to develop an asymptotic relation and the diffusion coefficient deduced from the experimental records is lower than that measured without restrictions. The model makes it possible to deduce the molecule step parameters, namely the step length and time, from data concerning confined and unrestricted diffusion coefficients. This is also possible using experimental results for sub-diffusive transport. The transition from normal to anomalous diffusion does not affect the molecule step parameters. The experimental literature data on molecular trajectories recorded at a high time resolution appear to confirm the modeled value of the mean free path length of DOPE for Brownian and anomalous diffusion. Although the step length and time give the proper values of diffusion coefficient, the DOPE speed calculated as their quotient is several orders of magnitude lower than the thermal speed. This is interpreted as a result of intermolecular interactions, as confirmed by lateral diffusion of other molecules in different membranes. The molecule step parameters are then utilized to analyze the problem of multiple visits in small compartments. The modeling of the diffusion exponent results in a smooth transition to normal diffusion on entering a large compartment, as observed in experiments.

Resistance switching mode transformation in SrRuO3/Cr-doped SrZrO3/Pt frameworks via a thermally activated Ti out-diffusion process

PubMed Central

Jo, Yongcheol; Jung, Kyooho; Kim, Jongmin; Woo, Hyeonseok; Han, Jaeseok; Kim, Hyungsang; Hong, Jinpyo; Lee, Jeon-Kook; Im, Hyunsik

2014-01-01

This work reports on a mechanism for irreversible resistive switching (RS) transformation from bipolar to unipolar RS behavior in SrRuO3 (SRO)/Cr-doped SrZrO3 (SZO:Cr)/Pt capacitor structures prepared on a Ti/SiO2/Si substrate. Counter-clockwise bipolar RS memory current-voltage (I–V) characteristics are observed within the RS voltage window of −2.5 to +1.9 V, with good endurance and retention properties. As the bias voltage increases further beyond 4 V under a forward bias, a forming process occurs resulting in irreversible RS mode transformation from bipolar to unipolar mode. This switching mode transformation is a direct consequence of thermally activated Ti out-diffusion from a Ti adhesion layer. Transition metal Ti effectively out-diffuses through the loose Pt electrode layer at high substrate temperatures, leading to the unintended formation of a thin titanium oxide (TiOx where x < 2) layer between the Pt electrode and the SZO:Cr layer as well as additional Ti atoms in the SZO:Cr layer. Cross-sectional scanning electron microscopy, transmission electron microscopy and Auger electron spectroscopy depth-profile measurements provided apparent evidence of the Ti out-diffusion phenomenon. We propose that the out-diffusion-induced additional Ti atoms in the SZO:Cr layer contributes to the creation of the metallic filamentary channels. PMID:25483325

Non-Additive Voltametric Currents From a Mixture of Two, Three and Four Redox-Active Compounds and Electroanalytical Implications

NASA Technical Reports Server (NTRS)

Dass, Amala; Oh, Woon Su; Gao, Xue-Rong; Rawashdeh, Abdel M.; Leventis, Nicholas

2004-01-01

We have published recently the effect of dissimilar diffusion coefficients on the size of the voltammetric waves from a mixture of two redox-active compounds. Similarly, at the potential range where three redox-active species, decamethylferrocene (dMeFc), ferrocene (Fc) and N-methylphenothiazine (MePTZ), are oxidized simultaneously with rates controlled by linear diffusion, electrogenerated radicals diffusing outwards from the electrode react with the original species diffusing towards the electrode from the bulk; thus, Fc(+) reacts with dMeFc producing Fc and dMeFc(+), while MePTZ(+) reacts both with dMeFc producing MePTZ and dMeFc(+), and with Fc producing MePTZ and Fc(+). These reactions replace dMeFc with Fc at the second plateau, and both dMeFc and Fc with MePTZ at the third plateau. Since the diffusion coefficients of the three species are not equal, the mass-transfer limited currents of the second and the third oxidation wave plateaus change by approx. 10%. Numerical simulations of the experimental voltamograms support this mechanism. Similar results were also obtained for a mixture of four redoxactive compounds. The implications of this non-additive nature of currents on: (a) the use of internal voltammetric standards for quantitative analysis of a mixture of redox-active compounds; and, (b) the half wave potentials (E1/2) of the 2nd, 3rd and 4th waves for qualitative analysis, will be discussed.

Electrochemical hydrogenation of thiophene on SPE electrodes

NASA Astrophysics Data System (ADS)

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

2017-01-01

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

An advanced model framework for solid electrolyte intercalation batteries.

PubMed

Landstorfer, Manuel; Funken, Stefan; Jacob, Timo

2011-07-28

Recent developments of solid electrolytes, especially lithium ion conductors, led to all solid state batteries for various applications. In addition, mathematical models sprout for different electrode materials and battery types, but are missing for solid electrolyte cells. We present a mathematical model for ion flux in solid electrolytes, based on non-equilibrium thermodynamics and functional derivatives. Intercalated ion diffusion within the electrodes is further considered, allowing the computation of the ion concentration at the electrode/electrolyte interface. A generalized Frumkin-Butler-Volmer equation describes the kinetics of (de-)intercalation reactions and is here extended to non-blocking electrodes. Using this approach, numerical simulations were carried out to investigate the space charge region at the interface. Finally, discharge simulations were performed to study different limitations of an all solid state battery cell. This journal is © the Owner Societies 2011

Feedback‐amplified electrochemical dual‐plate boron‐doped diamond microtrench detector for flow injection analysis

PubMed Central

Lewis, Grace E. M.; Gross, Andrew J.; Kasprzyk‐Hordern, Barbara; Lubben, Anneke T.

2015-01-01

An electrochemical flow cell with a boron‐doped diamond dual‐plate microtrench electrode has been developed and demonstrated for hydroquinone flow injection electroanalysis in phosphate buffer pH 7. Using the electrochemical generator‐collector feedback detector improves the sensitivity by one order of magnitude (when compared to a single working electrode detector). The diffusion process is switched from an analyte consuming “external” process to an analyte regenerating “internal” process with benefits in selectivity and sensitivity. PMID:25735831

Theoretical approach to oxygen atom degradation of silver

NASA Technical Reports Server (NTRS)

Fromhold, Albert T., Jr.; Noh, Seung; Beshears, Ronald; Whitaker, Ann F.; Little, Sally A.

1987-01-01

Based on available Rutherford backscattering spectrometry (RBS), proton induced X-ray emission (PIXE) and ellipsometry data obtained on silver specimens subjected to atomic oxygen attack in low Earth orbit STS flight 41-G, a theory was developed to model the oxygen atom degradation of silver. The diffusion of atomic oxygen in a microscopically nonuniform medium is an essential constituent of the theory. The driving force for diffusion is the macroscopic electrochemical potential gradient developed between the specimen surface exposed to the ambient and the bulk of the silver specimen. The longitudinal electric effect developed parallel to the gradient is modified by space charge of the diffusing charged species. Lateral electric fields and concentration differences also exist due to the nonuniform nature of the medium. The lateral concentration differences are found to be more important than the lateral electric fields in modifying the diffusion rate. The model was evaluated numerically. Qualitative agreement exists between the kinetics predicted by the theory and kinetic data taken in ground-based experiments utilizing a plasma asher.

A sphingolipid-dependent diffusion barrier confines ER stress to the yeast mother cell

PubMed Central

Clay, Lori; Caudron, Fabrice; Denoth-Lippuner, Annina; Boettcher, Barbara; Buvelot Frei, Stéphanie; Snapp, Erik Lee; Barral, Yves

2014-01-01

In many cell types, lateral diffusion barriers compartmentalize the plasma membrane and, at least in budding yeast, the endoplasmic reticulum (ER). However, the molecular nature of these barriers, their mode of action and their cellular functions are unclear. Here, we show that misfolded proteins of the ER remain confined into the mother compartment of budding yeast cells. Confinement required the formation of a lateral diffusion barrier in the form of a distinct domain of the ER-membrane at the bud neck, in a septin-, Bud1 GTPase- and sphingolipid-dependent manner. The sphingolipids, but not Bud1, also contributed to barrier formation in the outer membrane of the dividing nucleus. Barrier-dependent confinement of ER stress into the mother cell promoted aging. Together, our data clarify the physical nature of lateral diffusion barriers in the ER and establish the role of such barriers in the asymmetric segregation of proteotoxic misfolded proteins during cell division and aging. DOI: http://dx.doi.org/10.7554/eLife.01883.001 PMID:24843009

Light emitting ceramic device

DOEpatents

Valentine, Paul; Edwards, Doreen D.; Walker, Jr., William John; Slack, Lyle H.; Brown, Wayne Douglas; Osborne, Cathy; Norton, Michael; Begley, Richard

2010-05-18

A light-emitting ceramic based panel, hereafter termed "electroceramescent" panel, is herein claimed. The electroceramescent panel is formed on a substrate providing mechanical support as well as serving as the base electrode for the device. One or more semiconductive ceramic layers directly overlay the substrate, and electrical conductivity and ionic diffusion are controlled. Light emitting regions overlay the semiconductive ceramic layers, and said regions consist sequentially of a layer of a ceramic insulation layer and an electroluminescent layer, comprised of doped phosphors or the equivalent. One or more conductive top electrode layers having optically transmissive areas overlay the light emitting regions, and a multi-layered top barrier cover comprising one or more optically transmissive non-combustible insulation layers overlay said top electrode regions.

A theoretical model to determine the capacity performance of shape-specific electrodes

NASA Astrophysics Data System (ADS)

Yue, Yuan; Liang, Hong

2018-06-01

A theory is proposed to explain and predict the electrochemical process during reaction between lithium ions and electrode materials. In the model, the process of reaction is proceeded into two steps, surface adsorption and diffusion of lithium ions. The surface adsorption is an instantaneous process for lithium ions to adsorb onto the surface sites of active materials. The diffusion of lithium ions into particles is determined by the charge-discharge condition. A formula to determine the maximum specific capacity of active materials at different charging rates (C-rates) is derived. The maximum specific capacity is correlated to characteristic parameters of materials and cycling - such as size, aspect ratio, surface area, and C-rate. Analysis indicates that larger particle size or greater aspect ratio of active materials and faster C-rates can reduce maximum specific capacity. This suggests that reducing particle size of active materials and slowing the charge-discharge speed can provide enhanced electrochemical performance of a battery cell. Furthermore, the model is validated by published experimental results. This model brings new understanding in quantification of electrochemical kinetics and capacity performance. It enables development of design strategies for novel electrodes and future generation of energy storage devices.

Random Walk Analysis of the Effect of Mechanical Degradation on All-Solid-State Battery Power

DOE PAGES

Bucci, Giovanna; Swamy, Tushar; Chiang, Yet-Ming; ...

2017-09-06

Mechanical and electrochemical phenomena are coupled in defining the battery reliability, particularly for solid-state batteries. Micro-cracks act as barriers to Li-ion diffusion in the electrolyte, increasing the average electrode’s tortuosity. In our previous work, we showed that solid electrolytes are likely to suffer from mechanical degradation if their fracture energy is lower than 4 J m -2 [G. Bucci, T. Swamy, Y.-M. Chiang, and W. C. Carter, J. Mater. Chem. A (2017)]. Here we study the effect of electrolyte micro-cracking on the effective conductivity of composite electrodes. Via random analyzes, we predict the average diffusivity of lithium in a solid-statemore » electrode to decrease linearly with the extension of mechanical degradation. Furthermore, the statistical distribution of first passage times indicates that the microstructure becomes more and more heterogeneous as damage progresses. In addition to power and capacity loss, a non-uniform increase of the electrode tortuosity can lead to heterogeneous lithiation and further stress localization. Finally, the understanding of these phenomena at the mesoscale is essential to the implementation of safe high-energy solid-state batteries.« less

Eliminating micro-porous layer from gas diffusion electrode for use in high temperature polymer electrolyte membrane fuel cell

NASA Astrophysics Data System (ADS)

Su, Huaneng; Xu, Qian; Chong, Junjie; Li, Huaming; Sita, Cordellia; Pasupathi, Sivakumar

2017-02-01

In this work, we report a simple strategy to improve the performance of high temperature polymer electrolyte membrane fuel cell (HT-PEMFC) by eliminating the micro-porous layer (MPL) from its gas diffusion electrodes (GDEs). Due to the absence of liquid water and the general use of high amount of catalyst, the MPL in a HT-PEMFC system works limitedly. Contrarily, the elimination of the MPL leads to an interlaced micropore/macropore composited structure in the catalyst layer (CL), which favors gas transport and catalyst utilization, resulting in a greatly improved single cell performance. At the normal working voltage (0.6 V), the current density of the GDE eliminated MPL reaches 0.29 A cm-2, and a maximum power density of 0.54 W cm-2 at 0.36 V is obtained, which are comparable to the best results yet reported for the HT-PEMFCs with similar Pt loading and operated using air. Furthermore, the MPL-free GDE maintains an excellent durability during a preliminary 1400 h HT-PEMFC operation, owing to its structure advantages, indicating the feasibility of this electrode for practical applications.

Random Walk Analysis of the Effect of Mechanical Degradation on All-Solid-State Battery Power

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

Bucci, Giovanna; Swamy, Tushar; Chiang, Yet-Ming

Mechanical and electrochemical phenomena are coupled in defining the battery reliability, particularly for solid-state batteries. Micro-cracks act as barriers to Li-ion diffusion in the electrolyte, increasing the average electrode’s tortuosity. In our previous work, we showed that solid electrolytes are likely to suffer from mechanical degradation if their fracture energy is lower than 4 J m -2 [G. Bucci, T. Swamy, Y.-M. Chiang, and W. C. Carter, J. Mater. Chem. A (2017)]. Here we study the effect of electrolyte micro-cracking on the effective conductivity of composite electrodes. Via random analyzes, we predict the average diffusivity of lithium in a solid-statemore » electrode to decrease linearly with the extension of mechanical degradation. Furthermore, the statistical distribution of first passage times indicates that the microstructure becomes more and more heterogeneous as damage progresses. In addition to power and capacity loss, a non-uniform increase of the electrode tortuosity can lead to heterogeneous lithiation and further stress localization. Finally, the understanding of these phenomena at the mesoscale is essential to the implementation of safe high-energy solid-state batteries.« less

Superior ionic and electronic properties of ReN2 monolayers for Na-ion battery electrodes.

PubMed

Zhang, Shi-Hao; Liu, Bang-Gui

2018-08-10

Excellent monolayer electrode materials can be used to design high-performance alkali-metal-ion batteries. Here, we propose two-dimensional ReN 2 monolayers as superior sodium-ion battery materials. Our total energy optimization results in a buckled tetragonal structure for the ReN 2 monolayer, and our phonon spectrum and elastic moduli prove that it is dynamically and mechanically stable. Further investigations show that it is metallic and still keeps its metallic feature after the adsorption of Na or K atoms, and the adsorption of Na (or K) atoms changes the lattice parameters by 3.2% (or 3.8%) at most. Its maximum capacity reaches 751 mA h g -1 for Na-ion batteries or 250 mA h g -1 for K-ion batteries, and the diffusion barrier is only 0.027 eV for the Na atom or 0.127 eV for the K atom. The small lattice changes, high storage capacity, metallic feature, and extremely low ion diffusion barriers make the ReN 2 monolayers a superior electrode material for Na-ion rechargeable batteries with ultrafast charging/discharging processes.

Nitrogen-doped carbonaceous catalysts for gas-diffusion cathodes for alkaline aluminum-air batteries

NASA Astrophysics Data System (ADS)

Davydova, E. S.; Atamanyuk, I. N.; Ilyukhin, A. S.; Shkolnikov, E. I.; Zhuk, A. Z.

2016-02-01

Cobalt tetramethoxyphenyl porphyrin and polyacrylonitrile - based catalysts for oxygen reduction reaction were synthesized and characterized by means of SEM, TEM, XPS, BET, limited evaporation method, rotating disc and rotating ring-disc electrode methods. Half-cell and Al-air cell tests were carried out to determine the characteristics of gas-diffusion cathodes. Effect of active layer thickness and its composition on the characteristics of the gas-diffusion cathodes was investigated. Power density of 300 mW cm-2 was achieved for alkaline Al-air cell with an air-breathing polyacrylonitrile-based cathode.

Uranium migration in spark plasma sintered W/UO2 CERMETS

NASA Astrophysics Data System (ADS)

Tucker, Dennis S.; Wu, Yaqiao; Burns, Jatuporn

2018-03-01

W/UO2 CERMET samples were sintered in a Spark Plasma Sintering (SPS) furnace at various temperature under vacuum and pressure. High Resolution Transmission Electron Microscopy (HRTEM) with Energy Dispersive Spectroscopy (EDS) was performed on the samples to determine interface structures and uranium diffusion from the UO2 particles into the tungsten matrix. Local Electrode Atom Probe (LEAP) was also performed to determine stoichiometry of the UO2 particles. It was seen that uranium diffused approximately 10-15 nm into the tungsten matrix. This is explained in terms of production of oxygen vacancies and Fick's law of diffusion.

An electrocorticographic electrode array for simultaneous recording from medial, lateral, and intrasulcal surface of the cortex in macaque monkeys

PubMed Central

Fukushima, Makoto; Saunders, Richard C.; Mullarkey, Matthew; Doyle, Alexandra M.; Mishkin, Mortimer; Fujii, Naotaka

2014-01-01

Background Electrocorticography (ECoG) permits recording electrical field potentials with high spatiotemporal resolution over a large part of the cerebral cortex. Application of chronically implanted ECoG arrays in animal models provides an opportunity to investigate global spatiotemporal neural patterns and functional connectivity systematically under various experimental conditions. Although ECoG is conventionally used to cover the gyral cortical surface, recent studies have shown the feasibility of intrasulcal ECoG recordings in macaque monkeys. New Method Here we developed a new ECoG array to record neural activity simultaneously from much of the medial and lateral cortical surface of a single hemisphere, together with the supratemporal plane (STP) of the lateral sulcus in macaque monkeys. The ECoG array consisted of 256 electrodes for bipolar recording at 128 sites. Results We successfully implanted the ECoG array in the left hemisphere of three rhesus monkeys. The electrodes in the auditory and visual cortex detected robust event related potentials to auditory and visual stimuli, respectively. Bipolar recording from adjacent electrode pairs effectively eliminated chewing artifacts evident in monopolar recording, demonstrating the advantage of using the ECoG array under conditions that generate significant movement artifacts. Comparison with Existing Methods Compared with bipolar ECoG arrays previously developed for macaque monkeys, this array significantly expands the number of cortical target areas in gyral and intralsulcal cortex. Conclusions This new ECoG array provides an opportunity to investigate global network interactions among gyral and intrasulcal cortical areas. PMID:24972186

Electrochemical polishing of notches

DOEpatents

Kephart, A.R.; Alberts, A.H.

1989-02-21

An apparatus and method are disclosed for the selective electrochemical polishing of a lateral tip of a deep longitudinal notch in a work piece used to test crack initiation properties of materials. A DC power source is connected to the work piece and to an electrode disposed laterally along the distal end of an insulated body which is inserted in the longitudinal notch. The electrode and distal end of the body are disposed along the tip of the notch, but are spaced from the notch so as to provide a lateral passage for an electrolyte. The electrolyte is circulated through the passage so that the electrolyte only contacts the work piece adjacent the passage. Conveniently, the electrolyte is circulated by use of an inlet tube and an outlet tube provided at opposite ends of the passage. These tubes are preferably detachably located adjacent the ends of the passage and suitable seals are provided. A holding device including arms to which the tubes are attached is conveniently used to rapidly and easily locate the test specimen with the passage aligned with the tubes. The electrode is preferably a wire which is located in grooves along the distal end of the insulated body and up one side of the body or a plastic sheath insulated thin metal strip. 4 figs.

Electrochemical polishing of notches

DOEpatents

Kephart, Alan R.; Alberts, Alfred H.

1989-01-01

An apparatus and method are disclosed for the selective electrochemical polishing of a lateral tip of a deep longitudinal notch in a work piece used to test crack initiation properties of materials. A DC power source is connected to the work piece and to an electrode disposed laterally along the distal end of an insulated body which is inserted in the longitudinal notch. The electrode and distal end of the body are disposed along the tip of the notch, but are spaced from the notch so as to provide a lateral passage for an electrolyte. The electrolyte is circulated through the passage so that the electrolyte only contacts the work piece adjacent the passage. Conveniently, the electrolyte is circulated by use of an inlet tube and an outlet tube provided at opposite ends of the passage. These tubes are preferably detachably located adjacent the ends of the passage and suitable seals are provided. A holding device including arms to which the tubes are attached is conveniently used to rapidly and easily locate the test specimen with the passage aligned with the tubes. The electrode is preferably a wire which is located in grooves along the distal end of the insulated body and up one side of the body or a plastic sheath insulated thin metal strip.

Novel H+-Ion Sensor Based on a Gated Lateral BJT Pair

PubMed Central

Yuan, Heng; Zhang, Jixing; Cao, Chuangui; Zhang, Gangyuan; Zhang, Shaoda

2015-01-01

An H+-ion sensor based on a gated lateral bipolar junction transistor (BJT) pair that can operate without the classical reference electrode is proposed. The device is a special type of ion-sensitive field-effect transistor (ISFET). Classical ISFETs have the advantage of miniaturization, but  they are difficult to fabricate by a single fabrication process because of the bulky and brittle reference electrode materials. Moreover, the reference electrodes need to be separated from the sensor device in some cases. The proposed device is composed of two gated lateral BJT components, one of which had a silicide layer while the other was without the layer. The two components were operated under the metal-oxide semiconductor field-effect transistor (MOSFET)-BJT hybrid mode, which can be controlled by emitter voltage and base current. Buffer solutions with different pH values were used as the sensing targets to verify the characteristics of the proposed device. Owing to their different sensitivities, both components could simultaneously detect the H+-ion concentration and function as a reference to each other. Per the experimental results, the sensitivity of the proposed device was found to be approximately 0.175 μA/pH. This experiment demonstrates enormous potential to lower the cost of the ISFET-based sensor technology. PMID:26703625

Diffusion tensor imaging demonstrates brainstem and cerebellar abnormalities in congenital central hypoventilation syndrome.

PubMed

Kumar, Rajesh; Macey, Paul M; Woo, Mary A; Alger, Jeffry R; Harper, Ronald M

2008-09-01

Congenital central hypoventilation syndrome (CCHS) patients show reduced breathing drive during sleep, decreased hypoxic and hypercapnic ventilatory responses, and autonomic and affective deficits, suggesting both brainstem and forebrain injuries. Forebrain damage was previously described in CCHS, but methodological limitations precluded detection of brainstem injury, a concern because genetic mutations in CCHS target brainstem autonomic nuclei. To assess brainstem and cerebellar areas, we used diffusion tensor imaging-based measures, namely axial diffusivity, reflecting water diffusion parallel to fibers, and sensitive to axonal injury, and radial diffusivity, measuring diffusion perpendicular to fibers, and indicative of myelin injury. Diffusion tensor imaging was performed in 12 CCHS and 26 controls, and axial and radial diffusivity maps were compared between groups using analysis of covariance (covariates; age and gender). Increased axial diffusivity in CCHS appeared within the lateral medulla and clusters with injury extended from the dorsal midbrain through the periaqueductal gray, raphé, and superior cerebellar decussation, ventrally to the basal-pons. Cerebellar cortex and deep nuclei, and the superior and inferior cerebellar peduncles showed increased radial diffusivity. Midbrain, pontine, and lateral medullary structures, and the cerebellum and its fiber systems are injured in CCHS, likely contributing to the characteristics found in the syndrome.

Electric-field noise from carbon-adatom diffusion on a Au(110) surface: First-principles calculations and experiments

NASA Astrophysics Data System (ADS)

Kim, E.; Safavi-Naini, A.; Hite, D. A.; McKay, K. S.; Pappas, D. P.; Weck, P. F.; Sadeghpour, H. R.

2017-03-01

The decoherence of trapped-ion quantum gates due to heating of their motional modes is a fundamental science and engineering problem. This heating is attributed to electric-field noise arising from the trap-electrode surfaces. In this work, we investigate the source of this noise by focusing on the diffusion of carbon-containing adsorbates on the surface of Au(110). We show by density functional theory, based on detailed scanning probe microscopy, how the carbon adatom diffusion on the gold surface changes the energy landscape and how the adatom dipole moment varies with the diffusive motion. A simple model for the diffusion noise, which varies quadratically with the variation of the dipole moment, predicts a noise spectrum, in accordance with the measured values.

Imaging of the Li spatial distribution within V 2O 5 cathode in a coin cell by neutron computed tomography

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

Zhang, Yuxuan; Chandran, K. S. Ravi; Bilheux, Hassina Z.

An understanding of Lithium (Li) spatial distribution within the electrodes of a Li-ion cell, during charge and discharge cycles, is essential to optimize the electrode parameters for increased performance under cycling. In this work, it is demonstrated that the spatial distribution of Li within Vanadium Pentoxide (V 2O 5) electrodes of a small coin cell can be imaged by neutron computed tomography. The neutron attenuation data has been used to construct the three-dimensional Li spatial images. Specifically, it is shown that there is sufficient neutron imaging contrast between lithiated and delithiated regions of V 2O 5 electrode making it possiblemore » to map Li distributions even in small electrodes with thicknesses <1 mm. The images reveal that the Li spatial distribution is inhomogeneous and a relatively higher C-rate leads to more non-uniform Li distribution after Li insertion. The non-uniform distribution suggests the limitation of Li diffusion within the electrode during the lithiation process under the relatively high cycling rates.« less

Direct Inkjet Printing of Silver Source/Drain Electrodes on an Amorphous InGaZnO Layer for Thin-Film Transistors

PubMed Central

Ning, Honglong; Chen, Jianqiu; Fang, Zhiqiang; Tao, Ruiqiang; Cai, Wei; Yao, Rihui; Hu, Shiben; Zhu, Zhennan; Zhou, Yicong; Yang, Caigui; Peng, Junbiao

2017-01-01

Printing technologies for thin-film transistors (TFTs) have recently attracted much interest owing to their eco-friendliness, direct patterning, low cost, and roll-to-roll manufacturing processes. Lower production costs could result if electrodes fabricated by vacuum processes could be replaced by inkjet printing. However, poor interfacial contacts and/or serious diffusion between the active layer and the silver electrodes are still problematic for achieving amorphous indium–gallium–zinc–oxide (a-IGZO) TFTs with good electrical performance. In this paper, silver (Ag) source/drain electrodes were directly inkjet-printed on an amorphous a-IGZO layer to fabricate TFTs that exhibited a mobility of 0.29 cm2·V−1·s−1 and an on/off current ratio of over 105. To the best of our knowledge, this is a major improvement for bottom-gate top-contact a-IGZO TFTs with directly printed silver electrodes on a substrate with no pretreatment. This study presents a promising alternative method of fabricating electrodes of a-IGZO TFTs with desirable device performance. PMID:28772410

Nitrogen-Doped Banana Peel–Derived Porous Carbon Foam as Binder-Free Electrode for Supercapacitors

PubMed Central

Liu, Bingzhi; Zhang, Lili; Qi, Peirong; Zhu, Mingyuan; Wang, Gang; Ma, Yanqing; Guo, Xuhong; Chen, Hui; Zhang, Boya; Zhao, Zhuangzhi; Dai, Bin; Yu, Feng

2016-01-01

Nitrogen-doped banana peel–derived porous carbon foam (N-BPPCF) successfully prepared from banana peels is used as a binder-free electrode for supercapacitors. The N-BPPCF exhibits superior performance including high specific surface areas of 1357.6 m2/g, large pore volume of 0.77 cm3/g, suitable mesopore size distributions around 3.9 nm, and super hydrophilicity with nitrogen-containing functional groups. It can easily be brought into contact with an electrolyte to facilitate electron and ion diffusion. A comparative analysis on the electrochemical properties of BPPCF electrodes is also conducted under similar conditions. The N-BPPCF electrode offers high specific capacitance of 185.8 F/g at 5 mV/s and 210.6 F/g at 0.5 A/g in 6 M KOH aqueous electrolyte versus 125.5 F/g at 5 mV/s and 173.1 F/g at 0.5 A/g for the BPPCF electrode. The results indicate that the N-BPPCF is a binder-free electrode that can be used for high performance supercapacitors. PMID:28344275

Porous WO3/graphene/polyester textile electrode materials with enhanced electrochemical performance for flexible solid-state supercapacitors.

PubMed

Jin, Li-Na; Liu, Ping; Jin, Chun; Zhang, Jia-Nan; Bian, Shao-Wei

2018-01-15

In this work, a flexible and porous WO 3 /grapheme/polyester (WO 3 /G/PT) textile electrode was successfully prepared by in situ growing WO 3 on the fiber surface inside G/PT composite fabrics. The unique electrode structure facilitates to enhance the energy storage performance because the 3D conductive network constructed by the G/PT increase the electron transportation rate, nanotructured WO 3 exposed enhanced electrochemically active surface area and the hierarchically porous structure improved the electrolyte ion diffusion rate. The optimized WO 3 /G/PT textile electrode exhibited good electrochemical performance with a high areal capacitance of 308.2mFcm -2 at a scan rate of 2mVs -1 and excellent cycling stability. A flexible asymmetric supercapacitor (ASC) device was further fabricated by using the WO 3 /G/PT electrode and G/PT electrode, which exhibited a good specific capacitance of 167.6mFcm -3 and high energy density of 60μWhcm -3 at the power density of 2320 μWcm -3 . Copyright © 2017 Elsevier Inc. All rights reserved.

Direct Inkjet Printing of Silver Source/Drain Electrodes on an Amorphous InGaZnO Layer for Thin-Film Transistors.

PubMed

Ning, Honglong; Chen, Jianqiu; Fang, Zhiqiang; Tao, Ruiqiang; Cai, Wei; Yao, Rihui; Hu, Shiben; Zhu, Zhennan; Zhou, Yicong; Yang, Caigui; Peng, Junbiao

2017-01-10

Printing technologies for thin-film transistors (TFTs) have recently attracted much interest owing to their eco-friendliness, direct patterning, low cost, and roll-to-roll manufacturing processes. Lower production costs could result if electrodes fabricated by vacuum processes could be replaced by inkjet printing. However, poor interfacial contacts and/or serious diffusion between the active layer and the silver electrodes are still problematic for achieving amorphous indium-gallium-zinc-oxide (a-IGZO) TFTs with good electrical performance. In this paper, silver (Ag) source/drain electrodes were directly inkjet-printed on an amorphous a-IGZO layer to fabricate TFTs that exhibited a mobility of 0.29 cm²·V -1 ·s -1 and an on/off current ratio of over 10⁵. To the best of our knowledge, this is a major improvement for bottom-gate top-contact a-IGZO TFTs with directly printed silver electrodes on a substrate with no pretreatment. This study presents a promising alternative method of fabricating electrodes of a-IGZO TFTs with desirable device performance.

Nitrogen-Doped Banana Peel-Derived Porous Carbon Foam as Binder-Free Electrode for Supercapacitors.

PubMed

Liu, Bingzhi; Zhang, Lili; Qi, Peirong; Zhu, Mingyuan; Wang, Gang; Ma, Yanqing; Guo, Xuhong; Chen, Hui; Zhang, Boya; Zhao, Zhuangzhi; Dai, Bin; Yu, Feng

2016-01-15

Nitrogen-doped banana peel-derived porous carbon foam (N-BPPCF) successfully prepared from banana peels is used as a binder-free electrode for supercapacitors. The N-BPPCF exhibits superior performance including high specific surface areas of 1357.6 m²/g, large pore volume of 0.77 cm³/g, suitable mesopore size distributions around 3.9 nm, and super hydrophilicity with nitrogen-containing functional groups. It can easily be brought into contact with an electrolyte to facilitate electron and ion diffusion. A comparative analysis on the electrochemical properties of BPPCF electrodes is also conducted under similar conditions. The N-BPPCF electrode offers high specific capacitance of 185.8 F/g at 5 mV/s and 210.6 F/g at 0.5 A/g in 6 M KOH aqueous electrolyte versus 125.5 F/g at 5 mV/s and 173.1 F/g at 0.5 A/g for the BPPCF electrode. The results indicate that the N-BPPCF is a binder-free electrode that can be used for high performance supercapacitors.

The O2 reduction at the IFC modified O2 fuel cell electrode

NASA Technical Reports Server (NTRS)

Fielder, William L.; Singer, Joseph; Baldwin, Richard S.; Johnson, Richard E.

1992-01-01

The International Fuel Corporation (IFC) state of the art (SOA) O2 electrode (Au-10 percent Pt electrocatalyst by weight) is currently being used in the alkaline H2-O2 fuel cell in the NASA Space Shuttle. Recently, IFC modified O2 electrode, as a possible replacement for the SOA electrode. In the present study, O2 reduction data were obtained for the modified electrode at temperatures between 23.3 and 91.7 C. BET measurements gave an electrode BET surface area of about 2070 sq. cm/sq. cm of geometric surface area. The Tafel data could be fitted to two straight line regions. The slope for the lower region, designated as the 0.04 V/decade region, was temperature dependent, and the transfer coefficient was about 1.5. The 'apparent' energy of activation for this region was about 19 kcal/mol. An O2 reduction mechanism for this 0.04 region is presented. In the upper region, designated as the 0.08 V/decade region, diffusion may be the controlling process. Tafel data are presented to illustrate the increase in performance with increasing temperature.

Imaging of the Li spatial distribution within V2O5 cathode in a coin cell by neutron computed tomography

NASA Astrophysics Data System (ADS)

Zhang, Yuxuan; Chandran, K. S. Ravi; Bilheux, Hassina Z.

2018-02-01

An understanding of Lithium (Li) spatial distribution within the electrodes of a Li-ion cell, during charge and discharge cycles, is essential to optimize the electrode parameters for increased performance under cycling. In this work, it is demonstrated that the spatial distribution of Li within Vanadium Pentoxide (V2O5) electrodes of a small coin cell can be imaged by neutron computed tomography. The neutron attenuation data has been used to construct the three-dimensional Li spatial images. Specifically, it is shown that there is sufficient neutron imaging contrast between lithiated and delithiated regions of V2O5 electrode making it possible to map Li distributions even in small electrodes with thicknesses <1 mm. The images reveal that the Li spatial distribution is inhomogeneous and a relatively higher C-rate leads to more non-uniform Li distribution after Li insertion. The non-uniform distribution suggests the limitation of Li diffusion within the electrode during the lithiation process under the relatively high cycling rates.

Oriented Polyaniline Nanowire Arrays Grown on Dendrimer (PAMAM) Functionalized Multiwalled Carbon Nanotubes as Supercapacitor Electrode Materials.

PubMed

Jin, Lin; Jiang, Yu; Zhang, Mengjie; Li, Honglong; Xiao, Linghan; Li, Ming; Ao, Yuhui

2018-04-19

At present, PANI/MWNT composites have been paid more attention as promising electrode materials in supercapacitors. Yet some shortcomings still limit the widely application of PANI/MWNT electrolytes. In this work, in order to improve capacitance ability and long-term stability of electrode, a multi-amino dendrimer (PAMAM) had been covalently linked onto multi-walled carbon nanotubes (MWNT) as a bridge to facilitating covalent graft of polyaniline (PANI), affording P-MWNT/PANI electrode composites for supercapacitor. Surprisingly, ordered arrays of PANI nanowires on MWNT (setaria-like morphology) had been observed by scanning electron microscopy (SEM). Electrochemical properties of P-MWNT/PANI electrode had been characterized by cyclic voltammetry (CV) and galvanostatic charge-discharge technique. The specific capacitance and long cycle life of P-MWNT-PANI electrode material were both much higher than MWNT/PANI. These interesting results indicate that multi-amino dendrimer, PAMAM, covalently linked on MWNT provides more reaction sites for in-situ polymerization of ordered PANI, which could efficiently shorten the ion diffusion length in electrolytes and lead to making fully use of conducting materials.

Three-dimensional charge coupled device

DOEpatents

Conder, Alan D.; Young, Bruce K. F.

1999-01-01

A monolithic three dimensional charged coupled device (3D-CCD) which utilizes the entire bulk of the semiconductor for charge generation, storage, and transfer. The 3D-CCD provides a vast improvement of current CCD architectures that use only the surface of the semiconductor substrate. The 3D-CCD is capable of developing a strong E-field throughout the depth of the semiconductor by using deep (buried) parallel (bulk) electrodes in the substrate material. Using backside illumination, the 3D-CCD architecture enables a single device to image photon energies from the visible, to the ultra-violet and soft x-ray, and out to higher energy x-rays of 30 keV and beyond. The buried or bulk electrodes are electrically connected to the surface electrodes, and an E-field parallel to the surface is established with the pixel in which the bulk electrodes are located. This E-field attracts charge to the bulk electrodes independent of depth and confines it within the pixel in which it is generated. Charge diffusion is greatly reduced because the E-field is strong due to the proximity of the bulk electrodes.

Imaging of the Li spatial distribution within V 2O 5 cathode in a coin cell by neutron computed tomography

DOE PAGES

Zhang, Yuxuan; Chandran, K. S. Ravi; Bilheux, Hassina Z.

2017-11-30

An understanding of Lithium (Li) spatial distribution within the electrodes of a Li-ion cell, during charge and discharge cycles, is essential to optimize the electrode parameters for increased performance under cycling. In this work, it is demonstrated that the spatial distribution of Li within Vanadium Pentoxide (V 2O 5) electrodes of a small coin cell can be imaged by neutron computed tomography. The neutron attenuation data has been used to construct the three-dimensional Li spatial images. Specifically, it is shown that there is sufficient neutron imaging contrast between lithiated and delithiated regions of V 2O 5 electrode making it possiblemore » to map Li distributions even in small electrodes with thicknesses <1 mm. The images reveal that the Li spatial distribution is inhomogeneous and a relatively higher C-rate leads to more non-uniform Li distribution after Li insertion. The non-uniform distribution suggests the limitation of Li diffusion within the electrode during the lithiation process under the relatively high cycling rates.« less

Process for fabricating a charge coupled device

DOEpatents

Conder, Alan D.; Young, Bruce K. F.

2002-01-01

A monolithic three dimensional charged coupled device (3D-CCD) which utilizes the entire bulk of the semiconductor for charge generation, storage, and transfer. The 3D-CCD provides a vast improvement of current CCD architectures that use only the surface of the semiconductor substrate. The 3D-CCD is capable of developing a strong E-field throughout the depth of the semiconductor by using deep (buried) parallel (bulk) electrodes in the substrate material. Using backside illumination, the 3D-CCD architecture enables a single device to image photon energies from the visible, to the ultra-violet and soft x-ray, and out to higher energy x-rays of 30 keV and beyond. The buried or bulk electrodes are electrically connected to the surface electrodes, and an E-field parallel to the surface is established with the pixel in which the bulk electrodes are located. This E-field attracts charge to the bulk electrodes independent of depth and confines it within the pixel in which it is generated. Charge diffusion is greatly reduced because the E-field is strong due to the proximity of the bulk electrodes.

Sonography-guided recording for superficial peroneal sensory nerve conduction study.

PubMed

Kim, Ki Hoon; Park, Byung Kyu; Kim, Dong Hwee; Kim, Yuntae

2018-04-01

We sought to establish the optimal recording position for antidromic conduction of the superficial peroneal nerve (SPN) by using ultrasonography (USG). The sensory nerve action potentials (SNAPs) of the intermediate dorsal cutaneous nerve (IDCN) and medial dorsal cutaneous nerve (MDCN) in 64 limbs of 32 healthy participants were recorded (nerve conduction study [NCS]-1). Both nerves were identified by using USG, and the SNAPs were obtained from the USG-guided repositioned electrodes (NCS-2). The IDCN and MDCN were located at 29.3% ± 5.1% and 43.9% ± 4.9% of the intermalleolar distance from the lateral malleolus, respectively. Significantly greater amplitude was shown for SNAPs of both nerves in NCS-2 versus NCS-1. The optimal recording position is likely to be lateral, one-third from the lateral malleolus for the IDCN, and just lateral to the midpoint of the intermalleolar line for the MDCN. When the SPN response is unexpectedly attenuated, USG-guided repositioning of the electrodes should be considered. Muscle Nerve 57: 628-633, 2018. © 2017 Wiley Periodicals, Inc.

Application of a palladium hexacyanoferrate film-modified aluminum electrode to electrocatalytic oxidation of hydrazine.

PubMed

Razmi, Habib; Azadbakht, Azadeh; Sadr, Moayad Hossaini

2005-11-01

A palladium hexacyanoferrate (PdHCF) film as an electrocatalytic material was obtained at an aluminum (Al) electrode by a simple electroless dipping method. The modified Al electrode demonstrated a well-behaved redox couple due to the redox reaction of the PdHCF film. The PdHCF film showed an excellent electrocatalytic activity toward the oxidation of hydrazine. The electrocatalytic oxidation of hydrazine was studied by cyclic voltammetry and rotating disk electrode voltammetry techniques. A calibration graph obtained for the hydrazine consisted of two segments (localized at concentration ranges 0.39-10 and 20-75 mM). The rate constant k and transfer coefficient alpha for the catalytic reaction and the diffusion coefficient of hydrazine in the solution D, were found to be 3.11 x 10(3) M(-1) s(-1), 0.52 and 8.03 x 10(-6) cm2 s(-1) respectively. The modified electrode was used to amperometric determination of hydrazine in photographic developer. The interference of ascorbic acid and thiosulfate were investigated and greatly reduced using a thin film of Nafion on the modified electrode. The modified electrode indicated reproducible behavior and a high level of stability during electrochemical experiments, making it particularly suitable for analytical purposes.

Electrically induced mechanical precompression of ferroelectric plates

DOEpatents

Chen, P.J.

1987-03-02

A method of electrically inducing mechanical precompression of ferroelectric plate covered with electrodes utilizes the change in strains of the plate as functions of applied electric field. A first field polarizes and laterally shrinks the entire plate. An outer portion of the electrodes are removed, and an opposite field partially depolarizes and expands the central portion of the plate against the shrunk outer portion. 2 figs.

Electrically induced mechanical precompression of ferroelectric plates

DOEpatents

Chen, Peter J.

1987-01-01

A method of electrically inducing mechanical precompression of a ferroelectric plate covered with electrodes utilizes the change in strains of the plate as functions of applied electric field. A first field polarizes and laterally shrinks the entire plate. An outer portion of the electrodes are removed, and an opposite field partially depolarizes and expands the central portion of the plate against the shrunk outer portion.

LATERAL HEAT FLOW INFRARED THERMOGRAPHY FOR THICKNESS INDEPENDENT DETERMINATION OF THERMAL DIFFUSIVITY IN CFRP

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

Tralshawala, Nilesh; Howard, Don; Knight, Bryon

2008-02-28

In conventional infrared thermography, determination of thermal diffusivity requires thickness information. Recently GE has been experimenting with the use of lateral heat flow to determine thermal diffusivity without thickness information. This work builds on previous work at NASA Langley and Wayne State University but we incorporate thermal time of flight (tof) analysis rather than curve fitting to obtain quantitative information. We have developed appropriate theoretical models and a tof based data analysis framework to experimentally determine all components of thermal diffusivity from the time-temperature measurements. Initial validation was carried out using finite difference simulations. Experimental validation was done using anisotropicmore » carbon fiber reinforced polymer (CFRP) composites. We found that in the CFRP samples used, the in-plane component of diffusivity is about eight times larger than the through-thickness component.« less

Observational Inferences of Lateral Eddy Diffusivity in the Halocline of the Beaufort Gyre

NASA Astrophysics Data System (ADS)

Meneghello, Gianluca; Marshall, John; Cole, Sylvia T.; Timmermans, Mary-Louise

2017-12-01

Using Ekman pumping rates mediated by sea ice in the Arctic Ocean's Beaufort Gyre (BG), the magnitude of lateral eddy diffusivities required to balance downward pumping is inferred. In this limit—that of vanishing residual-mean circulation—eddy-induced upwelling exactly balances downward pumping. The implied eddy diffusivity varies spatially and decays with depth, with values of 50-400 m2/s. Eddy diffusivity estimated using mixing length theory applied to BG mooring data exhibits a similar decay with depth and range of values from 100 m2/s to more than 600 m2/s. We conclude that eddy diffusivities in the BG are likely large enough to balance downward Ekman pumping, arresting the deepening of the gyre and suggesting that eddies play a zero-order role in buoyancy and freshwater budgets of the BG.

Dynamics, Stability, and Evolutionary Patterns of Mesoscale Intrathermocline Vortices

DTIC Science & Technology

2016-12-01

physical oceanography, namely, the link between the basin-scale forcing of the ocean by air-sea fluxes and the dissipation of energy and thermal variance...at the microscale. 14. SUBJECT TERMS Meddy, intrathermocline, double diffusion, energy cascade, eddy, MITgcm, numerical simulation, interleaving...lateral intrusions, lateral diffusivity, heat flux 15. NUMBER OF PAGES 69 16. PRICE CODE 17. SECURITY CLASSIFICATION OF REPORT Unclassified 18

Molecular modification of highly degenerate semiconductor as an active electrode to enhance the performance of supercapacitors

NASA Astrophysics Data System (ADS)

Mundinamani, S. P.; Rabinal, M. K.

2014-12-01

Highly conducting antimony doped tin oxide (SnO2:Sb) films are electrografted with suitable organic molecules to study their electrolytic behavior. A series of organic molecules, such as heptanethiol, dodecanethiol and octadecanethiol are bonded to electrode surfaces. Electrolytic capacitors were formed on both unmodified and chemically modified electrodes using KCl and H2SO4 as electrolytes. This molecular modification significantly enhances the current levels in cyclic voltammograms, and there is a clear shift in oxidation/reduction peaks of these capacitors with scan rate. The results obey Randles-Sevcik relation, which indicates that there is enhancement of ionic diffusion at the electrode-electrolyte interface. There is a large enhancement in the values of specific capacitance (almost by 104 times) after the chemical modification. These measurements show that Faradaic reactions are responsible for charge storage/discharge process in these capacitors. Hence, the molecularly modified electrodes can be a good choice to increase the specific capacitance.

Evaluation of electrochemical, UV/VIS and Raman spectroelectrochemical detection of Naratriptan with screen-printed electrodes.

PubMed

Hernández, Carla Navarro; Martín-Yerga, Daniel; González-García, María Begoña; Hernández-Santos, David; Fanjul-Bolado, Pablo

2018-02-01

Naratriptan, active pharmaceutical ingredient with antimigraine activity was electrochemically detected in untreated screen-printed carbon electrodes (SPCEs). Cyclic voltammetry and differential pulse voltammetry were used to carry out quantitative analysis of this molecule (in a Britton-Robinson buffer solution at pH 3.0) through its irreversible oxidation (diffusion controlled) at a potential of +0.75V (vs. Ag pseudoreference electrode). Naratriptan oxidation product is an indole based dimer with a yellowish colour (maximum absorption at 320nm) so UV-VIS spectroelectrochemistry technique was used for the very first time as an in situ characterization and quantification technique for this molecule. A reflection configuration approach allowed its measurement over the untreated carbon based electrode. Finally, time resolved Raman Spectroelectrochemistry is used as a powerful technique to carry out qualitative and quantitative analysis of Naratriptan. Electrochemically treated silver screen-printed electrodes are shown as easy to use and cost-effective SERS substrates for the analysis of Naratriptan. Copyright © 2017 Elsevier B.V. All rights reserved.

Numerical modelling of needle-grid electrodes for negative surface corona charging system

NASA Astrophysics Data System (ADS)

Zhuang, Y.; Chen, G.; Rotaru, M.

2011-08-01

Surface potential decay measurement is a simple and low cost tool to examine electrical properties of insulation materials. During the corona charging stage, a needle-grid electrodes system is often used to achieve uniform charge distribution on the surface of the sample. In this paper, a model using COMSOL Multiphysics has been developed to simulate the gas discharge. A well-known hydrodynamic drift-diffusion model was used. The model consists of a set of continuity equations accounting for the movement, generation and loss of charge carriers (electrons, positive and negative ions) coupled with Poisson's equation to take into account the effect of space and surface charges on the electric field. Four models with the grid electrode in different positions and several mesh sizes are compared with a model that only has the needle electrode. The results for impulse current and surface charge density on the sample clearly show the effect of the extra grid electrode with various positions.

Simulations of induced-charge electro-osmosis in microfluidic devices

NASA Astrophysics Data System (ADS)

Ben, Yuxing

2005-03-01

Theories of nonlinear electrokinetic phenomena generally assume a uniform, neutral bulk electroylte in contact with a polarizable thin double layer near a metal or dielectric surface, which acts as a "capacitor skin". Induced-charge electro-osmosis (ICEO) is the general effect of nonlinear electro-osmotic slip, when an applied electric field acts on its own induced (diffuse) double-layer charge. In most theoretical and experimental work, ICEO has been studied in very simple geometries, such as colloidal spheres and planar, periodic micro-electrode arrays. Here we use finite-element simulations to predict how more complicated geometries of polarizable surfaces and/or electrodes yield flow profiles with subtle dependence on the amplitude and frequency of the applied voltage. We also consider how the simple model equations break down, due to surface conduction, bulk diffusion, and concentration polarization, for large applied voltages (as in most experiments).

Preparation and evaluation of advanced electrocatalysts for phosphoric acid fuel cells

NASA Technical Reports Server (NTRS)

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

1980-01-01

Results are presented for hydrogen oxidation and hydrogen oxidation poisoned by carbon monoxide at levels between 0 and 30%. Due to the high activities that are now being observed for our platinum based electrocatalysts, the hydrogen concentrations were reduced to 10% levels in the gas supplies. Perturbation techniques were used to determine that a mechanism for the efficient operation of our porous gas diffusion electrodes is diffusion of the carbon monoxide out of the electrode structure through the electrolyte film on the electro-catalyst. A survey of the literature on platinum group materials (PGM) was carried out so that an identification of successful electrocatalysts could be made. Two PGM electrocatalysts were prepared and performance data for hydrogen oxidation in hot phosphoric acid in the presence of high carbon monoxide concentrations showed that they matched the best platinum on carbon electrocatalysts but with an electrocatalyst cost that was half of the platinum catalyst cost.

Characterization of chaotic electroconvection near flat electrodes under oscillatory voltages

NASA Astrophysics Data System (ADS)

Kim, Jeonglae; Davidson, Scott; Mani, Ali

2017-11-01

Onset of hydrodynamic instability and chaotic electroconvection in aqueous systems are studied by directly solving the two-dimensional coupled Poisson-Nernst-Planck and Navier-Stokes equations. An aqueous binary electrolyte is bounded by two planar electrodes where time-harmonic voltage is applied at a constant oscillation frequency. The governing equations are solved using a fully-conservative second-order-accurate finite volume discretization and a second-order implicit Euler time advancement. At a sufficiently high amplitude of applied voltage, the system exhibits chaotic behaviors involving strong hydrodynamic mixing and enhanced electroconvection. The system responses are characterized as a function of oscillation frequency, voltage magnitude, and the ratio of diffusivities of two ion species. Our results indicate that electroconvection is most enhanced for frequencies on the order of inverse system RC time scale. We will discuss the dependence of this optimal frequency on the asymmetry of the diffusion coefficients of ionic species. Supported by the Stanford's Precourt Institute.

Microelectrode-assisted low-voltage atmospheric pressure glow discharge in air

NASA Astrophysics Data System (ADS)

Liu, Wenzheng; Zhao, Shuai; Niu, Jiangqi; Chai, Maolin

2017-09-01

During the process of discharge, appropriately changing the paths corresponding to electric field lines and the field strength distribution along these paths, as well as increasing the number of initial electrons, can effectively enhance the uniformity of discharge and inhibit the formation of filamentary discharge. A method is proposed that uses a microelectrode to initiate the macroscopic discharge phenomenon. An asymmetric structure was designed comprising a single electrode of carbon fiber; this electrode structure is of helical-contact type. Benefitting from the special electric field distribution and the microdischarge process, a three-dimensional atmospheric pressure glow discharge was achieved in air, characterized by low discharge voltage, low energy consumption, good diffusion performance, and less ozone generation. The plasma studied is uniform and stable with good diffusion characteristics and low levels of contaminants and hence has potential applications in the field of air purification.

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

Monolithic integration of a MOSFET with a MEMS device

DOEpatents

Bennett, Reid; Draper, Bruce

2003-01-01

An integrated microelectromechanical system comprises at least one MOSFET interconnected to at least one MEMS device on a common substrate. A method for integrating the MOSFET with the MEMS device comprises fabricating the MOSFET and MEMS device monolithically on the common substrate. Conveniently, the gate insulator, gate electrode, and electrical contacts for the gate, source, and drain can be formed simultaneously with the MEMS device structure, thereby eliminating many process steps and materials. In particular, the gate electrode and electrical contacts of the MOSFET and the structural layers of the MEMS device can be doped polysilicon. Dopant diffusion from the electrical contacts is used to form the source and drain regions of the MOSFET. The thermal diffusion step for forming the source and drain of the MOSFET can comprise one or more of the thermal anneal steps to relieve stress in the structural layers of the MEMS device.

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.

An electrochemical sensing platform based on local repression of electrolyte diffusion for single-step, reagentless, sensitive detection of a sequence-specific DNA-binding protein.

PubMed

Zhang, Yun; Liu, Fang; Nie, Jinfang; Jiang, Fuyang; Zhou, Caibin; Yang, Jiani; Fan, Jinlong; Li, Jianping

2014-05-07

In this paper, we report for the first time an electrochemical biosensor for single-step, reagentless, and picomolar detection of a sequence-specific DNA-binding protein using a double-stranded, electrode-bound DNA probe terminally modified with a redox active label close to the electrode surface. This new methodology is based upon local repression of electrolyte diffusion associated with protein-DNA binding that leads to reduction of the electrochemical response of the label. In the proof-of-concept study, the resulting electrochemical biosensor was quantitatively sensitive to the concentrations of the TATA binding protein (TBP, a model analyte) ranging from 40 pM to 25.4 nM with an estimated detection limit of ∼10.6 pM (∼80 to 400-fold improvement on the detection limit over previous electrochemical analytical systems).

Intraoperative seizure and cerebrospinal fluid leak during adult cochlear implant surgery.

PubMed

Musser, Alexander B; Golub, Justin S; Samy, Ravi N; Phero, James C

2016-01-01

To report a rare case of cerebrospinal fluid gusher and subsequent seizure immediately after cochlear implant electrode insertion. After the cochlear implant electrode was inserted, brisk flow of 10 mL of cerebrospinal fluid was seen. The electrode was promptly inserted and the leak was additionally sealed with fascia. Seconds later, the patient had a tonic-clonic seizure lasting 30 seconds. Two additional episodes occurred during the case. Her postoperative course was uneventful with no subsequent seizures. The device has been successfully activated. Intervention & Technique: Postoperative imaging showed correct intracochlear placement of the electrode as well as an incidental enlarged vestibular aqueduct. Neurology consultation including electroencephalogram was unremarkable. To our knowledge, this is the first report of a seizure temporally associated with cochlear implant electrode insertion. The significance and possible casual relationship between these two events is discussed.

Temperature-dependent electrochemical capacitive performance of the α-Fe2O3 hollow nanoshuttles as supercapacitor electrodes.

PubMed

Zheng, Xin; Yan, Xiaoqin; Sun, Yihui; Yu, Yinsheng; Zhang, Guangjie; Shen, Yanwei; Liang, Qijie; Liao, Qingliang; Zhang, Yue

2016-03-15

The design and optimization of supercapacitors electrodes nanostructures are critically important since the properties of supercapacitors can be dramatically enhanced by tunable ion transport channels. Herein, we demonstrate high-performance supercapacitor electrodes materials based on α-Fe2O3 by rationally designing the electrode microstructure. The large solid-liquid reaction interfaces induced by hollow nanoshuttle-like structures not only provide more active sites for faradic reactions but also facilitate the diffusion of the electrolyte into electrodes. These result in the optimized electrodes with high capacitance of 249 F g(-1) at a discharging current density of 0.5 A g(-1) as well as good cycle stability. In addition, the relationship between charge storage and the operating temperature has been researched. The specific capacitance has no significant change when the working temperature increased from 20 °C to 60 °C (e.g. 203 F g(-1) and 234 F g(-1) at 20 °C and 60 °C, respectively), manifesting the electrodes can work stably in a wide temperature range. These findings here elucidate the α-Fe2O3 hollow nanoshuttles can be applied as a promising supercapacitor electrode material for the efficient energy storage at various potential temperatures. Copyright © 2015 Elsevier Inc. All rights reserved.

Method of doping interconnections for electrochemical cells

DOEpatents

Pal, Uday B.; Singhal, Subhash C.; Moon, David M.; Folser, George R.

1990-01-01

A dense, electronically conductive interconnection layer 26 is bonded on a porous, tubular, electronically conductive air electrode structure 16, optionally supported by a ceramic support 22, by (A) forming a layer of oxide particles of at least one of the metals Ca, Sr, Co, Ba or Mg on a part 24 of a first surface of the air electrode 16, (B) heating the electrode structure, (C) applying a halide vapor containing at least lanthanum halide and chromium halide to the first surface and applying a source of oxygen to a second opposite surface of the air electrode so that they contact at said first surface, to cause a reaction of the oxygen and halide and cause a dense lanthanum-chromium oxide structure to grow, from the first electrode surface, between and around the oxide particles, where the metal oxide particles get incoporated into the lanthanum-chromium oxide structure as it grows thicker with time, and the metal ions in the oxide particles diffuse into the bulk of the lanthamum-chromium oxide structure, to provide a dense, top, interconnection layer 26 on top of the air electrode 16. A solid electrolyte layer 18 can be applied to the uncovered portion of the air electrode, and a fuel electrode 20 can be applied to the solid electrolyte, to provide an electrochemical cell 10.

Applicability of a diffusion model to lateral transport in the terrestrial and lunar exospheres.

NASA Technical Reports Server (NTRS)

Hodges, R. R., Jr.

1972-01-01

Kinetic theory is used to determine a series expansion of the vertical flux of particles in an exosphere in terms of time and space derivatives of particle concentration, exobase velocity, and temperature. For sufficiently large scale variations of these parameters in time and space, the series can be truncated to a form that is similar to a diffusion equation. Owing to this analogy, it is possible to unite the mathematical description of molecular diffusion, which governs thermospheric flow, and the corresponding exospheric equation by using effective transport coefficients which change smoothly with altitude through the transition from thermosphere to exosphere. A new definition of the exobase for lateral flow emerges from the analogy of exospheric and thermospheric diffusion, as the altitude where the horizontal mean free path length equals the mean horizontal extent of ballistic trajectories of the transported gas, as opposed to the scale height of the dominant gas which determines the exobase for escape. It is shown that the approximation of exospheric lateral flow as a diffusion process is applicable to global scale problems concerning terrestrial helium and heavier gases, and lunar gases heavier than helium.

Using Diffusion Bonding in Making Piezoelectric Actuators

NASA Technical Reports Server (NTRS)

Sager, Frank E.

2003-01-01

A technique for the fabrication of piezoelectric actuators that generate acceptably large forces and deflections at relatively low applied voltages involves the stacking and diffusion bonding of multiple thin piezoelectric layers coated with film electrodes. The present technique stands in contrast to an older technique in which the layers are bonded chemically, by use of urethane or epoxy agents. The older chemical-bonding technique entails several disadvantages, including the following: It is difficult to apply the bonding agents to the piezoelectric layers. It is difficult to position the layers accurately and without making mistakes. There is a problem of disposal of hazardous urethane and epoxy wastes. The urethane and epoxy agents are nonpiezoelectric materials. As such, they contribute to the thickness of a piezoelectric laminate without contributing to its performance; conversely, for a given total thickness, the performance of the laminate is below that of a unitary piezoelectric plate of the same thickness. The figure depicts some aspects of the fabrication of a laminated piezoelectric actuator by the present diffusion- bonding technique. First, stock sheets of the piezoelectric material are inspected and tested. Next, the hole pattern shown in the figure is punched into the sheets. Alternatively, if the piezoelectric material is not a polymer, then the holes are punched in thermoplastic films. Then both faces of each punched piezoelectric sheet or thermoplastic film are coated with a silver-ink electrode material by use of a silkscreen printer. The electrode and hole patterns are designed for minimal complexity and minimal waste of material. After a final electrical test, all the coated piezoelectric layers (or piezoelectric layers and coated thermoplastic films) are stacked in an alignment jig, which, in turn, is placed in a curved press for the diffusion-bonding process. In this process, the stack is pressed and heated at a specified curing temperature and pressure for a specified curing time. The pressure, temperature, and time depend on the piezoelectric material selected. At the end of the diffusion-bonding process, the resulting laminated piezoelectric actuator is tested to verify the adequacy of the mechanical output as a function of an applied DC voltage.

Tritium Fluxes through the Shallow Unsaturated Zone adjacent to a Radioactive Waste Disposal Facility in an Arid Environment

NASA Astrophysics Data System (ADS)

Maples, S.; Andraski, B. J.; Stonestrom, D. A.; Cooper, C. A.; Pohll, G.

2011-12-01

Studies at the U.S. Geological Survey's Amargosa Desert Research Site (ADRS) in southern Nevada have documented long-distance (>400-m) tritium (3H) transport adjacent to a commercial, low-level radioactive waste disposal facility. Transport at this scale is orders of magnitude greater than anticipated; however, lateral 3H fluxes through the shallow unsaturated zone (UZ) have not been investigated in detail. The objective of this study is to estimate and compare lateral and vertical tritiated water-vapor (3HHOg) fluxes in the shallow UZ and their relation to the observed plume migration. Previous studies have recognized two distinct plumes of 3H emanating from the facility. Shallow (0.5 and 1.5-m depth) soil-water vapor samples were collected yearly along 400-m long transects through both plumes from 2003-09. Within the south plume, 3H concentrations at 1.5-m depth have decreased by 44 ± 0.3% during this period, and plume advancement there has effectively ceased (i.e., rate of advance equals rate of decay). During the same period, the west plume showed a net decrease in concentration of 34 ± 0.9% within 100-m of the facility; however, plume advancement is observed at the leading edge of the plume, and concentrations 200-300-m from the facility show an increase in 3H concentration of 64 ± 28.4%. Lateral and vertical diffusive fluxes within both plumes were calculated using 3HHOg concentrations from 2006. Lateral 3HHOg diffusive fluxes within both plumes have been estimated 25-300-m from the facility at 1.5-m depth. Mean lateral 3HHOg diffusive fluxes are 10-14 g m-2 yr-1 within the south plume, and 10-13 g m-2 yr-1 within the west plume. Mean lateral fluxes in the south plume are an order of magnitude lower than in the west plume. This behavior corresponds with the observed relative immobility of the south plume, while the elevated west plume fluxes agree with the plume advancement seen there. Shallow, upward directed, mean vertical 3HHOg fluxes 25-300-m from the facility are estimated to be 10-12 g m-2 yr-1 in the south plume and 10-11 g m-2 yr-1 in the west plume. Within both plumes, mean vertical diffusive fluxes are two orders of magnitude greater than mean lateral diffusive fluxes. Lateral diffusive 3HHOg fluxes have been calculated similarly using 2001 south plume data and were compared to 2001 south plume vertical diffusive 3HHOg fluxes published by Andraski et al. (2005). Here, too, mean vertical fluxes dwarf mean lateral fluxes (10-11 g m-2 yr-1 vs. 10-14 g m-2 yr-1). This behavior highlights the importance of upward movement and release of 3H to the atmosphere. The potential role of advective lateral transport and its contribution to observed plume migration is also under investigation.

The Steady-State Transport of Oxygen through Hemoglobin Solutions

PubMed Central

Keller, K. H.; Friedlander, S. K.

1966-01-01

The steady-state transport of oxygen through hemoglobin solutions was studied to identify the mechanism of the diffusion augmentation observed at low oxygen tensions. A novel technique employing a platinum-silver oxygen electrode was developed to measure the effective diffusion coefficient of oxygen in steady-state transport. The measurements were made over a wider range of hemoglobin and oxygen concentrations than previously reported. Values of the Brownian motion diffusion coefficient of oxygen in hemoglobin solution were obtained as well as measurements of facilitated transport at low oxygen tensions. Transport rates up to ten times greater than ordinary diffusion rates were found. Predictions of oxygen flux were made assuming that the oxyhemoglobin transport coefficient was equal to the Brownian motion diffusivity which was measured in a separate set of experiments. The close correlation between prediction and experiment indicates that the diffusion of oxyhemoglobin is the mechanism by which steady-state oxygen transport is facilitated. PMID:5943608

Cycle stability of the electrochemical capacitors patterned with vertically aligned carbon nanotubes in an LiPF6-based electrolyte.

PubMed

Chiou, Yi-Deng; Tsai, Dah-Shyang; Lam, Hoa Hung; Chang, Chuan-hua; Lee, Kuei-Yi; Huang, Ying-Sheng

2013-09-07

The miniature ultracapacitors, with interdigitated electrodes of vertically aligned carbon nanotubes (VACNTs) and an inter-electrode gap of 20 μm, have been prepared in the LiPF6 organic electrolyte with and without PVdF-HFP gel. PVdF-HFP between two opposing electrodes enhances the device reliability, but lessens its power performance because of the extra diffusion resistance. Also noteworthy are the gel influences on the cycle stability. When the applied voltage is 2.0 or 2.5 V, both the LiPF6 and the gel capacitors exhibit excellent stability, typified by a retention ratio of ≥95% after 10,000 cycles. Their coulombic efficiencies quickly rise up, and hold steady at 100%. Nonetheless, when the applied voltage is 3.5 or 4.0 V, the cycle stability deteriorates, since the negative electrode potential descends below 0.9 V (vs. Li), leading to electrolyte decomposition and SEI formation. For the LiPF6 capacitor, its retention ratio could be around 60% after 10,000 cycles and the coulombic efficiency of 100% is difficult to reach throughout its cycle life. On the other hand, the gel capacitor cycles energy with a much higher retention ratio, >80% after 10,000 cycles, and a better coulombic efficiency, even though electrolyte decomposition still occurs. We attribute the superior stability of the gel capacitor to its extra diffusion resistance which slows down the performance deterioration.

B-Site Cation-Ordered Double-Perovskite Oxide as an Outstanding Electrode Material for Supercapacitive Energy Storage Based on the Anion Intercalation Mechanism.

PubMed

Xu, Zhenye; Liu, Yu; Zhou, Wei; Tade, Moses O; Shao, Zongping

2018-03-21

Perovskite oxides are highly promising electrodes for oxygen-ion-intercalation-type supercapacitors owing to their high oxygen vacancy concentration, oxygen diffusion rate, and tap density. Based on the anion intercalation mechanism, the capacitance is contributed by surface redox reactions and oxygen ion intercalation in the bulk materials. A high concentration of oxygen vacancies is needed because it is the main charge carrier. In this study, we propose a B-site cation-ordered Ba 2 Bi 0.1 Sc 0.2 Co 1.7 O 6-δ as an electrode material with an extremely high oxygen vacancy concentration and oxygen diffusion rate. A maximum capacitance of 1050 F g -1 was achieved, and a high capacitance of 780 F g -1 was maintained even after 3000 charge-discharge cycles at a current density of 1 A g -1 with an aqueous alkaline solution (6 M KOH) electrolyte, indicating an excellent cycling stability. In addition, the specific volumetric capacitance of Ba 2 Bi 0.1 Sc 0.2 Co 1.7 O 6-δ reaches up to 2549.4 F cm -3 based on the dense construction and high tap density (3.2 g cm -3 ). In addition, an asymmetric supercapacitor was constructed using activated carbon as a negative electrode, and it displayed the highest specific energy density of 70 Wh kg -1 at the power density of 787 W kg -1 in this study.

Development and characterization of membrane electrode assembly of direct methanol fuel cells using hydrocarbon membranes and supported catalysts

NASA Astrophysics Data System (ADS)

Huang, Xiaoming

Direct methanol fuel cell (DMFC) is an attractive power source for portable applications in the near future, due to the high energy density of liquid methanol. Towards commercialization of the DMFC, several technical and economic challenges need to be addressed though. The present study aims at developing and characterizing high performance membrane electrode assemblies (MEAs) for the DMFCs by using a hydrocarbon type membrane (PolyFuel 62) and supported catalysts (PtRu/C). First, methanol and water transport properties in the PolyFuel 62 membrane were examined by various material characterization methods. Compared with the currently used perflurosulfonated Nafion 212 membrane, the PolyFuel membrane has lower methanol crossover, especially at high testing temperature. In addition, based on results of water diffusivity test, water diffusion through the PolyFuel membrane was also lower compared with the Nafion membrane. In order to check the possible impacts of the low methanol and water diffusivities in the PolyFuel membrane, a MEA with this new type of membrane was developed and its performance was compared with a Nafion MEA with otherwise identical electrodes and GDLs. The results showed anode performance was identical, while cathode performance of the PolyFuel MEA was lower. More experiments combined with a transmission line model revealed that low water transport through the PolyFuel membrane resulted in a higher proton resistance in the cathode electrode and thus, leading to a low cathode performance. Thus increasing the water content in the cathode electrode is critical for using the PolyFuel membrane in the DMFC MEA. Then, a low loading carbon supported catalyst, PtRu/C, was prepared and tested as the anode electrode in a MEA of the DMFC. Compared with performance of an unsupported MEA, we could find that lower performance in the supported MEA was due to methanol transport limitation because of the denser and thicker supported catalyst layer. Accordingly, an addition of a pore former, Li 2CO3, was proposed during the catalyst ink preparation. This was proved to be very effective, largely improving anode performance with only 1/3 of catalyst loading. Finally, the PolyFuel membrane and supported catalysts were ready to be applied in the new MEA for the DMFCs. The new made MEA, with the catalyst loading of 2.6-time lower than a reference MEA, showed a very promising result, about only 10mV performance loss under the current density of 150mA/cm² compared with the reference MEA. Moreover, a short-term decay test indicated that the new MEA may have better durability and life because of its low methanol crossover on the cathode electrode due the PolyFuel membrane.

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

Chung, Sheng-Heng; Chang, Chi-Hao; Manthiram, Arumugam

Sulfur is an appealing cathode material for establishing advanced lithium batteries as it offers a high theoretical capacity of 1675 mA h g -1 at low material and operating costs. However, the lithium–sulfur (Li–S) electrochemical cells face several formidable challenges arising from both the materials chemistry (e.g., low electrochemical utilization of sulfur and severe polysulfide diffusion) and battery chemistry (e.g., dynamic and static instability and low sulfur loadings). Here in this study, we present the design of a core–shell cathode with a pure sulfur core shielded within a conductive shell-shaped electrode. The new electrode configuration allows Li–S cells to loadmore » with a high amount of sulfur (sulfur loadings of up to 30 mg cm -2 and sulfur content approaching 70 wt%). The core–shell cathodes demonstrate a superior dynamic and static electrochemical stability in Li–S cells. The high-loading cathodes exhibit (i) a high sulfur utilization of up to 97% at C/20–C/2 rates and (ii) a low self-discharge during long-term cell storage for a three-month rest period and at different cell-storage conditions. Finally, a polysulfide-trap cell configuration is designed to evidence the eliminations of polysulfide diffusion and to investigate the relationship between the electrode configuration and electrochemical characteristics. Finally, the comprehensive analytical results based on the high-loading cathodes suggest that (i) the core–shell cathode is a promising solution for designing highly reversible Li–S cells and (ii) the polysulfide-trap cell configuration is a viable approach to qualitatively evaluating the presence or absence of polysulfide diffusion.« less

Alkaline fuel cell: carbon nanobeads coated with metal catalyst over porous ceramic for hydrogen electrode

NASA Astrophysics Data System (ADS)

Chatterjee, A. K.; Sharon, Maheshwar; Banerjee, Rangan

The development of a hydrogen electrode using a porous ceramic coated with carbon nanobeads for an alkaline fuel cell (AFC) is reported. This electrode can provide necessary strength and porosity to enable hydrogen to diffuse without allowing electrolyte to percolate inside the electrode. Various catalysts (Pt, Ni, Co and Fe) are electrochemically dispersed over the carbon nanobeads to examine their performance in the alkaline fuel cell. Turpentine oil has been used as a precursor for preparing the carbon nanobeads by a chemical vapour deposition technique. Scanning electron microscopic and transmission electron microscopic images show that the carbon nanobeads have sizes between 500 and 650 nm and are spread uniformly over the entire ceramic substrate. X-ray diffraction (XRD) patterns indicate that the nanobeads are graphitic in nature. Thus, the electrode is highly conductive. The current-voltage characteristics and chronopotentiometry of a half cell (i.e. hydrogen electrode coated with different electrocatalysts) and a full cell (using both hydrogen and oxygen electrodes) with 30% KOH solution are measured. About 93% of the theoretical hydrogen dissociation voltage is obtained with Ni and Pt catalyst. All other metals (Co and Fe) give a lower voltage. Ni-coated carbon nanobeads deposited over a ceramic oxide can be used in place of Raney nickel electrode as their characteristics are similar to those of a platinum electrode.

Multilayer core-shell structured composite paper electrode consisting of copper, cuprous oxide and graphite assembled on cellulose fibers for asymmetric supercapacitors

NASA Astrophysics Data System (ADS)

Wan, Caichao; Jiao, Yue; Li, Jian

2017-09-01

An easily-operated and inexpensive strategy (pencil-drawing-electrodeposition-electro-oxidation) is proposed to synthesize a novel class of multilayer core-shell structured composite paper electrode, which consists of copper, cuprous oxide and graphite assembled on cellulose fibers. This interesting electrode structure plays a pivotal role in providing more active sites for electrochemical reactions, facilitating ion and electron transport and shorting their diffusion pathways. This electrode demonstrates excellent electrochemical properties with a high specific capacitance of 601 F g-1 at 2 A g-1 and retains 83% of this capacitance when operated at an ultrahigh current density of 100 A g-1. In addition, a high energy density of 13.4 W h kg-1 at the power density of 0.40 kW kg-1 and a favorable cycling stability (95.3%, 8000 cycles) were achieved for this electrode. When this electrode was assembled into an asymmetric supercapacitor with carbon paper as negative electrode, the device displays remarkable electrochemical performances with a large areal capacitances (122 mF cm-2 at 1 mA cm-2), high areal energy density (10.8 μW h cm-2 at 402.5 μW cm-2) and outstanding cycling stability (91.5%, 5000 cycles). These results unveil the potential of this composite electrode as a high-performance electrode material for supercapacitors.

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 Electrode and Electrolyte Configurations for Lithium-Oxygen Battery.

PubMed

Ulissi, Ulderico; Elia, Giuseppe Antonio; Jeong, Sangsik; Reiter, Jakub; Tsiouvaras, Nikolaos; Passerini, Stefano; Hassoun, Jusef

2018-03-02

Cathode configurations reported herein are alternative to the most diffused ones for application in lithium-oxygen batteries, using an ionic liquid-based electrolyte. The electrodes employ high surface area conductive carbon as the reaction host, and polytetrafluoroethylene as the binding agent to enhance the oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) reversibility. Roll-pressed, self-standing electrodes (SSEs) and thinner, spray deposited electrodes (SDEs) are characterized in lithium-oxygen cells using an ionic liquid (IL) based electrolyte formed by mixing lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt and N,N-diethyl-N-(2-methoxyethyl)-N-methylammonium bis(trifluoromethanesulfonyl)imide (DEMETFSI). The electrochemical results reveal reversible reactions for both electrode configurations, but improved electrochemical performance for the self-standing electrodes in lithium-oxygen cells. These electrodes show charge/discharge polarizations at 60 °C limited to 0.4 V, with capacity up to 1 mAh cm -2 and energy efficiency of about 88 %, while the spray deposited electrodes reveal, under the same conditions, a polarization of 0.6 V and energy efficiency of 80 %. The roll pressed electrode combined with the DEMETFSI-LiTFSI electrolyte and a composite Li x Sn-C alloy anode forms a full Li-ion oxygen cell showing extremely limited polarization, and remarkable energy efficiency. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

High Energy-Density Electrodes for Alkali-Metal Battery Systems

DTIC Science & Technology

1977-11-29

characteristics of real battery systems. In our laboratory, techniques for preparing well-characterized inter - calated Li TaS., and Na TaS. have been...to measure the variation of the chemical potential and diffusivity of sodium with composition x in Na TaSa where x varies from 0 to 1, 0, The...measure the chemical potential and diffusivity ■ Na (s)/Na (propylene carbonate)/Na TaSa (A) of sodium in Na TaSa . x Experimental Tantalum

POWER AND THERMAL TECHNOLOGIES FOR AIR AND SPACE-SCIENTIFIC RESEARCH PROGRAM Delivery Order 0018: Single Ion Conducting Solid-State Lithium Electrochemical Technologies (Task 4)

DTIC Science & Technology

2010-08-01

a mathematical equation relates the cathode reaction reversible electric potential to the lithium content of the cathode electrode. Based on the...Transport of Lithium in the Cell Cathode Active Material The Nernst -Einstein relation linking the lithium-ion mass diffusivity and its ionic...transient, isothermal and isobaric conditions. The differential model equation describing the lithium diffusion and accumulation in a spherical, active

Analysis of Double Layer and Adsorption Effects at the Alkaline Polymer Electrolyte-Electrode Interface

DTIC Science & Technology

2011-10-05

anion exchange mem - branes (AEM) are an attractive alternative to proton exchange mem - brane (PEM) fuel cells.1, 2 From electrocatalysts standpoint...gener- ally broken down into three distinct regions: the inner Helmholtz plane (IHP), the outer Helmholtz plane ( OHP ), and the diffuse layer. Figure 11...closest approach and is defined as OHP at a distance, x2. Nonspecifically adsorbed ions are distributed in a three dimensional region, called diffuse layer

Analysis of the geometrical-probabilistic models of electrocrystallization

NASA Astrophysics Data System (ADS)

Isaev, V. A.; Grishenkova, O. V.; Zaykov, Yu. P.

2016-08-01

The formation of a three-dimensional electrode deposit under potentiostatic conditions, including the stages of nucleation, growth, and overlap of growing new-phase clusters and their diffusion zones, is considered. The models of electrochemical phase formation for kinetics- and diffusion-controlled growth are analyzed, and the correctness of the approximations used in these models is estimated. The possibility of application of these models to an analysis of the electrodeposition of silicon from molten salts is discussed.

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

Investigation of the oxygen exchange mechanism on Pt|yttria stabilized zirconia at intermediate temperatures: Surface path versus bulk path

PubMed Central

Opitz, Alexander K.; Lutz, Alexander; Kubicek, Markus; Kubel, Frank; Hutter, Herbert; Fleig, Jürgen

2011-01-01

The oxygen exchange kinetics of platinum on yttria-stabilized zirconia (YSZ) was investigated by means of geometrically well-defined Pt microelectrodes. By variation of electrode size and temperature it was possible to separate two temperature regimes with different geometry dependencies of the polarization resistance. At higher temperatures (550–700 °C) an elementary step located close to the three phase boundary (TPB) with an activation energy of ∼1.6 eV was identified as rate limiting. At lower temperatures (300–400 °C) the rate limiting elementary step is related to the electrode area and exhibited a very low activation energy in the order of 0.2 eV. From these observations two parallel pathways for electrochemical oxygen exchange are concluded. The nature of these two elementary steps is discussed in terms of equivalent circuits. Two combinations of parallel rate limiting reaction steps are found to explain the observed geometry dependencies: (i) Diffusion through an impurity phase at the TPB in parallel to diffusion of oxygen through platinum – most likely along Pt grain boundaries – as area-related process. (ii) Co-limitation of oxygen diffusion along the Pt|YSZ interface and charge transfer at the interface with a short decay length of the corresponding transmission line (as TPB-related process) in parallel to oxygen diffusion through platinum. PMID:22210951

Electrode assembly for use in a solid polymer electrolyte fuel cell

DOEpatents

Raistrick, Ian D.

1989-01-01

A gas reaction fuel cell may be provided with a solid polymer electrolyte membrane. Porous gas diffusion electrodes are formed of carbon particles supporting a catalyst which is effective to enhance the gas reactions. The carbon particles define interstitial spaces exposing the catalyst on a large surface area of the carbon particles. A proton conducting material, such as a perfluorocarbon copolymer or ruthenium dioxide contacts the surface areas of the carbon particles adjacent the interstitial spaces. The proton conducting material enables protons produced by the gas reactions adjacent the supported catalyst to have a conductive path with the electrolyte membrane. The carbon particles provide a conductive path for electrons. A suitable electrode may be formed by dispersing a solution containing a proton conducting material over the surface of the electrode in a manner effective to coat carbon surfaces adjacent the interstitial spaces without impeding gas flow into the interstitial spaces.

High-capacity electrode materials for electrochemical energy storage: Role of nanoscale effects

DOE PAGES

Nanda, Jagjit; Martha, Surendra K.; Kalyanaraman, Ramki

2015-06-02

In this review, we summarize the current state-of-the art electrode materials used for high-capacity lithium-ion-based batteries and their significant role towards revolutionizing the electrochemical energy storage landscape in the area of consumer electronics, transportation and grid storage application. We discuss the role of nanoscale effects on the electrochemical performance of high-capacity battery electrode materials. Decrease in the particle size of the primary electrode materials from micron to nanometre size improves the ionic and electronic diffusion rates significantly. Nanometre-thick solid electrolyte (such as lithium phosphorous oxynitride) and oxides (such as Al 2O 3, ZnO, TiO 2 etc.) material coatings also improvemore » the interfacial stability and rate capability of a number of battery chemistries. Finally, we elucidate these effects in terms of different high-capacity battery chemistries based on intercalation and conversion mechanism.« less

Electrospray-deposition of graphene electrodes: a simple technique to build high-performance supercapacitors.

PubMed

Tang, Huaichao; Yang, Cheng; Lin, Ziyin; Yang, Quanhong; Kang, Feiyu; Wong, Ching Ping

2015-05-28

Here we report an electrostatic spray deposition method to prepare three-dimensional porous graphene electrodes for supercapacitor applications. The symmetric supercapacitor exhibits excellent specific capacitance (366 F g(-1) at 1 A g(-1) in 6 M KOH) and long cycle life (108% capacitance retention up to 40 000 cycles). Moreover, the energy densities of the organic and aqueous electrolyte based supercapacitors reach 22.9 and 8.1 Wh kg(-1) when the power densities are 119.2 and 15.4 kW kg(-1), respectively. Compared with the previously reported graphene based supercapacitors, the improved properties could be attributed to the excellent three-dimensional open porous electrode structure, which is favorable for the ion diffusion and electron transport. In addition, this method provides a simple electrode-fabrication route without the involvement of conducting additives and binders. It may find vast applications in thin and miniaturized energy storage scenarios.

Computational analysis of species transport and electrochemical characteristics of a MOLB-type SOFC

NASA Astrophysics Data System (ADS)

Hwang, J. J.; Chen, C. K.; Lai, D. Y.

A multi-physics model coupling electrochemical kinetics with fluid dynamics has been developed to simulate the transport phenomena in mono-block-layer built (MOLB) solid oxide fuel cells (SOFC). A typical MOLB module is composed of trapezoidal flow channels, corrugated positive electrode-electrolyte-negative electrode (PEN) plates, and planar inter-connecters. The control volume-based finite difference method is employed for calculation, which is based on the conservation of mass, momentum, energy, species, and electric charge. In the porous electrodes, the flow momentum is governed by a Darcy model with constant porosity and permeability. The diffusion of reactants follows the Bruggman model. The chemistry within the plates is described via surface reactions with a fixed surface-to-volume ratio, tortuosity and average pore size. Species transports as well as the local variations of electrochemical characteristics, such as overpotential and current density distributions in the electrodes of an MOLB SOFC, are discussed in detail.

Magnesia-stabilised zirconia solid electrolyte assisted electrochemical investigation of iron ions in a SiO2-CaO-MgO-Al2O3 molten slag at 1723 K.

PubMed

Gao, Yunming; Yang, Chuanghuang; Zhang, Canlei; Qin, Qingwei; Chen, George Z

2017-06-21

Production of metallic iron through molten oxide electrolysis using inert electrodes is an alternative route for fast ironmaking without CO 2 emissions. The fact that many inorganic oxides melt at ultrahigh temperatures (>1500 K) challenges conventional electro-analytical techniques used in aqueous, organic and molten salt electrolytes. However, in order to design a feasible and effective electrolytic process, it is necessary to best understand the electrochemical properties of iron ions in molten oxide electrolytes. In this work, a magnesia-stabilised zirconia (MSZ) tube with a closed end was used to construct an integrated three-electrode cell with a "MSZ|Pt|O 2 (air)" assembly functioning as the solid electrolyte, the reference electrode and also the counter electrode. Electrochemical reduction of iron ions was systematically investigated on an iridium (Ir) wire working electrode in a SiO 2 -CaO-MgO-Al 2 O 3 molten slag at 1723 K by cyclic voltammetry (CV), square wave voltammetry (SWV), chronopotentiometry (CP) and potentiostatic electrolysis (PE). The results show that the electroreduction of the Fe 2+ ion to Fe on the Ir electrode in the molten slag follows a single two-electron transfer step, and the rate of the process is diffusion controlled. The peak current on the obtained CVs is proportional to the concentration of the Fe 2+ ion in the molten slag and the square root of scan rate. The diffusion coefficient of Fe 2+ ions in the molten slag containing 5 wt% FeO at 1723 K was derived to be (3.43 ± 0.06) × 10 -6 cm 2 s -1 from CP analysis. However, a couple of subsequent processes, i.e. alloy formation on the Ir electrode surface and interdiffusion, were found to affect the kinetics of iron deposition. An ECC mechanism is proposed to account for the CV observations. The findings from this work confirm that zirconia-based solid electrolytes can play an important role in electrochemical fundamental research in high temperature molten slag electrolytes.

A Mid-scala Cochlear Implant Electrode Design Achieves a Stable Post-surgical Position in the Cochlea of Patients Over Time-A Prospective Observational Study.

PubMed

Dees, Guido; Smits, Jeroen Jules; Janssen, A Miranda L; Hof, Janny R; Gazibegovic, Dzemal; Hoof, Marc van; Stokroos, Robert J

2018-04-01

Cochlear implant (CI) electrode design impacts the clinical performance of patients. Stability and the occurrence of electrode array migration, which is the postoperative movement of the electrode array, were investigated using a mid-scalar electrode array and postoperative image analysis. A prospective observational study was conducted. A mid-scalar electrode was surgically placed using a mastoidectomy, followed by a posterior tympanotomy and an extended round-window or cochleostomy insertion. A few days after surgery and 3 months later Cone Beam Computed Tomography (CBCT) was performed. The two different CBCT's were fused, and the differences between the electrode positions in three dimensions were calculated (the migration). A migration greater than 0.5 mm was deemed clinically relevant. Fourteen subjects participated. The mid-scalar electrode migrated in one patient (7%). This did not lead to the extrusion of an electrode contact. The mean migration of every individual electrode contact in all patients was 0.36 mm (95% confidence interval 0.22-0.50 mm), which approximates to the estimated measurement error of the CBCT technique. A mid-scalar electrode array achieves a stable position in the cochlea in a small but representative group of patients. The methods applied in this work can be used for providing postoperative feedback for surgeons and for benchmarking electrode designs.

In situ growth of ceramic quantum dots in polyaniline host via water vapor flow diffusion as potential electrode materials for energy applications

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

Mombrú, Dominique; Romero, Mariano, E-mail: mromero@fq.edu.uy; Faccio, Ricardo, E-mail: rfaccio@fq.edu.uy

In situ preparation of polyaniline-ceramic nanocomposites has recently demonstrated that the electrical properties are highly improved with respect to the typical ex situ preparations. In this report, we present for the first time, to the best of our knowledge, the in situ growth of titanium oxide quantum dots in polyaniline host via water vapor flow diffusion as an easily adaptable route to prepare other ceramic-polymer nanocomposites. The main relevance of this method is the possibility to prepare ceramic quantum dots from alkoxide precursors using water vapor flow into any hydrophobic polymer host and to achieve good homogeneity and size-control. Inmore » addition, we perform full characterization by means of high-resolution transmission electron microscopy, X-ray powder diffraction, small angle X-ray scattering, thermogravimetric and calorimetric analyses, confocal Raman microscopy and impedance spectroscopy analyses. The presence of the polymer host and interparticle Coulomb repulsive interactions was evaluated as an influence for the formation of ~3–8 nm equally-sized quantum dots independently of the concentration. The polyaniline polaron population showed an increase for the quantum dots diluted regime and the suppression at the concentrated regime, ascribed to the formation of chemical bonds at the interface, which was confirmed by theoretical simulations. In agreement with the previous observation, the in situ growth of ceramic quantum dots in polyaniline host via water vapor flow diffusion could be very useful as a novel approach to prepare electrode materials for energy conversion and storage applications. - Highlights: • In situ growth of titanium oxide quantum dots in polyaniline host via water vapor flow diffusion. • Polyaniline charge carriers at the interface and charge interactions between quantum dots. • Easy extrapolation to sol-gel derived quantum dots into polymer host as potential electrode materials.« less

Understanding Performance Limitations to Enable High Performance Magnesium-Ion Batteries

DOE PAGES

Kim, Sun Ung; Perdue, Brian; Apblett, Christopher A.; ...

2016-05-18

We developed a mathematical model in order to investigate the performance limiting factors of Mg-ion battery with a Chevrel phase (Mg xMo 6S 8) cathode and a Mg metal anode. Furthermore, the model was validated using experimental data from the literature [Cheng et al., Chem. Mater., 26, 4904 (2014)]. Two electrochemical reactions of the Chevrel phase with significantly different kinetics and solid diffusion were included in the porous electrode model, which captured the physics sufficiently well to generate charge curves of five rates (0.1C–2C) for two different particle sizes. Limitation analysis indicated that the solid diffusion and kinetics in themore » higher-voltage plateau limit the capacity and increase the overpotential in the Cheng et al.’s thin (20-μm) electrodes. The model reveals that the performance of the cells with reasonable thickness would also be subject to electrolyte-phase limitations. Finally, the simulation also suggested that the polarization losses on discharge will be lower than that on charge, because of the differences in the kinetics and solid diffusion between the two reactions of the Chevrel phase.« less

Innovative discharge geometries for diffusion-cooled gas lasers

NASA Astrophysics Data System (ADS)

Lapucci, Antonio

2004-09-01

Large area, narrow discharge gap, diffusion cooled gas lasers are nowadays a well established technology for the construction of industrial laser sources. Successful examples exist both with the slab (Rofin-Sinar) or coaxial (Trumpf) geometry. The main physical properties and the associated technical problems of the transverse large area RF discharge, adopted for the excitation of high power diffusion cooled gas lasers, are reviewed here. The main problems of this technology are related to the maintenance of a uniform and stable plasma excitation between closely spaced large-area electrodes at high power-density loading. Some practical solutions such as distributed resonance of the discharge channel proved successful in the case of square or rectangular cross-sections but hardly applicable to geometries such as that of coaxial electrodes. In this paper we present some solutions, adopted by our group, for the development of slab and annular CO2 lasers and for CO2 laser arrays with linear or circular symmetry. We will also briefly mention the difficulties encountered in the extraction of a good quality beam from an active medium with such a cross section. A problem that has also seen some interesting solutions.

Photocurrent enhancement of n-type Cu2O electrodes achieved by controlling dendritic branching growth.

PubMed

McShane, Colleen M; Choi, Kyoung-Shin

2009-02-25

Cu(2)O electrodes composed of dendritic crystals were produced electrochemically using a slightly acidic medium (pH 4.9) containing acetate buffer. The buffer played a key role for stabilizing dendritic branching growth as a pH drop during the synthesis prevents formation of morphologically unstable branches and promotes faceted growth. Dendritic branching growth enabled facile coverage of the substrate with Cu(2)O while avoiding growth of a thicker Cu(2)O layer and increasing surface areas. The resulting electrodes showed n-type behavior by generating anodic photocurrent without applying an external bias (zero-bias photocurrent under short-circuit condition) in an Ar-purged 0.02 M K(2)SO(4) solution. The zero-bias photocurrent of crystalline dendritic electrodes was significantly higher than that of the electrodes containing micrometer-size faceted crystals deposited without buffer. In order to enhance photocurrent further a strategy of improving charge-transport properties by increasing dendritic crystal domain size was investigated. Systematic changes in nucleation density and size of the dendritic Cu(2)O crystals were achieved by altering the deposition potential, Cu(2+) concentration, and acetate concentration. Increasing dendritic crystal size consistently resulted in the improvement of photocurrent regardless of the method used to regulate crystal size. The electrode composed of dendritic crystals with the lateral dimension of ca. 12000 microm(2) showed more than 20 times higher zero-bias photocurrent than that composed of dendritic crystals with the lateral dimension of ca. 100 microm(2). The n-type nature of the Cu(2)O electrodes prepared by this study were confirmed by linear sweep voltammetry with chopped light and capacitance measurements (i.e., Mott-Schottky plots). The flatband potential in a 0.2 M K(2)SO(4) solution (pH 6) was estimated to be -0.78 vs Ag/AgCl reference electrode. The IPCE measured without applying an external bias was approximately 1% for the visible region. With appropriate doping studies and surface treatment to improve charge transport and interfacial kinetics more efficient n-type Cu(2)O electrodes will be prepared for use in various photoelectrochemical and photovoltaic devices.

Observational Inferences of Lateral Eddy Diffusivity in the Halocline of the Beaufort Gyre

NASA Astrophysics Data System (ADS)

Meneghello, G.; Marshall, J.; Cole, S. T.; Timmermans, M. L.

2017-12-01

Using Ekman pumping rates mediated by sea-ice in the Arctic Ocean's Beaufort Gyre (BG), the magnitude of lateral eddy diffusivities required to balance downward pumping is inferred. In this limit — that of vanishing residual-mean circulation — eddy-induced upwelling exactly balances downward pumping. The implied eddy diffusivity varies spatially with values of 50-400 m2/s, and decays with depth. Eddy diffusivity estimated using mixing length theory applied to BG mooring data exhibits a similar range of values from 100 m2/s to more than 600 m2/s, and also decays with depth. We conclude that eddy diffusivities in the BG are likely large enough to balance downward Ekman pumping, arresting the deepening of the gyre and suggesting that eddies play a zero-order role in buoyancy and freshwater budgets of the BG.