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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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Bacteria is detected electro-chemically by measuring evolution of hydrogen in test system with platinum and reference electrode. Using system, electrodes of platinum are used to detect and enumerate varieties of gram-positive and gram-negative organisms compared in different media.
A computationally efficient model serves as a critical prerequisite for battery performance analysis and advanced battery management algorithm design. Although battery models that capture cell-level behavior have been widely explored in existing literature, electrode-level battery models have received much lesser attention till to date. However, such electrode-level models can significantly increase battery performance and life by enabling electrode-level health-conscious control. Such electrode-level control can effectively expand usable energy and power limits of the battery cells by utilizing the knowledge of individual electrodes' charge and health. In this context, this paper presents a comprehensive battery model developed with a reference electrode insertion that captures (i) electrode-level charge/discharge dynamics, (ii) stoichiometric and temporal dependencies of electrode-level resistances, (iii) solid electrolyte interface (SEI) layer growth as key degradation phenomenon, and (iv) capacity fade and resistance rise in each electrode due to nominal battery aging. The proposed model is identified, and a preliminary validation is performed utilizing terminal voltage and negative electrode potential data collected from a pouch cell under one continuous cycling and accelerated aging conditions where the cell experienced 14% capacity loss.
We employ slow cyclic voltammetry to study the quasi-steady-state capacitive deionization (CDI) of aerated 10 mM NaCl from V cell =-0.2 to 2 V. The method allows for the deconvolution of capacitive and faradaic processes, which are significant even at low voltage, in conjunction with pH, conductivity, dissolved oxygen (DO), and electrode potential measurements. The pH at three locations and effluent DO data identify asymmetric electrosorption in the cell configured with pristine activated carbon electrodes, where charge is irreversibly consumed to produce H + /OH - instead of reversibly adsorbing Cl - /Na + . Implementing a reference electrode resolves ion adsorption as a function of the individual potential at each electrode. Near-electrode pH probes reveal pH environments that diverge by up to 8 units during cell polarization and allow more accurate calculation of faradaic redox potentials in a flow-by CDI cell. In the aerated NaCl solution that will be relevant to industrial-scale water treatment, we find that DO reduction occurs to a greater degree than Na + adsorption at the cathode until DO removal becomes mass transfer limited at <-0.2 V vs. SHE. Two cell architectures – flow-by and flow-through – corroborate our findings. Finally, we reconcile all measurements to generate a map displaying how the potential is partitioned amongst the capacitive and faradaic processes occurring during CDI operation over a 2.2 V window.
Introduction: Over the last two decades, several studies have been published on the impact of long-duration (i.e., 22 days or longer) spaceflight on the central nervous system (CNS). In consideration of the health and performance of crewmembers in flight and post-flight, we are conducting a controlled prospective longitudinal study to investigate the effects of spaceflight on the extent, longevity and neural bases of sensorimotor, cognitive, and neural changes. Multiple studies have demonstrated the effects of spaceflight on the vestibular system. One of the supporting tests conducted in this protocol is the Vestibular Evoked Myogenic Potential (VEMP) test that provides a unilateral measure of otolith (saccule and utricle) function. A different approach was taken for ocular VEMP (oVEMP) testing using a head striker system (Wackym et al. 2012). The oVEMP is generally considered to be a measure of utricle function. The the otolithic input to the inferior oblique muscle is predominately from the utricular macula. Thus, quantitatively, oVEMP tests utricular function. Another practical extension of these relationships is that the oVEMP reflects the superior vestibular nerve function. Methods: Ground testing was administered on 16 control subjects and for 8 subjects over four repeated sessions spanning 70 days. The oVEMP was elicitied via a hand held striker by a vibrotactile pulse presented at the rate of 1 Hz for 24 seconds on the side of the head as subjects lay supine on a gurney. Subjects were directed to gaze approximately 25 degrees above straight ahead in semi-darkness. For the oVEMP electromyograms will be recorded with active bipolar electrodes (Delsys Inc., Boston, MA) on the infra-orbital ridge 1 cm below the eyelid with a reference electrode on the below the knee cap. The EMG potentials were amplified; band-pass filtered using a BagnoliTM Desktop EMG System (Delsys Inc., Boston, MA, USA). This EMG signal is sampled at 10 kHz and the data stimulus onset to 100 MS was averaged over 24 trial repetitions for the vibrotactile VEMP. The typical oVEMP EMG response is an excitatory potential with first peak occurring at 11-12 ms and second peak at 18 ms. This requires a total recording time of approximately 29 seconds per trial which includes 5 seconds of no vibrotactile stimulation at the beginning of the protocol. The primary dependent measures consist of the latency and peak-to-peak amplitude from the EMG signals, which will be normalized to EMG levels at the beginning of the protocol. Data were collected for 3 repeated trials with striker stimulation on both the left and right side of the head Results: The oVEMP p1 range was observed at 3-14 ms and n1 at 7-19 ms. The striker system provided a consistent and rapid method for oVEMP testing. Discussion: Crew testing is in progress to determine changes in results between pre and post flight.
The ability to perform electrochemistry in the presence of large voltages and electric field magnitudes without concern for the local potential has many possible applications in micro/nanofluidic assays and in capillary electrophoresis. Traditionally, electrochemistry in the presence of significant external electric fields has been dominated by end-channel detection for capillary and microchip electrophoresis detection. Here, we describe novel instrumentation for potentiostatically controlled voltammetry that can be applied in the presence of high external voltages and electric fields. Cyclic voltammetry is demonstrated without significant shifts in the half-wave potential at working electrodes at local potentials of up to ~1500 V and field strengths of up to 3000 V/cm, using a standard Ag/AgCl reference electrode.
Trace level detection of hydrazine (N2H4), monomethyl hydrazine (MMH) and unsymmetrical dimethylhydrazine (UDMH) has been receiving increased attention over the past several years. In May 1995 the American Conference of Government Industrial Hygienists (ACGIH) lowered their acceptable threshold limit value (TLV) from 100 parts-per-billion (ppb) to 10 ppb. Several types of ppb-level detectors are being developed by the United States Air Force (USAF) Space and Missile Systems Center (SMSC). A breadboard version of a portable, lightweight hydrazine detection sensor was developed and produced by Giner Corp. for the USAF. This sensor was designed for ppb level UDMH and N2H4 vapor detection in near real-time. This instrument employs electrochemical sensing, utilizing a three electrode cell with an anion-exchange polymer electrolyte membrane as the only electrolyte in the system. The sensing, counter and reference electrodes are bonded to the membrane forming a single component. The only liquid required to maintain the sensor is deionized water which hydrates the membrane. At the request of the USAF SMSC, independent testing and evaluation of the breadboard instrument was performed at NASA's Toxic Vapor Detection Laboratory (TVDL) for response to ppb-level N2H4 and UDMH and MMH. The TVDL, located at Kennedy Space Center (KSC) has the unique ability to generate calibrated sample vapor streams of N2H4, UDMH, and MMH over a range from less than 10 ppb to thousands of parts per million (ppm) with full environmental control of relative humidity (0-90%) and temperature (0-50 C). The TVDL routinely performs these types of tests. Referenced sensors were subjected to extensive testing, including precision, linearity, response/recovery times, zero and span drift, humidity and temperature effects as well as ammonia interference. Results of these tests and general operation characteristics are reported.
A new liquid flow-cell designed for electronic structure investigations at the liquid-solid interface by soft X-ray absorption and emission spectroscopy is presented. A thin membrane serves simultaneously as a substrate for the working electrode and solid state samples as well as for separating the liquid from the surrounding vacuum conditions. In combination with counter and reference electrodes this approach allows in-situ studies of electrochemical deposition processes and catalytic reactions at the liquid-solid interface in combination with potentiostatic measurements. As model system in-situ monitoring of the deposition process of Co metal from a 10 mM CoCl{sub 2} aqueous solution by X-ray absorption and emission spectroscopy is presented.
The impact of gas evolution on the electrochemical characteristics of planar electrodes and microwire array electrodes has been analyzed using modeling and simulation. The impacts can mainly be broken into three phenomena: a) a shift in the local reversible hydrogen electrode potential; b) hyperpolarization; and c) an increase in the solution resistance of the electrolyte. The local reversible hydrogen electrode potential shift was found to play the most important role, constituting >40% of the total potential drop between the cathode and reference electrode, following correction for cell resistance. Compared to planar electrodes, a microwire array structure reduces the impact of bubbles on the solution conductance, but the shift in the local reversible hydrogen electrode potential varies with distance from the actual electrode surface.
A silver-ion bactericidal monitor is considered for the Space Shuttle Potable Water System. Potentiometric measurement using an ion-selective electrode is concluded to be the most feasible of available techniques. Four commercially available electrodes and a specially designed, solid-state, silver-sulfide electrode were evaluated for their response characteristics and suitability for space use. The configuration of the solid-state electrode with its Nernstian response of 10 to 10,000 ppb silver shows promise for use in space. A pressurized double-junction reference electrode with a quartz-fiber junction and a replaceable bellows electrolyte reservoir was designed verification-tested, and paired with a solid-state silver-sulfide electrode in a test fixture.
We demonstrate that ultrathin semiconductor working electrodes integrated into metal–insulator–semiconductor (MIS) stacks are an enabling platform for understanding non-Faradaic semiconductor electrochemistry. Furthermore, 5 nm thick ZnO electrodes were deposited on 30 nm HfO 2 dielectric on a Pd “gate” electrode. Application of a bias V G between the Pd gate and the ZnO electrode causes electrons to accumulate in the ZnO layer as measured by recording the in-plane sheet conductance. By contacting the top surface of the ZnO layer with the electrolyte in a conventional three-electrode electrochemical cell, we show that the gate voltage V G modulates the electrochemical potential V ZnO of the ZnO film with respect to a reference electrode. Electrochemical potential changes ΔV ZnO up to –1 V vs Ag/Ag + are achieved for V G = +7 V. Furthermore, by measuring V ZnO vs V G , we extract the quantum capacitance CQ of the ZnO film as a function of the Fermi-level position, which provides a direct measure of the ZnO electronic density of states (DOS). Finally, we demonstrate that the gated ZnO working electrodes can disentangle the two principal components of electrochemical potential, namely, the Fermi-level shift Δδ and the double-layer charging energy eΔΦ EDL . This disentanglement hinges on a fundamental difference between back-gating and normal electrochemical control, namely, that electrochemical control requires double-layer charging, while back-gate control does not. Collectively, the results show that the backside gate electrode is an effective fourth terminal that enables measurements that are difficult to achieve in conventional three-terminal electrochemical setups.
In this study, we assert that the apparent lithium diffusion coefficient in graphite active particles in the negative electrodes of lithium-ion cells increases appreciably with the intercalation rate. This assertion is based on an electrochemical model analysis of a wide range of electrochemical micro-reference electrode full cell studies on a coated natural graphite and other literature results. Although the mechanism for this increase is a subject of further investigation, the results of our study suggest that the lithium transport in the graphite does not limit the maximum attainable charging rate in typical lithium-ion cells for electric vehicles.
A research program to develop and evaluate electrodes for a nongassing negative limited nickel-cadmium cell is described. The concept of the negative limited cell and its implications on electrode structure are discussed. The key element is the development of a cadmium electrode with high hydrogen overvoltage. For this, Teflon-bonded Cd electrodes and silver-sinter based Gc electrodes were manufactured and in preliminary experiments their physical and electrochemical characteristics were evaluated. Hydrogen evolution on cadmium was found to occur approximately 100 mV more cathodic than on silver. Both electrode structures exhibit a fairly sharp potential rise at the end of the charging cycle and the advent of gas evolution occurs at potentials between -1.2 and -1.3 V versus a Hg/HgO reference electrode. These results are compared with conventional Ni-sinter based Cd electrodes.
In the present paper, a miniaturized boron-doped diamond electrode (BDDE) is proposed as a progressive electrochemical sensor for simple, fast and reliable quantification of dimethylxanthine alkaloid, theobromine (TB). Using cyclic voltammetry, the studied xanthine provided one well-shaped, irreversible and diffusion-controlled oxidation peak at relatively high potentials (+1.2 V vs. Ag/AgCl/3 M KCl reference electrode) in the presence of 0.1 M H2SO4. After selection of suitable experimental conditions, the linear calibration curves for TB were obtained in the concentration range from 0.99 up to 54.5 μM with the sensitivity of 0.07 μA/μM providing both differential pulse (DPV) and square-wave voltammetric (SWV) techniques, respectively. The elaborated voltammetric protocol yielded low detection limits of 0.42 and 0.51 μM accompanied by adequate intra-day repeatability (relative standard deviation of 2.5 and 1.7%) using DPV and SWV procedure, respectively. The interference study revealed the reasonable selectivity when taking the target food samples into account. The practical applicability of the voltammetric protocol using a miniaturized BDDE was verified in the analysis of six commercially available brands of chocolate products with the determined mass percentages of TB ranging from 0.75 to 2.24% and from 0.69 to 2.15% using DPV and SWV procedure, respectively. The obtained results were also in a good agreement with those achieved by reference titration method with potentiometric indication. The progressive electrochemical sensor based on a miniaturized BDDE has appeared to be an attractive candidate for practical applications in food quality control. Besides, the proposed voltammetric protocol presents advantages when compared to others techniques (e.g. chromatography), concerning simplicity, cost, speed of analysis, waste generation (environmentally friendly) and samples pretreatment (only dilution in electrolyte solution prior to analysis). © 2018 Elsevier B.V.
Ionic liquids (ILs) are considered functional electrolytes for the electrocatalytic reduction of CO 2 (ECO 2 R) due to their role in the double-layer structure formation and increased CO 2 availability at the electrode surface, which reduces the voltage requirement. However, not all ILs are the same, considering the purity and degree of the functionality of the IL. Further, there are critical experimental factors that impact the evaluation of ILs for ECO 2 R including the reference electrode, working electrode construction, cosolvent selection, cell geometry, and whether the electrochemical cell is a single compartment or a divided cell. Here, we describe improved synthesis methods of imidazolium cyanopyrrolide IL for electrochemical studies in consideration of precursor composition and reaction time. We explored how IL with cosolvents (i.e. acetonitrile, dimethylformamide, dimethyl sulfoxide, propylene carbonate, and n-methyl-2-pyrrolidone) affects conductivity, CO 2 mass transport, and ECO 2 R activation overpotential together with the effects of electrode materials (Sn, Ag, Au, and glassy carbon). Acetonitrile was found to be the best solvent for lowering the onset potential and increasing the catalytic current density for the production of CO owing to the enhanced ion mobility in combination with the silver electrode. Further, the ECO 2 R activity of molecular catalysts Ni(cyclam)Cl 2 and iron tetraphenylsulfonato porphyrin (FeTPPS) on the carbon cloth electrode maintained high Faradaic efficiencies for CO in the presence of the IL. This study presents best practices for examining nontraditional multifunctional electrolytes amenable to integrated CO 2 capture and conversion technologies for homogeneous and heterogeneous ECO 2 R.
Dual-membrane hollow-fiber electrode increases reliability and lowers costs. Leakage of fuel or oxidizer through fiber does not result in failure; excess product water migrates into electrolyte where it is removed by evaporation or distillation; constant exposure of fiber to electrolyte eliminates problems of drying and consequent failure; reference electrode monitors current collectors and overall cell performance.
Microstructure evolution plays an important role in the performance degradation of SOFC electrodes. In this work, we propose a much improved phase field model to simulate the microstructure evolution in the electrodes of solid oxide fuel cell. We demonstrate that the tunability of the interfacial energy in this model has been significantly enhanced. Parameters are set to fit for the interfacial energies of a typical Ni-YSZ anode, an LSM-YSZ cathode and an artificial reference electrode, respectively. The contact angles at various triple junctions and the microstructure evolutions in two dimensions are calibrated to verify the model. As a demonstration of the capabilities of the model, three dimensional microstructure evolutions are simulated applying the model to the three different electrodes. The time evolutions of grain size and triple phase boundary density are analyzed. In addition, a recently proposed bound charge successive approximation algorithm is employed to calculate the effective conductivity of the electrodes during microstructure evolution. Furthermore, the effective conductivity of all electrodes are found to decrease during the microstructure evolution, which is attributed to the increased tortuosity and the loss of percolated volume fraction of the electrode phase.
A continuum-model approach, analogous to porous electrode theory, was applied to a thin-layer cell of rectangular and cylindrical geometry. A reversible redox couple is assumed, and the local reaction current density is related to the potential through the formula of Hubbard and Anson for a uniformily accessible thin-layer cell. The placement of the reference electrode is also accounted for in the analysis. Primary emphasis is placed on the effect of the solution-phase ohmic potential drop on the voltammogram characteristics. Correlation equations for the peak-potential displacement from E(sup 0 prime) and the peak current are presented in terms of two dimensionless parameters.
Ergosterol (Erg) is the major sterol component in the plasma membranes of fungi. The main goal of this work was to develop rapid, reliable, and cost-effective method toward Erg detection based on application of unmodified boron-doped diamond electrode. Several organic solvents were tested (acetonitrile, dimethyformamide, dimethylsulfoxide, dichloromethane), and it was found that best analytical characteristics were achieved using acetonitrile containing 0.1 M tetrabutylammonium hexa-fluorophosphate as supporting electrolyte. Oval shaped and well-defined oxidation peak was recorded at potential of around 1.17 V versus Ag/Ag+ non-aqueous reference electrode. Under optimized experimental conditions, linear working range from 2 to 200 mu M was estimated, with limit of detection of 0.7 mu M, using square wave voltammetry. Negligible effect of possible interfering compound was observed. Proposed methodology was successfully applied for estimation of Erg content in mushrooms extract with satisfactory results in comparison with spectrophotometric procedure. Obtained results clearly show that developed analytical methodology can be adequate replacement for the, up to date, used methods and open-novel approach for ergosterol detection.