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At least 1,027 records · Page 57

“Virtual IED sensor” at an rf-biased electrode in low-pressure plasma

Energy distribution and the flux of the ions coming on a surface are considered as the key-parameters in anisotropic plasma etching. Since direct ion energy distribution (IED) measurements at the treated surface during plasma processing are often hardly possible, there is an opportunity for virtual ones. This work is devoted to the possibility of such indirect IED and ion flux measurements at an rf-biased electrode in low-pressure rf plasma by using a “virtual IED sensor” which represents “in-situ” IED calculations on the absolute scale in accordance with a plasma sheath model containing a set of measurable external parameters. The “virtual IED sensor” should also involve some external calibration procedure. Applicability and accuracy of the “virtual IED sensor” are validated for a dual-frequency reactive ion etching (RIE) inductively coupled plasma (ICP) reactor with a capacitively coupled rf-biased electrode. The validation is carried out for heavy (Ar) and light (H{sub 2}) gases under different discharge conditions (different ICP powers, rf-bias frequencies, and voltages). An EQP mass-spectrometer and an rf-compensated Langmuir probe (LP) are used to characterize plasma, while an rf-compensated retarded field energy analyzer (RFEA) is applied to measure IED and ion flux at the rf-biased electrode. Besides, the pulsed selfbias method is used as an external calibration procedure for ion flux estimating at the rf-biased electrode. It is shown that pulsed selfbias method allows calibrating the IED absolute scale quite accurately. It is also shown that the “virtual IED sensor” based on the simplest collisionless sheath model allows reproducing well enough the experimental IEDs at the pressures when the sheath thickness s is less than the ion mean free path λ{sub i} (s < λ{sub i}). At higher pressure (when s > λ{sub i}), the difference between calculated and experimental IEDs due to ion collisions in the sheath is observed in the low energy range. The effect of electron impact ionization in the sheath on the origin and intensity of low-energy peaks in IED is discussed compared to ion charge-exchange collisions. Obviously, the extrapolation of the “virtual IED sensor” approach to higher pressures requires developing some other sheath models, taking into account both ion and electron collisions and probably including even a model of the whole plasma volume instead of plasma sheath one.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Less can be more: Insights on the role of electrode microstructure in redox flow batteries from two-dimensional direct numerical simulations

Understanding how to structure a porous electrode to facilitate fluid, mass, and charge transport is key to enhancing the performance of electrochemical devices, such as fuel cells, electrolyzers, and redox flow batteries (RFBs). Here, using a parallel computational framework, direct numerical simulations are carried out on idealized porous electrode microstructures for RFBs. Strategies to improve an electrode design starting from a regular lattice are explored. By introducing vacancies in the ordered arrangement, it is possible to achieve higher voltage efficiency at a given current density, thanks to improved mixing of reactive species, despite reducing the total reactive surface. Careful engineering of the location of vacancies, resulting in a density gradient, outperforms disordered configurations. Our simulation framework is a new tool to explore transport phenomena in RFBs, and our findings suggest new ways to design performant electrodes.

25 ENERGY STORAGE↗

Investigating the Impact of Thickness, Calendering and Channel Structures of Printed Electrodes on the Energy Density of LIBs - 3D Simulation and Validation

Current lithium ion batteries (LIBs) are expensive and bulky, limited by relatively low charging rates. To increase the rate of charging and reduce weight, thin electrodes with high energy density are required. The increase in energy density can be achieved by several techniques including boosting electrolyte transport, high loading/utilization of active material, employing high conductive electrolytes and electrodes with advanced architectures, and increasing cell temperature. In this paper, a 3D physics-based electrochemical model of LIBs is developed in COMSOL simulation software for different thickness, calendering steps as well as channel structures (conical, cylindrical) to optimize the electrode design and in turn maximize volumetric energy density. The simulation results demonstrated that calendering the electrodes with high initial porosity increases the volumetric energy density of the cell. In addition, cylindrical channel structures with relatively lower edge-to-edge distance also results in increased volumetric energy density. The simulation results of the 3D model was validated by comparing it with experimental results.

improving volumetric energy density↗

SU-E-T-414: Experimental Correction of High-Z Electrode Effect in Mini-Ionization Chambers for Small Beam Dosimetry

Purpose: To correct for the over-response of mini-ionization chambers with high-Z central electrodes. The hypothesis is that by applying a negative/reverse voltage, it is possible to suppress the signal generated in the high-Z central electrode by low-energy photons. Methods: The mini-ionization chambers used in the experiments were a PTW-31014, PTW-31006 and IBA-CC01. The PTW-31014 has an aluminum central electrode while the PTW-31006 and IBA-CC01 have a steel one. Total scatter factors (Scp) were measured for a 6 MV photon beam down to a square field size of 0.5 cm. The measurements were performed in water at 10 cm depth with SAD of 100 cm. The Scp were measured with the dosimeters with +400V bias voltage. In the case of the PTW-31006 and IBA-CC01, the measurements were repeated with −400V bias voltage. Also, the field factors in water were calculated with Monte Carlo simulations for comparison. Results: The measured Scp at +400V with the PTW-31006 and IBA-CC01 detectors were in agreement within 0.2% down to a field size of 1.5 cm. Both dosimeters shown a systematic difference about 2.5% with the Scp measured with the PTW-31014 and the Monte Carlo calculated field factors. The measured Scp at −400V with the PTW-31006 and IBA-CC01 detectors were in close agreement with the PTW-31014 measured Scp and the field factors within 0.3 and 1.0%, respectively. In the case of the IBA-CC01 it was found a good agreement (1%) down to field size of 1.0 cm. All the dosimeters shown differences up to 17% between the measured Scp and the field factor for the 0.5 cm field size. Conclusion: By applying a negative/reverse voltage to the mini-ionization chambers with high-Z central electrode it was possible to correct for their over-response to low energy photons.

07 ISOTOPE AND RADIATION SOURCES↗

Influence of the electrode system on the emission characteristics of a vacuum spark

The influence of the electrode system on the emission characteristics of a high-current low-inductance vacuum spark is investigated. It is shown that the structure and composition of the spark plasma radiating in the X-ray spectral range depend substantially on the geometry and relative position of the electrodes. A mechanism related to the effect of the initial distribution of the electric field in the electrode gap is proposed to explain such a dependence. The conditions in which the radiating plasma forms from the erosion products of one or both electrodes are determined.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Study of the Heterogeneity of a Mixed-Conducting Electrochemical Electrode

The ionic resistance of membrane–electrode assemblies of oxygen–hydrogen fuel cell electrodes containing platinum nanoparticles on carbon black, carbon nanofibers, and proton-conducting Nafion polymer in a wide range of compositions (10–80 wt %) are studied in situ by the methods of current–voltage characteristics, electrochemical impedance spectroscopy, and simulation of the impedance hodograph. Conditions that make it possible to correctly determine the ionic resistance of the electrode on the basis of an analysis of the linear approximation of the high-frequency region of the impedance hodograph are found. It is shown that the occurrence of inhomogeneities and an anomalous increase in the ionic resistance with an increase in the content of Nafion in the electrode are associated with a decrease in the volume fraction of water-generation centers (particles of electrochemically active platinum), which leads to incomplete wetting of Nafion.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Operando Topography and Mechanical Property Mapping of CO 2 Reduction Gas-Diffusion Electrodes Operating at High Current Densities

Electrochemical atomic force microscopy (EC-AFM) enables measurement of electrode topography and mechanical properties during electrochemical reactions. However, for aqueous-based reactions that make gas products, such as CO 2 reduction and water splitting into CO/H 2 , current densities below 1 mA cm −2 have been necessary to prevent formation of bubbles at the electrode; such bubbles can stick to the AFM probe and prevent further AFM imaging. Here, we demonstrate a novel cell design with a gas-diffusion electrode (GDE) to exhaust the gas products, thereby enabling high current density EC-AFM measurements at 1, 10, and 100 mA cm −2 that are not disturbed by bubble formation at the electrode surface. These experiments revealed a stable morphological structure of Cu catalysts deposited on GDEs during high current density operation. Systematic spatially resolved maps of deformation and adhesion showed no signs of a gas-liquid interface between catalyst particles of the GDE.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantifying the Impact of Charge Rate and Number of Cycles on Structural Degeneration of Li-Ion Battery Electrodes

A quantitative link between crack evolution in lithium-ion positive electrodes and the degrading performance on cells is not yet well established nor is any single technique capable of doing so widely available. Here, we demonstrate a widely accessible high-throughput approach to quantifying crack evolution within electrodes. The approach applies super-resolution scanning electron microscopy (SEM) imaging of cross-sectioned NMC532 electrodes, followed by segmentation and quantification of crack features. Crack properties such as crack intensity, crack width and length are quantified as a function of charge rate (1C, 6C, and 9C) and cycle number (25, 225, and 600 cycles). Hundreds of particles are characterized for statistical confidence in the quantitative crack measurements. The data on crack evolution is compared to electrochemical data from full cells and half cells with the NMC532 positive electrodes. We show that while crack evolution strongly correlates with capacity fade in the first 25 cycles, it does not correlate well for the following hundreds of cycles indicating that cracking may not be the dominant cause of capacity fade throughout the cycle-life of cells.

25 ENERGY STORAGE↗

Identifying Critical Electrode Metrics for Efficient, Selective CO 2 Electrochemical Conversion

Low-temperature electrochemical CO 2 reduction (CO 2 R) in zero-gap membrane electrode assembly (MEA) reactors presents a scalable route to fuels and carbon utilization. However, performance at industrially relevant current densities hinges on mesoscale catalyst layer integration, particularly at the ionomer|catalyst interface. Here, we demonstrate a generalizable in situ electrochemical impedance spectroscopy (EIS) method. We utilize this technique to decouple electrode-level parameters that are correlated to the overall MEA performance. By performing this ex situ EIS method on CO 2 -to-CO catalyst-coated membranes with systematically varied ionomer-to-catalyst (I:C) ratios, we reveal a pronounced dependence of performance, ion transport resistance, and catalyst utilization on the I:C ratio as well as the electrode conditioning. We demonstrate that an optimal I:C ratio exists at which ion transport resistance is minimized and Faradaic efficiency for CO production is maximized. Beyond the electrodes examined, here we compare ion transport resistance to MEA selectivity/Faradaic efficiency obtained in prior studies, revealing a clear correlation between the two. These results suggest that ion transport resistance within the catalyst layer may be a quantitative predictor of MEA performance which underscores the importance of mesoscale integration in achieving scalable CO 2 R technologies.

08 HYDROGEN↗

Layered oxide, graphite and silicon-graphite electrodes for Lithium-ion cells: Effect of electrolyte composition and cycling windows

The electrochemical performance of cells with a Li 1.03 (Ni 0.5 Co 0.2 Mn 0.3 ) 0.97 O 2 (NCM523) positive electrode and a blended silicon-graphite (Si-Gr) negative electrode are investigated using various electrolyte compositions and voltage cycling windows. Voltage profiles of the blended Si-Gr electrode show a superposition of graphite potential plateaus on a sloped Si profile with a large potential hysteresis. The effect of this hysteresis is seen in the cell impedance versus voltage data, which are distinctly different for the charge and discharge cycles. We confirm that the addition of compounds, such as vinylene carbonate (VC) and fluoroethylene carbonate (FEC) to the baseline 1.2 M LiPF 6 in ethylene carbonate (EC): ethyl methyl carbonate (EMC) (3:7 w/w) electrolyte, improves cell capacity retention with higher retention seen at higher additive contents. We show that reducing the lower cutoff voltage (LCV) of full cells to 2.5 V increases the Si-Gr electrode potential to 1.12 V vs. Li/Li + ; this relatively-high delithiation potential correlates with the lower capacity retention displayed by the cell. Hence, we show that raising the upper cutoff voltage (UCV) can increase cell energy density without significantly altering capacity retention over 100 charge discharge cycles.

25 ENERGY STORAGE↗

Testing Lithium-Ion Battery with the Internal Reference Electrode: An Insight into the Blocking Effect

Long-term stability of reference electrode is a major issue in lithium-ion batteries. A composite Ni-Li reference electrode (RE) with a longer lifetime than traditional Cu-wire Li reference electrodes is proposed in this study. However, the larger size of the Ni-Li RE creates a blocking effect when positioned internally in the battery. The blocking effect manifests as an abnormal feature in the measured electrode potential. A two-dimensional (2D) finite element model of the cell with an internal RE is constructed to investigate the mechanism of the blocking effect. The internal RE blocks the path of local current flow in the electrolyte, and decreases the electrochemical reaction rate of particles in the anode and cathode, leading to measurement errors. Characteristic lengths of RE and applied currents were examined as parameters in the finite element model to determine their effect on the magnitude of error. A useful guide is provided for proper selection of size of RE and applied current in dynamic tests of lithium-ion batteries.

2-D finite element model↗

Enhancing Analytical Performance of (Mg,Fe)3O4/Glassy Carbon Electrodes by Tailoring Chemical Composition of (Mg,Fe)3O4 Nanoparticles

A series of MgxFe3-xO{sup 4} (x = 0-1) nanoparticles was synthesized in order to prepare novel MgxFe3-xO{sup 4}/glassy carbon modified electrodes. Effects of magnesium content (x) on the analytical performance of the modified electrodes in the detection of gallic acid were evaluated. It was found that magnesium concentration and crystallite/particle size of the prepared nanoparticles play significant roles in the sensing properties of modified electrodes. The increase of magnesium concentration up to the value of x = 0.4 in MgxFe3-xO{sup 4}/glassy carbon paste was accompanied by an increase of the corresponding oxidation current of gallic acid. However, further growth of x value caused decline of the obtained oxidation current. An electroanalytical procedure was established, and the analytical performance of the proposed Mg0.4Fe2.6O{sup }4#/glassy carbon paste electrode was monitored using previously optimized experimental conditions. A working linear range from 1-39 µM gallic acid was obtained with detection limit of 0.29 µM. According to these results, the developed procedure can be applied for detection of low concentrations of gallic acid with satisfactory selectivity in the presence of some common naturally occurring compounds. Experimental results indicate that the developed procedure could be a novel approach in the detection of antioxidant, overcoming some known disadvantages such as passivation, and could be a promising replacement for sophisticated chromatographic methods.

60 APPLIED LIFE SCIENCES↗

Copper-coated electrodes for electrical discharge machining of 38X2H2MA steel

The use of copper-coated aluminum electrodes in the electrical discharge machining of 38X2H2MA steel is assessed. Such electrodes prove effective. The use of coated electrodes improves the economics of electrical discharge machining by permitting the use of cheaper materials in the electrode core.

36 MATERIALS SCIENCE↗

Ni-BaTiO3-Based Base-Metal Electrode (BME) Ceramic Capacitors for Space Applications

A multi-layer ceramic capacitor (MLCC) is a high-temperature (1350C typical) co-fired ceramic monolithic that is composed of many layers of alternately stacked oxide-based dielectric and internal metal electrodes. To make the dielectric layers insulating and the metal electrode layers conducting, only highly oxidation-resistant precious metals, such as platinum, palladium, and silver, can be used for the co-firing of insulating MLCCs in a regular air atmosphere. MLCCs made with precious metals as internal electrodes and terminations are called precious-metal electrode (PME) capacitors. Currently, all military and space-level applications only address the use of PME capacitors.

Ceramic Capacitors↗

Electrochemical study of uranium cations in LiCl-KCl melt using a rotating disk electrode

A rotating disk electrode (RDE) measurement technique was employed to investigate the electrochemical REDOX reactions of actinide (An) and lanthanide (Ln) ions in LiCl-KCl molten salt. By using RDE, it is possible to access more exact values of the diffusion coefficient, Tafel slope, and exchange current density. In this work, we constructed RDE setup and electrodes for RDE measurements in high temperature molten salt and measured the electrochemical parameters of the An and Ln ions. The RDE setup is composed of a Pine model MSRX rotator equipped with a rod type of W electrode. The active electrode area was confined to the planar part of the W rod by making meniscus at the LiCl-KCl melt surface.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Freeze Tape Casting Electrode with Bilayered Architecture for High-Performance Lithium-Ion Batteries

A facile freeze tape casting (FTC) strategy is utilized to prepare bilayered 4 mAh cm –2 high-loading LiNi 0.6 Co 0.2 Mn 0.2 O 2 cathodes. The bottom layer is a conventional nonaqueous electrode, which has a dense structure for high-energy purposes. Further, the top layer is prepared by the proposed FTC, exhibiting a porous feature for high-power requirement. With the assistance of FTC, the bilayered electrodes successfully deliver enhanced rate and cyclic performance due to the improved lithium-ion diffusion kinetics and pathways. Therefore, the proposed FTC strategy and its delivered electrodes are promising for energy- and power-density lithium-ion batteries, potentially enlightening the research and development of lithium-ion battery manufacturing.

25 ENERGY STORAGE↗

Materials Science of Electrodes and Interfaces for High-Performance Organic Photovoltaics

The science of organic photovoltaic (OPV) cells has made dramatic advances over the past three years with power conversion efficiencies (PCEs) now reaching ~12%. The upper PCE limit of light-to-electrical power conversion for single-junction OPVs as predicted by theory is ~23%. With further basic research, the vision of such devices, composed of non-toxic, earth-abundant, readily easily processed materials replacing/supplementing current-generation inorganic solar cells may become a reality. Organic cells offer potentially low-cost, roll-to-roll manufacturable, and durable solar power for diverse in-door and out-door applications. Importantly, further gains in efficiency and durability, to that competitive with inorganic PVs, will require fundamental, understanding-based advances in transparent electrode and interfacial materials science and engineering. This team-science research effort brought together an experienced and highly collaborative interdisciplinary group with expertise in hard and soft matter materials chemistry, materials electronic structure theory, solar cell fabrication and characterization, microstructure characterization, and low temperature materials processing. We addressed in unconventional ways critical electrode-interfacial issues underlying OPV performance -- controlling band offsets between transparent electrodes and organic active-materials, addressing current loss/leakage phenomena at interfaces, and new techniques in cost-effective low temperature and large area cell fabrication. The research foci were: 1) Theory-guided design and synthesis of advanced crystalline and amorphous transparent conducting oxide (TCO) layers which test our basic understanding of TCO structure-transport property relationships, and have high conductivity, transparency, and tunable work functions but without (or minimizing) the dependence on indium. 2) Development of theory-based understanding of optimum configurations for the interfaces between oxide electrodes/interfacial layers and OPV active layer organic molecules/polymers. 3) Exploration and perfection of new processing strategies and cell architectures for the next-generation, large-area flexible OPVs. The goal has been to develop for the solar energy community the fundamental scientific understanding needed to design, fabricate, prototype, and ultimately test high-efficiency cells incorporating these new concepts. We achieved success in all of these directions.

14 SOLAR ENERGY↗

Mass Transfer and Reaction Kinetic Enhanced Electrode for High‐Performance Aqueous Flow Batteries

Abstract A scalable and efficient process to modify electrodes with enhanced mass transfer and reaction kinetics is critical for redox flow batteries (RFBs). For the first time, this work introduces electrochemical exfoliation as a surface modification method of graphite felt (GF) to enhance the mass transfer and reaction kinetics in RFBs. Anion intercalation and subsequent gas evolutions at room temperature for one minute expand the graphite layers that increase the electrode surface area. Meanwhile, sufficient oxygen functional groups are introduced to the electrode, resulting in enhanced reaction kinetics and improved hydrophilicity. Further, spin‐polarized density functional theory is employed to reveal the role of oxygen functional groups in accelerating the vanadium redox reaction. Benefitting from sufficient oxygen groups, larger surface area, and superior wettability, the as‐prepared exfoliated GF (E‐GF) shows exceptional electrocatalytic activity with minimized overpotential, higher volumetric capacity, and improved energy efficiency. The redox flow battery assembled with the E‐GF electrode delivers voltage and energy efficiencies of 89.72% and 86.41% at the current density of 100 mA cm −2 , respectively. Remarkably, compared to the traditional GF treatment method, the elimination of the high temperature and long‐time treatment processes make this approach much more energy and time efficient, scalable, and affordable for large‐scale manufacturing.

Mukhopadhyay, Alolika↗