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At least 649 records · Page 36

Simulation of Unidirectional Ion Ejection in an Asymmetric Half-Round Rod Electrode Linear Ion Trap Mass Analyzer

An asymmetric trapping field was generated from an asymmetric half-round rod electrode linear ion trap (A-HreLIT), and its performance of unidirectional ion ejection was studied. Two different asymmetric structures of A-HreLITs were constructed, one rotating y electrode pairs toward an x electrode with an angle θ, and the other stretching one x electrode with a distance α. The center of trapping field was displaced away from the geometrical center of the ion trap, defined to be the midpoint along the axis of y between x electrodes, which leads to unidirectional ion ejection through one x electrode. Computer simulations were used to investigate the relationship between asymmetric geometric parameter of θ (or α) and analytical performance. Both structures could result in similar asymmetric trapping fields, which mainly composed of dipole, quadrupole, and hexapole fields. The dipole and hexapole fields were approximately proportional to the asymmetric geometric parameter of rotation angle θ (or stretch distance α). In simulation, ion trajectories and ion kinetic energy were calculated. For ions with m/z 609 Th, the simulation results showed that mass resolution of over 2400 (FWHM) and ion unidirectional ejection efficiency of nearly 90% were achieved in an optimized A-HreLIT. Ion detection efficiency of A-HreLIT could be improved significantly with only one ion detector, while maintaining a considerable mass resolution. Furthermore, the A-HreLIT could be driven by a traditional balanced RF power supply. These advantages make A-HreLIT suitable for developing miniaturized mass spectrometer with high performance. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Application of electrospinning for the fabrication of proton-exchange membrane fuel cell electrodes

We report electrospun materials have been gaining great interest in the energy sector. Their tunability and robustness make them highly attractive, particularly for proton-exchange membrane fuel cell (PEMFC) electrodes. Conventional PEMFC electrodes, prepared by either spraying, painting, or slot-die coating, have not yet met the needs of large-scale PEMFC use. Electrospinning of fibrous materials has already shown great promise as an alternative methodology for electrode fabrication. Electrospinning has been used in fuel cell electrodes through two primary means: (1) segmented carbon or inorganic fibers to serve as precious metal catalyst support, and (2) high aspect ratio polymer/particle fibers to serve directly as the electrode. The use of electrospun fibrous electrodes has led to improved PEMFC durability and increased power output at low catalyst loadings, both of which are of paramount importance to large-scale commercialization of PEMFC electric vehicles.

36 MATERIALS SCIENCE↗

Evaluation of a Ag/Ag 2 S reference electrode with long-term stability for electrochemistry in ionic liquids

We report on a reference electrode designed for use in ionic liquids, based on a silver wire coated with silver sulfide. The reference electrode potential is determined by the concentrations of Ag + and S 2- , which are established by the solubility of the Ag 2 S coating on the Ag wire. While potential shifts of >100 mV during an experiment have been reported when using silver or platinum wire quasi-reference electrodes, the reference electrode reported here provides a stable potential over several months of experimental use. Additionally, our reference electrode can be prepared and used in a normal air atmosphere, and does not need to be assembled and used in a glovebox, or protected from light. In conclusion, the reference electrode has been characterized by voltammetry measurements of ferrocene and cobaltocenium hexafluorophosphate, and was found to slowly drift to more positive potentials at a rate of <1 mV/day for five of the six ionic liquids investigated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pore-scale study of multiphase reactive transport in fibrous electrodes of vanadium redox flow batteries

The electrode of a vanadium redox flow battery generally is a carbon fibre-based porous medium, in which important physicochemical processes occur. In this work, pore-scale simulations are performed to study complex multiphase flow and reactive transport in the electrode by using the lattice Boltzmann method (LBM). Four hundred fibrous electrodes with different fibre diameters and porosities are reconstructed. Both the permeability and diffusivity of the reconstructed electrodes are predicted and compared with empirical relationships in the literature. Reactive surface area of the electrodes is also evaluated and it is found that existing empirical relationship overestimates the reactive surface under lower porosities. Further, a pore-scale electrochemical reaction model is developed to study the effects of fibre diameter and porosity on electrolyte flow, V II /V III transport, and electrochemical reaction at the electrolyte-fibre surface. Finally, evolution of bubble cluster generated by the side reaction is studied by adopting a LB multiphase flow model. Effects of porosity, fibre diameter, gas saturation and solid surface wettability on average bubble diameter and reduction of reactive surface area due to coverage of bubbles on solid surface are investigated in detail. It is found that gas coverage ratio is always lower than that adopted in the continuum model in the literature. Furthermore, the current pore-scale studies successfully reveal the complex multiphase flow and reactive transport processes in the electrode, and the simulation results can be further upscaled to improve the accuracy of the current continuum-scale models.

25 ENERGY STORAGE↗

Calcium-bismuth electrodes for large-scale energy storage (liquid metal batteries)

Calcium is an attractive electrode material for use in grid-scale electrochemical energy storage due to its low electronegativity, earth abundance, and low cost. The feasibility of combining a liquid Ca-Bi positive electrode with a molten salt electrolyte for use in liquid metal batteries at 500-700 degrees C was investigated. Exhibiting excellent reversibility up to current densities of 200 mA cm(-2), the calcium bismuth liquid alloy system is a promising positive electrode candidate for liquid metal batteries. The measurement of low self-discharge current suggests that the solubility of calcium metal in molten salt electrolytes can be sufficiently suppressed to yield high coulombic efficiencies >98%. The mechanisms giving rise to Ca-Bi electrode overpotentials were investigated in terms of associated charge transfer and mass transport resistances. The formation of low density Ca11Bi10 intermetallics at the electrode electrolyte interface limited the calcium deposition rate capability of the electrodes; however, the co-deposition of barium into bismuth from barium-containing molten salts suppressed Ca-Bi intermetallic formation thereby improving the discharge capacity. (C) 2013 Elsevier B.V. All rights reserved.

Kim, H↗

Modification of lithium electrodeposition behavior by variation of electrode distance

Developing a better understanding and control over the lithium electrodeposition behavior will assist with the commercial application of lithium metal anodes for rechargeable batteries. Despite intensive research over the past decade, our understanding of the deposition of lithium is limited. Here a new observation on the effect of distance between the working electrode and the counter electrode for electrochemical lithium deposition behavior is reported. From this fundamental investigation of distance, the high lithium ion concentration regions formed by release of lithium ions from the counter electrode modify the lithium deposition behavior on the working electrode, resulting in the generation of non-uniform lithium dendrites with a thick diversely composed surface film. Alternatively, increasing the distance between the electrodes results in the deposition of a spherical lithium morphology with a thin LiF rich surface film. Here, this fundamental study provides a deeper understanding of correlation between lithium deposition behavior and electrode separation and provides insight to inhibit lithium dendrite formation.

25 ENERGY STORAGE↗

Mechanistic insights into structural parameters maximizing energy storage density in Si mesoporous electrodes for Li-ion batteries

Mesoporous Si electrodes have an interesting set of structural parameters, which, when carefully optimized, can lead to ultrahigh energy density Si electrodes for Li-ion batteries. We present here in this paper details of a systematic research leading to the discovery of an “ideal” structure of mesoporous Si electrode, which results in exceptional cracking/damage resistance, while simultaneously having very high specific (>2000 mAh g-1) and total (>1.5 mAh cm-2) capacities for large number of cycles. The electrodes near the “ideal” value of the characteristic structural parameter (the ratio of Si wall thickness to pore diameter) are free from first-cycle capacity degradation, and are efficient in accommodating the volume changes during lithiation by uniformly filling up the porous space between Si walls. Interestingly, these electrodes are also found to be structurally damage-resistant, surviving through many lithiation-delithiation cycles. Using charge-discharge cycling and electron microscopy we show that ideal structure is the key for achieving ultrahigh energy storage density in Si mesoporous electrodes for Li-ion batteries.

25 ENERGY STORAGE↗

Long carbon fibers boost performance of dry processed Li-ion battery electrodes

Dry processing (DP) is an advanced manufacturing technique for lithium-ion battery (LIB) electrodes. Unlike conventional wet-process-based manufacturing that involves dissolving polyvinylidene fluoride (PVDF) binder in n-methyl-2-pyrrolidone (NMP) solvent for slurry-casting, DP involves fibrillation of polymer binders. This method offers environmental and cost benefits by eliminating the need for expensive and environmentally hazardous organic solvents. However, DP-produced electrode films often lack mechanical stability due to the absence of a current collector substrate during electrode material layer fabrication. This reduced mechanical instability results in difficulty during fabricating of thin electrodes (≈5 mAh/cm 2 ). To address this issue, long (>8 mm) carbon fiber (CF) has been incorporated to reinforce the mechanical strength of the electrode films. In conclusion, the study demonstrates that the inclusion of long carbon fiber boosts the mechanical, electrical, thermal, and electrochemical performance of DP electrodes.

25 ENERGY STORAGE↗

Enhancement of the efficiency of dye-sensitized solar cell with multi-wall carbon nanotubes/polypyrrole composite counter electrodes prepared by electrophoresis/electrochemical polymerization

Graphical abstract: The overall energy conversion efficiency of the DSSC employing the MWCNT/PPy CE reached 3.78%. Compared with a reference DSSC using single MWCNT film CE with efficiency of 2.68%, the energy conversion efficiency was increased by 41.04%. Highlights: ► MWCNT/PPy composite film prepared by electrodeposition layer by layer was used as counter electrode in DSSC. ► The overall energy conversion efficiency of the DSSC was 3.78% by employing the composite film. ► The energy conversion efficiency increased by 41.04% compared with efficiency of 2.68% by using the single MWCNT film. ► We analyzed the mechanism and influence factor of electron transfer in the composite electrode by EIS. - Abstract: For the purpose of replacing the precious Pt counter electrode in dye-sensitized solar cells (DSSCs) with higher energy conversion efficiency, multi-wall carbon nanotube (MWCNT)/polypyrrole (PPy) double layers film counter electrode (CE) was fabricated by electrophoresis and cyclic voltammetry (CV) layer by layer. Atom force microscopy (AFM), scanning electron microscopy (SEM) and transmission electron microscope (TEM) demonstrated the morphologies of the composite electrode and Raman spectroscopy verified the PPy had come into being. The overall energy conversion efficiency of the DSSC employing the MWCNT/PPy CE reached 3.78%. Compared with a reference DSSC using single MWCNT film CE with efficiency of 2.68%, the energy conversion efficiency was increased by 41.04%. The result of impedance showed that the charge transfer resistance R{sub ct} of the MWCNT/PPy CE had the lowest value compared to that of MWCNT or PPy electrode. These results indicate that the composite film with high conductivity, high active surface area, and good catalytic properties for I{sub 3}{sup −} reduction can potentially be used as the CE in a high-performance DSSC.

36 MATERIALS SCIENCE↗

Facile preparation of porous nickel oxide membrane for flexible supercapacitors electrode via phase-separation method of polymer

Highlights: • Polymer/metal oxide hybrid membrane is fabricated for supercapacitors electrode. • Effects of membrane components on structure and performance are investigated. • The prepared electrode membrane shows high flexible property. • A capacitance of 794 F/g is obtained at a current density of 1.0 A/g. • Symmetric supercapacitor device exhibits an energy density of 39.6 Wh/kg. - Abstract: In this article, a porous flexible membrane electrode of nickel oxide is developed by a facile method based on liquid-liquid phase-separation. The effects of the membrane components on structures and electrochemical behaviors of membrane electrode are investigated. The results reveal that nano NiO and conducting graphite are imbedded into the polymer membrane of polyethersulfone to form a flexible hybrid membrane (M-NiO-G), which shows the highest specific capacitance of 794.0 F/g at a current density of 1.0 A/g. The asymmetrical supercapacitor device based on the as-synthesized of M-NiO-G (positive electrode) and activated carbon membrane (negative electrode) exhibits a high specific capacitance of 154.0 F/g at a current density of 0.2 A/g. The coulombic efficiency remains about 95.0%, and the capacitance retention is 84.8% after 5000 charging-discharging cycles at 1.0 A/g. The energy density of the asymmetrical supercapacitor device reaches 39.6 Wh/kg at a power density of 516.9 W/kg, still remains 20.0 Wh/kg at a high power density of 2567.4 W/kg in the potential window from 0 to 1.36 V in 6 M KOH aqueous solution.

36 MATERIALS SCIENCE↗

Electrode roughness dependent electrodeposition of sodium at the nanoscale

Na metal is an attractive anode material for rechargeable Na ion batteries, however, the dendritic growth of Na can cause serious safety issues. Along with modifications of solid-electrolyte interphase (SEI), engineering the electrode has been reported to be effective in suppressing Na dendritic growth, likely by reducing localized current density accumulation. However, fundamental understanding of Na growth at the nanoscale is still limited. Here, we report an in-situ study of Na electrodeposition in electrochemical liquid cells with the electrodes in different surface roughness, e.g., flat or sharp curvature. Real time observation using transmission electron microscopy (TEM) reveals the Na electrodeposition with remarkable details. Relatively large Na grains (in the micrometer scale) are achieved on the flat electrode surface. The local SEI thickness variations impact the growth rate, thus the morphology of individual grains. In contrast, small Na grains (in tens of nanometers) grow explosively on the electrode at the point with sharp curvature. The newly formed Na grains preferentially deposit at the base of existing grains close to the electrode. Further studies using continuum-based computational modeling suggest that the growth mode of an alkali metal (e.g. Na) is strongly influenced by the transport properties of SEI. Our direct observation of Na deposition in combination with the theoretical modeling provides insights for comprehensive understanding of electrode roughness and SEI effects on Na electrochemical deposition.

25 ENERGY STORAGE↗

Drying Temperature and Capillarity-Driven Crack Formation in Aqueous Processing of Li-Ion Battery Electrodes

Unlike conventional electrode processing for Li-ion batteries, which uses the expensive and highly toxic organic N -methyl-2-pyrrolidone (NMP) solvent, aqueous processing simply employs deionized water as the solvent. Yet, thick aqueous processed cathodes have been found to crack during drying. Here, the influence of electrode drying temperature and thickness on cracking was investigated. LiNi 1/3 Mn 1/3 Co 1/3 O 2 cathodes prepared with a hydrophilic binder, modified styrene–butadiene rubber (SBR), were coated at various thicknesses and dried at temperatures ranging from 20 to 70 °C. Experiments revealed cracking worsens with increased electrode thickness and elevated drying temperatures. Cracks were formed during the capillarity-driven phase during drying. Strong evaporation and weak diffusion played a critical role in the nonuniform distribution of the inactive phase. Images of electrode surfaces were processed to quantify crack dimensions and crack intensity factor (CIF). The average crack length and width, as well as CIF, increased with drying temperature and electrode thickness. Electrochemical performance revealed a strong and negative correlation between the crack density and performance in terms of specific capacity. Transport limitations associated with the presence of cracks adversely affect the advantage of high volume ratio of active materials in the thick electrodes.

25 ENERGY STORAGE↗

Towards uniformly dispersed battery electrode composite materials: Characteristics and performance

Battery electrodes are complex mesoscale systems comprised of electroactive components, conductive additives, and binders. In this report, methods for processing electrodes with dispersion of the components are described. To investigate the degree of material dispersion, a spin-coating technique was adopted to provide a thin, uniform layer that enabled observation of the morphology. Distinct differences in the distribution profile of the electrode components arising from individual materials physical affinities were readily identified. Hansen solubility parameter (HSP) analysis revealed pertinent surface interactions associated with materials dispersivity. Further studies demonstrated that HSPs can provide an effective strategy to identify surface modification approaches for improved dispersions of battery electrode materials. Specifically, introduction of surfactantlike functionality such as oleic acid (OA) capping and P3HT-conjugated polymer wrapping on the surface of nanomaterials significantly enhanced material dispersity over the composite electrode. The approach to the surface treatment on the basis of HSP study can facilitate design of composite electrodes with uniformly dispersed morphology and may contribute to enhancing their electrical and electrochemical behaviors. The conductivity of the composites and their electrochemical performance was also characterized. In conclusion, the study illustrates the importance of considering electronic conductivity, electron transfer, and ion transport in the design of environments incorporating active nanomaterials.

25 ENERGY STORAGE↗

Electrochemical and Spectroscopic Analysis of the Ionogel–Electrode Interface

Ionogels, pseudo-solid-state electrolytes consisting of an ionic liquid electrolyte confined in a mesoporous inorganic matrix, have attracted interest recently due to their high ionic conductivity and physicochemical stability. These traits, coupled with their inherent solution processability, make them a viable solid electrolyte for solid-state battery systems. Despite the promising properties of ionogels, there have been very few investigations of the electrode–ionogel interface. In the present study, X-ray photoelectron spectroscopy, Raman spectroscopy, and electrochemical measurements were utilized to probe the surface reactions occurring at the electrode–ionogel interface for several electrode materials. Our results indicate that the sol acidity initiates breakdown of the organic constituents of the sol and reduction of the transition metals present in the electrode materials. This chemical attack forms an organic surface layer and affects the electrode composition, both of which can impede Li+ access. By modifying the silica sol–gel reaction via a two-step acid–base catalysis, these interfacial reactions can be avoided. Results are shown for a LiCoO 2 electrode in which a high Li-ion capacity and stable cycling were achieved.

36 MATERIALS SCIENCE↗

Self-Supporting, Hydrophobic, Ionic Liquid-Based Reference Electrodes Prepared by Polymerization-Induced Microphase Separation

Interfaces of ionic liquids and aqueous solutions exhibit stable electrical potentials over a wide range of aqueous electrolyte concentrations. This makes ionic liquids suitable as bridge materials that separate in electroanalytical measurements the reference electrode from samples with low and/or unknown ionic strengths. However, methods for the preparation of ionic liquid-based reference electrodes have not been explored widely. We have designed a convenient and reliable synthesis of ionic liquid-based reference electrodes by polymerization-induced microphase separation. This technique allows for a facile, single-pot synthesis of ready-to-use reference electrodes that incorporate ion conducting nanochannels filled with either 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide or 1-dodecyl-3-methylimidazolium bis(trifluoromethyl sulfonyl)imide as ionic liquid, supported by a mechanically robust cross-linked polystyrene phase. This synthesis procedure allows for the straightforward design of various reference electrode geometries. These reference electrodes exhibit a low resistance as well as good reference potential stability and reproducibility when immersed into aqueous solutions varying from deionized, purified water to 100 mM KCl, while requiring no correction for liquid junction potentials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Surface restructuring of a perovskite-type air electrode for reversible protonic ceramic electrochemical cells

Reversible protonic ceramic electrochemical cells (R-PCECs) are ideally suited for efficient energy storage and conversion; however, one of the limiting factors to high performance is the poor stability and insufficient electrocatalytic activity for oxygen reduction and evolution of the air electrode exposed to the high concentration of steam. Here we report our findings in enhancing the electrochemical activity and durability of a perovskite-type air electrode, Ba 0.9 Co 0.7 Fe 0.2 Nb 0.1 O 3-δ (BCFN), via a water-promoted surface restructuring process. Under properly-controlled operating conditions, the BCFN electrode is naturally restructured to an Nb-rich BCFN electrode covered with Nb-deficient BCFN nanoparticles. When used as the air electrode for a fuel-electrode-supported R-PCEC, good performances are demonstrated at 650 °C, achieving a peak power density of 1.70 W cm –2 in the fuel cell mode and a current density of 2.8 A cm –2 at 1.3 V in the electrolysis mode while maintaining reasonable Faradaic efficiencies and promising durability.

30 DIRECT ENERGY CONVERSION↗

Thermal processing to modulate surface chemistry and bulk charge distribution in nickel-rich layered lithium positive electrodes

The broader application of nickel-rich layered oxides as positive electrode materials for lithium-ion batteries has been hindered by their high manufacturing cost and inferior cycling stability. Thermal processing, which is integral to electrode materials manufacturing and fundamental in materials science, has not been fully utilized to design advanced positive electrode materials. Herein, we demonstrate the capability of using quenching heat treatment to regulate Li distribution and modulate electronic structure near particle surface. The resulting materials exhibit less parasitic reactions with the electrolyte and an improved charge distribution homogeneity in secondary particles, leading to more stable cycling performance at high voltages (4.5 V vs Li/Li + ). Our synchrotron X-ray analyses reveal the underlying interplay between surface structure and bulk charge distribution in positive electrode materials particles. While strategies used to stabilize positive electrode materials through compositional control, surface modification, and electrolyte engineering have become mature, thermal processing can be advantageous to further improve positive electrode materials manufacturing.

36 MATERIALS SCIENCE↗

Effect of crystallite geometries on electrochemical performance of porous intercalation electrodes by multiscale operando investigation

Lithium-ion batteries are yet to realize their full promise because of challenges in the design and construction of electrode architectures that allow for their entire interior volumes to be reversibly accessible for ion storage. Electrodes constructed from the same material and with the same specifications, which differ only in terms of dimensions and geometries of the constituent particles, can show surprising differences in polarization, stress accumulation and capacity fade. Here, using operando synchrotron X-ray diffraction and energy dispersive X-ray diffraction (EDXRD), we probe the mechanistic origins of the remarkable particle geometry-dependent modification of lithiation-induced phase transformations in V2O5 as a model phase-transforming cathode. A pronounced modulation of phase coexistence regimes is observed as a function of particle geometry. Specifically, a metastable phase is stabilized for nanometre-sized spherical V2O5 particles, to circumvent the formation of large misfit strains. Spatially resolved EDXRD measurements demonstrate that particle geometries strongly modify the tortuosity of the porous cathode architecture. Greater ion-transport limitations in electrode architectures comprising micrometre-sized platelets result in considerable lithiation heterogeneities across the thickness of the electrode. These insights establish particle geometry-dependent modification of metastable phase regimes and electrode tortuosity as key design principles for realizing the promise of intercalation cathodes. Designing electrode architectures for Li-ion batteries that can be reversibly accessible for ion storage can be challenging. Using operando techniques the mechanistic origin of lithiation-induced phase transformations in a V2O5 model cathode is now clarified.

Luo, Yuting↗