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At least 1,639 records · Page 91

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

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 of 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.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Experimental Study of Heating of a Liquid Cathode and Transfer of Its Components into the Gas Phase under the Action of a DC Discharge

An atmospheric-pressure dc discharge in air (i = 10–50 mA) with metal and liquid electrolyte electrodes was studied experimentally. An aqueous solution of sodium chloride (0.5 mol/L) was used as the cathode or anode. The electric field strength in the plasma and the cathode (anode) voltage drops were obtained from the measured dependences of the discharge voltage on the electrode gap length. The gas temperature was deduced from the spectral distribution of nitrogen emission in the band N{sub 2}(C{sup 3}Π{sub u} → B{sup 3}Π{sub g}, 0–2). The time dependences of the temperatures of the liquid electrolyte electrodes during the discharge and in its afterglow, as well as the evaporation rate of the solution, were determined experimentally. The contributions of ion bombardment and heat flux from the plasma to the heating of the liquid electrode and transfer of solvent (water) into the gas phase are discussed using the experimental data obtained.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

High-Efficiency Electron Source with a Hollow Cathode in Technologies of Thin Film Deposition and Surface Treatment under Forevacuum Pressures

It is shown that low-energy beams with a high efficiency in a wide range of beam currents can be obtained in electron sources with a hollow cathode in the forevacuum pressure range. By varying the geometrical parameters of the electrode system and electromagnetic optics of the electron source, we succeeded in reaching the efficiency at a level of 0.9 for an accelerating potential of 1 kV and beam currents from 100 to 300 mA. The parameters affecting most strongly the efficiency and stability of operation of the electron source with a hollow cathode have been determined.

43 PARTICLE ACCELERATORS↗

Intercepting Grids Made of Anisotropic Pyrolytic Graphite in Electron Guns with a Dispenser Cathode

The results of experimental studies into the application of anisotropic pyrolytic graphite (APG) as grid structures in power microwave devices with a dispenser cathode are detailed. The dependences of emission characteristics of molybdenum, hafnium, and APG in diodes and electron guns on the electron-flow power dissipated at the studied samples and on cathode temperature are presented. It is demonstrated that the power dissipation capacity of APG grid structures (without parasitic thermionic emission) is up to 20 and 9 times higher than that of molybdenum and hafnium grids, respectively.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

The physical mechanism of the deviation of cathode thermionic emission from the Schottky law

The deviation of the I–V characteristics of cathode materials in microwave devices from the Schottky law is caused by the occurrence of drift and diffusion of oxygen vacancies in barium-oxide crystallites, which are emission-active components of the cathode materials. The processing of experimental dependences using the proposed mathematical tools makes it possible to determine the barium-oxide-crystallite thickness and diffusivity of oxygen vacancies. The known diffusivity allows determining the presence of microimpurities in barium oxide, which affect its emission properties.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Emission Properties of Metal Porous Cathodes Modified by Nanocarbon

The results of studying the emissive ability, structure, and elemental composition of the surface of an impregnated cathode with a fine-grained tungsten matrix with addition of polyhedral multilayer carbon nanostructures of the fulleroid type (0.2−0.7 wt %), impregnated with barium-calcium aluminate with addition of sulfoadduct of carbon nanoclusters (0.1−0.2 wt %), are presented. The tests in diode prototypes showed that these cathodes provide a current density of 20 A/cm{sup 2}.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Can Greener Cyrene Replace NMP for Electrode Preparation of NMC 811 Cathodes?

N-methyl-2-pyrrolidone (NMP) is the normally used solvent for cathode processing in lithium battery field. However, its high toxicity attracted more and more environmental scrutiny and was restricted by many chemical legislations in industry applications. So, it is necessary to find a greener and safer alternative to replace it. Dihydrolevoglucosenone (Cyrene), a newly reported green dipolar aprotic solvent, has very similar solvent properties as NMP, making it a very attractive candidate. The possibility to use Cyrene to replace NMP for NMC 811 cathode fabrication was studied. Although PVDF binder has very poor solubility in Cyrene at room temperature, increasing temperature can significantly change this. High temperature (above 80 °C) electrode processing with Cyrene gives promising performance, which is comparable to the conventional NMP fabricated electrode. A proof of principle was provided: Cyrene can be a good green alternative to replace NMP. So, the positive results reported here may also lead to a search for more Cyrene-like green solvents that have a higher solubility for PVDF, or of PVDF-like binders that are more soluble in Cyrene, to help making the electrode processing much greener.

36 MATERIALS SCIENCE↗

Time-Resolved X-ray Operando Observations of Lithiation Gradients across the Cathode Matrix and Individual Oxide Particles during Fast Cycling of a Li-Ion Cell

Lithiated transition metal oxides serve as active materials in the positive electrode (cathode) of lithium-ion cells. During electrochemical cycling, lithium ions intercalate and deintercalate into these oxide particles. This behavior causes two types of lithiation gradients to emerge: (i) a bulk gradient across the depth of the cathode matrix (averaged over individual oxide particles) and (ii) a microscopic gradient across the particles themselves, which also depends on their location in the electrode. Here we show how both gradients can be studied using operando X-ray diffraction during 4C charge and 4C discharge. The oxide (de)lithiation is estimated from the unit cell parameters by indexing the X-ray diffraction spectra. By fitting the lithiation profiles with orthogonal polynomials, the bulk gradients across the electrode thickness are quantified. These gradients develop as the current flows through the cell and dissipate during open-circuit and potentiostatic-hold periods. Further details of lithiation dynamics can be obtained through shape analysis of the Bragg peaks. In particular, from electrochemical model simulations, we show that the width and skewness of the (003) peak track (de)lithiation fronts moving across the individual oxide particles.

(003) peak↗

Influence of Single-Crystalline Morphology on the Electrochemical Behavior of High-Nickel Layered Oxide Cathodes

High-Nickel layered oxides are being pursued for their high specific capacities. With increasing nickel content, the layered oxides also suffer from structural and morphological instabilities, which degrade the electrochemical performance. Single-crystalline morphology presents an attractive solution to these problems, simultaneously reducing surface area available for parasitic reactions and preventing electrolyte penetration into the bulk with the removal of grain boundaries. Single-crystal cathodes have already shown promising results with NMC composition cathodes, but there are still gaps in the fundamental understanding of how single-crystalline morphology alters electrochemical behavior. We attempt to fill some of these gaps by studying in detail the electrochemical operation of polycrystalline and single-crystalline LiNiO 2 (LNO). Single-crystal LNO is prepared through a molten salt method yielding high-quality, distinct crystals with comparable lattice chemistry to polycrystalline LNO. The single-crystal LNO achieves far greater stability during long-term cycling, reaching 500 cycles with 82.5% capacity retention. Interestingly, the single-crystalline LNO also displays superior rate performance, delivering 157 mA h g −1 at 10C discharge rate. Investigation of the phase evolution behavior during cycling strongly suggests that the absence of grain boundaries in single-crystalline LNO is responsible for the superior performance.

25 ENERGY STORAGE↗

Tape Casting of Thin Electrolyte and Thick Cathode for Halide-Based All-Solid-State Batteries

Most previous studies about halide solid-state electrolytes have used pellets prepared by uniaxial pressing, which is a good approach for materials development but is not suitable for commercialization. Thinner electrolyte layers that can be scaled up to large cell areas are required, and tape casting is a promising approach. It is challenging, however, as halide materials are reactive with most of the conventional solvents used in the process. In this study, solvents with low polarity, such as toluene, are found to be compatible with the Li 3 YBr 6 halide material. A wide variety of candidate binders that are soluble in toluene are studied. MSB1–13 binder is preferred, based on the ionic conductivity and mechanical properties of the tape. Electrolyte tapes (<70 μ m) are successfully cast on Al substrates, using 2 wt% binder. The resulting room temperature ionic conductivity is 2 × 10 −4 S cm −1 . Two composite cathodes including active material (LiFePO 4 or LiNi 0.82 Mn 0.07 Co 0.11 O 2 ) and 1 to 1.5 wt% MSB1–13 are tape cast as proof-of-concept for a scalable cell fabrication approach. A LiFePO 4 cell shows good retention at 25 °C. The performance of NMC cells with tape electrolyte or pellet electrolyte is similar. This study demonstrates the feasibility of tape casting halide-based electrolytes and cathodes.

25 ENERGY STORAGE↗

Mixed polyanion glass cathodes: Glass-state conversion reactions

Mixed polyanion (MP) glasses can undergo glass-state conversion (GSC) reactions to provide an alternate class of high-capacity cathode materials. GSC reactions have been demonstrated in phosphate/vanadate glasses with Ag, Co, Cu, Fe, and Ni cations. These MP glasses provided high capacity and good high power performance, but suffer from moderate voltages, large voltage hysteresis, and significant capacity fade with cycling. Details of the GSC reaction have been revealed by x-ray absorption spectroscopy, electron microscopy, and energy dispersive x-ray spectroscopy of ex situ cathodes at key states of charge. Using the Open Quantum Materials Database (OQMD), a computational thermodynamic model has been developed to predict the near-equilibrium voltages of glass-state conversion reactions in MP glasses.

36 MATERIALS SCIENCE↗

Communication—Improving Intermediate-Temperature Performance of a Screen-Printed LSCF Cathode with Infiltrated LSCF Nanoparticles

Here, the present study investigates the mass loading effect of an infiltrated La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (LSCF) nanoparticles (NPs) catalyst on the area-specific polarization resistance (Rp) of a screen-printed porous LSCF cathode for solid oxide fuel cells. The results show that R p of the LSCF-NPs decorated LSCF cathode can be substantially reduced by as much as 89.3% after a single-step impregnation of 1.5 M nitrate solution containing La:Sr:Co:Fe = 0.6:0.4:0.2:0.8 with a mass loading of 3 wt%.

25 ENERGY STORAGE↗

Process design for calcination of nickel-based cathode materials by in situ characterization and multiscale modeling

Developing battery materials towards commercial use, from the early discovery through synthesis, processing, scaling up, and eventually to industrial production, may take decades. A notable example is Ni-based layered oxides, which were discovered as early as 1950s and intensively pursued as cathode active materials (CAMs) since the early 90s but have yet to realize their full commercial potential. Significant efforts have been devoted to materials development aiming at improving performance, far less to process development for large-scale synthesis and processing of CAMs. In this paper, we present a rational design of calcination for scalable production of Ni-based CAMs. We start with an overview of the current understanding and knowledge gaps hindering rational process design and scaling-up of the calcination process. Then with specific examples, we demonstrate how to tackle those fundamental challenges through in situ characterization and multiscale modeling. Finally, we conclude by providing perspectives on the remaining challenges and emerging opportunities in commercial development of Ni-based cathodes, calling for more endeavors in this field.

25 ENERGY STORAGE↗

Sulfur poisoning mechanism of LSCF cathode material in the presence of SO 2 : a computational and experimental study

Aiming at the comprehensive understanding of the single sulfur poisoning effect and, eventually, the multiple impurities poisoning phenomena on the SOFC (Solid Oxide Fuel Cell) cathode materials, the sulfur poisoning effect on the (La 0.6 Sr 0.4 ) 0.95 Co 0.2 Fe 0.8 O 3 (LSCF-6428) has been investigated in the presence of 10 ppm SO 2 at 800, 900, and 1000°C, respectively, with a combined computational and experimental approach. The good agreement between the CALPHAD (Computer Coupling of Phase Diagrams and Thermochemistry) simulations and the XRD (X-Ray Diffraction), SEM (Scanning Electron Microscopy), and TEM (Transmission Electron Microscopy) characterization results support the reliability of the CALPHAD approach in the SOFC field. Furthermore, comprehensive simulations were made to understand the impact of temperature, P(SO 2 ), P(O 2 ), and Sr concentration on the threshold of SrSO 4 stability. Results showed that the formation of SrSO4 is thermodynamically favored at lower temperatures, higher P(SO 2 ), higher P(O 2 ), and higher Sr concentration. Finally, comparisons were also made between LSCF-6428 and LSM20 (La 0.8 Sr 0.2 MnO 3 ) using simulations, which confirmed that LSCF-6428 is a poor sulfur-tolerant cathode, in agreement with the literature.

36 MATERIALS SCIENCE↗

Gated Field-Emission Cathode Radio-Frequency (RF) Gun

The goal of this CRADA was to procure the carbon nanotube cathode from Radiabeam, install it in HBESL and make current measurements as a function of the gun gradient. The gun was operated at 1.3 GHz. After testing, send the cathode back to RadiaBeam for surface analysis.

43 PARTICLE ACCELERATORS↗

Towards commercialization of fluorinated cation-disordered rock-salt Li-ion cathodes

Cation-disordered rock-salt cathodes (DRX) are promising materials that could deliver high capacities (>250 mAh g −1 ) with Earth abundant elements and materials. However, their electrochemical performances, other than the capacity, should be improved to be competitive cathodes, and many strategies have been introduced to enhance DRXs. Fluorination has been shown to inhibit oxygen loss and increase power density. Nevertheless, fluorinated cation-disordered rock-salts still suffer from rapid material deterioration and low scalability which limit their practical applications. This mini-review highlights the key challenges for the commercialization of fluorinated cation-disordered rock-salts, discusses the underlying reasons behind material failure and proposes future development directions.

25 ENERGY STORAGE↗

Cathode–Sulfide Solid Electrolyte Interfacial Instability: Challenges and Solutions

All-solid-state batteries are a candidate for next-generation energy-storage devices due to potential improvements in energy density and safety compared to current battery technologies. Due to their high ionic conductivity and potential scalability through slurry processing routes, sulfide solid-state electrolytes are promising to replace traditional liquid electrolytes and enable All-solid-state batteries, but stability of cathode-sulfide solid-state electrolytes interfaces requires further improvement. Herein we review common issues encountered at cathode-sulfide SE interfaces and strategies to alleviate these issues.

25 ENERGY STORAGE↗