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At least 523 records · Page 29

Evaluation of Lithium Metal Anode Volumetric Expansion through Laser Plasma Focused Ion Beam Cross-Sectional Imaging

Lithium metal is an ideal anode for high energy density batteries, however the implementation of lithium metal anodes remains challenging. Beyond the development of highly efficient electrolytes, degradation processes restrict cycle life and reduce practical energy density. Herein lithium volumetric expansion and degradation pathways are studied in half cells through coupling electrochemical analysis with cross-sectional imaging of the intact electrode stack using a cryogenic laser plasma focused ion beam and scanning electron microscope. Here, we find that the volumetric capacity is compromised as early as the first cycle, at best reaching values only half the theoretical capacity (1033 vs 2045 mAh cm -3 ). By the 101st electrodeposition, the practical volumetric capacity decreases to values ranging from 143 to 343 mAh cm -3 .

25 ENERGY STORAGE↗

ZrB 2 -HfB 2 solid solutions as electrode materials for hydrogen reaction in acidic and basic solutions

Spark plasma sintered transition metal diborides such as HfB 2 , ZrB 2 and their solid solutions were investigated as electrode materials for electrochemical hydrogen evolutions reactions (HER) in 1 M H 2 SO 4 and 1 M NaOH electrolytes. HfB 2 and ZrB 2 formed complete solid solutions when mixed in 1:1, 1:4, and 4:1 ratios and they were stable in both electrolytes. The HER kinetics of the diborides were slower in the basic solution than in the acidic solutions. The Tafel slopes in 1 M H 2 SO 4 were in the range of 0.15 - 0.18 V/decade except for pure HfB 2 which showed a Tafel slope of 0.38 V/decade. In 1 M NaOH the Tafel slopes were in the range of 0.12 - 0.27 V/decade. The composition of Hf x Zr 1-x B 2 solid solutions with x = 0.2 - 0.8, influenced the exchange current densities, overpotentials and Tafel slopes of the HER. As a result, the EIS data were fitted with a porous film equivalent circuit model in order to better understand the HER behavior. In addition, modeling calculations, using density functional theory approach, were carried out to estimate the density of states and band structure of the boride solid solutions.

25 ENERGY STORAGE↗

Study on the characteristics of barrier free surface discharge driven by repetitive nanosecond pulses at atmospheric pressure

Nanosecond pulsed plasma has an enormous potential in many applications. In this paper, the characteristics of barrier free nanosecond pulsed surface discharge are investigated by the use of an actuator with a strip-strip film electrode configuration, including the effect of electrode width and the gap distance on the plasma morphology and electrical characteristics at atmospheric pressure. It was found that it is relative easier to generate a quasi uniform discharge with a thinner electrode width and a smaller gap distance. The underlying physical mechanism was also discussed. Besides that, the influence of airflow on repetitive pulsed surface discharge was examined. By comparing to the discharge produced by two different pulse waveforms in airflows, we found that the discharge driven by a faster pulse behaves more stable. Finally, a model was developed to analyze the interaction of the airflow and the discharge channels.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Properties of HfLaO MOS capacitor deposited on SOI with plasma enhanced atomic layer deposition

Amorphous HfLaO dielectric film was successfully deposited on a silicon-on-insulator (SOI) substrate by plasma enhanced atomic layer deposition with in situ plasma treatment. The HfLaO film retained its insulating characteristics and is thermally stable even after annealing at 800 °C. The film has a dielectric constant of 27.3 and leakage of only 0.03 mA/cm{sup 2} at a gate bias of |Vg − V{sub fb}| = 1 V. The capacitance equivalent oxide thickness is 0.7 nm. A new parallel electrode testing structure was applied to measure C–V and J–V characteristics for the SOI samples. This testing method for metal–oxide–semiconductor capacitors has potential uses for measuring other layered substrates.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Dynamics of multiple double layers in high pressure glow discharge in a simple torus

Parametric characterization of multiple double layers is done during high pressure glow discharge in a toroidal vessel of small aspect ratio. Although glow discharge (without magnetic field) is known to be independent of device geometry, but the toroidal boundary conditions are conducive to plasma growth and eventually the plasma occupy the toroidal volume partially. At higher anode potential, the visibly glowing spots on the body of spatially extended anode transform into multiple intensely luminous spherical plasma blob structures attached to the tip of the positive electrode. Dynamics of multiple double layers are observed in argon glow discharge plasma in presence of toroidal magnetic field. The radial profiles of plasma parameters measured at various toroidal locations show signatures of double layer formation in our system. Parametric dependence of double layer dynamics in presence of toroidal magnetic field is presented here.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Ferroelectric properties of full plasma-enhanced ALD TiN/La:HfO{sub 2}/TiN stacks

We report the possibility of employment of low temperature (≤330 °C) plasma-enhanced atomic layer deposition for the formation of both electrodes and hafnium-oxide based ferroelectric in the metal-insulator-metal structures. The structural and ferroelectric properties of La doped HfO{sub 2}-based layers and its evolution with the change of both La content (2.1, 3.7 and 5.8 at. %) and the temperature of the rapid thermal processing (550–750 °C) were investigated in detail. Ferroelectric properties emerged only for 2.1 and 3.7 at. % of La due to the structural changes caused by the given doping levels. Ferroelectric properties were also found to depend strongly on annealing temperature, with the most robust ferroelectric response for lowest La concentration and intermediate 650 °C annealing temperature. The long term wake-up effect and such promising endurance characteristics as 3 × 10{sup 8} switches by bipolar voltage cycles with 30 μs duration and ± 3 MV/cm amplitude without any decrease of remnant polarization value were demonstrated.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Study of etching rate uniformity in SRF cavities

Plasma based surface modification is a promising alternative to wet etching of superconducting radio frequency (SRF) cavities. The crucial aspect of the technology development is dependence of the etching rate and surface roughness on the frequency of the power supply, pressure, power level, driven electrode shape and chlorine concentration in the gas mixture during plasma processing. To optimize the plasma parameters, we are using a single cell cavity with 20 sample holders symmetrically distributed over the cell. These holders are used as diagnostic ports for the measurement of the plasma parameters and as holders for the samples to be etched. The plasma properties are highly correlated with the shape of the driven electrode and chlorine concentration in the Argon/Chlorine gas mixtures.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Plasma-driven solution electrolysis

Plasmas interacting with liquids enable the generation of a highly reactive interfacial liquid layer due to a variety of processes driven by plasma-produced electrons, ions, photons, and radicals. These processes show promise to enable selective, efficient, and green chemical transformations and new material synthesis approaches. While many differences are to be expected between conventional electrolysis and plasma–liquid interactions, plasma–liquid interactions can be viewed, to a first approximation, as replacing a metal electrode in an electrolytic cell with a gas phase plasma. For this reason, we refer to this method as plasma-driven solution electrochemistry (PDSE). In this Perspective, we address two fundamental questions that should be answered to enable researchers to make transformational advances in PDSE: How far from equilibrium can plasma-induced solution processes be driven? and What are the fundamental differences between PDSE and other more traditional electrochemical processes? Different aspects of both questions are discussed in five sub-questions for which we review the current state-of-the art and we provide a motivation and research vision.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Plasma dynamics, instabilities and OH generation in a pulsed atmospheric pressure plasma with liquid cathode: a diagnostic study

Abstract While plasma–liquid interactions have been an important focus in the plasma research community, the impact of the strong coupling between plasma and liquid on plasma properties and processes remains not fully understood. In this work, we report on the impact of the applied voltage, pulse width and liquid conductivity on the plasma morphology and the OH generation for a positive pulsed DC atmospheric pressure plasma jet with He–0.1% H 2 O mixture interacting with a liquid cathode. We adopted diagnostic techniques of fast imaging, 2D laser induced fluorescence of OH and Thomson scattering spectroscopy. We show that plasma instabilities and enhanced evaporation occur and have a significant impact on the OH generation. At elevated plasma energies, it is found that the plasma contracts due to a thermal instability through Ohmic heating and the contraction coincides with a depletion in the OH density in the core due to electron impact dissociation. For lower plasma energies, the instability is suppressed/delayed by the equivalent series resistor of the liquid electrode. An estimation of the energy flux from the plasma to the liquid shows that the energy flux of the ions released into the liquid by positive ion hydration is dominant, and significantly larger than the energy needed to evaporate sufficient amount of water to account for the measured H 2 O concentration increase near the plasma–liquid interface.

Physics↗

Levitation and collection of diamond fine particles in the rf plasma chamber equipped with a hot filament

We demonstrate the levitation of diamond fine particles in a H{sub 2} rf plasma chamber equipped with a hot filament and heated electrodes. The levitation conditions should be carefully chosen to compensate the strong thermophoretic forces caused by the filament and the electrodes. This levitation technique with the existence of a hot filament can be applied, e.g., for the efficient growth of diamond layers on seed particles injected and levitated in an rf plasma with reactive gases, e.g., CH{sub 4}/H{sub 2}. Additionally, the method for direct capture of levitated particles on a planar substrate was established, which is useful if it is necessary to analyze the particles after the levitation.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Numerical model of the plasma formation at electron beam welding

The model of plasma formation in the keyhole in liquid metal as well as above the electron beam welding zone is described. The model is based on solution of two equations for the density of electrons and the mean electron energy. The mass transfer of heavy plasma particles (neutral atoms, excited atoms, and ions) is taken into account in the analysis by the diffusion equation for a multicomponent mixture. The electrostatic field is calculated using the Poisson equation. Thermionic electron emission is calculated for the keyhole wall. The ionization intensity of the vapors due to beam electrons and high-energy secondary and backscattered electrons is calibrated using the plasma parameters when there is no polarized collector electrode above the welding zone. The calculated data are in good agreement with experimental data. Results for the plasma parameters for excitation of a non-independent discharge are given. It is shown that there is a need to take into account the effect of a strong electric field near the keyhole walls on electron emission (the Schottky effect) in the calculation of the current for a non-independent discharge (hot cathode gas discharge). The calculated electron drift velocities are much bigger than the velocity at which current instabilities arise. This confirms the hypothesis for ion-acoustic instabilities, observed experimentally in previous research.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Preliminary results on the conversion of laser energy into electricity

A preliminary experiment was performed to investigate conversion of 10.6 micron laser energy to electrical energy via a laser-sustained argon plasma. Short-circuit currents of 0.7 A were measured between a thoriated-tungsten emitter and collector electrodes immersed in the laser-sustained argon plasma. Open-circuit voltages of about 1.5 V were inferred from the current-voltage load characteristics. The dominant mechanism of laser energy conversion is uncertain at this time. Much higher output powers appear possible.

Thompson, R. W.↗

Controlled deposition of sulphur-containing semiconductor and dielectric nano-structured films on metals in SF{sub 6} ion-ion plasma

In the present paper, the deposition processes and formation of films in SF{sub 6} ion-ion plasma, with positive and negative ion flows accelerated to the surface, are investigated. The PEGASES (acronym for Plasma Propulsion with Electronegative GASES) source is used as an ion-ion plasma source capable of generating almost ideal ion-ion plasma with negative ion to electron density ratio more than 2500. It is shown that film deposition in SF{sub 6} ion-ion plasma is very sensitive to the polarity of the incoming ions. The effect is observed for Cu, W, and Pt materials. The films formed on Cu electrodes during negative and positive ion assisted deposition were analyzed. Scanning electron microscope analysis has shown that both positive and negative ion fluxes influence the copper surface and leads to film formation, but with different structures of the surface: the low-energy positive ion bombardment causes the formation of a nano-pored film transparent for ions, while the negative ion bombardment leads to a continuous smooth insulating film. The transversal size of the pores in the porous film varies in the range 50–500 nm, and further analysis of the film has shown that the film forms a diode together with the substrate preventing positive charge drain, and positive ions are neutralized by passing through the nano-pores. The film obtained with the negative ion bombardment has an insulating surface, but probably with a multi-layer structure: destroying the top surface layer allows to measure similar “diode” IV-characteristics as for the nano-pored film case. Basing on results, practical conclusions for the probes and electrodes cleaning in ion-ion SF{sub 6} plasmas have been made. Different applications are proposed for the discovered features of the controlled deposition from ion-ion plasmas, from Li-sulphur rechargeable batteries manufacturing and nanofluidics issues to the applications for microelectronics, including low-k materials formation.

36 MATERIALS SCIENCE↗

Production of dense plasmas in a hypocycloidal pinch apparatus

A high-power pinch apparatus consisting of disk electrodes was developed, and diagnostic measurements to study its mechanism of dense plasma production have been made. The collapse fronts of the current sheets are well organized, and dense plasma foci are produced on the axis with radial stability in excess of 5 microsec. A plasma density greater than 10 to the 18th power per cu cm is determined with Stark broadening and CO2 laser absorption. Essentially complete absorption of a high-energy CO2 laser beam has been observed. A plasma temperature of approximately 1 keV is measured with differential transmission of soft X-rays through thin foils. The advantages of this apparatus over the coaxial plasma focus are improvements in (1) plasma volume, (2) stability, (3) containment time, (4) access to additional heating by laser or electron beams, and (5) the possibility of scaling up to a multiple array for high-power operation.

Lee, J. H.↗

Electrochromic performance of nanocomposite nickel oxide counter electrodes containing lithium and zirconium

Nickel oxide materials are suitable for counter electrodes in complementary electrochromic devices. The state-of-the-art nickel oxide counter electrode materials are typically prepared with multiple additives to enhance peformance. Herein, nanocomposite nickel oxide counter electrodes were fabricated via RF magnetron co-sputtering from Ni-Zr alloy and Li2O ceramic targets. The as-deposited nanocomposite counter electrodes were characterized with inductively coupled plasma mass spectrometry (ICP-MS), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), and X-ray absorption spectroscopy (XAS). It was found that the stoichiometry, crystal structure and electronic structure of the nickel oxide-based materials could be readily tuned by varying the Li2O sputter deposition power level. Comprehensive electrochromic evaluation demonstrated that the performance of the nickel oxide-based materials was dependent on the overall Li stoichiometry. Overall, the nanocomposite nickel oxide counter electrode containing lithium and zirconium synthesized with a Li2O deposition power of 45 W exhibited the optimal performance with an optical modulation of 71% and coloration efficiency of 30 cm2/C at 670 nm in Li-ion electrolyte.

36 MATERIALS SCIENCE↗

Plasma Cleaning Research for Z

Z is a high-current pulsed-power generator located at Sandia National Laboratories. It is capable of delivering 100-ns, 30-MA current pulses to loads used for materials studies, weapons-effects simulation, and nuclear-fusion research. Under some conditions, a significant fraction of the current does not reach the load but is shunted across the inter-electrode vacuum gap that leads to the load. That undesirable current loss is thought to be due to excessive plasma generation and flow from the electrodes into the vacuum gap. Much past work suggests that this current loss may be reduced if contaminants on or near the surfaces of the electrodes are removed by plasma discharge cleaning. This report describes light-lab work performed in the past year to evaluate and understand plasma cleaning, and to develop the technology required for future tests on Z.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Electron properties and air mixing in radio frequency driven argon plasma jets at atmospheric pressure

A time modulated radio frequency (RF) plasma jet operated with an Ar mixture is investigated by measuring the electron density and electron temperature using Thomson scattering. The measurements have been performed spatially resolved for two different electrode configurations and as a function of the plasma dissipated power and air concentration admixed to the Ar. Time resolved measurements of electron densities and temperatures during the RF cycle and after plasma power switch-off are presented. Furthermore, the influence of the plasma on the air entrainment into the effluent is studied using Raman scattering.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

1-D fluid model of atmospheric-pressure rf He+O{sub 2} cold plasmas: Parametric study and critical evaluation

In this paper atmospheric-pressure rf He+O{sub 2} cold plasmas are studied by means of a 1-D fluid model. 17 species and 60 key reactions selected from a study of 250+ reactions are incorporated in the model. O{sub 2}{sup +}, O{sub 3}{sup -}, and O are the dominant positive ion, negative ion, and reactive oxygen species, respectively. Ground state O is mainly generated by electron induced reactions and quenching of atomic and molecular oxygen metastables, while three-body reactions leading to the formation of O{sub 2} and O{sub 3} are the main mechanisms responsible for O destruction. The fraction of input power dissipated by ions is {approx}20%. For the conditions considered in the study {approx}6% of the input power is coupled to ions in the bulk and this amount will increase with increasing electronegativity. Radial and electrode losses of neutral species are in most cases negligible when compared to gas phase processes as these losses are diffusion limited due to the large collisionality of the plasma. The electrode loss rate of neutral species is found to be nearly independent of the surface adsorption probability p for p > 0.001 and therefore plasma dosage can be quantified even if p is not known precisely.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗