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Pseudocapacitive Charge Storage in Electrochromic Transition-Metal Oxide Thin Films

Electrochromic pseudocapacitive transition-metal oxide materials, such as tungsten oxide, which combine fast response, high energy density, and optical effects, can play a significant role as energy storage materials. Here we investigate the electrochemical kinetics of thin films of tungsten oxide, which turn transparent to sky-blue color in the lithiated state due to the reduction of W 6+ to W 5+ . In this study, we investigated the charge density, charge transfer, ion diffusion, and interfacial behavior upon Li + insertion/de-insertion in WO 3 . The electrochromic thin film's pseudocapacitive and electrical double layer mechanism was differentiated based on the power-law. Faradaic diffusion-controlled process dominates over the surface capacitive behavior at scan rates below 40 mV s –1 . These films exhibit an areal charge density of around 100 mC cm –2 and a capacitance of 80 mF cm –2 , superior to most comparable electrochromic materials and supercapacitors. This work combines electrochromics and energy storage properties and provides a fundamental understanding of pseudocapacitive and electrochromic mechanisms in WO 3 .

25 ENERGY STORAGE↗

Final technical report

This final report covers the final year of the project. Reports from previous years were included in the group report for that year. The objective of this part of the project was to compare results from two large-scale, nonlinear plasma simulation codes based on magnetohydrodynamics, M3D and M3D-C1, for plasma edge instabilities. This is a difficult undertaking and the comparison was only partially successful because, while the MHD equations are standard, there are a number of valid MHD models of the plasma dissipation that make different approximations to their physics and the numerical implementation of a given model can be quite different depending on the way that the rest of the equations are solved. Large differences arise, and have major effects on the predicted plasma behavior, in the case of the greatest interest to this project, the plasma edge region under conditions where the plasma edge instabilities are strongest and the background plasma changes abruptly from interior hot, dense conditions to an unconfined, cool, diffuse plasma outside the magnetic boundary surface. Experimental observations only partially measure the background plasma and there are many non-MHD processes that can have important effects (studied in the rest of the project). Comparisons for edge instabilities at very small amplitude, the so-called linear modes, had showed good agreement for a few interior plasma instabilities, but strong differences between the default models for the plasma edge.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Property Measurements of NaCl-UCl 3 and LiF-NaF-KF Molten Salts Doped with Surrogate Fission Products

Knowing thermophysical and thermochemical property values of salts over the expected range of operating temperatures is essential to modeling and simulation efforts that support the commercialization of molten salt reactor (MSR) technologies. Salt properties being measured at Argonne include thermal transitions, phase behavior, heat capacity, density, surface tension, volumetric thermal expansion, thermal diffusivity, thermal conductivity, and viscosity. The properties of several salts of interest including NaCl-UCl 3 and LiF-NaF-KF (FLiNaK) have been measured at Argonne and reported previously. These property measurements are suitable for use in evaluating reactor performance during startup and the early operating life of the reactor. The physical and chemical behavior of the fuel salt is altered by the buildup of fission products and the resulting changes in heat transfer and other properties must be understood by reactor developers. This report summarizes melting behavior, heat capacity, and thermal diffusivity values that were measured for mixtures of FLiNaK and NaCl-UCl 3 salts that have been doped with surrogate fission products. Additional heat capacity measurements were also performed on a separate mixture of FLiNaK without dopants. Measured properties are suitable for incorporation into the Molten Salt Thermal Properties Database–Thermochemical (MSTDB–TC) and the Molten Salt Thermal Properties Database–Thermophysical (MSTDB–TP) to support the development of MSRs. Salts were prepared by doping eutectic mixtures of NaCl-UCl 3 and FLiNaK with surrogate fission products. These salts were prepared for use in salt spill experiments being performed at Argonne and were subsequently used for thermal property measurements. Thermal transitions and heat capacities were measured by using differential scanning calorimetry (DSC) and thermal diffusivity was measured by using laser flash analysis (LFA) at temperatures spanning the typical MSR operating range. The measured property values of the doped salts were compared to measured property values of salts without fission products to quantify the effects of the doped fission products.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Impact of Annealing on the Chemical and Superconducting Properties of Ta Thin Films

Tantalum thin films are annealed to dissolve the surface oxide. The effect of annealing is studied using material characterization tools, XPS and TOF-SIMS, and electrical transport measurements of the annealed films are taken using standard PPMS methods to correlate with the surface chemistry. Annealing dissociates the surface oxide, and the oxygen produced diffuses into the thin film. The introduction of oxygen reduces the quality of the thin film, as shown by the suppression of Tc and a reduction in RRR.

Shinde, Maithilee [IIT, Chicago]↗

Formation of Non-Doped Cubic Lithium Lanthanum Zirconium Oxide Nanofibers: Insights from In Situ Synchrotron X-Ray Scattering

This study investigates the formation mechanism of non-doped cubic lithium lanthanum zirconium oxide (c-LLZO) nanofibers using in situ synchrotron X-ray scattering techniques. Electrospun polymer precursor nanofibers were annealed at temperatures up to 800 °C, enabling real-time tracking of phase transitions via simultaneous small-angle X-ray scattering (SAXS), wide-angle X-ray scattering (WAXS), and evolved CO 2 gas analysis. The results reveal a three-step transformation pathway: polymer decomposition, formation of La 2 Zr 2 O 7 (LZO), and direct conversion of LZO to c-LLZO without intermediate tetragonal phases detected within the sensitivity of our in situ WAXS measurement. Cryo-electron energy loss spectroscopy (EELS) further elucidates the role of lithium diffusion, showing Li enrichment at fiber surfaces and Li deficiency in the interior, which stabilizes the cubic phase. This Li segregation effect in nanostructured LLZO materials extends beyond the previously reported size effect. This work advances the understanding of c-LLZO formation mechanisms and provides practical insights for optimizing synthesis routes to achieve phase-pure c-LLZO for solid-state battery applications.

LLZO phase stability↗

Stagnation region heating of a phenolic-nylon ablator during return from planetary missions

The results of a stagnation-line analysis of the radiative heating of a phenolic-nylon ablator are reported. The analysis includes flowfield coupling with the ablator surface, equilibrium chemistry, multicomponent or binary diffusion and a coupled line and continuum radiation calculations. Users manual and operating instructions for the computer programs listed in the report are included.

Esch, D. D.↗

Twisted, multifilament Nb3Sn superconductive ribbon

An experimental study of superconductor stabilization has resulted in the successful application of the concepts of filamentary structure and conductor twist to Nb3Sn ribbon. The Nb3Sn is formed in parallel, helical paths, which are continuous around the ribbon. Short lengths (12-18cm) of 1.27 cm wide superconductive ribbon were produced. The filamentary and twist characteristics are incorporated in the ribbon by means of an inert mask formed on the ribbon surface early in the fabrication process. Diffusion reaction of the niobium and tin is prevented at the filament boundaries. Described are the conductor methods of fabrication, and test results obtained. The technology required to adapt the processes for the production of long lengths of ribbon is available.

Coles, W. D.↗

Radiation pressure and air drag effects on the orbit of the balloon satellite 1963 30D

Computed orbits of the balloon satellite 1963 30D are given every 2 days over an interval of 456 days near the beginning of the satellite's lifetime and an interval of 824 days near the end of its lifetime. The effects of radiation pressure on the satellite are examined in some detail. It is found that the variations in all the elements can be represented by use of a single parameter to specify the effect of diffuse reflection from the satellite's surface, and that this parameter remains constant, or nearly so, during the entire 7-year lifetime. Success in obtaining a consistent representation of the radiation-pressure effects is ascribed to the inclusion of the effects of terrestrial radiation pressure, using a model for the earth's albedo that includes seasonal and latitudinal variations. Anomalous effects in the orbital acceleration, as well as in the other elements, are represented quite well by including a small force at right angle to the solar direction and by allowing this to rotate about the solar direction. This implies that the satellite is aspherical, that it is rotating, and that the axis of rotation precesses.

Slowey, J. W.↗

Results of the first 150 days of the NTS-1 solar cell experiments

Twelve solar cell experiments were on the Naval Research Laboratory NTS-1 satellite launched on 14 July 1974, into a 13,260 km circular orbit at an inclination of 125 deg. The experiment comprises: 2 ohm-cm n/p, lithium-diffused p/n, violet n/p, p(+) back surface field, and ultra-thin wrap around contact cells. The short-circuit current of the experiments ranged from 2 to 12 percent higher in space than under solar simulators. During the 5 year life of the satellite, the experiments will be exposed to radiation equivalent to 2 x 10 to the 15th power 1-MeV electron cm/2 and to nearly 5500 thermal cycles.

Statler, R. L.↗

Experimentally determined aeroacoustic performance and control of several sonic inlets

Low speed wind tunnel tests were conducted to determine the aeroacoustic performance of several model sonic inlets. The results were analyzed to indicate how inlet aeroacoustic characteristics were affected by inlet design and operating conditions. A system for regulating sonic inlet noise reduction was developed and tested. Results indicate that pressure losses at forward velocity may be substantially less than those at static conditions. This is particularly true for translating centerbody inlets with the centerbody extended in the approach and landing position. Operation to simulated takeoff incidence angles of 50 degrees was demonstrated with good inlet performance. Inlet sound pressure level reduction was regulation was regulated to within approximately + or - 1 dB by controlling inlet surface static pressure measured at the diffuser exit.

Miller, B. A.↗

Experimentally determined aeroacoustic performance and control of several sonic inlets

Low speed wind tunnel tests were conducted to determine the aeroacoustic performance of several model sonic inlets. The results were analyzed to indicate how inlet aeroacoustic characteristics were affected by inlet design and operating conditions. A system for regulating sonic inlet noise reduction was developed and tested. Results indicate that pressure losses at forward velocity may be substantially less than those at static conditions. This is particularly true for translating centerbody inlets with the centerbody extended in the approach and landing position. Operation to simulated take-off incidence angles of 50 deg was demonstrated with good inlet performance. Results suggest that at takeoff, with 0 deg incidence angle, sonic inlet total pressure losses need not exceed those generated by skin friction for sound pressure level reductions to at least 15 dB. Inlet sound pressure level reduction was regulated to within approximately plus or minus 1 dB by controlling inlet surface static pressure measured at the diffuser exit.

Miller, B. A.↗

On the kinetics of pack aluminization

A theory of pack aluminization has been formulated by combining gaseous and solid-state diffusion rates. This theory relates the surface composition of the coating and therefore, in principle, the phase morphology and the growth rate of the coating, to pack operating parameters such as pack aluminum density, type of activator, temperature and others. Experimental data on the aluminization of unalloyed nickel in pure aluminum packs obtained to date are in good agreement with the predictions of the theory.

Gupta, B. K.↗

Theoretical investigations of plasma processes

System analyses are presented for electrically sustained, collision dominated plasma centrifuges, in which the plasma rotates under the influence of the Lorentz forces resulting from the interaction of the current density fields with an external magnetic field. It is shown that gas discharge centrifuges are technically feasible in which the plasma rotates at speeds up to 1 million cm/sec. The associated centrifugal forces produce a significant spatial isotope separation, which is somewhat perturbed in the viscous boundary layers at the centrifuge walls. The isotope separation effect is the more pronounced. The induced magnetic fields have negligible influence on the plasma rotation if the Hall coefficient is small. In the technical realization of collision dominated plasma centrifuges, a trade-off has to be made between power density and speeds of rotation. The diffusion of sputtered atoms to system surfaces of ion propulsion systems and the deposition of the atoms are treated theoretically by means of a simple model which permits an analytical solution. The problem leads to an inhomogeneous integral equation.

Wilhelm, H. E.↗

Determination of minority-carrier lifetime and surface recombination velocity with high spacial resolution

Quantitative analysis of the electron beam induced current in conjunction with high-resolution scanning makes it possible to evaluate the minority-carrier lifetime three dimensionally in the bulk and the surface recombination velocity two dimensionally, with a high spacial resolution. The analysis is based on the concept of the effective excitation strength of the carriers which takes into consideration all possible recombination sources. Two-dimensional mapping of the surface recombination velocity of phosphorus-diffused silicon diodes is presented as well as a three-dimensional mapping of the changes in the minority-carrier lifetime in ion-implanted silicon.

Watanabe, M.↗

Laser Techniques in Photovoltaic Research

High-power laser pulses were used to replace the conventional high temperature furnace processing for the p-n junction formation step in high speed, low cost solar cell fabrication. Three different approaches to junction formation were tested: (1) laser annealing of ion-implanted Si in which laser radiation is used to remove the radiation damage and to recover the electrical activity in the implanted layer; (2) a process in which a thin film of dopant is first deposited on the substrate and then incorporated into the near-surface region by laser-induced diffusion; and (3) a process in which a heavily doped amorphous silicon layer is deposited on the Si substrate and epitaxially regrown from the melted substrate layer by laser radiation. All three methods were found to provide suitable candidates for high efficiency Si solar cells.

Young, R. T.↗