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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 163 records · Page 9

Cations Enhance Hydride Transfer to Noncatalytic Metals in Concentrated Alkaline Electrolytes

Alkali metal cations are known to influence the kinetics of the hydrogen evolution reaction (HER), acting as either promoters or inhibitors to the rate-determining step depending on the metal surface, local pH, and cation concentration. Despite the importance of concentrated electrolytes for commercial electrochemical cells, the impact of cations on the HER in concentrated alkaline environments (>1 M) and in mixed cation systems remains poorly understood. Here, this study quantifies the HER kinetics at polycrystalline metal surfaces (Pt, Au, Cu, and Fe) and the equilibrium solvation environment in pure and mixed alkali metal hydroxide electrolytes at concentrations up to 3.0 M. Kinetic analyses of Au, Cu, and Fe revealed a positive cation-concentration-effect that was primarily driven by changes to the charge transfer coefficient. Multinuclear NMR spectroscopy examined the solvation of H 2 O/OH – species and the alkali cations as a function of (mixed) alkali cation concentration(s), and demonstrated rapid exchange between solvent, hydroxide, and solvated cations. Together, these findings support models where HER kinetics on noncatalytic metal surfaces in strongly alkaline conditions are primarily governed by the average polarization and polarizability of the metal/solution interface and that increasing cation activity continues to increase the transfer coefficient at metal-hydroxide concentrations up to 3.0 M. Electrolytes and additives which can outcompete weakly hydrated cations and disrupt the interfacial water structure are expected to suppress parasitic HER at electrodes for energy storage and electroplating.

Cations↗

Active Dendrite Suppression by Ferroelectric Membrane Separators in Rechargeable Batteries

Anodic dendrite formation is a critical issue in rechargeable batteries and often leads to poor cycling stability and quick capacity loss. Prevailing strategies for dendrite suppression aim at slowing down the growth rate kinetically but still leaving possibilities for dendrite evolution over time. Herein, we report a complete dendrite elimination strategy using a mesoporous ferroelectric polymer membrane as the battery separator. The dendrite suppression is realized by spontaneously reversing the surface energetics for metal ion reduction at the protrusion front, where a positive piezoelectric polarization is generated and superimposed as the protrusion compresses the separator. This effect is demonstrated first in a Zn electroplating process, and further in Zn–Zn symmetric cells and Zn–NaV 3 O 8 ·1.5H 2 O full cells, where the dendritic Zn anode surfaces are completely turned into featureless flat surfaces. Consequently, a substantially longer charging/discharging cycle is achieved. Furthermore, this study provides a promising pathway toward high-performance dendrite-free rechargeable batteries.

25 ENERGY STORAGE↗

Understanding the Polymorphism of Cobalt Nanoparticles Formed in Electrodeposition–An In Situ XRD Study

An advanced synchrotron-based in situ X-ray diffraction (XRD) technique is successfully developed and employed to track and monitor the formation and phase selection of cobalt (Co) in electrodeposition in real time and verify DFT computational results. The impacts of a number of controlling factors including the pH of the electrolyte and deposition overpotential are systematically studied. The results show that the yielded phase of the electrodeposited Co is controlled by both thermodynamics and kinetics. The low pH low overpotential condition favors the formation of the thermodynamically stable fcc phase. While the high pH high overpotential condition promotes the formation of the metastable hcp phase. The experimental results agree well with the nanometric phase diagram computed with DFT. Layer-by-layer alternative stacking of fcc-hcp polymorphic phases can be facilely fabricated by just varying the overpotential. This work not only offers an effective means to control the phase of electroplating of Co but also presents a new approach to reveal the fundamental insights of the formation of metals under electrochemical reduction driving force.

36 MATERIALS SCIENCE↗

Enabling “lithium-free” manufacturing of pure lithium metal solid-state batteries through in situ plating

Abstract The coupling of solid-state electrolytes with a Li-metal anode and state-of-the-art (SOA) cathode materials is a promising path to develop inherently safe batteries with high energy density (>1000 Wh L −1 ). However, integrating metallic Li with solid-electrolytes using scalable processes is not only challenging, but also adds extraneous volume since SOA cathodes are fully lithiated. Here we show the potential for “Li-free” battery manufacturing using the Li 7 La 3 Zr 2 O 12 (LLZO) electrolyte. We demonstrate that Li-metal anodes >20 μm can be electroplated onto a current collector in situ without LLZO degradation and we propose a model to relate electrochemical and nucleation behavior. A full cell consisting of in situ formed Li, LLZO, and NCA is demonstrated, which exhibits stable cycling over 50 cycles with high Coulombic efficiencies. These findings demonstrate the viability of “Li-free” configurations using LLZO which may guide the design and manufacturing of high energy density solid-state batteries.

25 ENERGY STORAGE↗

Heterogeneous doping via nanoscale coating impacts the mechanics of Li intrusion in brittle solid electrolytes

Lithium dendrite intrusion in solid-state batteries limits fast charging and causes short-circuiting, yet the underlying regulating mechanisms are not well-understood. Here, in this work, we discover that heterogeneous Ag + doping dramatically affects lithium intrusion into Li 6.6 La 3 Zr 1.6 Ta 0.4 O 12 (LLZO), a brittle solid electrolyte. Nanoscale Ag + doping is achieved by thermally annealing a 3-nm-thick metallic coating on LLZO, inducing Ag–Li ion exchange and Ag diffusion into grains and grain boundaries. Density functional theory calculations and experimental characterization show negligible impact on the electronic properties and surface wettability from Ag + incorporation. Mechanically, nanoindentation experiments show a fivefold increase in the mechanical force required to fracture the surface Ag + -doped LLZO, indicating substantial doping-induced surface toughening. Operando microprobe scanning electron microscopy experiments show that the Ag + -doped LLZO surface exhibits improved lithium plating at >250 mA cm −2 and an electroplating diameter that is expanded by over fourfold, even under an extreme indentation stress of 3 GPa. This demonstrates enhanced defect tolerance in LLZO, rather than electronic or adhesion effects. Our study reveals a chemo-mechanical mechanism via surface heterogeneous doping, complementing present bulk design rules to minimize mechanical failures in solid-state batteries.

36 MATERIALS SCIENCE↗

Multi-metallic conduction cooled superconducting radio-frequency cavity with high thermal stability

Superconducting radio-frequency cavities are commonly used in modern particle accelerators for applied and fundamental research. Such cavities are typically made of high-purity, bulk Nb and with cooling by a liquid helium bath at a temperature of ~2 K. The size, cost and complexity of operating a particle accelerator with a liquid helium refrigerator make the current cavity technology not favorable for use in industrial-type accelerators. We have developed a multi-metallic 1.495 GHz elliptical cavity conductively cooled by a cryocooler. The cavity has a ~2 µm thick layer of Nb 3 Sn on the inner surface, exposed to the rf field, deposited on a ~3 mm thick bulk Nb shell and a bulk Cu shell, of thickness $\geqslant\! 5$ mm deposited on the outer surface by electroplating. A bolt-on Cu plate 1.27 cm thick was used to thermally connect the cavity equator to the second stage of a Gifford-McMahon cryocooler with a nominal capacity of 2 W at 4.2 K. The cavity was tested initially in liquid helium at 4.3 K and reached a peak surface magnetic field of ~36 mT with a quality factor of 2 × 10 9 . The cavity cooled by the cryocooler achieved a peak surface magnetic field of ~29 mT, equivalent to an accelerating gradient of 6.5 MV m –1 . The conduction-cooled cavity could be operated in continuous-wave with as high as 5 W dissipation in the cavity for 1 h without any thermal breakdown, because of the Cu outer layer with high thermal conductivity. This result represents a paradigm shift in the technology of superconducting accelerator cavities.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

An experimental study to investigate magnetic field and winding force-dependent contact resistance of NI REBCO coil

Abstract This paper reports the magnetic field and winding force-dependent contact resistance, also known as characteristic resistance, of no-insulation (NI) REBCO coil. Three NI coils were wound with different winding forces ( < 1 kgf, 3 kgf, and 5 kgf) using the same REBCO-coated conductor, and they were tested at 4.2 K in a background field of 0, 5, 10, and 14 T. The contact resistance of each coil is measured at each field. As a result of the measurements, we draw two conclusions. First, a quadratic function for magnetic field intensity reasonably reproduces the measurement results of each NI test coil’s magnetic field-dependent contact resistance, where the practical fit function’s coefficients are determined depending on the winding force. Second, the contact resistance of each coil is partially inconsistent with the magnetoresistance of the electroplated material, i.e. copper, of the REBCO-coated conductor. This paper will present the measurement results in detail, discuss them with Kohler’s rule, and formulate the contact resistance using winding force and magnetic field terms.

Bang, Jeseok (ORCID:0000000247616334)↗

Effects of stabilizer strength on the delamination strength of ReBCO coated conductors

Delamination strengths (DSs) of ReBCO tapes were evaluated using a transverse tensile anvil test. This study first demonstrated that the electromechanical DS is nearly equivalent to the purely mechanical DS for ReBCO tapes exhibiting abrupt delamination behavior. Mechanical DS was then examined for tapes with and without stabilizer edges to assess the influence of stabilizer strength. Scanning electron microscopy/energy-dispersive x-ray spectroscopy analysis revealed the delamination sites and crack propagation in ReBCO tapes. Further investigation revealed that the DS of ReBCO tapes is primarily determined by two factors: (1) interfacial bonding strength between the layers and (2) mechanical strength of the stabilizer edges. These findings point to a potential approach to enhancing DS by increasing the strength of the stabilizer (e.g. by optimizing the Cu electroplating process).

Cu stabilizer↗

A Digital Twin Approach to Study Additive Manufacturing Processing Using Embedded Optical Fiber Sensors and Numerical Modeling

One of the major challenges for metal-powder-based additive manufacturing is measuring and mitigating residual strain induced during the manufacturing processes. This article reports distributed fiber optic sensors embedded in Inconel alloy components as experimental means to validate numerical models of additive manufacturing process. Electroplating was used to deposit a metal protective jacket onto standard telecom single-mode fibers for strain measurements, Fiber sensors were embedded in an Inconel alloy substrate using the laser engineered net shaping (LENS) process. Here by using a Rayleigh-scattering optical frequency domain reflectometer (OFDR), temperature changes, and residual strain in the metal substrate were monitored with 5 mm spatial resolution during the LENS process. Using finite element analysis, temperature and strain profiles induced by the LENS deposition processes were also numerically studied. Discrepancies between the simulated temperature and strain profiles and those measured directly were less than 10%. Results presented in this article demonstrates a digital twin approach to fuse modeling results with distributed fiber sensor measurement data to study additive manufacturing process toward design and fabrication process optimization.

36 MATERIALS SCIENCE↗

Spray-Coated Silver as Backside Metal for III–V Photovoltaic Devices on GaAs and Ge Substrates

The accelerated increase in demand for III-V space photovoltaics on GaAs and Ge substrates, as well as growing interests in terrestrial applications, motivate the development of cost-effective, high-throughput processing routes of these materials. Here, in this study, we assess spray-coated silver (Ag) back contact metallization as a substitute for electron-beam-evaporated metals currently used in industry. We find that the spray-coated Ag films are dense and continuous. By means of quantum efficiency, dark current-voltage, and illuminated current-voltage characterizations, we show that spray-coated GaAs and Ge solar cells perform similarly to baseline devices with electroplated Au, including under high current densities. We estimate that the thresholds for specific contact resistance below which back contacts do not significantly contribute to resistive loss are 2.1 x 10 -1 Ω•cm 2 for GaAs and 4.7 x 10 -2 Ω•cm 2 for Ge. We experimentally confirm that our spray-coated samples meet these requirements. Peel tests show that the adhesion of plain spray-coated Ag films to the back of p-type Ge substrates used in III-V solar cells is currently insufficient, whereas adhesion to p-type GaAs substrates is outstanding and requires no further optimization.

14 SOLAR ENERGY↗

Tutorial on forming through-silicon vias

Through-silicon vias (TSVs) are a critical technology for three-dimensional integrated circuit technology. These through-substrate interconnects allow electronic devices to be stacked vertically for a broad range of applications and performance improvements such as increased bandwidth, reduced signal delay, improved power management, and smaller form-factors. There are many interdependent processing steps involved in the successful integration of TSVs. This article provides a tutorial style review of the following semiconductor fabrication process steps that are commonly used in forming TSVs: deep etching of silicon to form the via, thin film deposition to provide insulation, barrier, and seed layers, electroplating of copper for the conductive metal, and wafer thinning to reveal the TSVs. Recent work in copper electrochemical deposition is highlighted, analyzing the effect of accelerator and suppressor additives in the electrolyte to enable void-free bottom-up filling from a conformally lined seed metal.

42 ENGINEERING↗

Application of templated vapor-liquid-solid growth to heteroepitaxy of InP on Si

Direct growth of III–V semiconductors on Si promises to combine the superior optoelectronic properties of III–Vs with the existing large-scale fabrication capabilities for Si. Vapor-liquid-solid-based growth techniques have previously been used to grow optoelectronic-quality III–Vs in polycrystalline films and various photolithography-defined features. We show that templated vapor-liquid-solid growth can produce epitaxial material when performed on crystalline substrates. In templated vapor-liquid-solid growth, the metal group-III precursor is evaporated along with a capping SiO 2 layer on the crystalline substrate, then melted and converted with exposure to a vapor-phase group-V precursor. We demonstrate homoepitaxial growth of InP on InP wafers using two forms of the SiO x capping layer to confine the liquid metal: evaporated SiO 2 and solgel SiO x , the latter of which is necessary for growth on Si. We then demonstrate heteroepitaxial growth of InP islands on Si substrates from both evaporated and electroplated In metals. The templated vapor-liquid-solid process provides better material utilization and growth rates than common vapor-phase techniques, with similar control and convenience, providing a path toward the large-scale fabrication of integrated optoelectronic components.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Editors’ Choice—Rapid Deactivation Convolutes Electrochemical CO 2 Reduction Selectivity Measurements on Gold Rotating Ring Disk Electrodes

Voltammetric measurements of electrochemical CO 2 reduction reaction (CO 2 RR) selectivity on rotating ring disk electrodes (RRDE) are a rapid and sensitive method for quantifying an electrocatalyst’s selectivity, i.e. faradaic efficiency (FE). This method has been applied to polycrystalline Au electrocatalysts where a Au disk electrode catalyzes both the CO 2 RR and hydrogen evolution reaction while the concentric Au ring electrode selectively senses CO by oxidizing CO back to CO 2 . Such measurements enabled fundamental mechanistic studies but suffer from poor inter-laboratory reproducibility. This work identifies causes of variability in RRDE selectivity measurements by comparing protocols with different electrochemical methods, reagent purities, and glassware cleaning procedures. We observed FE CO decrease by 56% during 5 min chronoamperometry measurements, a phenomenon that is not readily apparent in voltammetric scans due to their dynamic nature. Electroplating of electrolyte impurities onto the disk and ring surfaces were identified as a major contributor to Au deactivation. Additionally, the oxygen reduction reaction may lead to higher disk currents in inadequately purged electrolytes, causing an apparent underestimation of FE CO at low overpotentials. Lastly, we propose operational bounds for CO 2 RR selectivity measurements on Au using the RRDE method and provide suggestions on steps for improving the accuracy of this technique.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Light-Induced Al Plating on Si for Fabrication of an Ag-Free All-Al Solar Cell

Light-induced electroplating of Al as the front electrode on the n-type emitter of Si solar cells is proposed as a substitute for screen-printed Ag. The advantages and disadvantages of Al over Cu as the front electrode are discussed. The power of a green laser used for patterning of the SiN x antireflection coating is optimized. Conditions for removal of laser damage and contamination on the laser-patterned surface are identified. The effect of plating temperature and post-annealing temperature on Al morphology and resistivity are investigated. Several plating additives are explored to improve the morphology and resistivity of the Al film. Nicotinic acid produces the lowest resistivity of 3.1 μ Ω-cm. However, the lowest contact resistivity between light-induced Al and Si is 69 mΩ-cm 2 due to laser-induced damage to the emitter. The Al film spikes through the thin n-type emitter when annealed at 500 °C causing cell failure. The process reproducibility is also poor due to atmospheric moisture.

14 SOLAR ENERGY↗

Concentrated radiative cooling and its constraint from reciprocity

Concentrated radiative cooling, an analogous concept of the concentrated solar power technology, has the potential of amplifying both the cooling power and the temperature reduction. However, concentrators have not yet been systematically optimized. Moreover, a widely used theoretical approach to analyze such systems has neglected a fundamental constraint from reciprocity, which can lead to an overestimate of cooling performance and unclarified limits of amplification factors. Here we develop a theoretical framework addressing these shortcomings. Modeling suggests the optimized shape and geometric dimensions of concentrators, as well as the limiting cooling power and temperature reduction. Using an electroplated Al 2 O 3 emitter and an optimized conical concentrator, we experimentally amplify the nighttime radiative cooling by 26%.

Dong, Minghao↗

Fabrication and testing of high-performance all-metal neutron guides and axisymmetric mirrors by electrochemical replication

Neutron scattering is one of the most useful methods of studying the structure of matter, with applications to biomedical, structural, magnetic and energy-related materials. Neutron-scattering instruments are installed around research reactors or accelerator-based neutron sources, and neutron guides are critical components of these facilities. They are neutron-transport optical devices consisting of state-of-the-art mirrors often tens of meters long. Here we demonstrate a novel fabrication method of all-metallic neutron guides and axisymmetric mirrors by electroplating from precision mandrels. The process allows for the fabrication of single-piece all-metal guides of prismatic and axisymmetric shapes. We also demonstrate supermirror guides and axisymmetric focusing supermirrors produced with the same technology. We present the fabrication and tests of the multilayer-coated replicated guides and optic and show that the mandrel is reproduced with high fidelity and reliability. Furthermore, such supermirror optics will provide game-changing improvements in neutron techniques.

36 MATERIALS SCIENCE↗

Microbial potentiometric sensor technology for real-time detecting and monitoring of toxic metals in aquatic matrices

Considering that toxic metals can affect metabolic processes in microorganisms adversely, it can be hypothesized that these metals in water matrices would induce a decrease in metabolic activity of the biofilm microorganisms populating the surface of a sensing electrode, which could be registered as a change in the open-circuit potential (OCP) generated by the biofilm microorganisms. The goal of this study was to test this hypothesis and demonstrate the underlying principle that microbial potentiometric sensor (MPS) technology could be used for long-term and real-time monitoring and detection of rapid changes in metal concentrations in realistic aquatic environments. To address the goal, four objective were addressed: (1) a batch reactor with three graphite-based MPS electrodes was fabricated; (2) a set of single-ion solutions and one multiple ion solution were prepared reflecting realistic concentrations of metals found in electroplating wastewaters; (3) the responses of the MPS to the simultaneous presence of multiple toxic metal ions in a single solution were measured; and (4) the changes of the MPS signals to the presence of individual metal ion solutions were examined. While the hypothesis was validated, the study also revealed that the MPS was sufficiently sensitive to not only detect, but also quantify, toxic metal ion concentrations in aqueous solutions. The coefficients of determination, which were R 2 > 0.995, and responsiveness of <1 μmol/L for some toxic metal cations, strongly support the performance of MPS technology in the echelons of expensive analytical tools capable detecting and measuring trace elements.The magnitude of the MPS response was toxic metal specific. When the molar concertation normalizes the inhibition portion of the signal area, the assessed sensitivity order was: Se>Cd>Pb>Ag>Ni> Zn. The study provides valuable information for enforcement agents, environmental professionals, and wastewater treatment operators, so toxic metal pollution and its detrimental impacts can be prevented and mitigated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Novel Low-Cost Method of Manufacturing Nb3Sn Superconductors with Multiple-Tin-Tube Sources (CRADA FRA-2008-0001 Final Report)

In order to successfully sustain a fusion reaction, peak magnetic fields on the order of 12-13 Tesla will be required. Magnetic fields of this magnitude can only be accomplished by advanced superconductors such as Nb3Sn. However, the economic success of a fusion machine will depend on further improvements in the cost-performance of the Nb3Sn conductor. This project will develop a novel, low-cost, multiple-tin-tube process as a new manufacturing approach for large-scale Nb3Sn-conductor production. The process will be suitable for the efficient production of larger strands (0.83 mm), consistent with ITER (International Thermonuclear Experimental Reactor) specifications. In Phase I, Cu/Nb composites were manufactured and shaped into sub-elements. These sub-elements were tin-coated by electroplating, assembled into a precise-fit restack billet tube, and drawn to 0.83 mm diameter. In Phase II, the process will be scaled-up to full production levels. The improved Nb3Sn conductor should have an immediate benefit for high-field magnet applications. A prototype fusion machine, based on a cost effective Nb3Sn conductor, would have enormous economic and social benefits. In addition, the conductor should be applicable to nuclear magnetic resonance (NMR), which has requirements for use in chemical research, biochemistry, pharmaceutical chemistry, polymer science, petroleum research, agricultural chemistry, and medicine. Leszek Motowidlo, Principal Investigator, will be responsible for the overall coordination of the effort. He and others of SupraMagnetics staff will design and fabricate protoype PIT Nb3Sn conductors for evaluation at Fermilab. Emanuela Barzi will be responsible for the Fermilab subcontract and will coordinate and supervise critical current testing Nb3Sn strands and cable fabrication and evaluation.

43 PARTICLE ACCELERATORS↗