Rethinking the Design of Ionic Conductors Using Meyer?Neldel?Conductivity Plot
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The U.S. Domestic Agency is one of the six suppliers of the toroidal field (TF) conductor for ITER. To qualify conductors per ITER requirements, we prepared or provided to the Swiss Plasma Center (SPC) eight test articles, sixteen conductors total, that were tested in the SULTAN facility at SPC in the ITER relevant conditions. The strands that were used in these SULTAN samples were fully characterized in the laboratories. In this paper, we report both test results and analysis of the conductors' performance against expected strand performance. The U.S. TF conductors showed a slightly better than average current sharing temperature and a relatively low sensitivity to warm up-cooldown cycles in comparison with other suppliers' conductors. However, the trend in current sharing temperature versus cycles and warm ups did not saturate, which means a continuing slow degradation of the conductor performance if the number of warm up and cooldown cycles will be significantly higher than expected. The ac losses in the U.S. TF conductors are in line with losses in the other TF conductor suppliers.
Sulfide-based Na-ion conductors are promising candidates as solid-state electrolytes (SSEs) for fabrication of solid-state Na-ion batteries (NIBs) because of their high ionic conductivities and low grain boundary resistance. Currently, most of the sulfide-based Na-ion conductors with high conductivities are focused on Na 3 PS 4 phases and its derivatives. It is desirable to develop Na-ion conductors with new composition and crystal structure to achieve superior ionic conductivities. Here we report a new quaternary Na-ion conductor, Na 10.8 Sn 1.9 PS 11.8 , exhibiting a high ionic conductivity of 0.67mS cm -1 at 25 °C. This high ionic conductivity originates from the presence of a large number of intrinsic Na-vacancies and three-dimensional Na-ion conduction pathways, which has been confirmed by single-crystal X-ray diffraction and first-principles calculations. The Na 10.8 Sn 1.9 PS 11.8 phase is further evaluated as an electrolyte in a Na-Sn alloy/TiS 2 battery, demonstrating its potential application in all-solid-state NIBs.
A conductor assembly and method for constructing an assembly of the type which, when conducting current, generates a magnetic field or which, in the presence of a changing magnetic field, induces a voltage. In one embodiment the method provides a first insulative layer tubular in shape and including a surface along which a conductor segment may be positioned. A channel formed in the surface of the insulative layer defines a first conductor path and includes a surface of first contour in cross section along a first plane transverse to the conductor path. A segment of conductor having a surface of second contour in cross section is positioned at least partly in the channel and extends along the conductor path. Along the first plane, contact between the conductor surface of second contour and the channel surface of first contour includes at least two separate regions of contact.
A conductor assembly and method for constructing an assembly of the type which, when conducting current, generates a magnetic field or which, in the presence of a changing magnetic field, induces a voltage. In one embodiment the method provides a first insulative layer tubular in shape and including a surface along which a conductor segment may be positioned. A channel formed in the surface of the insulative layer defines a first conductor path and includes a surface of first contour in cross section along a first plane transverse to the conductor path. A segment of conductor having a surface of second contour in cross section is positioned at least partly in the channel and extends along the conductor path. Along the first plane, contact between the conductor surface of second contour and the channel surface of first contour includes at least two separate regions of contact.
This paper presents a non-conductor-contact surface wave reflectometry technique to locate insulation and jacket damage on multi-conductor cables at a distant location from the sensor. Simulation studies were conducted using Ansys high frequency structure simulator (HFSS). A GHz range surface wave launcher was employed such that maximum surface wave energies were confined in the insulation layer while minimizing attenuation. The wave launcher can potentially be mounted on the outer surface of live cables or cable conduits and requires no physical connection to the conductors. Multiple simulations involving a 4 GHz wave launcher and a three-conductor cable with an 8 mm outer diameter were carried out demonstrating the efficacy of the proposed method. Water leak and different types of insulation/jacket damage were simulated and detected.
Reversible solid oxide cells based on proton conductors (P-ReSOCs) have potential to be the most efficient and low-cost option for large-scale energy storage and power generation, holding promise as an enabler for the implementation of intermittent renewable energy technologies and the widespread utilization of hydrogen. Here, the rational design of a new class of hexavalent Mo/W-doped proton-conducting electrolytes with excellent durability while maintaining high conductivity is reported. Specifically, BaMo(W) 0.03 Ce 0.71 Yb 0.26 O 3-δ exhibits dramatically enhanced chemical stability against high concentrations of steam and carbon dioxide than the state-of-the-art electrolyte materials while retaining similar ionic conductivity. In addition, P-ReSOCs based on BaW 0.03 Ce 0.71 Yb 0.26 O 3-δ demonstrate high peak power densities of 1.54, 1.03, 0.72, and 0.48 W cm –2 at 650, 600, 550, and 500 °C, respectively, in the fuel cell mode. During steam electrolysis, a high current density of 2.28 A cm –2 is achieved at a cell voltage of 1.3 V at 600 °C, and the electrolysis cell can operate stably with no noticeable degradation when exposed to high humidity of 30% H 2 O at –0.5 A cm –2 and 600 °C for over 300 h. Altogether, this work demonstrates the promise of donor doping for obtaining proton conductors with both high conductivity and chemical stability for P-ReSOCs.
Commercial electrical conductor wires are currently produced from aluminum alloys by multi-step deformation processing involving rolling and drawing. These processes typically require 10 to 20 steps of deformation, since the plastic strain or reduction that can be imposed in a single step is limited by material workability and process mechanics. Here, we demonstrate a fundamentally different, single-step approach to produce flat wire aluminum products using machining-based deformation that also ensures adequate material workability in the formed product. Two process routes are proposed: (1) chip formation by free-machining (FM), with a post-machining, light drawing reduction (<20%) to achieve desired finish and (2) constrained chip formation by large strain extrusion machining (LSEM). Using commercially pure aluminum conductor alloys (Al 1100 and EC1350) as representative material systems, we demonstrate key features of the machining-based processing, including (a) single-step processing to achieve flat wire geometries, (b) surface finish (Ra = 0.2 to 1.0 μm) comparable to that of commercial wire products made by drawing/rolling, (c) deformation control independent of wire size, and (d) hardness increases of 50–150% over that of annealed wires, while retaining high electrical conductivity (>56% IACS). Here, the wire microstructure, which can also be varied via the large-strain deformation parameters, is correlated with mechanical and electrical properties. Implications for commercial manufacture of flat wire products are discussed.
Mixed-conducting perovskites are workhorse electrochemically active materials, but typical high-temperature processing compromises their catalytic activity and chemo-mechanical integrity. Low-temperature pulsed laser deposition of amorphous films plus mild thermal annealing is an emerging route to form homogeneous mixed conductors with exceptional catalytic activity, but little is known about the evolution of the oxide-ion transport and transference numbers during crystallization. Here the coupled evolution of ionic and electronic transport behavior and structure in room-temperature-grown amorphous (La,Sr)(Ga,Fe)O 3-x films as they crystallize is explored. In situ ac-impedance spectroscopy with and without blocking electrodes, simultaneous capturing-synchrotron-grazing-incidence X-ray diffraction, dc polarization, transmission electron microscopy, and molecular dynamics simulations to evaluate isothermal and non-isothermal crystallization effects and the role of grain boundaries on transference numbers is combined. Ionic conductivity increases by ≈2 orders of magnitude during crystallization, with even larger increases in electronic conductivity. Consequently, as crystallinity increases, LSGF transitions from a predominantly ionic conductor to a predominantly electronic conductor. The roles of evolving lattice structural order, microstructure, and defect chemistry are examined. Grain boundaries appear relatively nonblocking electronically but significantly blocking ionically. The results demonstrate that ionic transference numbers can be tailored over a wide range by tuning crystallinity and microstructure without having to change the cation composition.
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Owing to the high abundance and low cost of sodium (Na), Na-based rechargeable batteries hold great potential for large-scale applications in the future energy industry. However, as key component of the battery electrolyte, only a few Na-based superionic conductors can reach the ionic conductivity comparable to that of liquid or gel electrolytes. Here, we provide a guideline for the development of cluster-based Na-rich antiperovskite superionic conductors using computational studies. With a selected cluster ion BCl 4 – , we are able to achieve high-room-temperature Na-ionic conductivity over 10 –3 S/cm and low activation energies below 0.2 eV in the antiperovskite crystals Na 3 S(BCl 4 ) and Na 3 S(BCl 4 ) 0.5 I 0.5 . In addition, these materials have large bandgaps and favorable mechanical properties. Here, a comprehensive study of the stability and formation energy of these materials further illustrates possible routes for their synthesis. New insights into the conduction mechanism of these cluster-based superionic conductors are provided, including the cooperative motion of Na ions and the significant reduction of the migration barrier due to the changing orientation of the cluster ion.
The growth of materials databases has offered significant quantities of data to mine for new energy materials using high-throughput screening methodologies. One application of interest to energy and optoelectronics is the prediction of new high performing p-type transparent conductors (TCs). Yet, screening methods for such materials have never been validated over the breadth of computed materials properties. In this study, we compile an experimental data set of 74 bulk crystal structures corresponding to known state-of-the-art n-type and p-type TCs and compute a series of corresponding computational descriptor properties. Our goals are to (1) compare computational descriptors to experimentally demonstrated properties of real materials in the data set, (2) determine the ability of ground state, density functional theory (DFT)-based computational screening methodologies to identify these experimentally realized TCs, and (3) use this understanding to estimate reasonable screening cutoffs for four commonly used descriptors. First, stability calculations demonstrate that most materials in the data set have an energy above the convex hull ( E hull ) of <100 meV/atom, and we also propose a Pourbaix analysis technique to estimate moisture stability. Second, we find a lenient cutoff for the DFT PBE band gap of 0.5 eV is sufficient to include a majority of the wide gap candidates and exclude narrow gap compounds. Next, the effective mass, m *, is found to correlate weakly to conductivity in the p-type materials as compared with n-type materials, which may motivate an increase in the m * cutoff as well. Lastly, we perform an uncertainty analysis and literature comparison for the branch point energy (BPE), a qualitative descriptor for dopability. We discover the BPEs of most n-type materials to lie near the conduction band and those of most p-type materials to lie at midgap; this is a significant distinction, implying BPE to be a more definitive descriptor for n-type TC materials. By assessing the validity of this simple screening methodology via comparing experimental data to computational descriptors, we aim to motivate and strengthen future materials discovery efforts in the field of transparent conductors and beyond.
Cu–carbon nanotube (CNT) hybrids combine the advantages of the high electrical conductivity of Cu with the low temperature coefficient of resistance for CNTs, but require enhanced interfacing to improve the electrical performance when exposed to elevated temperatures. In this work, Ti and Ni were investigated as adhesion metals by thermally evaporating 10 nm layers onto a CNT conductor. SEM analysis shows Ni deposits as discrete nanoscale crystallites which coalesce after annealing to 400 °C in H 2 /Ar. Ti deposits uniformly along the CNT surface and is stable over such temperatures. A 100 nm deposition of Cu is shown to delaminate from the CNTs after annealing, and the resistance per length (R/L) increases by 40%. The Cu–Ni–CNT exhibits a 125% increase, while the Cu–Ti–CNT achieves a 12% decrease in R/L, for similar annealing conditions. Thus, Ti emerges as an effective adhesion metal, warranting its use in metal–CNT wire technologies for elevated temperature operation.
Oxygen non-stoichiometry is a fundamental feature of mixed ion and electron conductors (MIECs). In this work a general electrochemical method for determining non-stoichiometry in thin film MIECs, via measurement of the chemical capacitance, is demonstrated using ceria and ceria-zirconia (Ce 0.8 Zr 0.2 O 2-δ ) as representative materials. A.C. impedance data are collected from both materials at high temperature (750-900 °C) under reducing conditions with oxygen partial pressure (pO 2 ) in the range 10-13 to 10-20 atm. Additional measurements of ceria-zirconia films are made under relatively oxidizing conditions with pO 2 in the range 0.2 to 10 -4 atm and temperatures of 800-900 °C. Under reducing conditions, the impedance spectra are described by a simple circuit in which a resistor is in series with a resistor and capacitor in parallel, and thickness dependent measurements are used to resolve the capacitance into interfacial and chemical terms. Under more oxidizing conditions, the impedance spectra (of Ce 0.8 Zr 0.2 O 2-δ ) reveal an additional diffusional feature, which enables determination of the ionic resistance of the film in addition to the capacitance, and hence the transport properties. A generalized mathematical formalism is presented for recovering the non-stoichiometry from the chemical capacitance, without recourse to defect chemical models. The ceria non-stoichiometry values are in good agreement with literature values determined by thermogravimetric measurements but display considerably less scatter and are collected on considerably shorter timescales. Here, the thermodynamic analysis of Ce 0.8 Zr 0.2 O 2-δ corroborates earlier findings that introduction of Zr into ceria enhances its reducibility.
For the first time, proton conductors BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3–δ (BZCYYb) and La 2 Ce 2 O 7 (LCO) are combined to create an interface active and steam-tolerant electrolyte for high-performance proton-conducting solid oxide electrolysis cells. LCO shows good chemical compatibility with BZCYYb. The readily fabricated LCO/BZCYYb bilayer electrolyte can be densified at a temperature of as low as 1300 °C versus ~1600 °C for the benchmark steam-stable BaZr 0.8 Y 0.2 O 3–δ electrolyte. With Pr 2 NiO 4+δ as the anode and Ni as the cathode catalyst, this bilayer electrolyte cell yields a current density of 975 and 300 mA/cm 2 under a 1.3 V applied potential at 700 and 600 °C, respectively. This performance is among the best of all H-SOECs equipped with a chemically stable electrolyte so far. A BZCYYb layer in the bilayer electrolyte promotes the hydrogen evolution reaction at the cathode side, resulting in a 108% improvement over the cell without this layer. The LCO layer, on the other hand, effectively protects this functional BZCYYb layer from the high concentration of steam in a practical SOEC operation condition. The cell without the LCO layer shows degradation in terms of an increased electrolyzing potential from 1.07 to 1.29 V during a constant 400 mA/cm 2 operation at 700 °C. In contrast, the bilayer electrolyte cell maintains the same electrolyzing potential of 1.13 V under the same conduction for a 102 h operation. These findings demonstrate that this synergic bilayer electrolyte design is a vital strategy to overcome the dilemma between performance and stability faced by the current benchmark Zr- or Ce-rich Ba(CeZr)O 3–δ electrolysis cells to achieve excellent performance and stability at the same time.
We report structural, transport, and optical properties and electronic structure calculations of the delta'-(BEDT-TTF) 2CF3CF2SO3 (BEDT-TTF = bis(ethylenedithio)-tetrathiafulvalene) organic conductor that has been synthesized by electrocrystallization. Electronic structure calculations demonstrate the quasi-one-dimensional Fermi surfaces of the compound, while the optical spectra are characteristic for a dimer-Mott insulator. The single-crystal X-ray diffraction measurements reveal the structural phase transition at 200 K from the ambient-temperature monoclinic P2(1)/m phase to the low-temperature orthorhombic Pca2(1) phase, while the resistivity measurements clearly show the first order semiconductor-semiconductor transition at the same temperature. This transition is accompanied by charge-ordering as it is confirmed by splitting of charge-sensitive vibrational modes observed in the Raman and infrared spectra. The horizontal stripe charge-order pattern is suggested based on the crystal structure, band structure calculations, and optical spectra.