Operando XAFS on Hydrated Calcium Vanadium Bronze Cathode for Aqueous Zn-ion Storage
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99 GENERAL AND MISCELLANEOUS↗
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Rapid Nb 3 Sn film growth by sputtering Nb on hot bronze
Nb deposited by magnetron sputtering onto hot Cu-15 wt.%Sn bronze substrates at temperatures above 700 °C achieved Nb 3 Sn film growth at a rate of 33 nm min -1 , which was an order of magnitude faster than that achieved for deposition of Nb on bronze at low temperature followed by in situ post reaction at the same high temperatures. Tin content in the Nb 3 Sn films made on hot bronze was ~26.3%, which is significantly higher than ~24.5% obtained by post-reaction as well as for typical bulk reactions between Nb and α -bronze. The Nb 3 Sn lattice parameter was consistent with measured tin content and predicted elastic strain for both routes. Critical temperatures of 14 K–16 K, instead of 18 K, were consistent with elastic strain due to coefficient of thermal expansion mismatch between the Nb 3 Sn and bronze substrate and, for the hot-bronze samples, stress related to the growth mechanism. Films were fully coalesced and had surface roughness values <20 nm over a 100 μ m 2 scan. Grain structure of the Nb 3 Sn films produced by Nb sputtering on hot bronze resembles zone 2 in the Thornton structure-zone diagram, in contrast to the equiaxed grain structure reminiscent of microstructure observed in reacted Nb 3 Sn wires exhibited by the post-reaction route.
Physics↗
Solution-Phase Synthesis of Platinum-Decorated Hydrogen Tungsten Bronzes for Hydrogen Atom Transfer from Oxides to Molecules
Hydrogen bronzes can be used as hydrogen donors for the broad class of reactions involving proton-coupled electron transfer (PCET). Here, in this work, we describe a method to prepare platinum-decorated hydrogen tungsten bronzes, Pt@H x WO 3 · n H 2 O with n = 0, 1, and 2, by reacting the pristine oxides at modest temperatures with a mild reducing agent, H 3 PO 2 , and H 2 PtCl 6 in an aqueous solution. We explored the tunability and kinetics of this reaction and compared it with that of archetypal gas–solid hydrogen spillover. We demonstrate that the identity of the noble metal affects the extent of bronze reduction. This suggests that the mechanism proceeds via the adsorption of a hydrogen-atom species on the noble metal. Finally, we explored the ability of the Pt-decorated hydrogen tungsten bronzes to hydrogenate a model H + /e – acceptor, 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO). The bronze phases return to their fully oxidized states along with the subsequent reduction of TEMPO to TEMPOH. Overall, this work demonstrates a solution-phase method to obtain hydrogen bronzes, which can then be used to perform hydrogen transfer reactions, providing a pathway for the use of extended transition metal oxides as stoichiometric reagents for broad classes of hydrogenation reactions.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Structure and Electrochemical Properties of Bronze Phase Materials Containing Two Transition Metals
Bronze phase transition-metal oxides have recently attracted attention as high-rate lithium-ion battery anode materials. Their crystal structures are distinguished by large tunnels and an open framework, facilitating lithium-ion diffusion and high-rate charge–discharge properties. The presence of two transition metals also offers a route to achieve high energy density from multielectron redox. In this paper, we report the chemistry, structure, and electrochemical properties of two different bronze phase compositions having the same stoichiometry: W 3 Nb 2 O 14 and Mo 3 Nb 2 O 14 . These materials provide insight into how the transition metals affect the electrochemical behavior and structural stability of bronze phase materials. Mo 3 Nb 2 O 14 exhibits greater than 1 electron redox per transition metal leading to lithium capacities above 200 mAh g –1 at C/2 but is unable to maintain this high capacity at high rates due to incomplete Mo redox reactions. In contrast, W 3 Nb 2 O14 exhibits reversible redox reactions and retains its open structure on cycling. This study highlights the potential of bronze phase materials containing two transition metals to exhibit fast charging properties with a high energy density.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Operando pair distribution function analysis of nanocrystalline functional materials: the case of TiO 2 -bronze nanocrystals in Li-ion battery electrodes
Structural modelling of operando pair distribution function (PDF) data of complex functional materials can be highly challenging. To aid the understanding of complex operando PDF data, this article demonstrates a toolbox for PDF analysis. The tools include denoising using principal component analysis together with the structureMining , similarityMapping and nmfMapping apps available through the online service `PDF in the cloud' ( PDFitc , https://pdfitc.org/). The toolbox is used for both ex situ and operando PDF data for 3 nm TiO 2 -bronze nanocrystals, which function as the active electrode material in a Li-ion battery. The tools enable structural modelling of the ex situ and operando PDF data, revealing two pristine TiO 2 phases (bronze and anatase) and two lithiated Li x TiO 2 phases (lithiated versions of bronze and anatase), and the phase evolution during galvanostatic cycling is characterized.
Chemistry↗
On the Structural Origin of Fast Li-Ion Cycling in Tetragonal Bronze-Type Nb 8 W 9 O 47
Bronze and bronze-derived, mixed metal oxides are materials of growing interest for lithium-ion battery anodes due to their high-rate capabilities and the potential for high energy densities via multielectron redox. We report on the synthesis and electrochemical properties of the tetragonal tungsten bronzetype phase Nb 8 W 9 O 47 and our investigation into the structural evolution of this phase upon lithium (de)intercalation, with particular attention to how it relates to the fast-cycling capabilities. Electrochemical cycling shows Nb 8 W 9 O 47 can achieve greater than one Li + per transition metal at rates of C/2 or slower and maintains a capacity equivalent to 0.65 Li + per transition metal at a rate of 20C. Sequential Rietveld analysis of operando X-ray diffraction data reveals anisotropic changes to the unit cell parameters during discharge, accompanied by an off-centering of the transition metals within their octahedral environments. While higher capacities can be accessed below 1.2 V, cells discharged to 1.0 V exhibit a significant expansion of the unit cell volume and reduced Coulombic efficiencies. This report suggests that rigid crystal structures incapable of undergoing polyhedral rotational deformations can instead exploit displacive distortions of the transition metal redox center to enable fast Li-ion cycling with minimal atomic rearrangements.
25 ENERGY STORAGE↗
Probing Mg Intercalation in the Tetragonal Tungsten Bronze Framework V 4 Nb 18 O 55
While commercial Li-ion batteries offer the highest energy densities of current rechargeable battery technologies, their energy storage limit has almost been achieved. Therefore, there is considerable interest in Mg batteries, which could offer increased energy densities in comparison to Li-ion batteries if a high-voltage electrode material, such as a transition-metal oxide, can be developed. However, there are currently very few oxide materials which have demonstrated reversible and efficient Mg 2+ insertion and extraction at high voltages; this is thought to be due to poor Mg 2+ diffusion kinetics within the oxide structural framework. Here, in this paper, the authors provide conclusive evidence of electrochemical insertion of Mg 2+ into the tetragonal tungsten bronze V 4 Nb 18 O 55 , with a maximum reversible electrochemical capacity of 75 mA h g –1 , which corresponds to a magnesiated composition of Mg 4 V 4 Nb 18 O 55 . Experimental electrochemical magnesiation/demagnesiation revealed a large voltage hysteresis with charge/discharge (1.12 V vs Mg/Mg 2+ ); when magnesiation is limited to a composition of Mg 2 V 4 Nb 18 O 55 , this hysteresis can be reduced to only 0.5 V. Hybrid-exchange density functional theory (DFT) calculations suggest that a limited number of Mg sites are accessible via low-energy diffusion pathways, but that larger kinetic barriers need to be overcome to access the entire structure. The reversible Mg 2+ intercalation involved concurrent V and Nb redox activity and changes in crystal structure, as confirmed by an array of complementary methods, including powder X-ray diffraction, X-ray absorption spectroscopy, and energy-dispersive X-ray spectroscopy. Consequently, it can be concluded that the tetragonal tungsten bronzes show promise as intercalation electrode materials for Mg batteries.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Sn 0.24 WO 3 hexagonal tungsten bronze prepared via the metal chloride route
In this work, we report the synthesis of Sn 0.24 WO 3 single crystals via an alternative, less well-known, solid-state synthetic approach that involves the use of tin chloride as a starting material. The compound adopts an unusual variant of the hexagonal tungsten bronze structure in space group P6/mmm (a = 7.4264(7) Å and c = 3.7843(4) Å) with a previously unreported distribution of Sn cations, disordered over two distinct sites in the tunnels. Sn 0.24 WO 3 shows no signs of superconductivity down to 170 mK and exhibits weakly-metallic conducting behavior.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Water-Pillared Sodium Vanadium Bronze Nanowires for Enhanced Rechargeable Magnesium Ion Storage
Owing to the advantages of high safety, low cost, high theoretical volumetric capacities, and environmental friendliness, magnesium-ion batteries (MIBs) have more feasibility for large-scale energy storage compared to lithium-ion batteries. However, lack of suitable cathode materials due to sluggish kinetics of magnesium ion is one of the biggest challenges. Herein, water-pillared sodium vanadium bronze nanowires (Na 2 V 6 O 16 ·1.63H 2 O) are reported as cathode material for MIBs, which display high performance in magnesium storage. The hydrated sodium ions provide excellent structural stability. The charge shielding effect of lattice water enables fast Mg 2+ diffusion. It exhibits high specific capacity of 175 mAh g -1 , long cycle life (450 cycles), and high coulombic efficiency (≈100%). At high current density of 200 mA g -1 , the capacity retention is up to 71% even after 450 cycles (compared to the highest capacity), demonstrating excellent long-term cycling performance. The nature of charge storage kinetics is explored. Furthermore, a highly reversible structure change during the electrochemical process is proved by comprehensive electrochemical analysis. The remarkable electrochemical performance makes Na 2 V 6 O 16 ·1.63H 2 O a promising cathode material for low-cost and safe MIBs.
36 MATERIALS SCIENCE↗
The hydrogen-containing bronzes H 0.23 WO 3 and H 0.10 ReO 3 synthesized via a polymer route
We report the synthesis of two hydrogen-containing perovskite-type bronzes H 0.23 WO 3 and H 0.10 ReO 3 utilizing an unconventional solid-state synthetic approach, involving the use of the polymer Poly(vinylidene fluoride) (CH 2 CF 2 ) n. Powder neutron diffraction at ambient temperature shows that H 0.23 WO 3 crystallizes in a tetragonal symmetry distortion of the simple perovskite structure (space group P4/nmm), with lattice parameters a = 5.2279(2) Å, and c =3.8763(1) Å. H 0.10 ReO 3 , in contrast, crystallizes in a monoclinic distortion of a simple cubic perovskite (space group P2/m), with lattice parameters a = 5.3125(1) Å, b = 5.3155(3) Å, c = 3.7045(3) Å, and γ = 90.43(1)°. Both H 0.23 WO 3 and H 0.10 ReO 3 exhibit intrinsically diamagnetic behavior, with low temperature paramagnetic upturns and no signs of bulk superconductivity down to 0.35 K.
36 MATERIALS SCIENCE↗
The incommensurate modulation of tetragonal tungsten bronze quantified by high resolution 4D STEM
Many members of the tetragonal tungsten bronze (TTB) family of oxides display an incommensurate periodic lattice distortion, the nature of which has been the subject of some controversy. Here we present a study of this structural modulation in the relaxor ferroelectric Ba 5 SmSn 3 Nb 7 O 30 (BSSN) by quantitative scanning transmission electron microscopy (STEM). Additionally, we characterize the modulation in BSSN by employing a fast, pixelated direct electron detector to perform high resolution phase contrast STEM imaging of the crystalline lattice. By quantitatively analyzing the images, we visualize the atomic structural correlations present in the material on both the cation and anion sublattices. This analysis reveals the incommensurate structure to have an octahedral tilting pattern and cooperative A2 site cation displacements, analogous to an Ama2 commensurate cell. Finally, we show that the modulation is composed of a structural motif with a period of 3 x $d_{1\bar{1}0}$ and modified by discommensurations, likely arise from frustrated octahedral tilting in the odd-valued periodicity.
Differential phase contrast↗
Investigations Towards Ultra-Low Cost Nb 3 Sn SRF Fabrication via Melt Casted Bronze Route Processing
Here, a novel approach to fabricating Nb 3 Sn SRF cavities and other RF components using an ultra-low-cost melt casting fabrication process has been investigated. This simple, low cost melt casting technique has the potential to be used to fabricate nearly any superconducting Nb3Sn structure using either the Bronze Route (BR), Internal Tin (IT), External Tin (ET) processes as well as normal conducting pure copper (Cu) cavities. Most of the heat treated samples that were examined using SEM/EDX seemed to show a reasonable correlation of T c onset and transition width (ΔT c ) of the ingots initial/starting Sn content to the desired stoichiometric Nb 3 Sn phase, where the lower starting Sn content coupons resulted in lower T c 's with broader transition widths and the higher starting Sn coupons resulted in higher T c 's with narrower ΔT c ’s. The best samples had T c onsets ~17-18 K and ΔT c 's < 2 K. Two samples were further tested for RF surface resistance (R s ) and Quality Factor (Q) at JLAB. Here, these RF measurements were performed at 7.4 GHz using a calorimetric technique and showed two transitions, one at ~ 8 K and another at ~ 14 K; values of R s were at least two orders of magnitude higher than similar high quality Nb 3 Sn films directly deposited substrates by JLAB and with another superconducting transition close to the superconducting transition temperature of niobium. Substantial improvements in the processing variables ranging from higher quality of the initial ingots with higher Sn content, to better electropolishing and reaction heat treatment regimens will be necessary to realize improved RF performance metrics.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Protonated Tungsten Bronze (H x WO 3 ) Acts as an Easily Regenerable Reagent for PCET Reactions
In this study, protonated tungsten bronze powder (H x WO 3 ) was synthesized by a microwave heating technique from tungsten(VI) chloride in benzyl alcohol. This material facilitates a proton-coupled electron transfer (PCET) reaction with 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO) in toluene, an aprotic solvent, to form TEMPOH, evidenced by UV–vis analysis of the organic product and X-ray photoelectron spectroscopy (XPS) analysis showing the oxidation of W 5+ to W 6+ in the remaining powder. Then, under illumination in an acidic aqueous solution, the oxidized WO 3 powder reacts photochromically to regenerate H x WO 3 . The regenerated H x WO 3 reagent remains active for further PCET reactions.
Granular materials↗
Thermal behaviors during lithium diffusion in Li 0.4 WO 3 bronze studied by elastic and quasi-elastic neutron scattering
Crystal structure of Li 0.4 WO 3 bronze, showing 2aand 6bWyckoff sites and LiO x coordination. Upon heating, Li + moves from preferential 6bto 2asite, leading to thermal expansion anomaly due to interactions with the framework followed by WO 6 tilting.
Chemistry↗
Active and passive defects in tetragonal tungsten bronze relaxor ferroelectrics
Tetragonal tungsten bronze (TTB) based oxides constitute a large family of dielectric materials which are known to exhibit complex distortions producing incommensurately modulated superstructures as well as significant local deviations from their average symmetry. The local deviations produce diffuse scattering in diffraction experiments. The structure as well as the charge dynamics of these materials are anticipated to be sensitive to defects, such as cation or oxygen vacancies. In this work, in an effort to understand how the structural and charge dynamical properties respond to these two types of vacancy defects, we have performed measurements of dielectric susceptibilities and single crystal diffraction experiments of two types of TTB materials with both ‘filled’ (Ba 2 NdFeNb 4 O 15 and Ba 2 PrFeNb 4 O 15 ) and ‘unfilled’ (Sr 0.5 Ba 0.5 Nb 2 O 6 ) cation sublattices. We also perform these measurements before and after oxygen annealing, which alters the oxygen vacancy concentrations. Surprisingly, we find that many of the diffuse scattering features that are present in the unfilled structure are also present in the filled structure, suggesting that the random fields and disorder that are characteristic of the unfilled structure are not responsible for many of the local structural features that are reflected in the diffuse scattering. Furthermore, oxygen annealing clearly affected both color and dielectric properties, consistent with a diminishment of the oxygen vacancy concentration, but had little effect on observed diffuse patterns.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Atomic structure and formation mechanism of a newly discovered charge density wave in the m = 2 monophosphate tungsten bronze
The m = 2 member of the monophosphate tungsten bronze family had been thought to be the only one without an electronic instability at low temperature. In this paper, we report the discovery of a charge density wave phase in this compound, with a transition temperature of 290 K and an incommensurate modulation vector q = 0.245b* + ξc*, which reaches a lock-in with a commensurate vector at 130 K. The presence of this new phase is confirmed by diffraction and resistivity measurements. Pre-transitional dynamics are investigated using diffuse and inelastic X-ray scattering, revealing a clear Kohn anomaly. We analyze both structural and electronic contributions to the phase transition, providing a comprehensive picture of the mechanism driving this newly identified instability.
Minelli, Arianna [ORNL] (ORCID:0000000283103712)↗
Surface Finishing and Coating Parameters Impact on Additively Manufactured Binder-Jetted Steel–Bronze Composites
In this paper, electroless nickel plating is explored for the protection of binder-jetting-based additively manufactured (AM) composite materials. Electroless nickel plating was attempted on binder-jetted composites composed of stainless steel and bronze, resulting in differences in the physicochemical properties. We investigated the impact of surface finishing, plating solution chemistry, and plating parameters to attain a wide range of surface morphologies and roughness levels. We employed the Keyence microscope to quantitatively evaluate dramatically different surface properties before and after the coating of AM composites. Scanning electron microscopy revealed a wide range of microstructural properties in relation to each combination of surface finishing and coating parameters. We studied chempolishing, plasma cleaning, and organic cleaning as the surface preparation methods prior to coating. We found that surface preparation dictated the surface roughness. Taguchi statistical analysis was performed to investigate the relative strength of experimental factors and interconnectedness among process parameters to attain optimum coating qualities. The quantitative impacts of phosphorous level, temperature, surface preparation, and time factor on the roughness of the nickel-plated surface were 17.95%, 8.2%, 50.02%, and 13.21%, respectively. On the other hand, the quantitative impacts of phosphorous level, temperature, surface preparation, and time factor on the thickness of nickel plating were 35.12%, 41.40%, 3.87%, and 18.24%, respectively. The optimum combination of the factors’ level projected the lowest roughness of Ra at 7.76 µm. The optimum combination of the factors’ level projected the maximum achievable thickness of ~149 µm. This paper provides insights into coating process for overcoming the sensitivity of AM composites in hazardous application spaces via robust coating.
36 MATERIALS SCIENCE↗
Performance of a Printed Bimetallic (Stainless Steel and Bronze) Engine Head Operating under Stoichiometric and Lean Spark Ignited (SI) Combustion of Natural Gas
Additive manufacturing was used to fabricate a head for an automotive-scale single-cylinder engine operating on natural gas. The head was consisted of a bimetallic composition of stainless steel and bronze. The engine performance using the bimetallic head was compared against the stock cast iron head. The heads were tested at two speeds (1200 and 1800 rpm), two brake mean effective pressures (6 and 10 bar), and two equivalence ratios (0.7 and 1.0). The bimetallic head showed good durability over the test and produced equivalent efficiencies, exhaust temperatures, and heat rejection to the coolant to the stock head. Higher combustion temperatures and advanced combustion phasing resulted from use with the bimetallic head. The implication is that with optimization of the valve timing, an efficiency benefit may be realized with the bimetallic head.
42 ENGINEERING↗