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At least 739 records · Page 41

Co-Mo-P Based Electrocatalyst for Superior Reactivity in the Alkaline Hydrogen Evolution Reaction

Energy efficient hydrogen production via electrochemical and/or photoelectrochemical water splitting holds significant potential for clean and sustainable energy. Toward this end, a significant amount of research has been focused on developing active earth abundant metal catalysts for the hydrogen evolution reaction (HER) for use in acidic and alkaline media. Here, we report an earth abundant metal-based catalyst for HER under alkaline conditions. The catalyst consisting of Co, Mo and P had a similar HER activity as the precious metal platinum under the conditions used in the study. The Co-Mo-P catalyst is amorphous and was prepared by room temperature electrodeposition. The best Co-Mo-P catalyst exhibited an overpotential of ~30–35 mV for HER at a geometrical current density of 10 mA cm -2 in an alkaline medium. An amorphous Co-Mo-P model was used to simulate the energetics of HER intermediates with density functional theory (DFT). The DFT study suggests that a Co-Mo center acts as the water-dissociation site enhancing the alkaline medium HER.

catalysis (heterogeneous)↗

Atomic Layer Deposition of Li x Al y S Solid-State Electrolytes for Stabilizing Lithium-Metal Anodes

Increasing global demands for energy storage in electric vehicles and the grid necessitate “beyond-lithium-ion” batteries that simultaneously exhibit high capacity, long-term cyclability, and excellent safety. Several candidates, most notably lithium–air and lithium–sulfur batteries, utilize lithium-metal anodes. Although the specific capacity of lithium metal is unrivaled (3860 mA h g –1 ), the capacity fade and risk of catastrophic failure must be overcome. Herein, we describe ultrathin, ionically conducting lithium aluminum sulfide (Li x Al y S) coatings prepared on lithium-metal anodes by using atomic layer deposition, which stabilize the Li–electrolyte interface and reduce (up to five times) the interfacial impedance of lithium–metal anodes in contact with organic electrolyte. Here, we demonstrate that these thin films effectively suppress dendrite formation and preserve a smooth, low-surface-area morphology for electrodeposited lithium metal, thereby doubling the lifetime of Li–Cu asymmetric cells.

25 ENERGY STORAGE↗

Highly Efficient and Uniform 1 cm 2 Perovskite Solar Cells with an Electrochemically Deposited NiO x Hole-Extraction Layer

Here, given that the highest certified conversion efficiency of the organic-inorganic perovskite solar cell (PSC) already exceeds 22%, which is even higher than that of the polycrystalline silicon solar cell, the significance of new scalable processes that can be utilized for preparing large-area devices and their commercialization is rapidly increasing. From this perspective, the electrodeposition method is one of the most suitable processes for preparing large-area devices because it is an already commercialized process with proven controllability and scalability. Here, a highly uniform NiO x layer prepared by electrochemical deposition is reported as an efficient hole-extraction layer of a p-i-n-type planar PSC with a large active area of >1 cm 2 . It is demonstrated that the increased surface roughness of the NiO x layer, achieved by controlling the deposition current density, facilitates the hole extraction at the interface between perovskite and NiO x , and thus increases the fill factor and the conversion efficiency. The electrochemically deposited NiO x layer also exhibits extremely uniform thickness and morphology, leading to highly efficient and uniform large-area PSCs. As a result, the p-i-n-type planar PSC with an area of 1.084 cm 2 exhibits a stable conversion efficiency of 17.0% (19.2% for 0.1 cm 2 ) without showing hysteresis effects.

14 SOLAR ENERGY↗

Ionic Conductive and Highly-Stable Interface for Alkali Metal Anodes

Alkali metals are regarded as the most promising candidates for advanced anode for the next-generation batteries due to their high specific capacity, low electrochemical potential, and lightweight. However, critical problems of the alkali metal anodes, especially dendrite formation and interface stabilization, remain challenging to overcome. The solid electrolyte interphase (SEI) is a key factor affecting Li and Na deposition behavior and electrochemical performances. Herein, a facile and universal approach is successfully developed to fabricate ionic conductive interfaces for Li and Na metal anodes by modified atomic layer deposition (ALD). In this process, the Li metal (or Na metal) plays the role of Li (or Na) source without any additional Li (or Na) precursor during ALD. Moreover, the key questions about the influence of ALD deposition temperature on the compositions and structure of the coatings are addressed. The optimized ionic conductive coatings have significantly improved the electrochemical performances. In addition, the electrochemical phase-field model is performed to prove that the ionic conductive coating is very effective in promoting uniform electrodeposition. Further, this approach is universal and can be potentially applied to other different metal anodes. At the same time, it can be extended to other types of coatings or other deposition techniques.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Highly Reversible Sodium Metal Battery Anodes via Alloying Heterointerfaces

As a promising pathway toward low-cost, long-duration energy storage, rechargeable sodium batteries are of increasing interest. Batteries that incorporate metallic sodium as anode promise a high theoretical specific capacity of 1166 mAh g –1 , and low reduction potential of –2.71 V. The high reactivity and poor electrochemical reversibility of sodium anodes render sodium metal anode (SMA) cells among the most challenging for practical implementation. Here, the failure mechanisms of Na anodes are investigated and the authors report that loss of morphological control is not the fundamental cause of failure. Rather, it is the inherently poor anchoring/root structure of electrodeposited Na to the electrode substrate that leads to poor reversibility and cell failure. Poorly anchored Na deposits are prone to break away from the current collector, producing orphaning and poor anode utilization. Thin metallic coatings in a range of chemistries are proposed and evaluated as SMA substrates. Based on thermodynamic and ion transport considerations, such substrates undergo reversible alloying reactions with Na and are hypothesized to promote good root growth—regardless of the morphology. Among the various options, Au stands out for its ability to support long Na anode lifetime and high reversibility (Coulombic Efficiency > 98%), for coating thicknesses in the range of 10–1000 nm. Finally, as a first step toward evaluating practical utility of the anodes, their performance in Na||SPAN cells with N:P ratio close to 1:1 is evaluated.

25 ENERGY STORAGE↗

Electrochemically Dealloyed 3D Porous Copper Nanostructure as Anode Current Collector of Li-Metal Batteries

The commercialization of high-energy Li-metal batteries is impeded by Li dendrites formed during electrochemical cycling and the safety hazards it causes. Here, a novel porous copper current collector that can effectively mitigate the dendritic growth of Li is reported. This porous Cu foil is fabricated via a simple two-step electrochemical process, where Cu-Zn alloy is electrodeposited on commercial copper foil and then Zn is electrochemically dissolved to form a 3D porous structure of Cu. The 3D porous Cu layers on average have a thickness of ≈14 um and porosity of ≈72%. This current collector can effectively suppress Li dendrites in cells cycled with a high areal capacity of 10 mAh cm -2 and under a high current density of 10 mA cm -2 . This electrochemical fabrication method is facile and scalable for mass production. In conclusion, results of advanced in situ synchrotron X-ray diffraction reveal the phase evolution of the electrochemical deposition and dealloying processes.

36 MATERIALS SCIENCE↗

Nanopinhole-Enabled, Hole-Selective Poly-Si/SioxNy Passivating Contacts on Textured c-Si for Si Solar Cells

The next-generation silicon photovoltaics will be based on passivating electron- and hole-selective contacts with both very low interface recombination and contact resistivities. While the emerging mainstream TOPCon technology has developed excellent electron-selective poly-Si/tunneling SiOx contacts, hole-selective contacts, especially on textured surfaces, have remained a significant challenge. This contribution introduces novel high-performance hole selective poly-Si contacts on pyramid-textured Si, enabled by electrochemically produced hole transport nanopinholes in a 10 nm oxynitride passivating dielectric stack capped by p+ poly-Si. The highly passivating oxynitride layer is produced via atomic intermixing of O and N atoms in the initial SiOx/SiNy layer stack upon thermal annealing. Carrier transport is governed by nanopinhole density and size are tuned by Ag nanoparticle electrodeposition and surface attachment chemistries. This results in passivating hole contact resistivities in the m..omega..-cm2 range, while preserving interface recombination current prefactor around 5 fA/cm2.

14 SOLAR ENERGY↗

Substrate-Driven Catalyst Reducibility for Oxygen Evolution and Its Effect on the Operation of Proton Exchange Membrane Water Electrolyzers

To increase the efficiency of hydrogen production by proton exchange membrane water electrolyzers (PEMWEs), the relationships between the specific activity and stability of the membrane–electrode assembly (MEA) must be clarified. Ir oxide electrodeposited on Ti substrate is used as an oxygen electrode, and its electronic properties and electrochemical behavior in PEMWE operation are observed. The electrode, fabricated through a facile strategy based on annealing in the air atmosphere, enhances the specific oxygen evolution reaction (OER) activity and stability in PEMWE operation. Furthermore, the electronic catalyst–substrate interactions associated with different reducibilities in the heteroatom system are studied. The morphology, electronic properties, and chemical state of the oxygen electrode are investigated through X-ray spectroscopy, microscopy techniques, and computational analyses. Thermal treatment of the catalyst-coated substrate decreases the bulk oxidation state of Ir and increases the surface oxidation state. According to the electrochemical and physical behavior analyses of PEMWEs, the oxygen content in the Ir oxide structure, which defines the OER activity and its stability, is influenced by the crystalline structure and formation of a stable interface between the catalyst and substrate. The outcomes can facilitate the development of strategies for enhancing the performance of PEMWEs and designing rational MEAs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluating bis(2-ethylhexyl) methanediphosphonic acid (H 2 DEH[MDP]) based polymer ligand film (PLF) for plutonium and uranium extraction

This paper describes a new analyte extraction medium called polymer ligand film (PLF) that was developed to rapidly extract radionuclides. PLF is a polymer medium with ligands incorporated in its matrix that selectively and quickly extracts analytes. The main focus of the new technique is to shorten and simplify the procedure for chemically isolating radionuclides for determination through alpha spectroscopy. The PLF system was effective for plutonium and uranium extraction. The PLF was capable of co-extracting or selectively extracting plutonium over uranium depending on the PLF composition. As a result, the PLF and electrodeposited samples had similar alpha spectra resolutions.

36 MATERIALS SCIENCE↗

Synthesis of americium trichloride via chlorination of americium oxide using zirconium tetrachloride in LiCl-KCl molten salt

To better inform electrorefining operations of used nuclear fuel, a fundamental understanding of the electrochemical properties of each actinide in the molten salt electrolyte is needed. Access to actinide chlorides is thus required to support measurement of these properties. In this work, we synthesized americium trichloride through a novel pathway comprising chlorination of Am2O3 with ZrCl4 in a LiCl-KCl molten salt at 500 degrees C. The formation of AmCl3 was confirmed by cyclic voltammetry and gamma spectroscopy. This chlorination method does not produce mixed hazardous-radioactive waste and the byproduct, ZrO2, is not electrochemically active and does not affect the actinide electrodeposition reaction.

actinide chloride synthesis↗

Comparison of microprecipitation methods for polonium source preparation for alpha spectrometry

Detection of radioactive isotopes of polonium is important for understanding natural processes, management and assessment of radioactive waste, and nuclear forensics applications. Further, the most common methods for preparation of polonium samples for alpha spectrometry are electrodeposition and spontaneous deposition which are time consuming. Here, we compare three approaches utilizing rapid microprecipitation from bismuth phosphate, copper sulfide, or tellurium alongside traditional spontaneous deposition methods. From these experiments, results show that copper sulfide microprecipitation recoveries are similar to spontaneous deposition on silver and less time consuming with an approximate five-fold decrease in preparation time, including in the presence of complex matrices like seawater.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

An Investigation of the Effect of Sintering Conditions on the Mechanical Behavior of Electroplated Nickel Foams

This study investigates the effect of sintering temperature on the compression strength of nickel foams in an inert atmosphere. The nickel foams were produced by the electrodeposition technique on polyurethane foam substrate. As-plated Ni foams were sintered at 873 K, 1073 K, and 1273 K (600 °C, 800 °C, and 1000 °C) in order to eliminate polyurethane and to enhance ductility at a controlled atmosphere. A compression test was used to determine the mechanical behavior. The morphology of produced foams was analyzed by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and X-ray diffraction (XRD) techniques. Quantitative EDS analysis implied that carbon diffuses into nickel structure during the polyurethane decomposition. The amount of carbon in nickel foam increases with heat treatment temperature. The results also reveal that the oxygen impurity arisen from polymer vapors can diffuse into the nickel structure at elevated sintering temperature [i.e., 1273 K (1000 °C)]. The compression curve of as-plated foam showed brittle behavior due to the electroplating condition. The sintering process in the neutral atmosphere could create ductile foams, although the strength of the foams decreases with an increase in the sintering temperature.

36 MATERIALS SCIENCE↗

Butt Laser Welding–Brazing of AZ31 Mg to Nickel-Coated Ti-6Al-4V

Mg and Ti alloy are hard to be bonded due to their huge discrepancy in physical and metallurgical characteristics. As an intermediate element, Ni is feasible for joining of Mg and Ti. The interfacial microstructure and mechanical properties of laser-welded–brazed AZ31 Mg/Ti-6Al-4V joints in butt configuration were investigated with different thicknesses of electrodeposited Ni interlayer. The interfacial reaction products evolved from an ultra-thin Ti{sub 3}Al layer to Ti{sub 2}Ni layer mingled with Ti{sub 3}Al, and more Mg{sub 3}AlNi{sub 2} compounds were produced in the fusion zone (FZ) as Ni coating thickness increased. Slag inclusions and cracks were observed in interfacial layer when coating thickness exceeded 2.5 μm. The quantity of Mg{sub 3}AlNi{sub 2} and the thickness of interfacial layer decreased from the top to bottom of groove of the same joint owing to high thermal gradient during laser welding. The chemical potential of Al and Ni indicated that Al-Ti reaction product was produced more easily than Ni-Ti in 0.001Mg-(Ni-Al-Ti) system. The thermodynamic calculation results of Gibbs free energy suggested the preferential formation Ti-Al phase and Ti-Ni phase along the interface while the Mg-Al-Ni ternary phase in the FZ. Fracture loads of joints increased first followed by a decline with the increase in coating thickness. The joint fractured at the Mg base metal, reaching a maximum value of 3900 N with the Ni coating thickness of 1.5 μm. In the case of using thinner or thicker Ni coating, crack propagated along the interface due to the insufficient metallurgical bonding or defects existed in the interfacial layer. The characteristic of fracture surface changed from the tear ridges and terraces to river pattern when interfacial failure occurred.

36 MATERIALS SCIENCE↗

Nickel-Coated Super-Aligned Carbon Nanotube Reinforced Copper Composite for Improved Strength and Conductivity

Nickel (Ni)-coated super-aligned carbon nanotube (SACNT) films-reinforced copper (Cu) matrix composites were fabricated by electrodeposition. The microstructure, mechanical property and electrical conductivity of the prepared composites have been studied systematically. The results show that the mechanical properties of SACNT/Cu were significantly improved by coating SACNT with Ni. When the volume fraction of SACNT is 10.0%, the tensile strength and yield strength of the composite can reach 477.8 and 295.5 MPa, respectively, corresponding to 147 and 170% improvement compared to pure Cu prepared by the same method. Meanwhile, due to the super-aligned arrangement of SACNTs and the homogeneous distribution of Ni, which is not mixing or dissolving with Cu, the conductivities of all the Ni-coated SACNT-reinforced Cu composites are above 58% IACS, which is about 4 times higher than the results in previous research. The enhancement of the strength of the SACNT/Cu composites comes from the combined contribution of load transfer and grain refinement strengthening.

36 MATERIALS SCIENCE↗

Corrosion Protection of Cu Electrical Cable by W-Ni Composite Coatings Doped with TiO{sub 2} Nanoparticles: Influence of Pulse Currents

W-Ni-TiO{sub 2} nano-composite layers were electrodeposited on copper surface by both direct (DC) and pulse (PC) currents. The copper substrates are samples from the main electrical cable used for the Renault K-Z (the latest 100% electric vehicle). In order to investigate coating morphology, atomic force microscopy was used, while energy-dispersive x-ray analysis was applied to determine nano-composite composition. Based on surface morphology, the W-Ni-TiO{sub 2} (DC) alloy surface was covered by massive agglomerates, especially when the W-Ni-TiO{sub 2} (PC) nano-composite coating was more compact, thicker and exhibited smaller grain size. The coated surface revealed different contents such as 43.4 and 65.4% of W in DC and PC coatings, respectively, which are considered to be a novel composition of the W-Ni alloy. XRD studies revealed that the NiW{sub 2} phase only occurs in the W-Ni-TiO{sub 2} (PC) nano-composite alloy. Electrical and thermal conductivities, microhardness and porosity values are enhanced by the addition of TiO{sub 2} to the alloy.

36 MATERIALS SCIENCE↗

Solderability of AZ31B Magnesium Alloy Coated by Copper and Strength of the Solder Joints

Magnesium alloys are promising as light materials, while their high chemical reactivity makes them difficult to be soldered. In this study, the AZ31B alloy was pretreated by zincification and coated by an electrodeposited Cu layer, and then soldered with Sn-58Bi solder in air furnace. The microstructure and properties of the AZ31B/Cu(Zn)/SnBi solder joints were characterized to evaluate the solderability of the Cu-coated Mg alloy and the influence of soldering on the Cu coating. It was found that the Cu coating is dense, and little defect exists along the Cu(Zn)/AZ31B interface. The soldering process has little negative effect on the bonding between the Cu coating and the AZ31B substrate, and the AZ31B/Cu(Zn)/SnBi solder joints of high metallurgical quality were obtained. Tensile fracture of the solder joint occurs mainly in the solder, with no peeling of the Cu coating. Under shear loading, cracks initiate inside the SnBi solder and the final fracture of the joint occurs around the Cu{sub 6}Sn{sub 5}/solder interface or along the Cu(Zn)/AZ31B interface. The tensile and shear strength of the AZ31B/Cu(Zn)/SnBi solder joints are close to that of the SnBi/Cu solder joints. It is demonstrated that the Cu-coated Mg alloy shows superior solderability and can be soldered by the Sn-based low-melting solder in air.

36 MATERIALS SCIENCE↗