Electrodeposition Of Metals Research Articles

High-strength copper foil prepared with 2-mercaptothiazoline by direct current electrodeposition

A kind of new additive for ultra-thin copper foils with high tensile strength is reported in this work. The highest strength is about 700 MPa with 12 mg/L 2-mercaptothiazoline, and the strengthening effects and mechanisms in different concentrations are studied in detail. 2-Mercaptothiazoline significantly improves the tensile strength of electrolytic copper foils by refining the grains and effectively impeding the slips of dislocations. Fine grains also provide a smooth and flat surface for foils, and weaken the preferred orientation of grains in the cross-section, contributing to the high strength of copper foils at different aspects. The addition of the 2-mercaptothiazoline obviously inhibits the electron transfer process of metal electrodeposition and enhances the electrochemical polarization, resulting in high nucleation density and small nuclei to form fine grains. The high-strength copper foils with a very thin thickness are placed great expectations on the industrial application of lithium-ion batteries.

Ultrafast deposition of faceted lithium polyhedra by outpacing SEI formation.

Electrodeposition of lithium (Li) metal is critical for high-energy batteries1. However, the simultaneous formation of a surface corrosion film termed the solid electrolyte interphase (SEI)2 complicates the deposition process, which underpins our poor understanding of Li metal electrodeposition. Here we decouple these two intertwined processes by outpacing SEI formation at ultrafast deposition current densities3 while also avoiding mass transport limitations. Byusing cryogenic electron microscopy4-7, we discover the intrinsic deposition morphology of metallic Li to be that of a rhombic dodecahedron, which is surprisingly independent of electrolyte chemistry or current collector substrate. In a coin cell architecture, these rhombic dodecahedra exhibit near point-contact connectivity with the current collector, which can accelerate inactive Li formation8. We propose a pulse-current protocol that overcomes this failure mode by leveraging Li rhombic dodecahedra as nucleation seeds, enabling the subsequent growth of dense Li that improves battery performance compared with a baseline. While Li deposition and SEI formation have always been tightly linked in past studies, our experimental approach enables new opportunities to fundamentally understand these processes decoupled from each other and bring about new insights to engineer better batteries.

Y2O3 electrodeposited TiO2 nanotube arrays as photoanode for enhanced photoelectrochemical water splitting

Y2O3 deposited TiO2 nanotubes (Y-TNTs) are investigated as photoanodes for efficient photoelectrochemical water splitting. Y2O3 is electrodeposited on TiO2 nanotubes for 5–15 min. The physicochemical and optical properties of Y-TNTs reveal that Y2O3 anchored on the TNTs enhances the visible light absorption. The Y-TNTs show good photocurrent response compared to pristine TNTs. Y2O3 deposition for 10 min on TNTs produces highest photocurrent of 609 μA cm−2 at 1.23 VRHE. Presence of Y2O3 increases the lifetime of the charge carriers as revealed by the Nyquist plot analysis and Mott-Schottky analysis. Y-TNTs-10 min sample shows 2.75 times higher photoconversion efficiency compared to pristine TNTs. Computational analysis shows that Y–TiO2 has negative free energy of adsorption for OER intermediates as compared to bare TiO2 which has positive values. The rare earth metal electrodeposition on TiO2 nanotubes is another approach to improve the photoelectrochemical water splitting activity without distorting the nanotube structure.

Exploring the Impact of Concentration and Temperature Variations on Transient Natural Convection in Metal Electrodeposition: A Finite Volume Method Analysis

A mathematical model was developed to accurately determine the current density, concentration, and velocity profiles in electrochemical reactors operating under natural convection conditions. The model considers the interplay of key variables, such as potential, concentration, and temperature linked to the hydrodynamics through the density field using the Boussinesq approximation. Thus, a comprehensive analysis under both laminar and turbulent flow conditions is provided. The computational algorithm that represents the model is implemented in OpenFOAM and it offers the ability to operate the reactor at a fixed cell potential difference or under potentiostatic and galvanostatic control. The model’s accuracy was verified in different parallel-plate reactors using copper deposition as a test reaction from dilute and concentrated solutions, showing a strong agreement with the experimental results. This tool can be leveraged to optimize cell design and operating conditions in electrochemical systems that involve significant natural convection, such as in the electrowinning and electrorefining industries.

Ion Conducting Polymer Interfaces for Lithium Metal Anodes: Impact on the Electrodeposition Kinetics

AbstractElectrochemical cells that utilize metals (e.g., lithium, sodium, zinc) as anodes are under intense investigation as they are projected to replace the current lithium‐ion batteries to serve as a more energy‐dense option for commercial applications. In addition, metal electrodes provide opportunities for fundamental research of different phenomena, such as ion transport and electrochemical kinetics, in the complex environment of reactive metal‐electrodeposition. In this work, computationally and experimentally the competing effects related to transport and kinetics during the metal electrodeposition process are examined. Using Brownian dynamics simulations, it is shown that slower deposition kinetics results in a more compact and uniform Li morphology. This finding is experimentally implemented by designing ion‐containing polymeric coatings on the electrodes that simultaneously provide pathways for lithium‐ion transport, while impeding the charge transfer (Li+ + e− → Li) at heterogeneous surfaces. It is further shown that these ionic polymer interfaces can significantly extend the cell‐lifetime of a lithium metal battery in both ether‐based and carbonate‐based electrolytes. Through theoretical and experimental investigations, it is found that a low kinetic to transport rate ratio is a major factor in influencing the Li plating morphology. The plating morphology can be further fine‐tuned by increasing ionic conductivity.

Platinum and palladium nanoparticles on boron-doped diamond for the electrochemical detection of hydrogen peroxide: a comparison study.

Hydrogen peroxide (H2O2) plays a role in many facets - a household item, an important industrial chemical, a biomarker in vivo, and several others. For this reason, its measurement and quantification in a variety of media are important. While spectroscopic detection is primarily used for H2O2, electrochemical methods offer advantages in versatility, cost, and sensitivity. In this work, we investigate a 2-step surface metal nanoparticle (NP) modification for platinum (Pt) and palladium (Pd) on boron-doped diamond (BDD) electrodes for the detection of H2O2. Several parameters such as the metal salt concentration and electrodeposition charge in the 2-step modification were varied to find an optimum. Using cyclic voltammetry (CV), the BDD-PdNP electrode types were found to yield a sharper, more well-resolved H2O2 oxidation peak compared to the BDD-PtNP electrodes. Both metal NP electrode types significantly improved the response compared to the bare BDD electrode; a 150-200× improvement in sensitivity was observed across all modified electrode types. Calibration experiments were completed at both low and high concentration ranges in stagnant and flow-based solutions. The lowest limit of detection (LOD) obtained was 50 nM (5E-08 M) on a BDD-PdNP electrode modified with 1.0 mM PdCl2 to 5.0 mC in the wet chemical seeding and electrodeposition steps. 0.25 mM PdCl2 to 3.23 mC and 0.25 mM HPtCl6- to 3.23 mC also yielded a sufficient response for low-level H2O2, with LODs around 100 nM (1E-07 M). Overall, this work exemplifies the wide applicability of BDD and achieves sub-μM H2O2 LODs with a non-enzymatic electrode material.

A simple electrodeposition problem and the abundant knowledge it subserves to teach

This paper presents a handful of electrochemical experiments related to one single system that opens up the way to teach a bunch of topics related to physical and inorganic chemistry, hence serving experience-oriented education of otherwise hard-to-understand fields. The key idea is the electrodeposition of metals from the same bath containing Cu2+ and Ni2+ ions onto electrodes that differ from each other either in size or position within the electrochemical cell. With the proper optimization of the current densities, pure Cu and a Ni-rich coating with shiny silver colour can be obtained on electrodes of large and small surface area, respectively. It will be explained in detail how to drive the discussion on the experiment so that the audience learns which processes can be treated as parallel ones (i.e. the deposition of two metals, Cu and Ni), the mass transport taking place in serial with the electrochemical reaction, and the occurrence of the mass transport limitation in an electrode process. Didactic aspects of the experiment are presented for both high school and undergraduate levels, and control experiments are also suggested to verify the conclusions achieved. Collateral topics of chemistry and materials science that can be brought up in connection with the experiment are also enumerated.

How far does the Copper/Nickle recovery from the practical application in the electroplating wastewater?

Metal recovery from electroplating wastewater presents a promising alternative approach for Cu/Ni resource procurement, alleviating traditional mineral mining shortages. This article reviews diverse metal recovery technologies, including adsorption, electrocoagulation, chemical precipitation, resin adsorption, extraction, membrane separation, and electrodeposition. Most studies successfully transfer Cu2+ or Ni2+ from electroplating wastewater to intended metal carriers in lab-scale technologies, thus purifying the wastewater and concurrently enriching desired metals. However, these studies primarily focus on lab-scale heavy metal enrichment and purification, often yielding a mixture of metals with impurities or concentrated salt solution. The importance of reutilization of the recovered metal mixture or metal salt solution, largely unexplored in existing research, is pivotal for sustainability. We propose that future works prioritize pilot-scale experiments, emphasizing reutilization strategies for recovered materials. Consequently, a comprehensive environmental impact evaluation of metal recovery from electroplating wastewater could be made via life cycle assessment, underscoring the importance of reuse in this process.

Origin of high optical contrast in zinc-zinc oxide electrodeposits for dynamic windows

The control of solar light and heat emission through windows is an important strategy for increasing the energy efficiency of buildings. Reversible Zn electrodeposition has recently emerged as a promising method for constructing electronically tintable robust dynamic windows. In Zn electrodeposits formed from dimethyl sulfoxide (DMSO) electrolytes during device tinting, we observe extraordinary absorption that is in excess of what is predicted by the Beer-Lambert law for a uniform Zn thin film. The charge required to electroplate these films is abnormally low, significantly less than previously reported dynamic windows based on reversible metal electrodeposition, which facilitates the construction of large-area devices that switch uniformly. Finite-difference time-domain (FDTD) simulations are used to investigate the origin of this enhanced absorption, which arises from plasmonic effects among the Zn nanoparticles and ZnO dendrites in the film. The dielectric ZnO dendrites promote absorption via slit-like Zn-dielectric-Zn structures that from hybrid surface plasmon resonance at metal walls. Through these investigations, we provide design principles to construct low-charge and high-contrast metal and metal oxide-based dynamic windows.

Electrocrystallization of Metals in Channels of Porous Films of Anodic Aluminum Oxide: The Real Template Structure and the Quantitative Model of Electrodeposition

A method is proposed for analytical description of current transients at the template-assisted electrodeposition of metal into porous films in anodic aluminum oxide (AAO). The template-assisted electrodeposition of copper and gold is accomplished. For the copper electrodeposition, it is shown that the experimental data are in quantitative agreement with the calculated values of current without any fitting parameters. The parameters of the AAO film structure including the conicity of pores and the number of dead-end channels are measured and their effect on the process of template-assisted electrodeposition is studied .

An electrochemical sensor based on rGO/GaN nanowires for Pb(II) determination

In this work, rGO/GaN nanowires electrochemical sensors were fabricated on sapphire substrates by metal organic chemical vapor deposition (MOCVD) and electrodeposition method, and it was used for the detection of Pb2+ in water. Reduced graphene oxide (rGO) increases the specific surface area and active sites of gallium nitride nanowires (GaN NW), and GaN NW improves the stability of the rGO, thus a highly sensitive electrochemical sensor was established. Square wave anodic stripping voltammetry (SWASV) was used to detect Pb2+. Effects of experimental conditions such as rGO modification amount, pH, Pb2+ deposition potential/time on the detection performance were investigated. With optimized detection conditions, the rGO/GaN NW sensor features high sensitivity (0.7362 μA μg-1 L) in the linear range of 2.5-200 μg L-1, and the detection limit was 2.5 μg L-1. Furthermore, the rGO/GaN NW sensor exhibited a good stability and repeatability.

Dynamics of the Lithium Metal Electrodeposition: Effects of a Gas Bubble

AbstractUnderstanding the dynamics of lithium metal electrodeposition is crucial to designing safe and reliable lithium metal anodes. In this study, a grand potential‐based phase‐field model is developed to investigate the effect of a gas bubble (which forms due to the internal side reactions) on the dynamics of the dendrite growth during electrodeposition. It is observed that with the presence of a static gas bubble, the dendrite growth is largely accelerated, owing to the accumulation of lithium ions on the far side of the bubble away from the anode surface, which can serve as an ion “reservoir” for the dendrite growth, leading to the tilting of the lithium dendrites toward the bubble. The effects of the bubble size and distance to the anode are further studied, demonstrating that the larger the bubble size and the closer to the anode, the longer the lithium dendrites will grow. Notably, with a mobile bubble, the dendrite growth can be delayed due to the “stirring effect,” where the motion of the bubble can facilitate the ion migration. This effect is maximized when the bubble moving speed is close to the electrodeposition speed. It is hoped that this study can serve as an example to exploit the effect of extrinsic factors on the dendrite growth dynamics.

Ability of Li4Ti5O12 to suppress Li metal deposition under overpotential conditions confirmed by electrochemical surface plasmon resonance spectroscopy

Undesirable Li metal deposition on the negative electrode increases the risks associated with the use of Li-ion batteries. Generally, spinel-type lithium-titanium oxide Li4Ti5O12 (LTO)-based negative electrodes are well known as safe dendrite-free options, due to their higher working potential. However, the ability of LTO-based materials to prevent Li metal deposition has not been well confirmed under sudden overpotential application. This study examines the behavior of Li metal electrodeposition under various overpotential conditions for unloaded and LTO-loaded Cu electrodes. Electrochemical surface plasmon resonance spectroscopy (EC-SPR) is used as the optical diagnostic technique, owing to its sensitivity in detecting Li metal deposition. Li metal deposition is easily detected for the unloaded Cu electrode at overpotential of − 0.2 V (voltage) versus Li counter electrode (LiCE), whereas no Li metal deposition occurs for the LTO-loaded Cu electrode under the same overpotential. The safety of LTO is investigated by analyzing the reaction kinetics.

Bi-Cu Electrolytes with Aminocarboxylate Chelators for Reversible Metal Electrodeposition at High pH for Dynamic Windows

Dynamic windows, which possess electronically tunable light transmission, increase both the energy efficiency and aesthetics of spaces such as buildings and automobiles. Although reversible metal electrodeposition affords a promising approach to constructing high-performing dynamic windows, the acidic nature of the aqueous electrolytes frequently used in these windows has prevented their commercialization due to tin-doped indium oxide (ITO) etching. In this manuscript, we design neutral and alkaline electrolytes that support the reversible electrodeposition of Bi and Cu at rates comparable to existing acidic electrolytes. In these electrolytes, Bi3+ and Cu2+ are solubilized by using aminocarboxylate chelating ligands. By evaluating a series of ligands with varying denticities, we demonstrate that N-(2-hydroxyethyl)ethylenedianmine-N,N’,N’-triacetic acid (ED3A-OH) provides the optimal metal ion binding strength that enhances solubility while simultaneously supporting rapid metal electrodeposition. These results allow us to design alkaline ED3A-OH electrolytes that are compatible with ITO even after four weeks of immersion at 85 °C. This manuscript thus demonstrates that chelating ligands can be utilized to design alkaline reversible metal electrodeposition electrolytes that support dynamic windows with robust shelf lives.

Intermetallics Based on Sodium Chalcogenides Promote Stable Electrodeposition–Electrodissolution of Sodium Metal Anodes

AbstractSodiophilic micro‐composite films of sodium‐chalcogenide intermetallics (Na2Te and Na2S) and Cu particles are fabricated onto commercial copper foam current collectors (Na2Te@CF and Na2S@CF). For the first time a controllable capacity thermal infusion process is demonstrated. Enhanced wetting by the metal electrodeposition leads to state‐of‐the‐art electrochemical performance. For example, Na2Te@CF‐based half‐cells demonstrate stable cycling at 6 mA cm−2 and 6 mAh cm−2, corresponding to 54 µm of Na electrodeposited/electrodissolved by geometric area. Sodium metal batteries with Na3V2 (PO4)3 cathodes are stable at 30C (7 mA cm−2) and for 10 000 cycles at 5C and 10C. Cross‐sectional cryogenic focused ion beam (cryo‐FIB) microscopy details deposited and remnant dissolved microstructures. Sodium metal electrodeposition onto Na2Te@CF is dense, smooth, and free of dendrites or pores. On unmodified copper foam, sodium grows in a filament‐like manner, not requiring cycling to achieve this geometry. Substrate–metal interaction critically affects the metal–electrolyte interface, namely the thickness and morphology of the solid electrolyte interphase. Density functional theory and mesoscale simulations provide insight into support‐adatom energetics, nucleation response, and early‐stage morphological evolution. On Na2Te sodium atomic dispersion is thermodynamically more stable than isolated clusters, leading to conformal adatom coverage of the surface.

Non-contact gaseous microplasma electrode as anode for electrodeposition of metal and metal alloy in molten salt

Microplasma based on glow discharge could act as a non-contact gaseous electrode and has attracted much attention in both fundamental research and application. Herein, with microplasma as the anode, the electrodeposition process of a series of metal and metal alloys in molten salt has been systemically studied. Four metal cations with different valence states, silver (Ag+), nickel (Ni2+), copper (Cu2+), and iron (Fe3+), could all be reduced on the solid cathode with high current efficiency and the corresponding metal products were of high purity. The electrodeposition of aluminum-lanthanum (Al-Ln) alloy on the aluminum cathode was also successfully carried out with microplasma as the anode, and the same alloy was obtained by using the conventional anode electrode. These results indicated that microplasma anode based on non-contact direct-current (DC) glow discharge is a promising electrode to be applied in molten salt electrolysis.

Moss-like Growth of Metal Electrodes: On the Role of Competing Faradaic Reactions and Fast Charging

Uncontrolled crystal growth during electroreduction of reactive metals in liquid electrolytes produces mossy metal deposits. Here, we use electroanalytical rotating disk electrode (RDE) studies to elucidate the origin of moss-like electrodeposition of metals. Competing Faradaic reactions on the electrode surface are shown to be the source of the phenomenon. A moss-like growth regime can be accessed by subtle shifts in electrolyte chemistry and deposition rate. For Zn─a metal that conventionally is not known to form moss-like electrodeposits─obvious moss-like patterns emerge at low-current densities in strongly alkaline electrolytes. Conversely, under conditions where the electroreduction rate is large relative to competing Faradaic reactions, moss-like Zn growth is eliminated. The same principle holds for Li metal deposition. On that basis, an empirical rule is proposed─an applied current density i that satisfies the relation 10 is < i < 0.8 ilim is required for achieving favorable metal electrodeposit morphology and fast charging in batteries.

Surface modification of ABS polymer by electroless deposition of thin nickel film from a solution without reducing agent

ABSTRACT For preparation of acrylonitrile–butadiene-styrene (ABS) polymer, suitable for electrodeposition of a subsequent metal coating, a modification of the activated polymer surface by electroless nickel deposition in an alkaline nickel citrate-based solution without reducing agent is proposed. The influence of the main components of the solution and the working conditions on the mass of the nickel deposit has been studied. The modified surface was characterised using SEM, EDS and XPS analyses. The obtained nickel in oxidised state is sufficient to conduct current for subsequent electrodeposition of copper coating.

Sulfolane-containing aqueous electrolyte solutions for producing efficient ampere-hour-level zinc metal battery pouch cells

Aqueous zinc metal batteries are appealing candidates for grid energy storage. However, the inadequate electrochemical reversibility of the zinc metal negative electrode inhibits the battery performance at the large-scale cell level. Here, we develop practical ampere-hour-scale aqueous Zn metal battery pouch cells by engineering the electrolyte solution. After identifying the proton reduction as the primary source of H2 evolution during Zn metal electrodeposition, we design an electrolyte solution containing reverse micelle structures where sulfolane molecules constrain water in nanodomains to hinder proton reduction. Furthermore, we develop and validate an electrochemical testing protocol to comprehensively evaluate the cell’s coulombic efficiency and zinc metal electrode cycle life. Finally, using the reverse micelle electrolyte, we assemble and test a practical ampere-hour Zn||Zn0.25V2O5•nH2O multi-layer pouch cell capable of delivering an initial energy density of 70 Wh L−1 (based on the volume of the cell components), capacity retention of about 80% after 390 cycles at 56 mA g−1cathode and ~25 °C and prolonged cycling for 5 months at 56 mA g−1cathode and ~25 °C.

In-situ imaging of the electrode surface during electrochemical reactions with a beetle-type electrochemical scanning tunneling microscope

In this paper, we present the design and performances of a beetle-type electrochemical scanning tunneling microscope (EC-STM) which allows horizontal tip motion at millimeter range (5 mm × 5 mm). With its symmetrical scanner design inducing a relatively low thermal drift, the beetle-type EC-STM has the desirable ability to operate in a variety of chemical reactions. Atom-resolved high-resolution STM images of highly oriented pyrolytic graphite (HOPG) and Au(111) surfaces in the liquid phase are presented to confirm the scan performance of the beetle-type EC-STM, which also provides in situ information on the electrode surface during electrochemical reactions, including adsorbed– and desorbed– electrolyte and metal electrodeposition. These systemically obtained STM images on the electrode surface clearly demonstrate the high stability of the newly developed EC‐STM under reaction conditions.