Effect of Thiourea Containing Composite Additives on Nickel Electrodeposition in Ammoniacal Solution

Composite additives have an important influence on the process of metal electrodeposition and the quality of a metal deposited layer. In this work, the additive thiourea (TU) was compounded with cetyltrimethyl ammonium chloride (CTAC), sodium dodecyl sulfate (SDS) and polyethylene glycol 20,000 (PEG20000), and their effect on the cyclic voltammetric behavior, electrochemical nucleation mechanism, crystallographic orientations and surface morphology of the nickel electrodeposition in ammoniacal solution were experimentally investigated. The results show that the introduction of composite additives resulted in a stronger cathodic polarization and increased the nucleation overpotential (NOP) values significantly, which had an important impact on forming compact and smooth nickel deposits. The chronoamperometry analysis indicated that the reduction in nickel followed the 3D progressive nucleation mechanism in the presence of composite additives at the step potential of −1.16 V and −1.18 V. Smoother and finer nickel films were found using scanning electron microscopy (SEM) images as the composite additives were used. X-ray diffraction revealed that all nickel deposit samples had the face-centered cubic structure, and five main crystal planes were displayed by the presence of composite additives in the electrolyte. Furthermore, the diffraction peaks of (111) and (200) crystal planes were slightly shifted toward lower 2θ values when thiourea was used in combination with additive CTAC or PEG20000. These results were beneficial for understanding the mechanisms and facilitating the rational design of additives for metal nickel electrodeposition.

Electrodeposition of Cu-Ag Alloy Films at n-Si(001) and Polycrystalline Ru Substrates

Electrodeposition of Cu-Ag films from acidic sulfate bath was conducted at n-Si(001) and polycrystalline Ru substrates. Significant nucleation overpotential of 0.4 V is observed with the Cu-Ag bath at n-Si(001) substrate, whereas the electrodeposition of Cu-Ag at Ru substrate is influenced by Ru oxides at the surface. Incomplete coverage of Si substrate by Cu-Ag deposit was observed from the deposition systems without Ag(I), or with 0.1 mM Ag(I), comparing with the compact Cu-Ag film obtained with the deposition bath containing 0.01 mM Ag(I). Layered and faceted Cu-Ag deposit was observed at small Cu deposition overpotential with the Ru substrate. Phase composition of the Cu-Ag deposits at n-Si(001) substrate from electrolyte with various Ag(I) concentrations is examined by XRD. Limited solubility of Ag (0.4 at.%) was observed in fcc-Cu until phase separation occurs. The classical model for nucleation kinetics in electrodeposition was used to examine the potentiostatic transients of the Cu-Ag electrodeposition at n-Si(001) substrate.

Novel electrolyte additive of graphene oxide for prolonging the lifespan of Zinc-ion batteries

Aqueous zinc-ion batteries have attracted the attention of the industry due to their low cost, good environmental friendliness, and competitive gravimetric energy density. However, zinc anodes, similar to lithium, sodium and other alkali metal anodes, are also plagued by dendrite problems. Zinc dendrites can penetrate through polymer membranes, and even glass fiber membranes which seriously hinders the development and application of aqueous zinc-ion batteries. To resolve this issue, certain additives are required. Here we have synthesized an electrochemical graphene oxide with novel electrolyte based on tryptophan, which allows to obtain few-layered sheets with a remarkably uniform morphology, good aqueous solution dispersion, easy preparation and environmental friendliness. We used this electrochemical graphene oxide as an additive to the electrolyte for aqueous zinc-ion batteries. The results of phase-field model combined with experimental characterization revealed that the addition of this material effectively promotes the uniform distribution of the electric field and the Zn-ion concentration field, reduces the nucleation overpotential of Zn metal, and provides a more uniform deposition process on the metal surface and improved cyclability of the aqueous Zn-ion battery. The resultant Zn|Zn symmetric battery with the electrochemical graphene oxide additive affords a stable Zn anode, which provided service for more than 500 hours at 0.2 mA cm-2 and even more than 250 hours at 1.0 mA cm-2. The Coulombic efficiency (98.7%) of Zn|Cu half-cells and thus cyclability of aqueous Zn-ion batteries using electrochemical graphene oxide is significantly better compared to the additive-free electrolyte system. Therefore, our approach paves a promising avenue to foster the practical application of aqueous Zn-ion batteries for energy storage.

Oxygen-rich interface enables reversible stibium stripping/plating chemistry in aqueous alkaline batteries

Aqueous alkaline batteries see bright future in renewable energy storage and utilization, but their practical application is greatly challenged by the unsatisfactory performance of anode materials. Herein, we demonstrate a latent Sb stripping/plating chemistry by constructing an oxygen-rich interface on carbon substrate, thus providing a decent anode candidate. The functional interface effectively lowers the nucleation overpotential of Sb and strengthens the absorption capability of the charge carriers (SbO2− ions). These two advantageous properties inhibit the occurrence of side reactions and thus enable highly reversible Sb stripping/plating. Consequently, the Sb anode delivers theoretical-value-close specific capacity (627.1 mA h g−1), high depth of discharge (95.0%) and maintains 92.4% coulombic efficiency over 1000 cycles. A robust aqueous NiCo2O4//Sb device with high energy density and prominent durability is also demonstrated. This work provides a train of thoughts for the development of aqueous alkaline batteries based on Sb chemistry.

A highly reversible sodium metal anode by mitigating electrodeposition overpotential

Herein, we successfully introduce a sodiophilic Na–Cu–P composites via in situ alloying reaction, which can greatly mitigate the tip/growth/nucleation overpotential during Na deposition, thereby to realize a stable Na plating/stripping behaviors.

Electrochemical Behavior and Electrodeposition of Sn Coating from Choline Chloride–Urea Deep Eutectic Solvents

The electrochemical behavior and electrodeposition of Sn were investigated in choline chloride (ChCl)–urea deep eutectic solvents (DESs) containing SnCl2 by cyclic voltammetry (CV) and chronoamperometry techniques. The electrodeposition of Sn(II) was a quasi-reversible, single-step two-electron-transfer process. The average transfer coefficient and diffusion coefficient of 0.2 M Sn(II) in ChCl–urea at 323 K were 0.29 and 1.35 × 10−9 cm2∙s−1. The nucleation overpotential decreased with the increase in temperature and SnCl2 concentration. The results of the chronoamperometry indicated that the Sn deposition on tungsten electrode occurred by three-dimensional instantaneous nucleation and diffusion controlled growth using the Scharifker–Hills model. Scanning electron microscopy (SEM) showed that the morphology of the deposits is uniform, as a dense and compact film prepared by potentiostatic electrolysis on Cu substrate. X-ray diffraction (XRD) analysis revealed that the deposits were pure metallic Sn.

Lithiophilicity chemistry of heteroatom-doped carbon to guide uniform lithium nucleation in lithium metal anodes

The uncontrollable growth of lithium (Li) dendrites seriously impedes practical applications of Li metal batteries. Various lithiophilic conductive frameworks, especially carbon hosts, are used to guide uniform Li nucleation and thus deliver a dendrite-free composite anode. However, the lithiophilic nature of these carbon hosts is poorly understood. Herein, the lithiophilicity chemistry of heteroatom-doped carbon is investigated through both first principles calculations and experimental verifications to guide uniform Li nucleation. The electronegativity, local dipole, and charge transfer are proposed to reveal the lithiophilicity of doping sites. Li bond chemistry further deepens the understanding of lithiophilicity. The O-doped and O/B–co-doped carbons exhibit the best lithiophilicity among single-doped and co-doped carbons, respectively. The excellent lithiophilicity achieved by O-doping carbon is further validated by Li nucleation overpotential measurement. This work uncovers the lithiophilicity chemistry of heteroatom-doped carbons and affords a mechanistic guidance to Li metal anode frameworks for safe rechargeable batteries.

Electrochemically induced highly ion conductive porous scaffolds to stabilize lithium deposition for lithium metal anodes

The electrochemically-induced lithiophilic Li–Zn alloy scaffold with high ionic conductivity, together with the Li2O passivated surface, can reduce the nucleation overpotential of Li deposition, enhance the Li+ ions diffusion and guide the homogeneous nucleation of Li, and thus suppressing the lithium dendrite growth.