Solvent‐Mediated Li2S Electrodeposition: A Critical Manipulator in Lithium–Sulfur Batteries

Controlling electrochemical deposition of lithium sulfide (Li₂S) is a major challenge in lithium–sulfur batteries as premature Li₂S passivation leads to low sulfur utilization and low rate capability. In this work, the solvent's roles in controlling solid Li₂S deposition are revealed, and quantitative solvent‐mediated Li₂S growth models as guides to solvent selection are developed. It is shown that Li₂S electrodeposition is controlled by electrode kinetics, Li₂S solubility, and the diffusion of polysulfide/Li₂S, which is dictated by solvent's donicity, polarity, and viscosity, respectively. These solvent‐controlled properties are essential factors pertaining to the sulfur utilization, energy efficiency and reversibility of lithium–sulfur batteries. It is further demonstrated that the solvent selection criteria developed in this study are effective in guiding the search for new and more effective electrolytes, providing effective screening and design criteria for computational and experimental electrolyte development for lithium–sulfur batteries.     

Stable Li Metal Anode Enabled by Space Confinement and Uniform Curvature through Lithiophilic Nanotube Arrays

The application of lithium (Li) metal anodes in rechargeable batteries is primarily restricted by Li dendrite growth on the metal's surface, which leads to shortened cycle life and safety concerns. Herein, well‐spaced nanotubes with ultrauniform surface curvature are introduced as a Li metal anode structure. The ultrauniform nanotubular surface generates uniform local electric fields that evenly attract Li‐ions to the surface, thereby inducing even current density distribution. Moreover, the well‐defined nanotube spacing offers Li diffusion pathways to the electroactive areas as well as the confined spaces to host deposited Li. These structural attributes create a unique electrodeposition manner; i.e., Li metal homogenously deposits on the nanotubular wall, causing each Li nanotube to grow in circumference without obvious sign of dendritic formation. Thus, the full‐cell battery with the spaced Li nanotubes exhibits a high specific capacity of 132 mA h g^?1 at 1 C and an excellent coulombic efficiency of ≈99.85% over 400 cycles.     

On the Reversibility and Fragility of Sodium Metal Electrodes

Metallic sodium is receiving renewed interest as a battery anode material because the metal is earth‐abundant, inexpensive, and offers a high specific storage capacity (1166 mAh g^?1 at ?2.71 V vs the standard hydrogen potential). Unlike metallic lithium, the case for Na as the anode in rechargeable batteries has already been demonstrated on a commercial scale in high‐temperature Na||S and Na||NiCl₂ secondary batteries, which increases interest. The reversibility of room temperature sodium anodes is investigated in galvanostatic plating/stripping reactions using in situ optical visualization and galvanostatic polarization measurements. It is discovered that electronic disconnection of mossy metallic Na deposits (“orphaning”) is a dominant source of anode irreversibility in liquid electrolytes. The disconnection is shown by means of direct visualization studies to be triggered by a root‐breakage process during the stripping cycle. As a further step toward electrode designs that are able to accommodate the fragile Na deposits, electrodeposition of Na is demonstrated in nonplanar electrode architectures, which provide continuous and morphology agnostic access to the metal at all stages of electrochemical cycling. On this basis, nonplanar Na electrodes are reported, which exhibit exceptionally high levels of reversibility (Coulombic efficiency >99.6% for 1 mAh cm^?2 Na throughput) in room‐temperature, liquid electrolytes.     

Accurate Determination of Coulombic Efficiency for Lithium Metal Anodes and Lithium Metal Batteries

Lithium (Li) metal is an ideal anode material for high energy density batteries. However, the low Coulombic efficiency (CE) and the formation of dendrites during repeated plating and stripping processes have hindered its applications in rechargeable Li metal batteries. The accurate measurement of Li CE is a critical factor to predict the cycle life of Li metal batteries, but the measurement of Li CE is affected by various factors that often lead to conflicting values reported in the literature. Here, several parameters that affect the measurement of Li CE are investigated and a more accurate method of determining Li CE is proposed. It is also found that the capacity used for cycling greatly affects the stabilization cycles and the average CE. A higher cycling capacity leads to faster stabilization of Li anode and a higher average CE. With a proper operating protocol, the average Li CE can be increased from 99.0% to 99.5% at a high capacity of 6 mA h cm^?2 (which is suitable for practical applications) when a high‐concentration ether‐based electrolyte is used.     

The Removal of Pb and Cd from Heavily Contaminated Soil in Kayseri,Turkey by a Combined Process of Soil Washing and Electrodeposition

In this study, a combined system of soil washing and electrodeposition was designed to remove Pb (16381±643 mg/kg) and Cd (34347±1310 mg/kg) from contaminated soil. 0.05 M Na₂EDTA was used as a chelating agent for the remediation of soil, taken from the nearby city Kayseri, Turkey. As a result of the batch extraction tests, maximum removals were determined as; at the 20:1 liquid: soil ratio for Pb is 60.7%, for Cd at the 30:1 liquid: soil ratio is 67.4%. An electrochemical treatment was applied to the waste washing solution which appeared to be the second pollutant after the Na₂EDTA extraction from the soil. With extraction tests of Pb and Cd, being transformed from the solid phase to the liquid phase. The electrochemical treatment (electrodeposition), performed in three different potential (6 V, 8 V and 10 V) and maximum removal efficiencies, were found 99.7% and 80.3% at 10 V for Pb and Cd, respectively.

Speciation tests (BCR) were carried out, both before and after the soil washing process, to evaluate the redistribution of metal fraction in the soil. The fraction, associated with the organic substance, was found as 10.67% for Pb and 1.81% for Cd. The metal bioavailability factor increased after soil washing, which indicates that EDTA could enhance the mobility of Pb and Cd.     

Colloidal gold as a biocompatible immobilization matrix suitable for the fabrication of enzyme electrodes by electrodeposition

Glucose oxidase, horseradish peroxidase, xanthine oxidase, and carbonic anhydrase have been adsorbed to colloidal gold sols with good retention of enzymatic activity. Adsorption of xanthine oxidase on colloidal gold did not result in a change in enzymatic activity as determined by active site titration with the stoichiometric inhibitor pterin aldehyde and by measurement of the apparent Michaelis constant (K'(M)). Gold sols with adsorbed glucose oxidase, horseradish peroxidase, and xanthine oxidase have also been electrodeposited onto conducting matrices (platinum gauze and/or glassy carbon) to make enzyme electrodes. These electrodes retained enzymatic activity and, more importantly, gave an electrochemical response to the enzyme substrate in the presence of an appropriate electron transfer mediator. Our results demonstrate the utility of colloidal gold as a biocompatible enzyme imobilization matrix suitable for the fabrication of enzyme electrodes. (c) 1992 John Wiley & Sons, Inc.     

Near‐Infrared Light‐Induced Photocurrent from a (NaYF4:Yb‐Tm)/(Cu2O) Composite Thin Film

Utilization of photons of sub‐bandgap energy, mostly near‐infrared (NIR) photo­ns, is highly desirable for photovoltaic devices. We show that (NaYF₄:Yb‐Tm)/(Cu₂O) composite films formed by electrodeposition exhibit robust photoactive current generation under NIR light excitation. The composite films consist of homogeneous crystalline particles of the fluoride and Cu₂O in sub‐micrometer size. From spectroscopic characterization, it is found that the NaYF₄:Yb‐Tm layer in the composite film converts NIR radiation by up‐conversion into visible emission, which is efficiently absorbed by the covering semiconducting Cu₂O film, producing photoelectrons. Accordingly, the composite films exhibit highly photoactive current generation by means of a photoelectrochemical process driven by NIR irradiation. The methodology demonstrated here may have certain implications for the utilization of NIR radiation in solar cells, photocatalysts, and infrared photodetectors.     

Understanding and Improving Mechanical Stability in Electrodeposited Cu and Bi for Dynamic Windows Based on Reversible Metal Electrodeposition

Dynamic windows based on reversible metal electrodeposition (RME) can electronically adjust light transmission from ≈70% to <0.1% to improve building aesthetics and energy efficiency by controlling light and heat flow. For RME devices using Cu and Bi, the windows reach “privacy state” (<0.1% transmission) when ≈180 nm of metal is electrodeposited on the transparent conducting electrode. When films with a plated atomic Cu–Bi ratio of ≈2:1 rest in the privacy state, sinusoidal cracks form across the entire film, and the metal delaminates in <1 day. This mechanical failure renders the window unusable as specks of metal are visually unattractive and reduce the dynamic range of the window. The Cu–Bi film is stress free upon deposition, but after 4 h of resting, 38 MPa of tensile stress develops. The tension in Cu–Bi and Cu films combined with the Cu(ClO₄)₂ in the electrolyte results in severe, widespread fractures and delamination due to stress corrosion cracking. In contrast, electrodeposited Bi films have compressive stress, likely due to high self-diffusion and insertion of atoms into grain boundaries while plating, which results in a Bi-based dynamic window with crack-free resting stability that exceeds 9 weeks.     

Silver electrodeposition catalyzed by colloidal gold on carbon paste electrode: application to biotin–streptavidin interaction monitoring

A new electrochemical method to monitor biotin–streptavidin interaction on carbon paste electrode, based on silver electrodeposition catalyzed by colloidal gold, was investigated. Silver reduction potential changed when colloidal gold was attached to an electrode surface through the biotin–streptavidin interaction. Thus, the direct reduction of silver ions on the electrode surface could be avoided and therefore, they were only reduced to metallic silver on the colloidal gold particle surface, forming a shell around these particles. When an anodic scan was performed, this shell of silver was oxidized and an oxidation process at +0.08 V was recorded in NH₃ 1.0 M. Biotinylated albumin was adsorbed on the pretreated electrode surface. This modified electrode was immersed in colloidal gold-streptavidin labeled solutions. The carbon paste electrode was then activated in adequate medium (NaOH 0.1 M and H₂SO₄ 0.1 M) to remove proteins from the electrode surface while colloidal gold particles remained adsorbed on it. Then, a silver electrodeposition at −0.18 V for 2 min and anodic stripping voltammetry were carried out in NH₃ 1.0 M containing 2.0×10⁻⁵ M of silver lactate. An electrode surface preparation was carried out to obtain a good reproducibility of the analytical signal (5.3%), using a new electrode for each experiment. In addition, a sequential competitive assay was carried out to determine streptavidin. A linear relationship between peak current and logarithm of streptavidin concentration from 2.25×10⁻¹⁵ to 2.24×10⁻¹² M and a limit of detection of 2.0×10⁻¹⁵ M were obtained.