3D-printed microchip electrophoresis device containing spiral electrodes for integrated capacitively coupled contactless conductivity detection.

In this work, we demonstrate for the first time the design and fabrication of microchip electrophoresis devices containing cross-shaped channels and spiral electrodes around the separation channel for microchip electrophoresis and capacitively coupled contactless conductivity detection. The whole device was prepared in a digital light processing-based 3D printer in poly(ethylene glycol) diacrylate resin. Outstanding X-Y resolution of the customized 3D printer ensured the fabrication of 40-µm cross section channels. The spiral channels were filled with melted gallium to form conductive electrodes around the separation channel. We demonstrate the applicability of the device on the separation of sodium, potassium, and lithium cations by microchip electrophoresis. Graphical abstract.

ZnO Thin Films Growth Optimization for Piezoelectric Application.

The piezoelectric response of ZnO thin films in heterostructure-based devices is strictly related to their structure and morphology. We optimize the fabrication of piezoelectric ZnO to reduce its surface roughness, improving the crystalline quality, taking into consideration the role of the metal electrode underneath. The role of thermal treatments, as well as sputtering gas composition, is investigated by means of atomic force microscopy and x-ray diffraction. The results show an optimal reduction in surface roughness and at the same time a good crystalline quality when 75% O2 is introduced in the sputtering gas and deposition is performed between room temperature and 573 K. Subsequent annealing at 773 K further improves the film quality. The introduction of Ti or Pt as bottom electrode maintains a good surface and crystalline quality. By means of piezoelectric force microscope, we prove a piezoelectric response of the film in accordance with the literature, in spite of the low ZnO thickness and the reduced grain size, with a unipolar orientation and homogenous displacement when deposited on Ti electrode.

Electrochemical process employing scrap metal waste as electrodes for dye removal.

In the present study, efficiency of electro-coagulation-flotation (EC-F) process using waste metal scrap of Al and Fe collected from construction and demolition waste of Indian Institute of Technology Madras (IIT M) campus for the removal of double azo bond dye Acid Red 66 (AR66) was studied. The key operating parameters such as current density and electrical conductivity were optimized individually with an initial dye concentration of 50 mg/L, at pH 7. Different electrode combinations and connection modes (parallel MP-P, series (MP-S, BP-S)) were tested, at pre-optimized conditions, in order to achieve better removal of AR66 dye with minimum energy consumption. Series connection in bipolar electrode mode (BP-S) showed better COD reduction from 164 mg/L to 26.2 mg/L with complete decolourization (BDL). Hybrid electrode system of Fe-Al-Fe-Al-Fe-Al showed maximum reduction of COD from 164 mg/L to 11.3 mg/L along with 86.3% TSS reduction and complete decolourization. LC-MS analysis showed the formation of intermediates with m/z 195, m/z 210.6 and m/z 159.3 due to the destruction of AR66 dye during electrolysis. Highest current efficiency (CE φ = 107%) was observed in case of hybrid electrode system compared to Al (φ = 30.1%) and Fe (φ = 98.3%) electrode system at similar operating conditions. Compared to the same electrode material as anode and cathode, use of appropriate hybrid electrode combination can improve the removal efficiency and reduce the energy consumption (ENC). The influence of aeration on the performance of the system was also studied. Aeration significantly improved the COD removal efficiency (98.3%) along with complete decolourization (100%). The use of waste metal scrap as electrodes reduced the overall cost of the treatment process from 1.6 $/m3 to 0.06 $/m3. Using waste metal scrap as electrodes not only reduces the metal accumulation in the environment but also reduces the cost of EC-F process.

Emerging Novel Metal Electrodes for Photovoltaic Applications.

Emerging novel metal electrodes not only serve as the collector of free charge carriers, but also function as light trapping designs in photovoltaics. As a potential alternative to commercial indium tin oxide, transparent electrodes composed of metal nanowire, metal mesh, and ultrathin metal film are intensively investigated and developed for achieving high optical transmittance and electrical conductivity. Moreover, light trapping designs via patterning of the back thick metal electrode into different nanostructures, which can deliver a considerable efficiency improvement of photovoltaic devices, contribute by the plasmon-enhanced light-mattering interactions. Therefore, here the recent works of metal-based transparent electrodes and patterned back electrodes in photovoltaics are reviewed, which may push the future development of this exciting field.

Electrolyte Additives for Lithium Metal Anodes and Rechargeable Lithium Metal Batteries: Progress and Perspectives.

Lithium metal (Li0 ) rechargeable batteries (LMBs), such as systems with a Li0 anode and intercalation and/or conversion type cathode, lithium-sulfur (Li-S), and lithium-oxygen (O2 )/air (Li-O2 /air) batteries, are becoming increasingly important for electrifying the modern transportation system, with the aim of sustainable mobility. Although some rechargeable LMBs (e.g. Li0 /LiFePO4 batteries from Bolloré Bluecar, Li-S batteries from OXIS Energy and Sion Power) are already commercially viable in niche applications, their large-scale deployment is hampered by a number of formidable challenges, including growth of lithium dendrites, electrolyte instability towards high voltage intercalation-type cathodes, the poor electronic and ionic conductivities of sulfur (S8 ) and O2 , as well as their corresponding reduction products (e.g. Li2 S and Li2 O), dissolution, and shuttling of polysulfide (PS) intermediates. This leads to a short lifecycle, low coulombic/energy efficiency, poor safety, and a high self-discharge rate. The use of electrolyte additives is considered one of the most economical and effective approaches for circumventing these problems. This Review gives an overview of the various functional additives that are being applied and aims to stimulate new avenues for the practical realization of these appealing devices.

Comparison of Ultrasonic Welding and Thermal Bonding for the Integration of Thin Film Metal Electrodes in Injection Molded Polymeric Lab-on-Chip Systems for Electrochemistry.

We compare ultrasonic welding (UW) and thermal bonding (TB) for the integration of embedded thin-film gold electrodes for electrochemical applications in injection molded (IM) microfluidic chips. The UW bonded chips showed a significantly superior electrochemical performance compared to the ones obtained using TB. Parameters such as metal thickness of electrodes, depth of electrode embedding, delivered power, and height of energy directors (for UW), as well as pressure and temperature (for TB), were systematically studied to evaluate the two bonding methods and requirements for optimal electrochemical performance. The presented technology is intended for easy and effective integration of polymeric Lab-on-Chip systems to encourage their use in research, commercialization and education.

Contact Engineering of III-Nitrides and Metal Schemes toward Efficient Deep-Ultraviolet Light-Emitting Diodes.

Throughout the development of III-nitride electronic and optoelectronic devices, electrically interfacing III-nitride semiconductors and metal schemes has been a long-standing issue that determines the contact resistance and operation voltage, which are tightly associated with the device performance and stability. Compared to the main research focus of the crystal quality of III-nitride semiconductors, the equally important contact interface between III-nitrides and metal schemes has received relatively less attention. Here, we demonstrate a comprehensive contact engineering strategy to realize low resistance to Al-rich n-AlGaN via pretreatment and metal scheme optimization. Prior to the metal deposition, the introduction of CHF3 treatment is conducive to the substantial resistance reduction, with the effect becoming more distinct by prolonging the treatment time. Furthermore, we compare different metal schemes, namely, Ti/Al/Ti/Au, Ti/Al/Ti/Pt/Au, and Cr/Ti/Al/Ti/Pt/Au, to form electrical contact on n-AlGaN. From microscale analysis based on multiple characterization methods, we reveal the correlation between electrical properties and the nature of the contact interface, attributing the contact improvement to the low-resistance Pt- and Cr-related alloy formation. Under the circumstance that no efforts have been devoted to optimizing the epitaxial growth, engineering the metal-semiconductor contact properties alone leads to a resistance value of 8.96 × 10-5 Ω·cm2. As a result, the fabricated deep-ultraviolet LEDs exhibit an ultralow forward voltage of 5.47 V at 30 A/cm2 and a 33% increase in the peak wall-plug efficiency.

Operando Spatial Pressure Mapping Analysis for Prototype Lithium Metal Pouch Cells Under Practical Conditions.

Monitoring and diagnosing the battery status in real-time are of utmost importance for clarifying failure mechanism, improving battery performance, and ensuring safety, particularly under fast charging conditions. Recently, advanced operando techniques have been developed to observe changes in the microstructures of lithium deposits using laboratory-scale cell designs, focusing on understanding the nature of Li metal electrodes. However, the macroscopic spatial inhomogeneity of lithium electroplating/stripping in the prototype pressurized pouch cells has not been measured in real-time under practical conditions. Herein, a new noninvasive operando technique, spatial pressure mapping analysis, is introduced to macroscopically and quantitatively measure spatial pressure changes in a pressurized pouch cell during cycling. Moreover, dynamic spatial changes in the macroscopic morphology of the lithium metal electrode are theoretically visualized by combining operando pressure mapping data with mechanical analyses of cell components. Additionally, under fast charging conditions, the direct correlation between abrupt capacity fading and sudden increases in spatial pressure distribution inhomogeneity is demonstrated through comparative analysis of pouch cells under various external pressures, electrolyte species, and electrolyte weight to cell capacity (e/c) ratios. This operando technique provides insights for assessing the current battery status and understanding the complex origin of cell degradation behavior in pressurized pouch cells.

Electrochemical Biosensors for Monitoring of Drug-DNA Interactions.

The binding of the therapeutic agents to the nucleic acids is one of the paramount issues in the drug development area that is studied by various techniques. Electrochemical studies have a big portion in this area due to the fact that they allow designing of novel monitoring systems that have superior properties such as being feasible and sustainable. These electrochemical monitoring tools analyze these interactions in in vitro conditions and give the results precisely and rapidly. In the scope of this manuscript, the electrochemical monitoring platforms developed for the determination of DNA-drug interactions were under the spotlight. The electrode types mostly used for the electrochemical monitoring of drug-DNA interactions were described. The binding mechanisms of the drugs to the DNA structure were explained, and the evaluation strategies of the interactions using electrochemical techniques were stated. Most of the reports of the last 25 years were given, and some of the electrochemical biosensor applications including both voltammetric and impedimetric studies were explained in detail. Furthermore, it is possible to reach nanomaterials/biomaterials-based biosensor platforms for the monitoring of DNA-drug interactions, and these applications were in the scope of this manuscript. The future aspects of these areas were also stated.

Ordered Porous Electrodes Obtained Using LIFT for Electrochemical Applications.

Numerous synthetic techniques for the fabrication of porous metal electrodes were developed in recent decades. A very promising and facile route is the 3D printing of structures, which can be designed directly on the computer first. However, the current techniques allow structures to be printed with a resolution down to 20 µm, which is still quite rough regarding tuning the pore distribution and diameter of electrode materials for potential applications. For the first time, a laser-induced forward transfer (LIFT) process was used to 3D print metal voxels on a solid surface, resulting in a porous electrocatalytically active gold (Au) electrode film. Porous Au electrodes produced using LIFT showed an increase in the electrochemically active surface area (SA) by a factor of four compared with a sputtered dense Au film when characterized using cyclic voltammetry (CV) in Ar-saturated 0.1 M KOH. Therefore, the LIFT process can be considered very promising for the printing of ordered porous electrodes with high surface areas for electrochemical applications.

Porosity of Solid Electrolyte Interphases on Alkali Metal Electrodes with Liquid Electrolytes.

Despite the fact that solid electrolyte interphases (SEIs) on alkali metals (Li and Na) are of great importance in the utilization of batteries with high energy density, growth mechanism of SEIs under an open-circuit potential important for the shelf life and the nature of ionic transport through SEIs are yet poorly understood. In this work, SEIs on Li/Na formed by bringing the electrodes in contact with ether- and carbonate-based electrolyte in symmetric cells were systematically investigated using diverse electrochemical/chemical characterization techniques. Electrochemical impedance spectroscopy (EIS) measurements linked with activation energy determination and cross-section images of Li/Na electrodes measured by ex situ FIB-SEM revealed the liquid/solid composite nature of SEIs, indicating their porosity. SEIs on Na electrodes are shown to be more porous compared to the ones on Li in both carbonate and glyme-based electrolytes. Nonpassivating nature of such SEIs is detrimental for the performance of alkali metal batteries. We laid special emphasis on evaluating time-dependent activation energy using EIS.

Design Principles and Applications of Next-Generation High-Energy-Density Batteries Based on Liquid Metals.

Increasing need for the renewable energy supply accelerated the thriving studies of Li-ion batteries, whereas if the high-energy-density Li as well as alkali metals should be adopted as battery electrodes is still under fierce debate for safety concerns. Recently, a group of low-melting temperature metals and alloys that are in liquid phase at or near room-temperature are being reported for battery applications, by which the battery energy could be improved without significant dendrite issue. Besides the dendrite-free feature, liquid metals can also promise various high-energy-density battery designs on the basis of unique materials properties. In this review, the design principles for liquid metals-based batteries from mechanical, electrochemical, and thermodynamical aspects are provided. With the understanding of the theoretical basis, currently reported relevant designs are summarized and analyzed focusing on the working mechanism, effectiveness evaluation, and novel application. An overview of the state-of-the-art liquid metal battery developments and future prospects is also provided in the end as a reference for further research explorations.

z-Piezo Pulse-Modulated STM Break Junction: Toward Single-Molecule Rectifiers with Dissimilar Metal Electrodes.

Fabricating single-molecule junctions with asymmetric metal electrodes is significant for realizing single-molecule diodes, but it remains a big challenge. Herein, we develop a z-piezo pulse-modulated scanning tunneling microscopy break junction (STM-BJ) technique to construct a robust asymmetric junction with different metal electrodes. The asymmetric Ag/BPY-EE/Au single-molecule junctions exhibit a middle conductance value in between those of the two individual symmetric metal electrode junctions, which is consistent with the order of calculated energy-dependent transmission coefficient T(E) of the asymmetric junctions at EF. Furthermore, the single-molecule conductance of Ag/BPY-EE/Au decreases by about 70% when reversing the bias voltage from 100 to -100 mV, and a clear asymmetric I-V feature at the single-molecule level is observed for these junctions. This rectifying behavior could be ascribed to a different interfacial coupling of molecules at the two end electrodes, which is confirmed by the different displacement of T(E) at the two bias voltages. Other asymmetric junctions exhibit similar rectifying behavior. The current work provides a feasible way to fabricate hybrid junctions based on asymmetric metal electrodes and investigate their electron transport toward the design of molecular rectifiers.

Lithium Metal Electrode with Increased Air Stability and Robust Solid Electrolyte Interphase Realized by Silane Coupling Agent Modification.

The quality of the solid electrolyte interphase (SEI) layer is the decisive factor for the electrochemical performance of Li-metal-based batteries. Due to the absence of effective bonding, a natural SEI layer may exfoliate from the Li anode during interfacial fluctuations. Here, a silane coupling agent is introduced to serve as an adhesion promoter to bridge these two dissimilar materials via both chemical bonding and physical intertwining effects. Its inorganic reactive groups can combine with the Li substrate by forming LiOSi bonds, while organic functional groups can take part in the formation of the SEI layer and thereby bond with SEI components. Li metal electrodes with silane coupling agent modification exhibit excellent electrochemical performance, even under extreme testing conditions. This modification layer with dense structure could also protect the Li metal from corrosion by air, evidenced by the comparable electrochemical activity of the modified Li metal electrodes even after being exposed in air for 2 h. This design provides a promising pathway for the development of Li metal electrodes that will be stable both in electrolyte and in air.

Following in Situ the Deposition of Gold Electrodes on Low Band Gap Polymer Films.

Metal top electrodes such as gold are widely used in organic solar cells. The active layer can be optimized by modifications of the polymer band gap via side-chain engineering, and low band gap polymers based on benzodithiophene units such as PTB7 and PTB7-Th are successfully used. The growth of gold contacts on PTB7 and PTB7-Th films is investigated with in situ grazing incidence small-angle X-ray scattering (GISAXS) and grazing incidence wide-angle X-ray scattering (GIWAXS) during the sputter deposition of gold. From GIWAXS, the crystal structure of the gold film is determined. Independent of the type of side chain, gold crystals form in the very early stages and improve in quality during the sputter deposition until the late stages. From GISAXS, the nanoscale structure is determined. Differences in terms of gold cluster size and growth phase limits for the two polymers are caused by the side-chain modification and result in a different surface coverage in the early phases. The changes in the diffusion and coalescence behavior of the forming gold nanoparticles cause differences in the morphology of the gold contact in the fully percolated regime, which is attributed to the different amount of thiophene rings of the side chains acting as nucleation sites.

Degradation Mechanism of Silver Metal Deposited on Lead Halide Perovskites.

Lead halide perovskite solar cells have significantly increased in both efficiency and stability over the last decade. An important aspect of their long-term stability is the reaction between the perovskite and other materials in the solar cell. This includes the contact materials and their degradation if they can potentially come into contact through, e.g., pinholes or material diffusion and migration. Here, we explore the interactions of silver contacts with lead halide perovskites of different compositions by using a model system where thermally evaporated silver was deposited directly on the surface of the perovskites. Using X-ray photoelectron spectroscopy with support from scanning electron microscopy, X-ray diffraction, and UV-visible absorption spectroscopy, we studied the film formation and degradation of silver on perovskites with different compositions. The deposited silver does not form a continuous silver film but instead tends to form particles on a bare perovskite surface. These particles are initially metallic in character but degrade into AgI and AgBr over time. The degradation and migration appear unaffected by the replacement of methylammonium with cesium but are significantly slowed down by the complete replacement of iodide with bromide. The direct contact between silver and the perovskite also significantly accelerates the degradation of the perovskite, with a significant loss of organic cations and the possible formation of PbO, and, at the same time, changed the surface morphology of the iodide-rich perovskite interface. Our results further indicate that an important degradation pathway occurred through gas-phase perovskite degradation products. This highlights the importance of control over the interface materials and the use of completely hermetical barrier layers for the long-term stability and therefore the commercial viability of silver electrodes.

Inexpensive, Three-Dimensional, Open-Cell, Fluid-Permeable, Noble-Metal Electrodes for Electroanalysis and Electrocatalysis.

This study describes the fabrication of three-dimensional, open-cell, noble-metal (Au, Ag, and Pt) electrodes that have a complex geometry, i.e., wire mesh, metallic foam, "origami" wire mesh, and helix wire mesh. The electrodes were fabricated using an ultrasonication-assisted electroplating method that deposits a thin, continuous, and defect-free layer of noble metal (i.e., Au, Ag, or Pt) on an inexpensive copper substrate that has the desired geometry. The method is inexpensive, easy to use, and capable of fabricating noble-metal electrodes of complex geometries that cannot be fabricated using established techniques like screen printing or physical vapor deposition. By minimizing the amount of the pure noble metal in the electrodes, their cost drops significantly and could become low enough even for single-use applications; for example, the cost of metal in a Au wire-mesh electrode is $0.007/cm2 of exposed area that is about 400 times lower than that of a wire-mesh electrode composed entirely of Au. The electrodes exhibit an almost identical electrochemical performance to noble-metal electrodes of similar shape composed of bulk noble metal; therefore, these electrodes could replace two-dimensional noble-metal electrodes (e.g., rods, disks, foils) in numerous electroanalytical and electrocatalytical systems or even allow the use of noble-metal electrodes in new applications such as flow-based electrochemical systems. In this study, wire-mesh and metallic foam noble-metal electrodes have been successfully used as working electrodes for the electrocatalytical oxidation of methanol and for the electrochemical detection of redox mediators, lead ions, and nitrobenzene using various electroanalytical techniques.

A Liquid-Metal-Based Dielectrophoretic Microdroplet Generator.

This paper proposes a novel microdroplet generator based on the dielectrophoretic (DEP) force. Unlike the conventional continuous microfluidic droplet generator, this droplet generator is more like "invisible electric scissors". It can cut the droplet off from the fluid matrix and modify droplets' length precisely by controlling the electrodes' length and position. These electrodes are made of liquid metal by injection. By applying a certain voltage on the liquid-metal electrodes, the electrodes generate an uneven electric field inside the main microfluidic channel. Then, the uneven electric field generates DEP force inside the fluid. The DEP force shears off part from the main matrix, in order to generate droplets. To reveal the mechanism, numerical simulations were performed to analyze the DEP force. A detailed experimental parametric study was also performed. Unlike the traditional droplet generators, the main separating force of this work is DEP force only, which can produce one droplet at a time in a more precise way.

DBD Plasma Combined with Different Foam Metal Electrodes for CO2 Decomposition: Experimental Results and DFT Validations.

In the last few years, due to the large amount of greenhouse gas emissions causing environmental issue like global warming, methods for the full consumption and utilization of greenhouse gases such as carbon dioxide (CO2) have attracted great attention. In this study, a packed-bed dielectric barrier discharge (DBD) coaxial reactor has been developed and applied to split CO2 into industrial fuel carbon monoxide (CO). Different packing materials (foam Fe, Al, and Ti) were placed into the discharge gap of the DBD reactor, and then CO2 conversion was investigated. The effects of power, flow velocity, and other discharge characteristics of CO2 conversion were studied to understand the influence of the filling catalysts on CO2 splitting. Experimental results showed that the filling of foam metals in the reactor caused changes in discharge characteristics and discharge patterns, from the original filamentary discharge to the current filamentary discharge as well as surface discharge. Compared with the maximum CO2 conversion of 21.15% and energy efficiency of 3.92% in the reaction tube without the foam metal materials, a maximum CO2 decomposition rate of 44.84%, 44.02%, and 46.61% and energy efficiency of 6.86%, 6.19%, and 8.85% were obtained in the reaction tubes packed with foam Fe, Al, and Ti, respectively. The CO2 conversion rate for reaction tubes filled with the foam metal materials was clearly enhanced compared to the non-packed tubes. It could be seen that the foam Ti had the best CO2 decomposition rate among the three foam metals. Furthermore, we used density functional theory to further verify the experimental results. The results indicated that CO2 adsorption had a lower activation energy barrier on the foam Ti surface. The theoretical calculation was consistent with the experimental results, which better explain the mechanism of CO2 decomposition.

Effect of Metal Electrodes on Aging-Induced Performance Recovery in Perovskite Solar Cells.

For commercialization of perovskite solar cells (PSCs), it is important to substitute the alternative electrode for Au to decrease the unit cost. From the early stage, Ag exhibits a potential to be a good counter electrode in PSCs; however, there is an abnormal s-shaped J-V curve with the Ag electrode, and it is recovered as time passes. The perception of the aging-induced recovery process and refutation of the raised stability issues are required for commercial application of Ag electrodes. Herein, we compared the aging effect of PSCs with Ag and Au electrodes and found that only devices with Ag electrodes have a dramatical aging-induced recovery process. We observed the change of photoelectronic properties only in the devices with Ag electrodes as time passes, which mainly contributes to recovery of the s-shaped J-V curve. We verified the work function change of an aged Ag electrode and its mechanism by photoelectron spectroscopy analysis. By comparing the light stability under 1 sun intensity illumination, we can assure the practical stability of Ag electrodes in case of being encapsulated. This work suggests the profound understanding of the aging-induced recovery process of PSCs and the possibility of commercial application of Ag electrodes.