Electrochemical Behavior Research Articles

Investigation on electrochemical corrosion behavior and mechanical properties of Fe-nano particles produced by high-energy ball milling technique

Abstract This study focuses on converting iron particles from grinding sludge, after removing impurities, into Fe-nanoparticles using high-energy ball billing. The goal is to examine the corrosion behaviors and mechanical properties of these Fe-nanoparticles. Nanostructured Fe-powder was synthesized through a process involving 10 h of high-energy ball milling, followed by conventional hot pressing and sintering. Structural and microstructural properties were thoroughly examined using techniques such as X-ray diffraction (XRD), optical microscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and elemental diffraction spectroscopy. Upon sintering, SEM and TEM analyses unveiled the formation of a nanostructured alloy within the samples. Notably, the milled sample exhibited high hardness value, measuring at 155 HV. However, it is noteworthy that the un-milled sample demonstrated superior compression strength compared to its milled counterpart. Furthermore, the corrosion behavior of the samples was evaluated through electrochemical corrosion studies. Interestingly, the sample subjected to 10 h of milling (coin number 5) displayed a significantly lower corrosion rate, measuring at 1.3921 mm/year, suggesting enhanced corrosion resistance attributed to the nano structuring process.

Comparative analysis of electrochemical behaviors of lithium-ion batteries using the dual potential MSMD battery models: case studies on various thermal conditions

Comparative analysis of electrochemical behaviors of lithium-ion batteries using the dual potential MSMD battery models: case studies on various thermal conditions

Revealing and Overcoming Unfavorable Electrochemical Behaviors of Thick LiNbO3-Coated NCM523 for All-Solid-State Lithium Batteries

Revealing and Overcoming Unfavorable Electrochemical Behaviors of Thick LiNbO₃-Coated NCM523 for All-Solid-State Lithium Batteries

Visualizing Electrochemical CO2 Conversion via the Emerging Scanning Electrochemical Microscope: Fundamentals, Applications and Perspectives.

With the rapid development and maturity of electrochemical CO2 conversion involving cathodic CO2 reduction reaction (CO2RR) and anodic oxygen evolution reaction (OER), conventional ex situ characterizations gradually fall behind in detecting real-time products distribution, tracking intermediates, and monitoring structural evolution, etc. Nevertheless, advanced in situ techniques, with intriguing merits like good reproducibility, facile operability, high sensitivity, and short response time, can realize in situ detection and recording of dynamic data, and observe materials structural evolution in real time. As an emerging visual technique, scanning electrochemical microscope (SECM) presents local electrochemical signals on various materials surface through capturing micro-current caused by reactants oxidation and reduction. Importantly, SECM holds particular potentials in visualizing reactive intermediates at active sites and obtaining instantaneous morphology evolution images to reveal the intrinsic reactivity of active sites. Therefore, this review focuses on SECM fundamentals and its specific applications toward CO2RR and OER, mainly including electrochemical behavior observation on local regions of various materials, target products and onset potentials identification in real-time, reaction pathways clarification, reaction kinetics exploration under steady-state conditions, electroactive materials screening and multi-techniques coupling for a joint utilization. This review undoubtedly provides a leading guidance to extend various SECM applications to other energy-related fields.

Understanding the effect of microstructure and composition on localized corrosion susceptibility of 6xxx aluminum alloys

The corrosion performance of 6xxx series Al alloys has been found to depend on small changes in composition and microstructure. The corrosion behaviors of three aluminum alloys, AA6111, AA6451, and AA6016, were investigated. AA6111, containing primarily α (Al15 (Fe,Mn)3Si2) intermetallic particles (IMPs), and AA6016, containing primarily β (Al8Fe2Si) IMPs, exhibited the best and the worst overall corrosion performances, respectively, as indicated by the extent of corrosion in exposure tests. However, this ranking was not predicted by the standard interpretation of potentiodynamic polarization curves measured on the alloys. The corrosion susceptibilities of the three alloys were further investigated by evaluating the electrochemical behavior of the component phases separately. Bulk analogs of the component phases were fabricated using standard alloy casting techniques. The fabricated bulk analogs of α and β IMPs, as well as the three alloy matrix phases, were tested using either macrocell or microcell testing. An explanation for the alloy performances was developed by combining the behavior of the component phases.

Surfactant Effects in Porous Electrodes for Microemulsion Redox Flow Batteries

Abstract The effect of surfactant additives on electrochemical behavior in porous electrodes was investigated using vanadium redox flow battery half-cells and the dependence of volumetric kinetics and mass transport on electrolyte, surfactant, and electrode type was explored. Without surfactant added, carbon paper electrodes demonstrated greater kinetics and transport compared to carbon felt, for a given electrolyte. Additionally, posolyte kinetics are greater than negolyte kinetics by one to three orders of magnitude, depending on the electrode type. Addition of surfactant increased electrode wettability and possibly electrochemical surface area. However, this was accompanied by a decrease in volumetric mass transport, due to stronger electrolyte-electrode interactions. The presence of sodium dodecyl sulfate (SDS) influenced posolyte and negolyte kinetics differently. Kinetics showed a dependence on electrode type and surfactant. On carbon felt, volumetric kinetics decreased for both posolyte and negolyte with SDS addition. On carbon paper, SDS decreased volumetric kinetics for the posolyte but increased (>2X) kinetics for the negolyte! This kinetic enhancement depends on surfactant chemistry: cetyltrimethylammonium bromide, a cationic surfactant, failed to increase kinetics. Furthermore, SDS did not increase areal specific resistance. These findings show the superior performance of carbon paper compared to carbon felt and suggest SDS as a possible VRFB negolyte additive

Reduced Order Electrochemical-thermal Modeling of Cylindrical Cells Containing Graphite-Silicon Anodes Considering Thermal Gradients and Hysteresis

Abstract Electrochemical thermal modeling of cylindrical cells presents unique challenges compared to other cell formats due to the effect of internal temperature gradients, which typically requires time-consuming simulations due to the number of mesh elements solved numerically. Adding to the difficulty, the emergence of silicon anodes induces voltage hysteresis that affects the cell behavior. In this paper, a reduced-order electrochemical-thermal model is developed for a 21700 cell, which is highlighted by three microcells considering the effects of internal temperature gradients, and an anodic stress model capturing the hysteresis effects caused by the silicon content. The electrochemical, thermal, and mechanical behaviors are investigated. During operations, a temperature gradient arises in the radial direction, resulting in a decrease in local resistance and an increase in reaction rate at the high-temperature core location. The presence of silicon causes a voltage hysteresis that is dominant in the low SOC range, which affects not only the irreversible but also the entropic heat generation. The proposed method achieves an 85% calculation time reduction compared with the existing literature method and a 95% reduction compared with the full order method, while maintaining the accuracy of the terminal voltage and heat generation rate predictions that are validated by experiments.

Homogeneously Planar-Exposure LiB Fiber Skeleton Toward Long-Lifespan Practical Li Metal Pouch Cells.

LiB alloy is promising lithium (Li) metal anode material because the continuous internal LiB fiber skeleton can effectively suppress Li dendrites and structural pulverization. However, the unvalued surface states limit the practical application of LiB alloy anodes. Herein, the study examined the influence of the different exposure manners of the internal LiB fiber skeleton owing to the various surface states of the LiB alloy anode on electrochemical performance and targetedly proposed a scalable friction coating strategy to construct a lithiated fumed silica (LFS) functional layer with abundant electrochemically active sites on the surface of the LiB alloy anode. The LFS significantly suppresses the inhomogeneous interfacial electrochemical behavior of the LiB alloy anode and enables the exposure of the internal LiB fiber skeleton in a homogeneously planar manner (LFS-LiB). Thus, a 0.5Ah LFS-LiB||LiCoO2 (LCO) pouch cell exhibits a discharge capacity retention rate of 80% after 388 cycles. Moreover, a 6.15Ah LFS-LiB||S pouch cell with 409.3Whkg-1 exhibits a discharge capacity retention rate of 80% after 30 cycles. In conclusion, the study findings provide a new research perspective for Li alloy anodes.

High-Entropy Prussian Blue Analogues Enable Lattice Respiration for Ultra-Stable Aqueous Aluminum-Ion Batteries.

Aqueous aluminum ion batteries (AAIBs) hold significant potential for grid-scale energy storage owing to their intrinsic safety, high theoretical capacity, and abundance of aluminum. However, the strong electrostatic interactions and delayed charge compensation between high-charge-density aluminum ions and the fixed lattice in conventional cathodes impede the development of high-performance AAIBs. To address this issue, we introduce, for the first time, high-entropy Prussian blue analogs (HEPBAs) as cathodes in AAIBs with unique lattice tolerance and efficient multipath electron transfer. Benefiting from the intrinsic long-range disorder and robust lattice strain field, HEPBAs enable the manifestation of the lattice respiration effect and minimize lattice volume changes, thereby achieving one of the best long-term stabilities (91.2% capacity retention after 10,000 cycles at 5.0 A g-1) in AAIBs. Additionally, the interaction between the diverse metal atoms generates a broadened d-band and reduced degeneracy compared with conventional PBAs, which enhances the electron transfer efficiency with one of the best rate performance (79.2 mAh g-1 at 5.0 A g-1) in AAIBs. Furthermore, exceptional element selectivity in HEPBAs with unique cocktail effect could facile tune electrochemical behavior. Overall, the newly developed HEPBAs with a high-entropy effect exhibit promising solutions for advancing AAIBs and multivalent-ion batteries. This article is protected by copyright. All rights reserved.

Time‐Resolved Oxidation State Changes Are Key to Elucidating the Bifunctionality of Perovskite Catalysts for Oxygen Evolution and Reduction

In a unified regenerative fuel cell (URFC) or reversible fuel cell, the oxygen bifunctional catalyst must switch reversibly between the oxygen reduction reaction (ORR), fuel cell mode, and the oxygen evolution reaction (OER), electrolyzer mode. However, it is often unclear what effect alternating between ORR and OER has on the electrochemical behavior and physiochemical properties of the catalyst. Herein, operando X‐ray absorption spectroscopy (XAS) is utilized to monitor the continuous and dynamic evolution of the Co, Mn, and Fe oxidation states of perovskite catalysts Ba0.5Sr0.5Co0.8Fe0.2O3‐δ (BSCF) and La0.4Sr0.6MnO3‐δ (LSM), while the potential is oscillated between reducing and oxidizing potentials with cyclic voltammetry. The results reveal the importance of investigating bifunctional catalysts by alternating between fuel cell and electrolyzer operation and highlight the limitations and challenges of bifunctional catalysts. It is shown that the requirements for ORR and OER performance are divergent and that the oxidative potentials of OER are detrimental to ORR activity. These findings are used to give guidelines for future bifunctional catalyst design. Additionally, it is demonstrated how sunlight can be used to reactivate the ORR activity of LSM after rigorous cycling.

Synthesis, Structural Characterisation, and Electrochemical Properties of Copper(II) Complexes with Functionalized Thiosemicarbazones Derived from 5-Acetylbarbituric Acid

The reaction between 5-acetylbarbituric acid and 4-dimethylthiosemicarbazide or 4-hexamethyleneiminyl thiosemicarbazide produces 5-acetylbarbituric-4-dimethylthiosemicarbazone (H2AcbDM) and 5-acetylbarbituric-4N-hexamethyleneiminyl thiosemicarbazone (H2Acbhexim). Eight new complexes with different copper(II) salts have been prepared and characterized using elemental analysis, molar conductance, UV–Vis, ESI-HRMS, FT-IR, magnetic moment, EPR, and cyclic voltammetry. In addition, three-dimensional molecular structures of [Cu(HAcbDM)(H2O)2](NO3)·H2O (3a), [Cu(HAcbDM)(H2O)2]ClO4 (4), and [Cu(HAcbHexim)Cl] (6) were determined by single crystal X-ray crystallography, and an analysis of their supramolecular structure was carried out. The H-bonded assemblies were further studied energetically using DFT calculations and MEP surface and QTAIM analyses. In these complexes, the thiosemicarbazone coordinates to the metal ion in an ONS-tridentate manner, in the O-enolate/S-thione form. The electrochemical behavior of the thiosemicarbazones and their copper(II) complexes has been investigated at room temperature using the cyclic voltammetry technique in DMFA. The Cu(II)/Cu(I) redox system was found to be consistent with the quasi-reversible diffusion-controlled process.

Electrodeposited Cobalt Hydroxide Thin Films: A Comprehensive Investigation from Synthesis to Advanced Electrochemical Behavior for High-Performance Energy Storage

Electrodeposited Cobalt Hydroxide Thin Films: A Comprehensive Investigation from Synthesis to Advanced Electrochemical Behavior for High-Performance Energy Storage

Wired for Success: Probing the Effect of Tissue-Engineered Neural Interface Substrates on Cell Viability.

This study investigates the electrochemical behavior of GelMA-based hydrogels and their interactions with PC12 neural cells under electrical stimulation in the presence of conducting substrates. Focusing on indium tin oxide (ITO), platinum, and gold mylar substrates supporting conductive scaffolds composed of hydrogel, graphene oxide, and gold nanorods, we explored how the substrate materials affect scaffold conductivity and cell viability. We examined the impact of an optimized electrical stimulation protocol on the PC12 cell viability. According to our findings, substrate selection significantly influences conductive hydrogel behavior, affecting cell viability and proliferation as a result. In particular, the ITO substrates were found to provide the best support for cell viability with an average of at least three times higher metabolic activity compared to platinum and gold mylar substrates over a 7 day stimulation period. The study offers new insights into substrate selection as a platform for neural cell stimulation and underscores the critical role of substrate materials in optimizing the efficacy of neural interfaces for biomedical applications. In addition to extending existing work, this study provides a robust platform for future explorations aimed at tailoring the full potential of tissue-engineered neural interfaces.

High‐Voltage Spinel Cathode Materials: Navigating the Structural Evolution for Lithium‐Ion Batteries

AbstractHigh‐voltage LiNi0.5Mn1.5O4 (LNMO) spinel oxides are highly promising cobalt‐free cathode materials to cater to the surging demand for lithium‐ion batteries (LIBs). However, commercial application of LNMOs is still challenging despite decades of research. To address the challenge, the understanding of their crystallography and structural evolutions during synthesis and electrochemical operation is critical. This review aims to illustrate and update the fundamentals of crystallography, phase transition mechanisms, and electrochemical behaviors of LNMOs. First, we outline the research history of LNMO and its development into a LIB cathode material. Then we review the structural basics of LNMOs including the classic and updated views of the crystal polymorphism, interconversion between the polymorphs, and structure‐composition relationship. Afterwards, the phase transition mechanisms of LNMOs that connect structural and electrochemical properties are comprehensively discussed from fundamental thermodynamics to operando dynamics at intra‐ and inter‐particle levels. In addition, phase evolutions during overlithiation as well as thermal‐/electrochemical‐driven phase transformations of LNMOs are also discussed. Finally, we offer recommendations for the further development of LNMOs as well as other complex materials to unlock their full potential for future sustainable and powerful batteries.This article is protected by copyright. All rights reserved

Correction to: Effect of Cu(I) on electrochemical behavior and surface morphology of electrodeposited copper for different accelerators

Correction to: Effect of Cu(I) on electrochemical behavior and surface morphology of electrodeposited copper for different accelerators

Influence of the concentration of KOH-based aqueous electrolyte on the electrochemical behavior of NiO thin film

In this research, we explored the influence of varying concentrations of KOH electrolyte (0.5, 1, and 2 M) on the electrochemical characteristics of Nickel Oxide (NiO) thin film. The deposition of NiO material onto glass and Fluor Tin Oxide (FTO) coated glass substrates was achieved through the chemical spray pyrolysis method. Subsequent examinations encompassed structural, morphological, optical, and electrochemical assessments, employing X-ray diffraction (XRD), Raman spectroscopy, Scanning Electron Microscopy coupled with Energy Dispersive X-ray Spectroscopy (SEM-EDS), UV-VIS-NIR spectrophotometry, and cyclic voltammetry (CV), respectively. XRD analysis unveiled a polycrystalline cubic structure of NiO with a preference for orientation along the (111) plane. Raman spectroscopy confirmed the presence of the NiO phase, whereas SEM images depicted the emergence of interconnected nanograins with occasional minor cracks. EDS examination and elemental mapping further substantiated a homogeneous dispersion of elements. Optical analysis disclosed a band gap energy of 3.54 eV and an average transmittance of 71 % in the visible range. Electrochemical analysis indicated that the specific capacitance reached its peak at [1 M] (70 F. g−1). The [2 M] electrolyte exhibited the highest optical modulation (29 %), the most substantial charge density (Qi = 9.5 mC/cm2), and the most favorable switching kinetics. However, the coloration efficiency slightly decreased from 30.94 cm2/C in [1 M] to 30.47 cm2/C in the [2 M] solution, despite these improvements.

The effect of Al on the corrosion resistance of binary Mg-Al solid solutions: Combining in-situ electrochemistry with combinatorial thin films

The effect of varying Al concentrations on the electrochemical corrosion resistance of binary Mg-Al solid solutions thin films under alkaline immersion conditions was investigated via a combination of in-situ flow-cell, scanning vibrating electrode technique and microscopy analysis. These spatially resolving characterization techniques are employed along the Al concentration gradient of the combinatorically grown thin films enabling efficient screening of the Al concentration dependent electrochemical corrosion behaviour. The analysis revealed an increasing corrosion resistance with increasing Al concentration, as a consequence of Al induced hydroxide reinforcement. Specifically, the addition of >4 wt.% Al decreases the corrosion current density in the range of 70–90 % compared to pure Mg.

Operando insights into ammonium-mediated lithium metal stabilization: surface morphology modulation and enhanced SEI development

Lithium-ion batteries (LiBs) with graphite as an anode and lithiated transition metal oxide as a cathode are approaching their specific energy and power theoretical values. To overcome the limitations of LiBs, lithium metal anode with high specific capacity and low negative redox potential is necessary. However, practical application in rechargeable cells is hindered by uncontrolled lithium deposition manifesting, for instance, as Li dendrite growth which can cause formation of dead Li, short circuits and cell failure.The electrochemical behaviour of a protic additive (NH4PF6) in a carbonate-based electrolyte has been investigated by operando confocal Raman spectroscopy, in situ optical microscopy, and X-ray photoelectron spectroscopy, elucidating its functional mechanism. The ammonium cation promotes a chemical modification of the lithium metal anode-electrolyte interphase by producing an N-rich solid electrolyte interphase and chemically modifying the lithium surface morphology by electrochemical pitting. This novel method results in stable lithium deposition and stripping by a decreasing the local current density on the electrode, thus limiting dendritic deposition.

Carbon/C3N4 heterostructures constructed from lignin toward enhanced lithium-ion storage

Lithium-ion batteries (LIBs) are widely used in portable energy storage. The capacity of commercial graphite is difficult to improve due to the stoichiometry limit of LiC6 of graphite, thus new anodes need to be developed to meet the demand of high-energy–density LIB. The growing interest in graphitized carbon nitride (g-C3N4) stems from its structural resemblance to graphite and its capacity to offer abundant adsorption and intercalation sites. However, g-C3N4, as a semiconductor, has a low lithium transfer rate due to its poor conductivity and high diffusion resistance. Improving the electron transport rate of g-C3N4 and reducing the adsorption energy barrier of Li+ in g-C3N4 are the keys to improving the electrochemical performances of g-C3N4. In this study, lignin and melamine were homogeneously mixed using the spray drying method, followed by the preparation of covalently bonded C3N4/LC material through a one-step carbonization process. The uniform dispersion of g-C3N4 in amorphous carbon can improve the conductivity and reduce the diffusion energy barrier of Li+. As a result, the C3N4/LC-x anode has better electrochemical behavior, including higher reversible capacity, better rate performance, and cycle stability.

Mechanistic Insights into Electrocatalytic Hydrogen Evolution by an Exceptionally Stable Cobalt Complex.

Co(aPPy) is one of the most stable and active molecular first-row transition-metal catalysts for proton reduction reported to date. Understanding the origin of its high performance via mechanistic studies could aid in developing even better catalysts. In this work, the catalytic mechanism of Co(aPPy) was electrochemically probed, in both organic solvents and water. We found that different mechanisms can occur depending on the solvent and the acidity of the medium. In organic solvent with a strong acid as the proton source, catalysis initiates directly after a single-electron reduction of CoII to CoI, whereas in the presence of a weaker acid, the cobalt center needs to be reduced twice before catalysis occurs. In the aqueous phase, we found drastically different electrochemical behavior, where the Co(aPPy) complex was found to be a precatalyst to a different electrocatalytic species. We propose that in this active catalyst, the pyridine ring has dissociated and acts as a proton relay at pH ≤ 5, which opens up a fast protonation pathway of the CoI intermediate and results in a high catalytic activity. Furthermore, we determined with constant potential bulk electrolysis that the catalyst is most stable at pH 3. The catalyst thus functions optimally at low pH in an aqueous environment, where the pyridine acts as a proton shuttle and where the high acidity also prevents catalyst deactivation.