Electrochemical Properties 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.

3D-Printed Carbon Nanoneedle Electrodes for Dopamine Detection in Drosophila.

In vivoelectrochemistry in small brain regions or synapses requires nanoelectrodes with long straight tips for submicron scale measurements. Nanoelectrodes can be fabricated using a Nanoscribe two-photon printer, but annealed tips curl if they are long and thin. We propose a new pulling-force strategy to fabricate a straight carbon nanoneedle structure. A micron-width bridge is printed between two blocks. The annealed structure shrinks during pyrolysis, and the blocks create a pulling force to form a long, thin, and straight carbon bridge. Parameterization study and COMSOL modeling indicate changes in the block size, bridge size and length affect the pulling force and bridge shrinkage. Electrodes were printed on niobium wires, insulated with aluminum oxide, and the bridge cut with focused ion beam (FIB) to expose the nanoneedle tip. Annealed needle diameters ranged from 400 nm to 5.25 µm and length varied from 50.5 µm to 146 µm. The electrochemical properties are similar to glassy carbon, with good performance for dopamine detection with fast-scan cyclic voltammetry. Nanoelectrodes enable biological applications, such as dopamine detection in a specificDrosophilabrain region. Long and thin nanoneedles are generally useful for other applications such as cellular sensing, drug delivery, or gas sensing.

Enhancing dye-sensitized solar cell performance: Optimizing Cu2ZnSnS4/ZnCo2O4 nanocomposites as efficient and cost-effective counter electrodes

This study investigates the utilization of Cu2ZnSnS4/ZnCo2O4 (CZTS/ZCO) nanocomposites prepared through hydrothermal and combustion methods as counter electrodes in Dye-Sensitized Solar Cells (DSSCs). Different ratios of Cu2ZnSnS4 and ZnCo2O4 were explored, and comprehensive analyses were conducted using X-ray Diffraction (XRD), Transmission Electron Microscopy (TEM), High-Resolution TEM (HRTEM), Brunauer–Emmett–Teller (BET) surface area analysis, Raman Spectroscopy, Electrochemical Impedance Spectroscopy (EIS), cyclic voltammetry (CV), Tafel analysis, Field Emission Scanning Electron Microscopy (FESEM), and Incident Photon-to-Electron Conversion Efficiency (IPCE), alongside long-term stability assessments. The CZTS:ZCO ratio of 2:1 exhibited the highest efficiency, reaching 8.81 %, with an open-circuit voltage of 729 mV, short-circuit current of 17.80 mAcm−2, and a fill factor of 67.9 %. This surpasses the efficiency of the reference Pt cell (8.42 %), which had an open-circuit voltage of 735 mV, short-circuit current of 17.16 mAcm−2, and a fill factor of 66.8 %. The average crystallite sizes for the main peaks of CZTS and ZCO samples were estimated to be 19.8 and 16.7 nm, respectively. The crystallite size can significantly affect the charge transfer and conductivity in the counter electrode during electrochemical processes; the presence of nanocrystals with these sizes can notably enhance the electrochemical properties and conductivity of the synthesized samples. Raman analysis results indicate that no additional phases or secondary phases such as ZnS and CuSnS3 have formed in the kesterite CZTS structure, and the crystal has formed as a single phase. Additionally, the F2g modes in the Raman spectrum of ZCO indicate tetrahedral units in the spinel ZCO structure, and the A1g modes represent octahedral structures in this phase, indicating the formation of suitable ZCO phase. The superior performance of the CZTS/ZCO nanocomposite can be attributed to its enhanced crystalline structure, superior charge transport characteristics, and improved electrocatalytic behaviours.

Direct Drive Friction Welding Influence on Metallurgical, Mechanical, and Electrochemical Properties of AISI 316

Direct Drive Friction Welding Influence on Metallurgical, Mechanical, and Electrochemical Properties of AISI 316

Tuning Electron Delocalization of Redox‐Active Porous Aromatic Framework for Low‐Temperature Aqueous Zn−K Hybrid Batteries with Air Self‐Chargeability

AbstractAir self‐charging aqueous batteries promise to integrate energy harvesting technology and battery systems, potentially overcoming a heavy reliance on energy and the spatiotemporal environment. However, the exploitation of multifunctional air self‐charging battery systems using promising cathode materials and suitable charge carriers remains challenging. Herein, for the first time, we developed low‐temperature self‐charging aqueous Zn−K hybrid ion batteries (AZKHBs) using a fully conjugated hexaazanonaphthalene (HATN)‐based porous aromatic framework as the cathode material, exhibiting redox chemistry using K+ as charge carriers, and regulating Zn‐ion solvation chemistry to guide uniform Zn plating/stripping. The unique AZKHBs exhibit the exceptional electrochemical properties in all‐climate conditions. Most importantly, the large potential difference causes the AZKHBs discharged cathode to be oxidized using oxygen, thereby initiating a self‐charging process in the absence of an external power source. Impressively, the air self‐charging AZKHBs can achieve a maximum voltage of 1.15 V, an impressive discharge capacity (466.3 mAh g−1), and exceptional self‐charging performance even at −40 °C. Therefore, the development of self‐charging AZKHBs offers a solution to the limitations imposed by the absence of a power grid in harsh environments or remote areas.

Microwave irradiation-induced yield enhancement of coconut shell biomass-derived graphene-like material

This paper reports a new strategy (rapid and selective microwave irradiation) to achieve an improved yield of graphene-like material derived from coconut shell biomass. The influence of various microwave irradiation (MWI) powers (80, 240, and 400 W) treatment on the crystalline structures, morphology, and electrochemical performance of the produced samples was determined and compared with the virgin-untreated specimen. The obtained samples were analyzed using varied analytical techniques. The FESEM images of the irradiated samples revealed the existence of graphene-like morphologies accompanied by some thin and transparent sheets. The sample at 80 W displayed the best quality with the highest yield, improving the carbon content, reducing the oxygen functional groups, and increasing the BET-specific surface area by as much as 1238.48 m2/g. The electrochemical properties of the sample treated at 80 W (optimum MWI power treatment) exhibited rectangular curves against scanning speeds, indicating an ideal capacitive behaviour called electric double-layer capacitance (EDLC). It is asserted that the proposed systematic and eco-friendly approach in obtaining the high-performance graphene-like material at low cost may open up sundry opportunities for practical applications, leading towards sustainable development.

Exploring Li-Ion Transport Properties of Li3TiCl6: A Machine Learning Molecular Dynamics Study

Abstract We performed large-scale molecular dynamics simulations based on a machine-learning force field (MLFF) to investigate the Li-ion transport mechanism in cation-disordered Li3TiCl6 cathode at six different temperatures, ranging from 25°C to 100°C. In this work, the deep neural network method and data generated by ab-initio molecular dynamics (AIMD) simulations were deployed to build a high-fidelity MLFF. Radial distribution functions, Li-ion mean square displacements (MSD), diffusion coefficients, ionic conductivity, activation energy, and crystallographic direction-dependent migration barriers were calculated and compared with corresponding AIMD and experimental data to benchmark the accuracy of the MLFF. Our MSD analysis captured both the self and distinct parts of Li-ion dynamics. The latter reveals that the Li-ions are involved in anti-correlation motion that was rarely reported for solid-state materials. The obtained trajectory from molecular dynamics infers that the Li-ion transportation is mainly through interstitial hopping, which was confirmed by intra- and inter-layer Li-ion displacement with respect to simulation time. Ionic conductivity (1.06 mS/cm) and activation energy (0.29eV) calculated by our simulation are highly comparable with that of experimental values. Overall, the MLFF-based simulation is a promising method to explain the intricate electrochemical properties of the Li3TiCl6 cathode with remarkably reduced computational time

Nanostructured binary transition-metal-sulfides and nanocomposites as high-performance electrodes for hybrid supercapacitors

Supercapacitors (SCs) are attractive as promising energy storage devices because of their distinctive attributes, such as high power density, good current charge/discharge ability, excellent cyclic stability, reasonable safety, and low cost. Electrode materials play key roles in achieving excellent performance of these SCs. Among them, binary transition metal sulfides (BTMSs) have received significant attention, attributed to their high conductivity, abundant active sites, and excellent electrochemical properties. This topic review aims to summarize recent advances in principles, design, and evaluation of the electrochemical performance for nanostructured BTMSs (including nickel–cobalt sulfides, zinc–cobalt sulfides, and copper–cobalt sulfides.) and their nanocomposites (including those carbon nanomaterials, transition metal oxides, binary transition metal oxides, transition metal sulfides, and polymers). Nanostructuring of these BTMSs and nanocomposites as well as their effects on the performance were discussed, including nanoparticles, nanospheres, nanosheets, nanowires, nanorods, nanotubes, nanoarrays, and hierarchitectured nanostructures. Their electrochemical performance has further been reviewed including specific capacitance, conductivity, rate capability, and cycling stability. In addition, the performance of hybrid supercapacitors (HSCs) assembled using the nanostructured BTMSs as the cathodes also have been summarized and compared. Finally, challenges and further prospects in the HSCs-based BTMS electrodes are presented.

Electronic Effect of the [Au(PPh3)]+ Fragment in the Stabilization of Imidazolium Salts and the Destabilization of NHCs

AbstractThis work presents the synthesis and characterization of mono‐ (1) and di‐nuclear (2) imidazolium salts stabilized by [AuPPh3]+ fragments. The presence of the gold moiety induces a significant decrease in the carbenic proton‘s acidic character (high pKa). This high stability is consistent with the pronounced instability of the conjugate bases obtained through deprotonation using strong bases. The formation of carbene species is accompanied by the identification of a 1,2‐rearrangement process in which a preference for the C‐bound species over the N‐bound species is observed. Experimental techniques such as NMR, single‐crystal X‐ray diffraction analysis, mass spectrometry, and computational calculations are employed to investigate the reactivity exhibited by the imidazolium salts. Additionally, the electrochemical properties of the two imidazolium salts were also investigated. This study reveals that both species 1 and 2 display two cathodic peaks which are related to two electro‐chemical irreversible reduction events. The results obtained from both experimental and theoretical studies of this system reveal a strong tendency of the [AuPPh3]+ fragment to stabilize imidazolium salts. Additionally, they demonstrate the preference of this fragment for C‐bound species over N‐bound ones, with the former proving to be highly unstable even under severe conditions of air and moisture exclusion.

Enhancement of electrochromic efficiency of TiO2 nanorods

In this study, the rutile TiO2 nanorods thin films were deposited via hydrothermal method on fluorine-doped tin oxide (FTO) substrate. To form a porous morphology layer, a thin film of amorphous titanium oxide (TiOx) was deposited on the TiO2 nanorods through sputtering at high pressure. The samples were annelid at 450ᵒC to transform the amorphous surface to anatase phase. Structural, optical, morphology and electrochemical properties of the samples were examined via X-ray diffraction (XRD), Raman scattering, UV–Vis NIR and photoluminescence (PL) spectroscopies, field-emission scanning electron microscopy (FE-SEM) and Potentiostat device respectively. The samples exhibited a large optical bandgap of 3.35–3.40 eV and high transparency of over 77 % at a wavelength of 555 nm. Raman analysis confirmed the formation of anatase phase on the rutile nanorods under thermal treatment. PL analysis indicated that the oxygen vacancies reached their maximum after sputtering, while the intensity of PL emission significantly increased after annealing. Investigation of the electrochromic properties revealed an increase in coloration efficiency from 2.6 C−1cm2 for bare nanorods to 10.0 C−1cm2 for nanorods after sputtering deposition, which decreased to 5.4 C−1cm2 after thermal treatment.

Effect of Mo and W co-doping on optical, morphological, electrical and electrochemical properties of Co3O4 thin film

In this study, it was aimed to produce cobalt oxide (Co3O4) thin films with improved optical, electrical, and electrochemical properties for device applications with a simple and low-cost method. Mo, W, and dual Mo and W at the ratio 10 wt% of Co3O4 were added into the solutions. The prepared solutions were coated on glass substrates by spin coating method. The produced thin films' structural, morphological, optical, electrical, and electrochemical properties were examined. As a result of doping, the optical, morphological, conductivity, and electrochemical properties of Co3O4 thin films improved and more stable structures were formed. The Mo and W co-doping provided the most improvement in the properties of the Co3O4 thin film. The results obtained showed that the Mo and W co-doped Co3O4 thin film is a potential candidate for highly efficient electrochemical applications.

On the formation and properties of amorphous and crystalline Li3-yBay/2OCl electrolytes

All-solid-state batteries (ASSBs) have potential to provide higher specific energy, higher power, and longer cycle life than Li-ion batteries (LIBs) for continuously increasing demands of high-performance rechargeable batteries with intrinsic safety. However, one of the barriers for successful design and fabrication of ASSBs is the lack of solid-state electrolytes (SSEs) that can meet multi-functional requirements for ASSBs. To address this issue, the present study investigates hydrothermal synthesis of amorphous and crystalline Ba-doped Li3OCl solid electrolytes and develops the understanding of the relationships between the synthesis conditions and electrochemical properties of the products. It is shown that the formation of an amorphous/crystalline Ba-doped Li3OCl mixture with little hydroxide impurities depends strongly on the hydrothermal reaction temperature, drying temperature, Ba concentration, and rate of removing OH− and H+ ions as steam from water solvated Ba-doped Li3OCl. The key to generate amorphous Li3OCl-based electrolytes with high ionic conductivities (7.65 × 10−3 S/cm) at room temperature is to create non-equilibrium synthesis conditions such as the one identified in this study. The understanding developed in this study will offer critical guidelines for synthesizing amorphous and crystalline Li3OCl-based electrolytes with superior electrochemical properties for ASSBs reliably and reproducibly in the near future.

Multilayer boron doped Si@SiOx/C from Si-Ca alloy for lithium-ion battery anodes

SiOx has been considered as a promising anode for next-generation lithium-ion batteries. However, the poor rate performance caused by the low electrical conductivity is a bottleneck of its application. Approaches involving carbon composites, boron doping and two-dimensional structure have been pursued to improve the electrical conductivity. In this work, through the combination of these strategies, a multilayer boron doped Si@SiOx/C composites are fabricated by a chemical exfoliation of CaSi2 with B2O3 and CaCO3. The production exhibits favorable properties for lithium-ion battery anodes, such as proper specific surface area, complete multilayer structure, boron doped and carbon composite structure. The as-obtained B-Si@SiOx/C-700 delivers a capacity of 659.3 mAh g−1 after 500 cycles at 1 A g−1. Especially, at 4 A g−1, the capacity retention of the B-Si@SiOx/C-700 anode is still 40.9 % of its average discharge capacity at 0.2 A g−1. The capacitive contribution to the total Li+ storage capacity for the B-Si@SiOx/C-700 electrode is 83.6 % at 1.0 mV s−1. This work presents a simple and efficient strategy to construct a multilayer doped structure to improve electrochemical properties.

Electro‐Induced Self‐Reduction TiO2 in Viologen‐Based Ionogels for Multi‐Color Electrochromic Displays

AbstractReflective electrochromic (EC) technology is expected to e‐paper display field, and integrating optical reflective electrolyte as the optical reflective layer is a common strategy for constructing reflective EC devices. Compositing inorganic particles and electrolytes is one of the simplest and most efficient composite methods, but these composite electrolytes usually cannot perform well together in terms of both optical and electrochemical properties. Herein, the TiO2 nanoparticles are added to the ethyl viologen‐based ionogel (T‐EVG, one typical kind of EC/electrolyte) to have the highest visible light reflectivity and the best electrochemical performance compared with SiO2, Al2O3, and ZnO nanoparticles, which is attributed to the electro‐induced self‐reduction TiO2 produced in T‐EVG during EC cycling. Meanwhile, the corresponding EC devices can display red, green, and blue, and have high optical contrast (CIE Lab: ΔE>38), fast switching spend (<4 s, the fastest is 5 Hz), ultra‐low power density (<4.0 mW cm−2), and excellent cycling stability (>85% retained after 10 000 cycles). Finally, a simple 3×3 pixelated EC display array is prepared, and single‐ and multi‐point (including diagonal points) multi‐color display effects are realized through active‐matrix driving and high‐frequency refresh, demonstrating its application value in the high‐performance e‐paper display.

Development of Nd doped AlFeO3 electrode material for supercapacitor applications

The development of metal oxides nanoscale structures with enhanced chemically active surfaces, faster ion/charge transport kinetics with shorter ion-diffusion paths is demand in the field of supercapacitor. The issue of transition metal oxides has been successfully resolved through the utilization of metal doping, which concurrently enhances surface area, accelerates ion migration and enhances thermal and structural stability. The Nd doped AlFeO3 electrode substance fabricated hydrothermal process for electrochemical properties. The different analytical tools determined physical and electrochemical characteristics of prepared electrode material. Nd@AlFeO3 electrode material demonstrates specific capacitance of 1326 F/g at 1 A/g measured from galvanostatic charging/discharging plot which maintains remarkable stability after 5000th cycles. The Nyquist plot determines lower charge transfer resistance of Nd@AlFeO3 electrode material (1.15 Ω). The Nd@AlFeO3 electrode material exhibited improved electrochemical properties which makes it promising candidate for integration into supercapacitor devices.

Ru(II) Oligothienyl Complexes with Fluorinated Ligands: Photophysical, Electrochemical, and Photobiological Properties.

A series of Ru(II) complexes incorporating two 4,4'-bis(trifluoromethyl)-2,2'-bipyridine (4,4'-btfmb) coligands and thienyl-appended imidazo[4,5-f][1,10]phenanthroline (IP-nT) ligands was characterized and assessed for phototherapy effects toward cancer cells. The [Ru(4,4'-btfmb)2(IP-nT)]2+ scaffold has greater overall redox activity compared to Ru(II) polypyridyl complexes such as [Ru(bpy)3]2+. Ru-1T-Ru-4T have additional oxidations due to the nT group and additional reductions due to the 4,4'-btfmb ligands. Ru-2T-Ru-4T also exhibit nT-based reductions. Ru-4T exhibits two oxidations and eight reductions within the potential window of -3 to +1.5 V. The lowest-lying triplets (T1) for Ru-0T-2T are metal-to-ligand charge-transfer (3MLCT) excited states with lifetimes around 1 μs, whereas T1 for Ru-3T-4T is longer-lived (∼20-24 μs) and of significant intraligand charge-transfer (3ILCT) character. Phototoxicity toward melanoma cells (SK-MEL-28) increases with n, with Ru-4T having a visible EC50 value as low as 9 nM and PI as large as 12,000. Ru-3T and Ru-4T retain some of this activity in hypoxia, where Ru-4T has a visible EC50 as low as 35 nM and PI as high as 2900. Activity over six biological replicates is consistent and within an order of magnitude. These results demonstrate the importance of lowest-lying 3ILCT states for phototoxicity and maintaining activity in hypoxia.

Fabrication and electrochemical properties of Mn, N, and S co-doped carbon fiber composite bamboo-based woodceramics electrodes

Prepared in this study, Mn, N and S co-doped woodceramics electrodes (WC@Mn-N/S) were prepared using waste bamboo as the base material, carbon fiber as the reinforcement fiber, KMnO4 and CH4N2S as dopants and activators. Mechanical analysis revealed a 68 % increase in the flexural strength of the matrix material reinforced with carbon fibers. Scanning electron microscopy observation indicated that WC@Mn-N/S retained the original natural pore structure of bamboo. The specific surface area (BET) analysis revealed that WC@Mn-N/S exhibited a specific surface area of 861.7 m2/g, with its pore size structure mainly distributed in the range of 1.3–3.8 nm. Electrochemical performance tests showed that the introduction of Mn, N and S elements endowed the bamboo-based electrode with pseudocapacitance characteristics. Additionally, the synergistic effect between these three elements imparted pseudocapacitance to the electrode material. WC@Mn-N/S performent a specific capacitance of 615 F/g, at 0.2 A/g with excellent capacitance retention (99.4 % after 5000 cycles). In the practical assembled in symmetrical capacitor the material showed high power density 500 W/kg and energy density 57.9 Wh/kg, indicating its excellent electrochemical performance.

Molecular Dyad vs Multi‐Component Approach‐Photocatalytic Hydrogen Evolution by Combining Oligothiophene Photosensitizers with [FeFe]‐Hydrogenase Mimics

AbstractA molecular dyad (PS‐CAT) consisting of a metal‐free photosensitiser (PS) and a [FeFe]‐hydrogenase‐inspired [Fe2S2] cluster (CAT) has been synthesized for hydrogen evolution under visible light irradiation. The electrochemical properties of PS‐CAT in the absence and presence of acid were investigated by CV and IR‐SEC. The ground state and excited state photophysical properties of PS and PS‐CAT, and the non‐chemically connected reference system [PS, CAT] were investigated to elucidate the effect of a covalent linkage between PS and CAT on the electronic communication and hence on the catalytic performance. The photo‐relaxation pathway of PS‐CAT was revealed computationally by scalar‐relativistic time‐dependent density functional theory simulations. These studies are complemented by comparative analyses of photocatalytic hydrogen evolution between PS‐CAT and [PS, CAT] under visible light irradiation.

Novel binary regulated silicon-carbon materials as high-performance anodes for lithium-ion batteries.

The massive volume dilation, unsteady solid electrolyte interphase, and weak conductivity about Si have failed to bring it to practical applications, although its potential capacity is up to 4200 mAh g-1. For solving these problems, novel binary regulated silicon-carbon materials (Si/BPC) were done by a sol-gel procedure combined with single carbonization. Analytical techniques were systematically utilized to examine the effects of element doping at several gradients on morphology, structure and electrochemical properties of composites, thus the optimal content was identified. Si/BPC preserves a discharge specific capacity of 1021.6 mAh g-1with a coulomb efficiency of 99.27% after 180 cycles at 1000 mA g-1, within the upgrade than single-doped and undoped. In rate test, it has a specific capacity of 1003.2 mAh g-1at a high current density of 5000 mA g-1, quickly back towards 2838.6 mAh g-1at 200 mA g-1. The inclusion of B and P elements is linked to the electrochemical characteristics. In the co-doped carbon layers, the synergistic impact of doping B and P accelerates the diffusion kinetics of lithium ions, boosts diffusion rate of Li+, offers low electrochemical impedance (45.75 Ω). This brings more defects to provide transport carriers and induces a substantial amount of electrochemically active sites, which fosters the storage of Li+, thus making silicon material electrochemically more active and potential.

Enhancing the electrochemical properties of TiNb2O7 anodes with SP-CNT binary conductive agents for both liquid and solid state lithium ion batteries.

A high performance oxide composite electrode is obtained with a two-step solid state calcined titanium niobium oxide TiNb2O7 (TNO) anode and super P-carbon nanotube (SP-CNT) binary conductive agents. The solid state synthesized TNO-0.2C (the proportion of CNTs in the binary conductive agent is 20% wt) anode exhibits a high reversible discharge capacity of 278.6 mA h g-1 at 0.5C, a competitive rate capability with reported works that employed wet chemical methods at moderate rates (178.1 mA h g-1 at 10C), and an excellent capacity retention of 92.2% after 200 cycles at 1.5C/1.5C. The enhancement in electrochemical properties of the TNO-0.2C anode is mainly attributed to the combination of the short range and long range conductive agents in the SP-CNT binary conductive system, which guarantees an efficient electronic conductive network. The Li|Li1.3Al0.3Ti1.7(PO4)3 composite polymer electrolyte (LATPCPEs)|TNO-0.2C solid state batteries are also assembled, which deliver a high initial reversible discharge capacity of 241.3 mA h g-1 at 1C and a good capacity retention rate of 93% after 50 cycles. This work provides an efficient way to improve the electrochemical properties of TNO anodes in lithium ion batteries, especially for solid state batteries.