Electrochemical Impedance Spectra Research Articles

Efficient manufacture of high-performance electroplated diamond wires utilizing Cr-coated diamond micro-powder

The slicing of silicon ingots using electroplated diamond wires is a fundamental process in the creation of semiconductor devices such as chips and photovoltaic cells. Composite electroplating, a process that uses nickel (Ni) plating to fix diamond particles onto a steel wire, is a critical step in the manufacturing of these diamond wires. In this work, chromium (Cr)-coated diamond was used to achieve rapid and high-quality composite electroplating, thereby aiding the production of high-performance diamond wire saws. The Cr-coated diamond micro-powder was prepared utilizing vacuum slow evaporation technology at a temperature of 850 °C. This resulted in a uniform and firm Cr coating that was firmly bonded to the diamond surface via Cr3C2. Subsequent electrochemical tests were conducted in the composite electroplating bath. Linear scanning voltammetric curves revealed that the Cr-coated diamond was capable of inducing a more positive shift in the overpotential of Ni deposition, thus enhancing the reaction beyond that of uncoated diamond micro-powder. Additionally, the electrochemical impedance spectra indicated a decrease in charge transfer resistance during composite electroplating, attributable to the conductivity of the Cr-coated diamond. Electroplated diamond wires incorporating Cr-coated diamond demonstrated a greater abrasive density per unit length. SEM results showed that Ni was able to deposit on the Cr-coated diamond surface, resulting in the abrasives being completely covered by the Ni plating. The Cr-coated diamond wire exhibits a stronger resistance to abrasive detachment after cutting, which could increase the diamond-protrusion of the wire. The utilization of Cr-coated diamond micro-powder as an abrasive is anticipated to enhance the manufacturing efficiency of diamond wires and improve product quality, thereby promoting advancements in hard and brittle material processing technology.

Development and characterization of fly ash enriched epoxy coatings for corrosion protection in deep sea water

Fly ash (FA) has recently received increasing attention as inexpensive and readily abundant filler for development of epoxy-based anticorrosive coatings. In the present investigation a series of FA enriched epoxy coatings (FECs) has been developed and investigated for their anticorrosive behaviour under immersion in DSW (pH 8.2) over 48 h. The development of FECs was conducted through enrichment of FA ranging 0 to 80 phr (parts of FA per 100 g of epoxy) into epoxy matrix. The formation of FECs was ascertained through spectral, thermal, electrical and microscopic methods. Electrochemical impedance spectra in coherence with DC polarization measurements reveal enhanced corrosion protection efficiency (83 %) of FECs derived at 40 phr enrichment of FA. Enrichment of FA (phr) ranging 40 to 60 has rendered fair (0.01) to moderate (0.05) resistance (mm/year) to FECs against pitting corrosion in DSW. Whereas, FECs derived at 60 phr of FA has shown promising electrical behaviour, moderate heat resistance (TG onset 200 °C with 94.70 % weight residue) with enhanced limiting oxygen index (38.50 %). FECs developed in the present investigation may find their possible applications as anticorrosive coatings sustainable in DSW over 48 h.

Facile synthesis of Zn2V2O7/RGO nanocomposite for enhancing the electrochemical performance and evaluating the supercapacitor device

Pyrochlore-structured zinc vanadium oxide with RGO (Zn2V2O7/RGO) composite was synthesized using the simple hydrothermal process for energy storage device fabrication. The structural, vibration spectrum, surface morphology, and elemental of the Zn2V2O7/RGO composite were analyzed using different analytical methods. Then, the electrochemical performance was examined using Zn2V2O7/RGO composite modified electrode with 3-electrode and 2-electrode setup by cyclic voltammetry (CV), galvanostatic charge–discharge (GCD), and electrochemical impedance spectrum (EIS) techniques. Consequently, the Zn2V2O7/RGO composite revealed notable pseudo-capacitive behavior which has been confirmed through CV analysis. The nano size-based Zn2V2O7/RGO composite electrode material obtained notable specific capacitance (Csp) of 1400.52F/g owing to the synergistic promotion of Zinc and vanadium oxides. Furthermore, the ASC device of Zn2V2O7/RGO ||RGO displayed the efficient power density of 1371 kW/kg at the energy density of 8Wh/kg and the device has enhanced cycling performance with 72.8 % capacitance.

Boosting the photocatalytic activity of bismuth vanadate (BiVO4) via optimization of the internal polarization

Photocatalytic performance can be improved by optimizing the morphology and surface texture of the photocatalyst or forming different p-n and/or n-n heterojunctions. Although the heterojunction system enhances photocatalytic property; however, an internal spontaneous polarization electric field may be much more effective due to the separation of electron-hole pairs when the polarization field forces them to move in different directions. The present study demonstrated this insight where the BiVO4 synthesis condition and polarization field forces were controlled via homogeneous precipitation in the presence of polyvinylpyrrolidone (PVP). The as-synthesized BiVO4 photocatalysts' structure and morphology were investigated using XRD, SEM, Raman, DRS, and PL. The result revealed that the increase of PVP concentration reformed the shaping to the truncated bipyramid-like shape and creates a spontaneous internal polarization that enhanced BiVO4 photocatalytic performance. The photocatalytic activity of BiVO4 was evaluated by monitoring the photocurrent enhancement using chronoamperometry, electrochemical impedance spectra and the photodegrading of methylene blue (MB) aqueous solution to harmless compounds in the presence of light. The spontaneous polarization between the different facets of BiVO4 crystal enhances the e−/h+ separation during internal facets homojunction and leads to four times photocurrent enhancement and the MB photocatalytic degradation rate increased from 0.43 to 1.92 min−1.

Characteristics of hydride electrodes using Mg-Ti-Ni-Co-Al-based alloys synthesized by mechanical milling

For Ni-MH batteries, crystalline Mg-based alloys such as MgNi, Mg2Ni, REMg12, and La2Mg17 are regarded as hopeful negative electrode materials. Even though these alloys are inexpensive and have promising discharge capacity, they hardly ever electrochemically absorb or desorb hydrogen at room temperature. In this paper, the MgNi-based Mg50-xTixNi45Al3Co2 (x = 0, 1, 2, 3, 4) alloy electrodes were fabricated. The surface of the as-cast alloys was modified by mechanical Ni coating. The nanocrystalline and amorphous Mg50-xTixNi45Al3Co2 (x = 0, 1, 2, 3, 4) + 50 wt.%Ni alloys for Ni-MH batteries were prepared using mechanical ball milling. The effects of Ti content and ball milling time on the structure and electrochemical hydrogen storage properties of the alloys were investigated. The electrochemical testing reveals that the as-milled alloys can electrochemically absorb and desorb hydrogen well at room temperature. Without any activation, the milled alloys can achieve maximum discharge capacity in the first cycle. With the extension of ball milling time and the increase of Ti content, the cycle stability and discharge capacity of the alloys are significantly enhanced. The electrochemical impedance spectrum, high rate discharge ability, potentiodynamic polarization curve, and potential-step measurement all indicate that the electrochemical kinetics of the prepared alloys initially increase and subsequently decrease with the increase of Ti content, while significantly improve with the prolongation of milling time.

In situ growth of CoO on MXene sheets for modification of all‑vanadium redox flow battery electrodes

In order to greatly improve the energy efficiency and electrolyte utilization efficiency of vanadium redox flow batteries (VRFBs) and to enable them to operate at high current densities, MXene/CoO composites were used for the first time in this research as electrocatalysts for the V3+/V2+ reaction. The catalytic effect of the materials was characterized by cyclic voltammetry (CV) and electrochemical impedance spectra (EIS) tests. Then battery performance of MXene/CoO composite modified plasma-treated graphite felt (GF) negative electrodes (MXene/CoO/GF) were tested in a VRFB. The results show that MXene/CoO composites can improve the catalytic activity. There is a 22.93 % increase in energy efficiency and 124.94 % increase in electrolyte utilization efficiency when MXene/CoO/GF is applied as VRFB negative electrode at a current density of 200 mA cm−2 compared to GF. At a current density of 250 mA cm−2, the energy efficiency of MXene/CoO/GF is maintained at 75.55 %. The excellent performance is attributed to the addition of MXene/CoO, which increases the active sites for redox reactions and thus improves the kinetics of the V3+/V2+ reaction.

Fabrication of g-C3N4 films with enhanced mechanical and charge transfer properties by electrophoretic deposition and subsequent citric acid modification

A low-cost 2D metal-free material based on a graphitic carbon nitride (g-C3N4) film functionalized with a citric acid molecule has been successfully fabricated by Electrophoretic Deposition (EPD) and thermal techniques, aiming to evaluate its suitability for optoelectronic devices. The thickness-controlled g-C3N4 film having a good mechanical property was successfully performed. The chemical stability and photostability of the citric-modified g-C3N4 films deposited on indium tin oxide (ITO) glass were investigated. New chemical links were clarified such that it could possibly become a bridge for enhancing charge transport. The modified samples exhibited a significant increase in their photocurrent response, reaching 25 μA/cm2 at a thickness of about 20 μm. Electrochemical impedance spectra (EIS) verified the enhanced conductivity, efficient charge transfer, and reduced electron-hole recombination rate. This research revealed a facile synthetic route and environmentally benign materials, thereby suggesting promising prospects for their application in the optoelectronic field.

Metal-free g-C3N5 photocatalysts with defect sites as efficient peroxymonosulfate activators for antibiotic removal in aqueous media

Nitrogen-rich graphitic carbon nitride (g-C3N5) has emerged as a promising and fascinating photocatalyst for tackling problems related to antibiotic pollution. Herein, porous O-doped g-C3N5 with N vacancy (g-C3N5-x-O) was fabricated via a facile two-step pyrolysis technique using 3-amino-1,2,4-triazole and oxalic acid as precursors. The sample modified with 2.0 mol.% oxalic acid (CN-2.0) exhibits a porous structure with a specific surface area of 249.78 m2. g−1, 2.77 times greater than that of pristine g-C3N5 (CN-0). In addition, the existence of O-doping and N vacancies in g-C3N5 framework not only promotes charge transfer properties but also suppresses photogenerated electron-hole recombination according to the results of transient photocurrent responses, photoluminescence and electrochemical impedance spectra. The CN-2.0 sample displays the highest photocatalytic activity, which eliminates 77.3% sulfamethoxazole (SMX, 20 mg. L−1) after 60 min irradiation under UV 365 nm light source. The addition of peroxymonosulfate (PMS, HSO5-) significantly accelerates SMX photodegradation rate as well as reduces the influence of pH solution during treatment process. The reactive oxygen species including •O2−, 1O2, SO4•−, •OH, h+ contribute to SMX removal. The efficient degradation of numerous antibiotic classes highlights the possible applicability of g-C3N5-x-O. Interestingly, the catalyst retains its high activity and stability even after four consecutive reuse cycles. The intermediates of SMX degradation were determined and plausible SMX degradation pathways were proposed. Toxicity assessments demonstrated that the overall toxicity of the solution decreased after treatment. This work provides a feasible strategy to design and modulate g-C3N5 photocatalyst activated by PMS for antibiotic removal in wastewater.

Extracting and Interpreting Electrochemical Impedance Spectra (EIS) from Physics-Based Models of Lithium-Ion Batteries

Abstract This paper implements a highly efficient algorithm to extract electrochemical impedance spectra (EIS) from physics-based battery models (e.g., a P2D model). The mathematical approach is different from how EIS is practiced experimentally. Experimentally, the voltage (current) is harmonically perturbed over a wide range of frequencies and the amplitude and phase shift of the corresponding current (voltage) is measured. The experimental approach can be implemented in simulation software, but is computationally expensive. The approach here is to determine locally linear state-space models from the full physical model. The four Jacobian matrices that are the basis of the state-space models can be derived by numerical differentiation of the physical model. The EIS is then extracted from the state-space model using computationally efficient matrix-manipulation techniques. The algorithm can evaluate the full EIS at an instant in time during a transient, independent of whether the battery is in a stationary state. The approach is also able to separate the full-cell impedance to evaluate partial EIS, such as for a battery anode alone. Although such partial EIS is difficult to measure experimentally, the partial EIS provides valuable insights in interpreting the full-cell EIS.

Sr and Fe substituted LaCoO3 nano perovskites: Electrochemical energy storage and sensing applications

Perovskite-type LaCoO3 (LCO), La0.8Sr0.2CoO3 (LSCO), and La0.8Sr0.2Co0.9Fe0.1O3 (LSCFO) were prepared though a sol gel assisted hydrothermal method for supercapacitors and electrochemical sensors for heavy metal ions detection applications. Rhombohedral crystal structure was confirmed using experimental and DFT based computational XRD pattern. LCO, LSCO and LSCFO based modified carbon paste electrodes were prepared for cyclic voltammetry, electrochemical impedance spectra and galvanostatic charge discharge measurements. Among all electrodes, LSCFO results with 715.5 Fg−1 specific capacitance with 97 % retention after 1500 cycles. Cyclic voltammetry measurements for the sensing and detection of heavy metal ions (chromium and mercury) were carried out using all three electrodes and observed that LSCFO showed better response comparatively to that of other two electrodes, thus can be claimed as a potential mixed metal oxide nanomaterial for the fabrication of electrodes for storage of energy and sensor applications.

G-C3N4/TiO2 nanotube array for enhanced photoelectrochemical water splitting

Graphitic carbon nitride (g-C3N4) and TiO2 nanotubes (TNT) have made significant breakthroughs in the field of photocatalysis because of their unique features, such as environmental friendliness, low cost and good stability. Herein, we present the improved photo-electrochemical performance under AM 1.5G irradiation of three different photoanodes based on TNT coated with g-C3N4 via the effortless thermal treatment of anodized TNT sheets over melamine (TNT-M), urea (TNT-U) and dicyanamide (TNT -D). A maximum photocurrent of up to 0.14 mA cm−2 at 1.23 V (vs. RHE) is obtained under illumination using AM 1.5 G light source for TNT-D, which is ten times greater than pristine TNT (0.014 mA cm−2). A good photoelectrochemical stability with efficient charge transfer is observed, and electrochemical impedance spectra reveal that better photoelectrochemical performance is due to the reduced electron-hole pair recombination via the development of heterojunction between TNT and g-C3N4 compared to the bare-TNT electrode.

Corrosion resistance of Cu-Fe deformation processed in situ alloy in chloride ion environment

To assess the corrosion resistance of Cu-Fe deformation in situ alloys in a chloride ion environment, Cu-Fe alloys with varying Fe contents (5 wt%, 10 wt%, and 14 wt%) were prepared using vacuum induction melting, and the impact of Fe content on the corrosion resistance was examined. The corrosion morphology and corrosion products were analyzed, and the corrosion rate, corrosion period, dynamic potential polarization curves, electrochemical parameters, and electrochemical impedance spectra with different Fe contents were determined. However, the corrosion resistance of Cu-Fe alloys initially increased with an increase in Fe content before decreasing, with Cu-10 wt% Fe alloys (95% reduction rate) exhibiting the best corrosion resistance. As the Fe content increased, the amount of primary Fe phase gradually increased and became more densely distributed. This led to an increase in the dense oxide film on the surface, thereby enhancing the corrosion resistance of the material. Moreover, with a further increase in Fe, the primary Fe phase exhibited coarsening and non-uniform distribution. This resulted in the oxide film becoming looser, leading to a decreased corrosion resistance of the alloy.

Effect of the operating temperature on the degradation of solid oxide electrolysis cells

The present work aims to better understand the effect of operating temperature on the degradation of Solid Oxide Electrolysis Cells (SOECs). The studied SOECs consist of La0.6Sr0.4Co0.2Fe0.8O3-δ-Ce0.8Gd0.2O2-δ (LSCF-GDC) oxygen electrode, GDC diffusion barrier layer, Y0.16Zr0.84O1.92 (YSZ) electrolyte and Ni-YSZ hydrogen electrode. Durability tests are carried out at 750, 800 and 850 °C for 2000 h at −1 A cm−2, using 10/90 vol% H2/H2O and dry air at the hydrogen and oxygen electrodes, respectively. The electrochemical impedance spectra measured before and after ageing reveal a strong evolution related to the hydrogen electrode, while the change in the oxygen electrode contribution remains negligible. A set of advanced characterization techniques are employed to study the cell degradation. For the hydrogen electrode, a large Ni depletion is observed after ageing, which increases with the operating temperature. The analysis of the oxygen electrode shows an elemental inter-diffusion between the LSCF-GDC/GDC/YSZ layers on the manufactured cells that seems to not evolve significantly upon operation. Moreover, the presence of SrZrO3 is not detected in the pristine cell and in the operated ones. Besides, only a limited LSCF decomposition is found in good agreement with the electrochemical characterizations. Hypotheses that could explain the good oxygen electrode stability are discussed.

Ternary Rotational Polyanion Coupling Enables Fast Li Ion Dynamics in Tetrafluoroborate Ion Doped Antiperovskite Li2OHCl Solid Electrolyte

Li‐rich antiperovskite (LiRAP) hydroxyhalides are emerging as attractive solid electrolyte (SEs) for all‐solid‐state Li metal batteries (ASSLMBs) due to their low melting point, low cost, and ease of scaling‐up. The incorporation of rotational polyanions can reduce the activation energy and thus improve the Li ion conductivity of SEs. Herein, we propose a ternary rotational polyanion coupling strategy to fasten the Li ion conduction in tetrafluoroborate (BF4–) ion doped LiRAP Li2OHCl. Assisted by first‐principles calculation, powder X‐ray diffraction, solid‐state magnetic resonance and electrochemical impedance spectra, it is confirmed that Li ion transport in BF4– ion doped Li2OHCl is strongly associated with the rotational coupling among OH–, BF4– and Li2–O–H octahedrons, which enhances the Li ion conductivity for more than 1.8 times with the activation energy lowering 0.03 eV. This work provides a new perspective to design high‐performance superionic conductors with multi‐polyanions.

Ternary Rotational Polyanion Coupling Enables Fast Li Ion Dynamics in Tetrafluoroborate Ion Doped Antiperovskite Li2OHCl Solid Electrolyte.

Li-rich antiperovskite (LiRAP) hydroxyhalides are emerging as attractive solid electrolyte (SEs) for all-solid-state Li metal batteries (ASSLMBs) due to their low melting point, low cost, and ease of scaling-up. The incorporation of rotational polyanions can reduce the activation energy and thus improve the Li ion conductivity of SEs. Herein, we propose a ternary rotational polyanion coupling strategy to fasten the Li ion conduction in tetrafluoroborate (BF4-) ion doped LiRAP Li2OHCl. Assisted by first-principles calculation, powder X-ray diffraction, solid-state magnetic resonance and electrochemical impedance spectra, it is confirmed that Li ion transport in BF4- ion doped Li2OHCl is strongly associated with the rotational coupling among OH-, BF4- and Li2-O-H octahedrons, which enhances the Li ion conductivity for more than 1.8 times with the activation energy lowering 0.03 eV. This work provides a new perspective to design high-performance superionic conductors with multi-polyanions.

Effect of Ce replacing La on the electrochemical performance of amorphous grain boundaries Mg-Ni-based materials

Aiming at enhancing the electrochemical characteristic of RE-Mg-based composite, the partial substituting La with Ce experiment in the composites was conducted, and the surface modification treatment of the alloys was performed by mechanical coating Ni. By means of mechanical trituration, The La10-xCexMg80Ni5 (x = 0–2) + y wt% Ni (y = 50–200) compound materials which have the structures of nanocrystalline and amorphous were synthesized. In order to make sense of the principle action of Ce and Ni elements in structural and electrochemical properties of the material, some deep research were carried out. According to the final results, the as-milled composites have the electrochemical hydrogen absorption and hydrogen desorption abilities at room temperature. Having no use for activation, the as-milled composites can reach the maximum discharge capacities when the first cycling was carried out. With the Ni value x changed from 50 to 200, the discharge capacity was varied from 70.5 mAh/g to 902.1 mAh/g; moreover, the capacity retention rate at 20th cycle (S20) and high rate dischargeability (HRD) of the (x = 0) composite were heightened from 67.2 % to 82.3 %, from 50.6 % to 55.7 % respectively. The composites' (y = 100) discharge capacity has a maximum value 118.5 mAh/g when the Ce value x is 1. The capacity retention rate (S20) is enhanced from 53.3 % to 68.5 % by lifting Ce content from x = 0 to x = 2. what's more, the high-rate discharge ability (HRD), the electrochemical impedance spectrum (EIS), potentiodynamic polarization curves, and potential-step measurements all intimate that substituting La with Ce clearly promotes the composites' electrochemical kinetic properties, but maximum values emerge only when the x value is 1.

An Active Equalization Method for Cascade Utilization Lithium Battery Pack With Online Measurement of Electrochemical Impedance Spectroscopy

Abstract With the rapid development of new energy vehicles, a large number of lithium batteries have been produced, used and retired. The full utilization and safe use of the whole life cycle of the batteries have become a hot topic in the research field. Compared to brand new batteries, retired power batteries exhibit significant inconsistency and safety risks due to aging, thus necessitating effective battery equalization and safety monitoring methods. In this article, an active equalization method for cascade utilization lithium battery pack with online measurement of electrochemical impedance spectroscopy is proposed to actively equalize the retired battery pack and alleviate the inconsistency of the battery pack. Besides, the electrochemical impedance spectrum of the single battery is measured online without adding additional hardware circuit, so as to realize real-time safety monitoring and solve the safety problem of the battery. Finally, in order to verify the feasibility of the active equalization and electrochemical impedance spectrum monitoring scheme designed in this article, a simulation model is built based on MATLAB-Simulink platform. The simulation results show that the six batteries in the proposed scheme model complete the active equalization in about 710s, 850s and 740s respectively in the balance mode, charge mode and discharge mode, and the electrochemical impedance spectrum in the frequency range of 1-20KHz can be successfully measured.

Rapid estimation of battery state of health using partial electrochemical impedance spectra and interpretable machine learning

The longevity and efficacy of lithium-ion batteries diminish over time, making accurate estimation of their health state essential. Traditional methods, based on long-term charge and discharge data, are limited in speed and data richness. This study introduces a novel approach using partial Electrochemical Impedance Spectroscopy (EIS) and interpretable machine learning for rapid and precise battery health state estimation. Our method selects partial impedance spectra, in contrast to conventional techniques that rely on global impedance spectra, and applies interpretable machine learning. The SHAP (SHapley Additive exPlanations) framework is used to interpret the contribution of each impedance feature, enhancing model transparency and reliability. Comparative evaluations demonstrate that SHAP-enhanced partial impedance spectra provide higher prediction accuracy and are more quickly obtained than global spectra. This innovative application of interpretable machine learning in acquiring partial impedance spectra represents a significant advancement in battery health state estimation. Our findings propose a new paradigm in employing EIS for battery health analysis, promising enhanced precision and speed in practical applications.

MoSe2 in flower spheres provides abundant active sites for TiO2 photocatalytic degradation of RhB

In this paper, a MoSe2/TiO2 composite photocatalyst was constructed by modifying TiO2 with MoSe2 as a group catalyst. The results showed that pure TiO2 and MoSe2 had no degradation activity for RhB, and the composite catalyst of 0.03 g MoSe2 had the best photocatalytic degradation activity for RhB. Through SEM, TEM, UV-VIS absorption spectrum, transient photocurrent curve, photoluminescence spectrum, and electrochemical impedance spectrum analysis, it can be seen that the excellent performance of 0.03 g MoSe2 composite sample is due to its excellent nanostructure, and uniform TiO2 nanosheets are attached to MoSe2 flower spheres. The active site of RhB photocatalytic degradation was increased, the visible light response and photobiological carrier separation were enhanced, and TiO2 had photocatalytic activity under simulated sunlight.

Enhanced photoelectrochemical water splitting via 3D flow field structure: Unveiling the decisive role of interfacial mass transfer

The efficiency of photoelectrochemical water splitting is not only related to the electrode material, but also influenced by the mass transport at the electrode surface. Here, we design a novel photoelectrochemical water splitting reactor, which generates a turbulent flow (0–145 mL/min) at the electrode/electrolyte interface. It was revealed that the reactor has a significant effect on the electrolyte flow, and the flow rate on the photocurrent density was more significant during the transition period of the flow state and the high flow rate. The 3D flow field structure improved the water splitting reaction of TiO2 photoelectrode by 130% at the flow rate of 130 mL/min, and consequently, the TiO2 exhibited a photocurrent density of 0.142 mA·cm−2 at 1.23 V versus the reversible hydrogen electrode. Then we changed the temperature (20–90 °C) of the electrolyte, and electrochemical impedance spectra results indicated that the ion transport impedance decreased with increasing electrolyte temperature in the experimental range. The photocurrent density increased by about 2.2 times at 90 °C compared to that at 20 °C. This work provided insights of the structure design on the photoelectrode/electrolyte interface in solar water splitting and revealed the non-negligible effect of interfacial mass transport in photoelectrochemical performance.