Constant Voltage Conditions Research Articles

Effects of electrode configuration on the current density distribution of the electrolytic reducer

Pyroprocessing for the recycling of light water reactor spent fuel into metal nuclear fuel involves the electrolytic reduction process to convert oxides into metals. Optimization of the electrolytic cell is essential in the current engineering-scale development stage of electrolytic reduction research. This study investigates the effects of the conventional impermeable anode shroud, typically used in the development of laboratory-scale electrolytic reducers, and the effects of parallel multiple electrode configurations, aimed at the scale-up of the electrolytic reducer, on the current density distribution of the electrolytic reducer. The current density distribution was analyzed using COMSOL modeling. The exclusion of the impermeable anode shroud resulted in increased total currents under constant cell voltage conditions and contributed to the narrowing of the current density distribution on the electrodes. In addition, parallel multiple electrode configurations proved effective in increasing total currents and narrowing the current density distribution on the electrodes. These results emphasize the need to use a permeable anode shroud and a parallel multiple electrode configuration to scale-up the electrolytic reducer.

A 3D PtCo degradation model for long-term performance prediction of a scaled-up PEMFC under constant voltage operation

The non-uniform distribution of reactants, pressure, temperature and reaction rate in a scaled-up proton exchange membrane fuel cell (PEMFC) can lead to different catalyst degradation rate, impacting the long-term performance of PEMFCs. However, the local catalyst degradation behaviors in a PEMFC stack have not yet been fully understood due to the lack of experimental approaches and catalyst degradation model. In the present study, a numerical model is established for a 200 cm2 commercial-sized PEMFC stack with realistic anode and cathode flow fields. PtCo is employed as the cathode catalyst, and a 3D PtCo catalyst degradation model is developed to analyze the non-uniform evolution of the electrochemical active surface area (ECSA), current density, and Co2+ in the catalyst layers under the constant voltage conditions. The modeling results demonstrated that catalyst degradation is more severe downstream as well as under land of the cathode flow field, and the cathode catalyst layer (CCL) is the area most contaminated by the Co2+. The non-uniform catalyst degradation as well as Co2+ contamination increased the activation losses and local oxygen transport resistance. The catalyst degradation leads to a total power loss of 43.3 % after 80,000 h operation. The aging model provides a better understanding for large scale PEMFC stacks regarding its non-uniform PtCo degradation and can assist the future design of commercial PEMFCs with better lifetime.

Double Conductive Ni-pads for a kW-class micro-tubular solid oxide fuel cell stack

Double Conductive Ni-pads (DCNPs) are prepared for the anode collector of micro-tubular solid oxide fuel cells (MTSOFCs) to fabricate a kW-class MTSOFC stack. The dimensions of the pad, in terms of width and length, are approximately 3.1 mm and 11.3 mm respectively. COMSOL Multiphysics software is utilized to simulate the multi-physical field of a single cell and SOFC stack to study anodic DCNPs current distribution and mass transfer operated at various voltages. A 160-cell stack consists of eight 20-cell sub-stacks exhibits a maximum power output exceeding 1 kW at an operating temperature of 700 °C. Furthermore, long-term operation tests under constant current or constant voltage conditions are conducted on both the 20-cell sub-stack and the 80-cell stack, demonstrating excellent performance and stability when utilizing DCNPs as anode collectors. The application potential for DCNPs as anode collectors in micro-tubular solid oxide fuel cells extends to various fields including auxiliary power units or high-power stacks, thereby introducing new possibilities for MTSOFC technology.

Numerical simulation for non-uniform PtCo catalyst degradation under constant voltage condition and its impact on PEMFC performance

PtCo alloys are commonly utilized as catalysts in proton exchange membrane fuel cell (PEMFC) to reduce Pt loading and to achieve higher oxygen reduction reaction (ORR) activity. However, long-time operation can result in a reduction in electrochemical surface area (ECSA) in PEMFC. Meanwhile, the dissolved Co2+ may also contribute to additional local oxygen transport resistance. In this study, catalyst aging model and Co2+ transport and its effect on oxygen transport model have been integrated with the 3D single phase PEMFC performance model to develop a long-term performance model for investigating the impact of non-uniform catalyst degradation and Co2+ contamination on PEMFC performance during constant voltage operation. The results show that Co2+ contamination causes additional mass transfer losses and reduces the peak power of PEMFC. And it is found that the non-uniform degradation of catalyst and Co2+contamination eventually affects the current density distribution in aged PEMFCs. In addition, the model is also applied to study a 50 cm2 PEMFC under long time constant voltage operation. The predicted ECSA loss is 73.1 % and 62.0 %, and output power reduction is 55.9 % and 43.0 % after 80,000 h at a constant voltage of 0.75 V and 0.65 V, respectively.

Lifetime prediction and reliability analysis for aluminum electrolytic capacitors in EV charging module based on mission profiles

The charging modules of Electric vehicles (EVs) always run in a complex and variable state. As the weakness in the reliable operation of charging modules, the accurate lifetime prediction of aluminum electrolytic capacitors (Al-caps) is important for the later maintenance and reliability design. The hotspot temperature calculation method and lifetime model limit the accuracy of aluminum electrolytic capacitors lifetime prediction methods, which cannot meet the increasing requirements for reliability. In order to solve the problems above, this paper has proposed a hotspot temperature calculation method based on the ripple current with frequency characteristics and the cooling conditions on the heat generation and thermal conductivity of the capacitors. Furthermore, the lifetime model under reference voltage has been constructed with 3D surface fitting toolbox, which describes the trends of capacitor lifetime with ambient temperature and hotspot temperature under the constant voltage condition. Considering the variation of voltage, the multiple lifetime model of capacitor is established with a voltage correction coefficient. With the proposed method, it can be realized about the real-time lifetime prediction of capacitors under multiple operating profiles such as ripple current, thermal dissipation conditions, ambient temperature and operating voltage. Finally, the effectiveness of the proposed method is verified with the annual profiles of a 30 kW EV charging module.

Enhanced NH4+ Removal and Recovery from Wastewater Using Na-Zeolite-based Flow-Electrode Capacitive Deionization: Insight from Ion Transport Flux.

Flow-electrode capacitive deionization (FCDI) is a promising electromembrane technology for wastewater treatment and materials recovery. In this study, we used low-cost Na-modified zeolite (Na-zeolite) to prepare a composite flow-electrode (FE) suspension with a small amount of highly conductive carbon black (CB) to remove and recover NH4+ from synthetic and actual wastewater (200 mg-N/L). Compared with conventional activated carbon (AC), the Na-zeolite electrode exhibited a 56.2-88.5% decrease in liquid-phase NH4+ concentration in the FE suspension due to its higher NH4+ adsorption capacity (6.0 vs. 0.2 mg-N/g). The resulting enhancement of NH4+ diffusion to the electrode chamber contributed to the improved performance of FCDI under both constant current (CC) and constant voltage (CV) conditions. The addition of CB to the FE suspension increased the conductivity and facilitated Na-zeolite charging for NH4+ electrosorption, especially in CV mode. NH4+-rich zeolite can be easily separated by sedimentation from CB in the FE suspension, producing a soil conditioner with a high N-fertilizer content suitable for soil improvement and agricultural applications. Overall, our study demonstrates that the novel Na-zeolite-based FCDI can be developed as an effective wastewater treatment technology for both NH4+ removal and recovery as a valuable fertilizer resource.

Effect of Pulse Duty Cycle and Oxidation Time on Microstructure and Properties of Micro-arc Oxidation Coatings on Ti6Al4V Alloy

Micro-arc oxidation (MAO) technology can in-suit generate coatings with high hardness and strong adhesion on the surface of titanium alloy, thereby greatly improve the application range of titanium alloy. The morphology and properties of coatings are controlled by changing electrical parameters such as duty cycle and oxidation time. This work mainly aims to study the influence of different duty cycles and oxidation times on MAO coatings microstructures and properties of Ti6Al4V alloy under the condition of constant voltage and pulse frequency. The scanning electron microscopy (SEM) and X-ray Diffractometer (XRD) were used to investigate into MAO coatings microstructure and phase composition. The roughness, porosity, thickness, and microhardness of MAO coatings were evaluated respectively by roughness tester, thickness gauge, and microhardness tester. The results show that surface morphology of the MAO coatings change from crater-like micropores to foam-like protrusions with the enhancement of duty cycle and oxidation time. When duty cycle is 50% and oxidation time is 30 min respectively, the ejection of the molten material made the MAO coating surface appear foam-like protrusions, and the surface morphology is seriously damaged. When the oxidation time and the duty cycle are 30 min and 10% respectively, the rutile phase intensity is the maximum, and further increasing the duty cycle will lead to a rutile phase decrease. In a limit range, the hardness rise with increase of oxidation time and duty cycle. The highest hardness is 668.85 HV.

Growth characteristics and the mass transfer mechanism of single bubble on a photoelectrode at different electrolyte concentrations.

In the photoelectrochemical water splitting reaction, the bubble attached to the working electrode is an essential factor affecting the reaction resistance, current density and gas-liquid mass transfer. An experimental measurement system based on an electrochemical workstation synchronously coupled with a high-speed microscopic camera was proposed and used to systematically study the growth kinetics and mass transfer mechanism of single oxygen bubbles at different electrolyte concentrations (Na2SO4, 0.1-2.0 M) on the TiO2 photoanode surface. Under constant voltage and constant current control conditions, when the electrolyte concentration increases, the bubble detachment diameter and the bubble detachment frequency gradually decrease. The bubble coverage equation expressed in terms of gas evolution efficiency is proposed and is associated with the photocurrent and bubble radius. The average bubble coverage and average gas evolution efficiency decrease when the electrolyte concentration is increased. According to the Sherwood dimensionless number, various mass transfer coefficients during bubble growth were calculated. The results show that the average total mass transfer coefficient is positively correlated with the change trend of the electrolyte concentration, and the mass transfer coefficient of single-phase natural convection is one order of magnitude larger than the mass transfer coefficient of bubble-induced convection. Finally, a conclusion on the transient mass transfer process in the bubble evolution process was obtained, that is, the mass transfer coefficient of single-phase natural convection and the total mass transfer coefficient remain high during the first growth stage, and gradually decrease during the second growth stage. Therefore, regulating the electrolyte concentration can effectively promote the gas-liquid mass transfer in the photoelectrochemical water splitting reaction.

Accelerated constant-voltage quantum mechanical/molecular mechanical method for molecular systems at electrochemical interfaces.

The structure and electronic properties of a molecule at an electrochemical interface are changed by interactions with the electrode surface and the electrolyte solution, which can be significantly modulated by an applied voltage. We present an efficient self-consistent quantum mechanics/molecular mechanics (QM/MM) approach to study a physisorbed molecule at a metal electrode-electrolyte interface under the constant-voltage condition. The approach employs a classical polarizable double electrode model, which enables us to study the QM/MM system in the constant-voltage ensemble. A mean-field embedding approximation is further introduced in order to overcome the difficulties associated with statistical sampling of the electrolyte configurations. The results of applying the method to a test system indicate that the adsorbed molecule is no less or slightly more polarized at the interface than in the bulk electrolyte solution. The geometry of the horizontally adsorbed molecule is modulated by their electrostatic interactions with the polarizable electrode surfaces and also the interactions with cations attracted toward the interface when the adsorbate is reduced. We also demonstrate that the approach can be used to quantitatively evaluate the reorganization energy of a one electron reduction reaction of a molecule in an electrochemical cell.

Potential‐Driven Semiconductor‐to‐Metal Transition in Monolayer Transition Metal Dichalcogenides

AbstractThe potential‐driven semiconductor‐to‐metal transition is investigated in monolayer transition metal dichalcogenides by employing a new proposed method, i.e., the fixed‐potential method (FPM). Under the same voltage, the semiconducting and metallic phases will be charged differently due to their different electronic properties. The potential‐driven phase transition process is simulated by the injection of unequal electrons in the semiconducting and metallic phases. The unequal electron injection is more consistent with the actual experimental process, although equal electron injection also can theoretically induce a phase transition. MoTe2 is chosen as a prototypical example to examine the physical mechanism. When the fixed electrode potential is above the potential of zero‐charge, excess electrons are injected into the metallic 1T’ phase instead of the semiconducting 2H phase, stabilizing the 1T’ phase. In addition, the potential‐dependent kinetics, in which the charge transfer is fluctuating, suggests that increasing the electrode potential will decrease the kinetic barrier of the 2H→1T’ transition process. The calculated relative transition voltage of 2.5 V agrees well with the experimental results, demonstrating the validity of the FPM. This study provides new insight into potential‐driven semiconductor‐to‐metal phase transitions and suggests a new theoretical approach for studies under constant voltage conditions.

Scaling study of contact operation at constant current in self-aligned top-gated oxide semiconductor field-effect transistors

An extraction framework that can precisely reflect the metal-semiconductor contact behavior is developed for self-aligned top-gated oxide semiconductor field-effect transistors (SA-TG OS FETs). In contrast to the conventional transfer length method, where the extraction is performed at a constant drain voltage condition, an improved constant current scheme, resilient to bias-dependent series resistance, is employed to enhance the extraction accuracy. This technique enables one to unveil the underlying device physics at the metal-OS interface under top-gated operation. Furthermore, the resistance of contact and extension regions can be accurately differentiated by exploiting the extraction results from the three-terminal FETs and two-terminal resistors using the present framework. Moreover, the significant role of the specific contact resistivity at the metal-OS interface is highlighted as the dominating factor that detrimentally affects the electrical performance of OS FETs.

Modelling electroforming process under constant bias voltage conditions

In order to understand changes in defect concentration during the electroforming process, we modelled the electroforming process in Ta/HfO2/Pt under constant bias voltage. For this purpose, kinetic Monte-Carlo and finite element methods were utilized. Vacancy profiles were obtained for forming voltages from 3 V to 5 V; modelling of lower stresses is time-consuming. It was found that with decreasing voltage, vacancies begin to accumulate near the inert electrode. When the voltage was dropped from 5 to 3 V, the thickness of such a layer increased by 1 nm, and electroforming time exponentially increase.

Unlocking the Potential of High-Throughput Experimentation for Electrochemistry with a Standardized Microscale Reactor.

Organic electrochemistry has emerged as an enabling and sustainable technology in modern organic synthesis. Despite the recent renaissance of electrosynthesis, the broad adoption of electrochemistry in the synthetic community, and especially in industrial settings, has been hindered by the lack of general, standardized platforms for high-throughput experimentation (HTE). Herein, we disclose the design of the HTe–Chem, a high-throughput microscale electrochemical reactor that is compatible with existing HTE infrastructure and enables the rapid evaluation of a broad array of electrochemical reaction parameters. Utilizing the HTe–Chem to accelerate reaction optimization, reaction discovery, and chemical library synthesis is illustrated using a suite of oxidative and reductive transformations under constant current, constant voltage, and electrophotochemical conditions.

Interaction Regulation Between Ionomer Binder and Catalyst: Active Triple-Phase Boundary and High Performance Catalyst Layer for Anion Exchange Membrane Fuel Cells.

As one of the most crucial components, the catalyst layer (CL) plays a critical role in the performance of anion exchange membrane fuel cells (AEMFCs). However, the effect of the structural evolution of ionomer binder on the micromorphology and catalytic activity of CL is yet to be clarified. In this study, pyrrolidinum and quaternary ammonium cations are attached to the polyphenylene oxide (PPO) backbone through flexible spacer units (five, seven, or nine carbon atoms) with different terminal alkyl groups. The Van der Waals force and electrostatic repulsion between the ionomer binder and catalyst are regulated through the flexible spacer units and terminal alkyl groups to alleviate the agglomeration of catalyst particles and acquire a high catalytic activity. To evaluate the electrochemical stability of the cationic groups, the alkaline stability of the ionomer binder is tested under a constant voltage to simulate the true operational environment of the fuel cells. The results reveal that the degradation of the cation groups of ionomer binder is accelerated under a constant voltage condition. This phenomenon in neglect earlier, may serve as a useful reference for the synthesis and performance enhancement of ionomer binders.

Deep learning for pH prediction in water desalination using membrane capacitive deionization

The pH of a solution has a large influence on the ion removal efficiency of the membrane capacitive deionization (MCDI) process, an electrochemical ion separation process. We developed a convolutional neural network linked with a long short-term memory (CNN-LSTM) model based on an artificial intelligence algorithm to predict the effluent pH of MCDI, as effluent pH is difficult to predict using conventional numerical modeling. The model accurately predicted effluent pH (R2≥0.998) based on the analysis of five input variables (current, voltage, influent conductivity and pH, and effluent conductivity) under standard operating conditions of MCDI using either constant-current or constant-voltage conditions. The developed model predicted effluent pH using only limited input variables, current and voltage, with high accuracy (R2≥0.997). Thus, the CNN-LSTM model can be used in practical applications as only the current and voltage of MCDI cells are often monitored in field applications.

Communication—Current Oscillations in Photoelectrochemical Etching of Monocrystalline 4H Silicon Carbide

Photoelectrochemical etching of monocrystalline 4H silicon carbide was performed under constant voltage condition. For the first time current oscillations were observed that caused a periodic modulation of the resulting pore diameter in etching direction. The period length of the pore diameter variation could be estimated to be about 20 nm. Additionally, it was observed that the assembly of the pores in a top down view is a Turing pattern.

Computational study of simultaneous positive and negative streamer propagation in a twin surface dielectric barrier discharge via 2D PIC simulations

The propagation mechanisms of plasma streamers have been observed and investigated in a surface dielectric barrier discharge (SDBD) using 2D particle in cell simulations. The investigations are carried out under a simulated air mixture, 80% N2 and 20% O2, at atmospheric pressure, 100 kPa, under both DC conditions and a pulsed DC waveform that represent AC conditions. The simulated geometry is a simplification of the symmetric and fully exposed SDBD resulting in the simultaneous ignition of both positive and negative streamers on either side of the Al2O3 dielectric barrier. In order to determine the interactivity of the two streamers, the propagation behavior for the positive and negative streamers are investigated both independently and simultaneously under identical constant voltage conditions. An additional focus is implored under a fast sub nanosecond rise time square voltage pulse alternating between positive and negative voltage conditions, thus providing insight into the dynamics of the streamers under alternating polarity switches. It is shown that the simultaneous ignition of both streamers, as well as using the pulsed DC conditions, providing both an enhanced discharge and an increased surface coverage. It is also shown that additional streamer branching may occur in a cross section that is difficult to experimentally observe. The enhanced discharge and surface coverage may be beneficial to many applications such as, but are not limited to: air purification, volatile organic compound removal, and plasma enhanced catalysis.

Electrochemical esterification via oxidative coupling of aldehydes and alcohols

An electrolytic method for the direct oxidative coupling of aldehydes with alcohols to produce esters is described. Our method involves anodic oxidation in presence of TBAF as supporting electrolyte in an undivided electrochemical cell equipped with graphite electrodes. This method successfully couples a wide range of alcohols to benzaldehydes with yields ranging from 70 to 90%. The protocol is easy to perform at a constant voltage conditions and offers a sustainable alternative over conventional methods.

An investigation of variable welding current on impact strength of metal inert gas welded specimen

Metal Inert Gas (MIG) welding is one of the most commonly used welding process for joining different grades and alloys of steel. Its productivity and quality depends upon many factors like arc voltage, current, weld speed and heat generated during welding. There have been many studies performed on impact of welding parameters on mechanical strength during MIG welding. In this particular study, an attempt has been made to investigate the effect of varying welding current with constant voltage on the impact strength of the weld bead of similar and different material. The objective of this is to design a V- joint and evaluate the strength of the similar and dissimilar metal pieces on different current and constant voltage conditions. The materials used in this study are mild steel and stainless steel. The method used for the impact testing is IZOD test.

Accelerated Failure in Li[Ni0.5Mn0.3Co0.2]O2/Graphite Pouch Cells Due to Low LiPF6 Concentration and Extended Time at High Voltage

Li[Ni0.5Mn0.3Co0.2]O2/graphite pouch cells were cycled using protocols that included 24 h spent at high voltage (≥ 4.3 V) under constant voltage or open circuit conditions to accelerate failure. Compared to traditional cycling, failure was reached up to 3.5 times faster. When this protocol was applied to cells containing low LiPF6 concentrations (≤ 0.4 M) failure was achieved up to 17.5 times faster than traditional cycling with normal LiPF6 concentrations. This represents a time improvement on the order of years and therefore can be used as a high-throughput screening method. Failure mechanisms for cells containing a range of LiPF6 concentrations undergoing these aggressive protocols were investigated using charge-discharge cycling, impedance spectroscopy (including symmetric cell analysis) and isothermal microcalorimetry. Long times at high voltage rapidly increase positive electrode impedance but do not seem to consume lithium inventory. The use of lower LiPF6 concentrations does not seem to introduce new failure mechanisms but makes cells less tolerant to positive electrode impedance growth. The utility of this method is demonstrated by screening cells with a variety of electrolyte additive combinations. Fewer than 3 months were required to distinguish cells containing 1% lithium difluorophospate as superior to cells with other additive combinations.