Cathode Field Research Articles

Comparison of lifetime performance of PEMFC stacks with two cooling strategies under different humidity

While reducing the size and Pt loading can achieve a lower proton exchange membrane fuel cell (PEMFC) stack cost, it is also very important to focus on the performance changes of the PEMFC stack during the long-term operation. A 3D PtCo catalysts long-term performance model is established in this study, and PEMFC stacks with one cooling unit per cell (1-cell stack) and three cells (3-cell stack) are employed as the computational domains, respectively. The effective area of each cell is 50 cm2, and the changes in current density as well as effective catalytic area of PEMFC stacks with two cooling strategies before and after long-term operation under different humidity conditions are investigated at low Pt loadings. The results show that there are large differences in the output voltage and current density distributions between the three cells due to the poor membrane hydration affected by the non-uniform temperature distribution, although the 3-cell stack can significantly reduce the size. Localized catalyst degradation in both 3-cell and 1-cell stacks is closely related to the geometry of the cathodic flow field, and non-uniform catalyst degradation is found to increase the activation and mass transfer losses and change the distribution of current density within the membrane. In addition, the 3-cell stack is found to perform even better in terms of durability, especially under high humidity conditions, which provides a potential solution to improve the durability of PEMFC stacks operating in harsh conditions.

Electrochemical activation of peracetic acid with activated carbon fiber cathode for sulfamethoxazole elimination: Long-lasting catalytic performance and mechanism

Advanced oxidation processes (AOPs) based on peracetic acid (PAA) could generate various radicals with low by-product generation, making them a vital technology in the remediation of organic pollution. Maintaining the activity and continuous operation of catalytic systems in water treatment processes was a highly challenging research topic. Herein, the electrochemical process with an activated carbon fiber (E-ACF) cathode was devised to boost the activation of PAA (E-ACF-PAA) for persistent elimination of organics. Compared to other commonly used electrodes, the ACF cathode displayed superior PAA activation ability and higher sulfamethoxazole (SMX) removal. The applied cathodic electric field could protect ACF from PAA oxidation, maintaining its long-term catalytic ability over 50 cycles. Based on radical quenching studies, the EPR test, and the estimation of radical contribution, the E-ACF-PAA process was identified as a radical dominant system. Importantly, isolated chamber experiments proved that PAA was mainly decomposed on the cathode to produce hydroxyl radicals (OH) for SMX degradation, while the anode played a negligible role. According to toxicity prediction and algae growth tests, the degradation products were harmless to the aquatic ecology. Remarkably, continuous flow experiments over a 24 h and different water matrix tests have also proven applicability in practical scenarios. This work provided novel insights into the electrochemical activation of PAA and further expanded the potential applications of PAA-based AOPs in the remediation of organic pollution.

Thermophysical model of a thermonic cathode with induction heating

A thermophysical model was built and the temperature field of a cylindrical thermionic cathode with induction heating was calculated, taking into account the initial and boundary conditions, based on the adoption of assumptions to simplify the mathematical model. During the induction heating of the cathode, a non-stationary heat conduction process is established, which is described by the differential equation of heat conduction with internal sources of Joule heat. The distribution of internal heat sources in the volume of the cathode is determined by the distribution of the ring induced current. The cylindrical design of the inductive thermionic cathode, due to spatial symmetry, allows to reduce the number of spatial variables, significantly simplify functional dependencies, and limit the algorithm for solving the problem. The problem was solved in the cylindrical coordinate system. The obtained approximate solutions were assessed for the correctness of the accepted simplifications when finding the distribution of the temperature field with a sufficient degree of accuracy. Despite the high thermal conductivity of the cathode material, when the cathode is inductively heated, there can be a significant temperature difference between its outer and inner surfaces. The article shows the permissible temperature difference on the surface of the cathode, which limits the choice of geometric dimensions of the cathode. The temperature difference on the surfaces of the induction thermionic cathode is most affected on the end (annular) surfaces of the cathode, so it is better to apply emitting coatings to the side surfaces of the cylindrical cathode, thus complicating the design of the cathode. The application of induction heating of the thermionic cathode allows to simplify the heating unit, increase the reliability and service life of powerful electronic devices. The obtained results are planned to be used in further research as test data for the analysis of more complex problems of numerical calculation of the thermal regimes of the cathode unit with heat shields and focusing elements of thermoelectron flows.

Silver Nanoparticle-PEDOT:PSS Composites as Water-Processable Anodes: Correlation between the Synthetic Parameters and the Optical/Morphological Properties.

The morphological, spectroscopic and rheological properties of silver nanoparticles (AgNPs) synthesized in situ within commercial PEDOT:PSS formulations, labeled PP@NPs, were systematically investigated by varying different synthetic parameters (NaBH4/AgNO3 molar ratio, PEDOT:PSS formulation and silver and PEDOT:PSS concentration in the reaction medium), revealing that only the reagent ratio affected the properties of the resulting nanoparticles. Combining the results obtained from the field-emission scanning electron microscopy analysis and UV-Vis characterization, it could be assumed that PP@NPs' stabilization occurs by means of PSS chains, preferably outside of the PEDOT:PSS domains with low silver content. Conversely, with high silver content, the particles also formed in PEDOT-rich domains with the consequent perturbation of the polaron absorption features of the conjugated polymer. Atomic force microscopy was used to characterize the films deposited on glass from the particle-containing PEDOT:PSS suspensions. The film with an optimized morphology, obtained from the suspension sample characterized by the lowest silver and NaBH4 content, was used to fabricate a very initial prototype of a water-processable anode in a solar cell prepared with an active layer constituted by the benchmark blend poly(3-hexylthiophene) and [6,6]-Phenyl C61 butyric acid methyl ester (PC60BM) and a low-temperature, not-evaporated cathode (Field's metal).

Plasma electrolytic oxidation of tantalum in an aluminate electrolyte: Effect of cathodic polarization and frequency

The effect of cathodic polarization on plasma electrolytic oxidation (PEO) of the refractory metal of tantalum is investigated in 10 g/l NaAlO2+2 g/l KOH under 1000 and 100 Hz. Ceramic coatings are formed under various cathodic-to-anodic current densities ratios (R = jc/ja) of 0, 0.6, 1.3 and 2.3. For PEO under 1000 Hz, the plasma discharges intensify with the increase of R from 0 to 1.3, with optical emission from Ta being detected at later stage of PEO under cathodic polarization. However, excessive R ratio of 2.3 has caused early extinguishment of the plasma discharges. Correspondingly, thicker coatings are formed as the R ratio increases from 0 to 1.3, and the coating under R = 1.3 exhibits a most porous outer layer. A thin and compact coating is formed under R = 2.3. It is also found that the application of cathodic polarization increases the Na content in the resultant coatings, with a new crystalline phase NaTaO3 being formed under R = 2.3. Cathodic polarization also decreases the corrosion resistance of the coatings. Surface wettability tests show that the coatings formed under R = 1.3 are the most hydrophilic. PEO under 100 Hz shows some differences in discharge and coating formation. Larger sized discharges are also observed at the later stage under R = 0.6, but Ta species are detected at a delayed time. For the R values of 1.3 and 2.3, patches of soft sparking occur on the sample surface, leading to non-uniform coatings. This study shows that both cathodic polarization and frequency significantly affect the PEO process. Moreover, compared with the PEO of Al, tantalum responds quite differently to cathodic polarization. Mechanisms of coating formation have been illustrated: Protons and other cations are attracted by cathodic electric field into the coatings, where they undergo a series of reactions to significantly affect the PEO behaviors.

Numerical simulation of two-phase flow in gas diffusion layer and gas channel of proton exchange membrane fuel cells

Liquid water within the cathode Gas Diffusion Layer (GDL) and Gas Channel (GC) of Proton Exchange Membrane Fuel Cells (PEMFCs) is strongly coupled to gas transport properties, thereby affecting the electrochemical conversion rates. In this study, the GDL and GC regions are utilized as the simulation domain, which differs from previous studies that only focused on any one of them. A Volume of Fluid (VOF) method is adopted to numerically investigate the two-phase flow (gas and liquid) behavior, e.g., water transport pattern evolution, water coverage ratio as well as local and total water saturation. To obtain GDL geometries, an in-house geometry-based method is developed for GDL reconstruction. Furthermore, to study the effect of GDL carbon fiber diameter, the same procedure is used to reconstruct three GDL structures by varying the carbon fiber diameter but keeping the porosity and geometric dimensions constant. The wall wettability is introduced with static contact angles at carbon fiber surfaces and channel walls. The results show that the GDL fiber microstructure has a significant impact on the two-phase flow patterns in the cathode field. Different stages of two-phase flow pattern evolution in both cathode domains are observed. The liquid water in the GDL experiences water invasion, spreading, and rising, followed by the droplet breakthrough in the GDL/GC interface. In the GC, the water droplets randomly experience accumulation, combination, attachment, and detachment. Due to the difference in surface wettability, the water coverage of the GDL/GC interface is smaller than that of the channel side and top walls. It is also found that the water saturation inside the GDL stabilizes after the water breakthrough, while local water saturation at the interface keeps irregular oscillations. Last but not the least, a water saturation balance requirement between the GDL and GC is observed. In terms of varying fiber diameter, a larger fiber diameter would result in less water saturation in the GDL but more water in the GC, in addition to faster water movement throughout the total domain.

Low-cobalt active cathode materials for high-performance lithium-ion batteries: synthesis and performance enhancement methods

This review describes the advancements in the field of Ni-rich NCM cathodes in terms of manufacturing processes, material challenges, modification techniques, and future research directions, and discusses the correlation between the synthesis and electrochemical performance.

Exploring the Basic Physical Mechanisms of Cathode- and Anode-Initiated High-Voltage Surface Flashover

Surface flashover in vacuum imposes a substantial physical limit on modern, large-scale pulsed power. One of the ramifications is a minimum size requirement for new machines, which in itself becomes a hard barrier to the modernization and improvement of existing infrastructure. Pulsed power topologies require the physical mechanisms of both anode- and cathode-initiated flashover to be considered. Originally, the geometrical implications of field emission at the cathode triple junction (CTJ) motivated the usage of configurations that avoid electrons impinging on the insulating material. This will largely suppress the cathode-initiated flashover, which is best described by the secondary electron avalanche mechanism, gas desorption, and final breakdown in the desorbed gas. It depends on the cascade growth of a conducting plasma along the length of the insulator from the cathode. Mitigating the cathode-initiated flashover typically comes at the cost of a significant field enhancement at the anode triple junction (ATJ). In a typical implementation, the anode field may be three times higher than the cathode field for a given voltage, making the corresponding anode-initiated flashover much more common than otherwise. In the case of pulsed, anode-initiated flashover, experimental evidence suggests that charge is directly extracted from the insulator resulting in the insulator taking on a net positive charge advancing the anode potential. Along with accompanying gas desorption from the surface, the potential will then propagate from the anode toward the cathode until the effective length of the gap is sufficiently reduced to support flashover. The underlying physical mechanisms of cathode- and anode-directed flashover are discussed in light of previously gathered experimental data and recent experiments with pulsed, high-gradient, anode-initiated flashover.

Research on AC corrosion behavior and corrosion product film evolution of X70 steel under the combined action of AC interference and CP

Corrosion behavior and corrosion product film evolution under AC interference and CP were investigated by corrosion tests. High CP AC corrosion could be identified according to corrosion rate map. In case of high CP AC corrosion, corrosion products gradually grew into compete film to provide protection, and subsequently it was destroyed and re-built during two successive stages in cyclic pattern. This pattern was tentatively attributed to the interplay of destructive action of cathodic reaction processes and AC electric field upon protective film, together with constructive action of anodic reaction processes leading to recovery of protective film upon bare metallic surface.

Enhanced Field Emission of Single-Wall Carbon Nanotube Cathode Prepared by Screen Printing with a Silver Paste Buffer Layer.

A high emission current with relatively low operating voltage is critical for field emission cathodes in vacuum electronic devices (VEDs). This paper studied the field emission performance of single-wall carbon nanotube (SWCNT) cold cathodes prepared by screen printing with a silver paste buffer layer. The buffer layer can both enforce the adhesion between the SWCNTs and substrate, and decrease their contact resistance, so as to increase emission current. Compared with paste mixing CNTs and screen printed cathodes, the buffer layer can avoid excessive wrapping of CNTs in the silver slurry and increase effective emission area to reduce the operating voltage. The experimental results show that the turn-on field of the screen-printed SWCNT cathodes is 0.9 V/μm, which is lower than that of electrophoretic SWCNT cathodes at 2.0 V/μm. Meanwhile, the maximum emission current of the screen-printed SWCNT cathodes reaches 5.55 mA at DC mode and reaches 10.4 mA at pulse mode, which is an order magnitude higher than that of electrophoretic SWCNTs emitters. This study also shows the application insight of small or medium-power VEDs.

A novel double dielectric barrier discharge reactor with high field emission and secondary electron emission for toluene abatement

Dielectric barrier discharge (DBD) has been extensively investigated in the fields of environment and energy, whereas its practical implementation is still limited due to its unsatisfactory energy efficiency. In order to improve the energy efficiency of DBD, a novel double dielectric barrier discharge (NDDBD) reactor with high field emission and secondary electron emission was developed and compared with traditional DDBD (TDDBD) configuration. Firstly, the discharge characteristics of the two DDBD reactors were analyzed. Compared to TDDBD, the NDDBD reactor exhibited much stronger discharge intensity, higher transferred charge, dissipated power and gas temperature due to the effective utilization of cathode field emission and secondary electron emission. Subsequently, toluene abatement performance of the two reactors was evaluated. The toluene decomposition efficiency and mineralization rate of NDDBD were much higher than that of TDDBD, which were 86.44%–100% versus 28.17%–80.48% and 17.16%–43.42% versus 7.17%–16.44% at 2.17–15.12 W and 1.24–4.90 W respectively. NDDBD also exhibited higher energy yield than TDDBD, whereas the overall energy constant of the two reactors were similar. Finally, plausible toluene decomposition pathway in TDDBD and NDDBD was suggested based on organic intermediates that generated from toluene degradation. The finding of this study is expected to provide reference for the design and optimization of DBD reactor for volatile organic compounds control and other applications.

Molecular-Scale Insights into Electrochemical Reduction of CO2 on Hydrophobically Modified Cu Surfaces.

Depressing the competitive hydrogen evolution reaction (HER) to promote current efficiency toward carbon-based chemicals in the electrocatalytic CO2 reduction reaction (CO2RR) is desirable. A strategy is to apply the hydrophobically molecular-modified electrodes. However, the molecular-scale catalytic process remains poorly understood. Using alkanethiol-modified hydrophobic Cu as an electrode and CO2-saturated KHCO3 as an electrolyte, we reveal that H2O, rather than HCO3-, is the major H+ source for the HER, determined by differential electrochemical mass spectrometry with isotopic labeling. As a result, using in situ Raman, we find that the hydrophobic molecules screen the cathodic electric field effect on the reorientation of interfacial H2O to a "H-down" configuration toward Cu surfaces that corresponds to the decreased content of H-bonding-free water, leading to unfavorable H2O dissociation and thus decreased H+ source for the HER. Further, density functional theory calculations suggest that the absorbed alkanethiol molecules alter the electronic structure of Cu sites, thus decreasing the formation energy barrier of CO2RR intermediates, which consequently increases the CO2RR selectivity. This work provides a molecular-level understanding of improved CO2RR on hydrophobically molecule-modified catalysts and presents general references for catalytic systems having H2O-involved competitive HER.

The Parameters of the Field Emission Model and the Fabrication of Zinc Oxide Nanorod Arrays/Graphene Film

A large-scale growth of zinc oxide (ZnO) nanorod arrays on graphene sheets was fabricated by a hydrothermal technique, and the Fowler–Nordheim theory was used to build a model to describe the properties of the arrays’ field emission. The results indicated that the morphological characteristics of the ZnO nanorods grown on the graphene sheets can be easily tuned by varying the reaction time and concentrations of the reaction solution. The regular ordered ZnO nanorods arrays on the graphene sheets were obtained under the appropriate experimental conditions. Further, this composite cathode was demonstrated to possess excellent field emission properties due to the outstanding mechanical and electrical properties of graphene. The field emission current density of the composite cathode reached 1,448 μA cm–2 at the electric field of 16.5 V μm–1. The key parameter, field enhancement factor, reached 6,366, while the pure graphene cathode field is about 1,660. These specific nanorod arrays with enhancement of the field emission properties would be useful to sensor or modulator units for accessing networks.

Cathode-sheath model for field emission sustained atmospheric pressure discharges

The cathode-sheath region of a discharge in atmospheric pressure air with a flat copper cathode is numerically investigated by using a simple fluid model that takes into account non-local ionization. The effects of the cathode temperature are considered. Results are obtained in a wide current density range of 1–102 A/cm2, which spans from normal glow discharge, through abnormal glow discharge, up to the early stages of the arcing transition. It is shown that the glow-to-arc transition arises from a field-emission instability at the cathode when the current density is larger than ∼10 A/cm2, i.e., when the cathode field exceeds a critical value of about 45 V/μm for the conditions considered. It is also shown that the cathode temperature significantly influences the cathode-sheath region. The proposed model is validated by comparing the numerical results with available experimental data.

Proton exchange membrane fuel cells using new cathode field designs of multi‐inlet shunt intake design

This article proposes an idea of using the multi-inlet divergent inlet in proton exchange membrane fuel cell (PEMFC) to replenish the reaction gas for the main flow channel. New cathode flow field models such as the divergent flow field and the confluent flow field are developed and analyzed to mitigate some bad influences caused by the linear consumption of the reaction gas. The single layer PEMFC models are developed and simulated by using the ANSYS FLUENT software. Then, the performances and flow characteristics of PEMFC models are compared, and different inlet flow ratios are optimized in the multi-inlet design scheme. Finally, the results show good improvements of the performance and water removal effect while reducing the pressure drop.

Surface modification via silver nanoparticles attachment: An ex-situ approach for enhancing the electron field emission properties of CNT field emitters

A novel one-dimensional carbon material Known as carbon nanotubes (CNTs), having their high aspects ratio and as well as advance electrical properties which make them best candidate for cathode field emitters. In this work, we have introduced the easy and cost-effective approach to improving the CNT field emitters emission properties. Here we have modified the surface of CNT field emitter via decorating with silver nanoparticles (Ag NPs). Attachment of Ag NPs on CNT surface via thermal evaporation technique. The as-prepared samples of pristine CNTs and decorated CNTs with Ag NPs were characterized by the scanning electron microscope for morphology analysis, quality and qualitative analysis done by Raman spectroscopy. Here we have applied the Fowler Nordheim hypothesis for the analysis of electron field emission of as-prepared cathode field emitters. The turn-on (Eto) and threshold (Eth) field reduced after CNT field emitters coated with Ag NPs. The field enhancement factor (β) and emission current density (J) enhanced after coating. Ag NPs decorated/coated CNT field emitters can be utilized in field emission device applications.

Enhanced field emission properties of single-walled carbon nanotube from dip-coating catalyst

Here we use a simple method of dip-coating catalyst to prepare single walled carbon nanotube (SWCNT), and study its cathode field emission property. The field emission performances of SWCNT films are not significantly different when the hydrogen flow quantities are in the range of 10–50 sccm. SWCNT prepared by different catalyst are also used as cathode to test field emission performance. SWCNT fabricated by Mo and Co (SWCNT-MoCo) cathode has a better field emission property than SWCNT prepared by Mo, Co and Fe, with lower Eon and Eth (electric field at the emission current density of 10 μA/cm2 and 0.1 mA/cm2) of 1.95 V/μm and 2.47 V/μm, which is because that SWCNT-MoCo cathode has a higher density of field emitter, so that under the same electric field SWCNT-MoCo cathode has more tips and sites to emit electrons. This method is simple and easy to operate, and the purity of the cathode film is high, with few impurities, which can be further applied in the future.

Numerical simulation and optimization of cooling flow field of cylindrical cathode with annular magnetic field

In order to solve the problems of unstable discharge, low deposition rate and large difference in ionization rate between different targets in high power impulse magnetron sputtering, a novel cylindrical cathode with annular magnetic field based on hollow cathode effect is proposed, which can be used to produce ion beam with high ionization rate, high plasma density and no large particles. However, the traditional channel structure could not guarantee its high efficiency and uniform heat dissipation. The sealing ring may be damaged by ablation due to high power density, which restricts the further improvement of power density. Therefore, it is necessary to optimize the design of the channel structure. SolidWorks flow simulation software is used to simulate the cooling channel of plasma source. The influence of water hole structure parameters on cooling effect is analyzed, including distribution angle, hole number, diameter and inlet hole height. And the channel structure parameters are optimized. The results show that the increasing of the circumferential distribution range of the water hole is beneficial to the uniformity of heat dissipation, ensuring a large temperature difference between cooling water and copper sleeve, and strengthening heat exchange. The water inlet hole set in the upper layer of the structure is conducive to alleviating the temperature stratification phenomenon of the cooling water, so that the copper sleeve and sealing ring are in good cooling condition. Appropriately reducing the aperture is beneficial to increasing the cooling water jet velocity, enhancing the jet impact effect, and then increasing the turbulence degree, strengthening the heat transfer and improving the heat transfer efficiency. By systematically studying the influencing factors, the optimized cooling flow field structure of cylindrical cathode with an annular magnetic field is obtained. The distribution angle is 30°, the number of holes is 6, the aperture is 4 mm, and the height of water inlet hole is 36 mm. The optimized channel structure can improve the utilization rate of cooling water, obtaining better cooling effect at the same flow rate, and improving the discharge stability of the plasma source, which provides a basis for designing the cooling structure of the cylindrical cathode with annular magnetic field.

Aqueous ionic effect on electrochemical breakdown of Si-dielectric\u2013electrolyte interface

The breakdown of thin dielectric films (SiO2, Si3N4, HfO2) immersed in aqueous electrolyte was investigated. The current and the kinetics of dielectric breakdown caused by large cathodic electric field applied across the dielectric layer reveal the electrochemical nature of dielectric materials. Electrolytes play a huge role in the established dielectric-electrolyte interface with respect to the overall electrical behavior of the system. Although aqueous cations are considered as spectator ions in most electrochemical systems, in dielectric interfaces the current–potential characteristics depend on the type of cation. Computer simulation based on density functional theory and molecular dynamics showed cations affect the dielectric strength. The responses of various dielectric films to solution components provide invaluable information for dielectric-incorporated electrochemical systems.

Study of high DC voltage breakdown between stainless steel electrodes separated by long vacuum gaps

High voltage (HV) insulation across a single gap in vacuum and low-pressure gas is a critical issue in relation to the development and realization of the electrostatic accelerator for the ITER neutral beam injector (NBI) (Toigo et al 2017 New J. Phys. 19 085004). The present paper describes and analyzes the recent experimental results obtained at the High Voltage Padova Test Facility (HVPTF), the laboratory aimed at supporting the development of the prototype for the ITER NBI (De Lorenzi et al 2011 Fusion Eng. Des. 86 742–5). A voltage up to 800kVDC was achieved in the HVPTF during the experimental campaigns with a sphere-plane configurations having variable gap length (from 30 to 150 mm) and pressure ranging from high vacuum (10–7 mbar) to 10–3 mbar in argon. Such an experimental campaign represents one of the few examples where voltages higher than 500–550 kV DC are sustained by a single vacuum gap between electrodes (Rohrbach 1971 CERN Report 71-5) and therefore constitutes additional experience to improve the knowledge of voltage holding across large vacuum gaps. The results in high vacuum indicate that at the beginning of voltage conditioning the breakdown events occur at the same cathodic electric field irrespective of the electrode geometry. However, after sufficient conditioning time, the breakdown voltage distribution seems to depend also on the electric field at the anode and on the total voltage between electrodes. A benchmark between a numerical tool previously developed to predict the voltage holding in high vacuum (voltage holding prediction model, VHPM (Pilan et al 2011 Fusion Eng. Des. 86 742–5)) and the experimental results is also reported and discussed.