Diffusion Layer Research Articles

A unique clamping mechanism for a cylindrical PEMFC for an enhanced performance

Polymer electrolyte membrane fuel cells with planar structures have been proven beneficial; however, cylindrical cells have higher gravimetric and volumetric power density with possible applications in aviation and portable power sources. In this study, a unique clamping mechanism for a cylindrically structured polymer electrolyte membrane fuel cell is developed to improve the performance of the cell through reduced contact resistance over the active area of the cell. The design is structurally modelled and simulated for the contact pressure distribution, followed by experimental validation of contact pressure distribution at the interface of the gas diffusion layer and current collector. The study results in a lower ohmic resistance due to the better electrical contact at the interface of gas diffusion layer and current collector using the new clamping system. The average contact pressure with the new system is observed to be 0.40 MPa, i.e. 33% higher than that of the strap clamping system. In addition, the contact resistance of the cell with new clamps is found to decrease by 18 %, thus resulting in 36 % better performance (55 mW/cm2 at 0.6 V) than that of the conventional clamping system (40 mW/cm2 at 0.6 V). Such enhancement is also attributed to more oxidant supply (12%) at the cathode current collectors due to better cell clamping design.

Chromium diffusion coatings for improving the oxidation behavior of refractory metals at intermediate temperatures

Due to their very high melting points and high mechanical strength at elevated temperatures, refractory metals are promising structural materials for high temperature applications. However, their application is strongly restricted by their insufficient oxidation resistance. In this fundamental study, four different refractory metals (Mo, Nb, Ta, and W) were chromized by pack cementation to investigate the influence of chromium diffusion coatings on their oxidation resistance at intermediate temperatures. Thermodynamic calculations were used to find the most suitable conditions for the pack cementations. The formation of a homogeneous single-phase bcc Cr layer with a thickness below 10 μm on the sample surface was observed on all four refractory metals. In the case of Nb and Ta, intermetallic Cr2X-Laves phases (X = Nb, Ta) formed underneath the bcc Cr layer while an interdiffusion zone formed on Mo. The concentration profiles of the deposited Cr layers were used to determine the diffusion coefficients graphically via Boltzmann-Matano analysis. The Cr-coated samples were analyzed via thermogravimetric analysis at 700 °C and 900 °C for up to 100 h in dry synthetic air. Optical and electron microscopy, EPMA, EBSD and XRD were used to investigate the chromium diffusion layers and the oxide scales.

Thermal diffusion and microstructural evolution of Cu-Zn binary system under hypergravity

It has long been a common assumption that the stress conditions for materials operating in hypergravity could be simplified to traditional stress conditions. However, such simplification has not been experimentally verified. In this study, we examined the thermal diffusion and microstructural evolution of the Cu-Zn binary system under hypergravity levels of up to 4700 g (g: gravity of Earth, 9.8 m/s2). Our findings revealed distinct differences when compared to the behaviour of the materials under traditional stress. Under hypergravity, we observed an enhancement in interfacial diffusion of atoms up to 3500 g, and this enhancement was suppressed under 4700 g hypergravity. Additionally, a directional effect was observed, where the diffusion layer formed in hypergravity from Cu to Zn direction was thicker than that formed under the opposite direction of hypergravity. Furthermore, the reduction of dislocations in the diffusion layer was observed as the hypergravity increased. The study suggests that the hypergravity-induced centrifugal force (Fg) and buoyancy force (Fb) significantly influence the diffusion characteristics of the Cu-Zn binary system. Fg enhances interfacial contact and promotes interfacial diffusion, while Fb promotes the diffusivity of vacancies, and thereby atoms, contributing to the observed directional effects. These factors ultimately lead to the formation of a biphasic phase and the suppression of precipitation under hypergravity. Additionally, as the hypergravity increases, defects/vacancies reduce, resulting in the suppression of diffusion. Our findings provide valuable insights into the diffusion and microstructural evolution of materials under hypergravity conditions.

Effect of water salinity and sodicity on soil least limiting water range

AbstractThis study aimed to evaluate the effects of water salinity and sodicity on the least limiting water range (LLWR) of two clay loam and sandy loam soils. The undisturbed soil samples were subjected to different water qualities, including three levels of sodium adsorption ratio (SAR, 1, 5, and 12) and electrical conductivity (EC, 1, 6, and 10 dS m−1). Our findings indicate that increasing EC at each SAR led to greater soil water retention. This was attributed to salinity affecting pore size distribution toward smaller pores by altering the diffuse double layer and causing soil particle flocculation. With increasing SAR levels at each EC level, soil water content at the wilting point also rose due to structural changes, clay swelling, and dispersion, resulting in more micropores and increased adsorptive surfaces in the soil. Additionally, soil volumetric water content at a 10% air‐filled porosity decreased, while values at a critical penetration resistance of 2 MPa increased with higher bulk density across all treatments. The LLWR showed a negative correlation with bulk density in clay loam soil across all SAR and EC treatments. The LLWR increased with higher water EC but decreased with increasing water SAR. The highest LLWR was observed at SAR = 1 and EC = 10 dS m−1, while the lowest occurred at SAR = 12 and EC = 1 dS m−1. The results revealed that elevated values of SAR in irrigation water reduced soil water accessibility for plants. However, as irrigation water salinity increased, the detrimental effects of SAR diminished.

Membrane behavior of clay under mixed solution conditions

Compacted clay is employed as the buffer material for landfills, and multiple ions are dissolved in the leachate restricted by the compacted clay layer. The membrane efficiency is an important indicator to assess the barrier properties of the compacted clay layer and is measured through membrane tests. However, most membrane tests are currently conducted with a single solute solution, which does not reflect the mixed solution characteristics of leachates. To assess the membrane efficiency of compacted clay under mixed solution conditions, 13 membrane tests were conducted on a bentonite-amended soil using KCl–NaCl mixed solutions, KCl–CaCl2 mixed solutions, and KCl–AlCl3 mixed solutions with different mixing ratios at a total concentration of 20 mM. Nuclear magnetic resonance (NMR) tests were conducted on the soil specimen after the membrane tests to investigate the micromechanism of the membrane behavior under mixed solution conditions. Results indicate that the membrane efficiency increased with the mixing ratio of Na+ but decreased with the mixing ratio of Ca2+ or Al3+. In the 13 membrane tests, the lowest membrane efficiency was achieved when the specimen was tested with pure AlCl3 solution. The relationship between the membrane efficiency and mixing ratio was also investigated at the microscopic scale. As the ion valence increases, the diffuse double layer thickness is smaller and the proportion of macropores is larger, as verified by NMR tests.

Toward high stability of O3‐type NaNi1/3Fe1/3Mn1/3O2 cathode material with zirconium substitution for advanced sodium‐ion batteries

AbstractWe successfully synthesized a series of O3‐type NaNi1/3Fe1/3Mn1/3−xZrxO2 (x = 0, 0.01, 0.02, 0.04) cathode materials by the solid‐state reaction method. Energy dispersion spectroscopy, X‐ray diffraction (XRD), and X‐ray photoelectron spectroscopy results confirmed the successful incorporation of Zr elements into the lattice to substitute Mn. Due to the introduction of Zr4+, the crystal structure modulation of O3‐NaNi1/3Fe1/3Mn1/3O2 has been realized. By increasing the Zr4+ content, the width of the sodium diffusion layer expands, thereby facilitating the diffusion of sodium ions. Consequently, the material exhibits a remarkable enhancement in high‐rate capability. At the same time, increasing the Zr4+ content results in a notable decrease in both the average bond length of TM−O and the thickness of the TMO6 octahedron in the transition metal layer, resulting in a significant improvement in the cycling performance and structural stability of the cathode material. Additionally, the in‐situ XRD results demonstrate that the optimized cathode composition of O3‐NaNi1/3Fe1/3Mn1/3–0.02Zr0.02O2 (NFMZ2) undergoes a reversible phase transition of O3 → O3 + P3 → P3 → O3 + P3 → O3 during the charge–discharge process.

Interfacial Stability between High-Entropy (La0.2Yb0.2Sm0.2Eu0.2Gd0.2)2Zr2O7 and Yttria-Stabilized Zirconia for Advanced Thermal Barrier Coating Applications

(La0.2Yb0.2Sm0.2Eu0.2Gd0.2)2Zr2O7 (HEZ) has shown considerable promise as a novel thermal barrier coating material for temperatures exceeding 1300 °C. This study systematically investigates the interfacial stability of (La0.2Yb0.2Sm0.2Eu0.2Gd0.2)2Zr2O7 with yttria-stabilized zirconia (YSZ), which is of paramount importance for its application in double-layer thermal barrier coatings. Our findings highlight that rare earth elements with a smaller radius diffuse more easily into the YSZ lattice, resulting in a broader diffusion zone. Simultaneously, the incorporation of rare earth elements into the YSZ lattice inhibits tetragonal-to-monoclinic phase transformation. Compared to La2Zr2O7/YSZ, HEZ/YSZ demonstrates superior high-temperature stability, which could be attributed to the higher fracture toughness and lower thermal expansion coefficient of HEZ, the absence of t-m transformation and the formation of a continuous gradient diffusion layer that minimizes interface stress. This study offers a practical strategy for designing materials for durable double-layer thermal barrier coating systems.

Polysulfide-mediated solvation shell reorganization for fast Li+ transfer probed by in-situ sum frequency generation spectroscopy

Understanding of interfacial Li+ solvation shell structures and dynamic evolution at the electrode/electrolyte interface is requisite for developing high-energy-density Li batteries. Herein, the reorganization of Li+ solvation shell at the sulfur/electrolyte interface along with the presence of a trace amount of lithium polysulfides is verified by in-situ sum frequency generation (SFG) spectroscopy together with density functional theory (DFT) calculations. Both the spectroelectrochemical and DFT calculation results reveal a strongly competitive anion adsorption of the polysulfide anion additive against the pristine electrolyte anion on the sulfur cathode surface, reorganizing the interfacial local solvation shell structure facilitating rapid Li ion transfer and conduction. Meanwhile, the evolution of the SFG signals along with the discharging/charging cycle exhibits improved reversibility, indicating the transformation of the inner Helmholtz plane layer into a stable molecular-layer polysulfide interphase rather than a dynamic diffusion layer. Consequently, applications in practical Li-S batteries reveal the capacity and cycling stability of the corresponding cells are significantly enhanced. Our work provides a methodology using in-situ SFG for probing solvation reorganization of charge carriers at electrochemical interfaces.

Determining Liquid Limit and Plastic Limit of Clay Soils by Electrical Surface Conduction and Diffuse Double Layer Thickness

The aim of this study was to propose a new approach to determine the liquid limit and plastic limit of clay soils by considering electrical conductivity (EC) measurements. The proposed method included incorporating a new parameter, F, which is the ratio of the volumetric water contents of diffuse double layer (DDL) water and free water. In addition, the EC parameter, σ, was considered as the ratio of electrical surface conductivity and electrical conductivity of water. The changes in the thickness of DDL (χ) were also assessed to obtain corresponding equations to establish a connection with clay mineralogy, water content, and specific gravity in the final prediction. Three-dimensional surface analyses were conducted to find a correlation among F, σ, and χ to identify an appropriate method to predict liquid limit and plastic limit. The study was conducted with 39 different types of samples, and the outcomes from the EC approach were validated against the conventional methods. Overall, the coefficient of determination, R2 = 0.90, and Lin’s concordance correlation coefficient, (LCCC) = 0.91, were obtained for liquid limit prediction, whereas R2 = 0.64 and LCCC = 0.80 were obtained for plastic limit determination.

Synergistic Fe and Co binary single atoms based air cathodes for high performance and ultra-stable Zn-air batteries

Cost-effective highly efficient and stable air cathodes are critical for practical applications of rechargeable Zn-air batteries (ZABs). In this work, air cathodes constructed by loading carbon nanotube supported N-doped carbon anchored Fe and Co binary single atoms, f-Fe1Co1/CNT, in carbon paper composited nickel foams, NF/CP, were developed for ZABs, exhibiting outstanding bifunctional oxygen electrocatalytic activities (ΔE = 0.671 V) with a half-wave potential (E1/2) of 0.880 V (vs. RHE) for oxygen reduction reaction (ORR) and an overpotential of 321 mV at 10 mA cm−2 (η10) for oxygen evolution reaction (OER) in 0.1 M KOH, which outperformed the benchmark (Pt/C+IrO2)-based air cathode (ΔE = 0.773 V, E1/2 = 0.850 V, η10 = 393 mV). With the unique air cathode design of compositing catalyst-loading layer (nickel foam) with gas diffusion layer (carbon paper), the f-Fe1Co1/CNT@NF/CP//Zn ZAB delivered a remarkable discharge peak power density of 282.1 mW cm−2 at an ultra-high current density of 427.7 mA cm−2 and maintained an ultra-small potential gap of 0.75 V after operations at 10 mA cm−2 for 3300 cycles (1100 h), largely outperforming the (Pt/C+IrO2)@NF/CP//Zn ZAB (162.4 mW cm−2 at 247.3 mA cm−2, 0.86 V, 590 cycles). Density functional theory calculations revealed the positive long-range synergy between Fe-N4 and Co-N4 single atoms, significantly reducing the free energies of the rate-determining steps, oxygen protonation for ORR and formation of oxyhydroxides for OER at the main active site Fe-N4, to realize the much enhanced oxygen electrocatalytic activities.

Fines migration characteristics of illite in clayey silt sediments induced by pore water under the depressurization of natural gas hydrate

Marine gas hydrate is widely distributed in clayey silt sediments, which have high clay content and low permeability. The decomposition of natural gas hydrate will cause the mechanical failure of the reservoir and the decrease of pore water salinity, inducing the migration of clay minerals to clog the pore throat, which has a significant impact on the production efficiency of natural gas hydrate. In this work, the migration behaviour of illite in clayey silt sediments driven by pore water under the depressurization of hydrate was studied through pressure difference, pore throat and content changes. We studied the migration process of silt, excluding the interference of synergistic migration of silt and illite, and then studied the migration of illite under the change of flow rate and salinity. The results show that illite will migrate before silt and that critical flow rate and critical salinity exist. The flow rate mainly affects the torque generated by the forces detaching the illite particles. Illite particle detachment will occur if the flow rate exceeds the critical value and the torque balance is disrupted, and then the pore throat is clogged. There are two effects of salinity decrease on illite migration. Above the critical salinity, the expansion of the pore throat due to decomposition has a significant effect on illite migration. Below the critical salinity, the increase of the diffuse electric double layer thickness and the electrostatic repulsion will lead to an increase of the particle concentration in the pore water, making clogging more likely to occur even at low flow rates. This work suggests that clay migration has a complex impact on the development of clayey silt hydrate, and helps to consider the reasonable combination of saturation and production rate when designing a development plan to reduce the impact of permeability decline due to continuous pore throat clogging on development efficiency.

Solar to hydrogen conversion by a 25 cm2-photoelectrochemical cell with upscaled components

An innovative tandem photoelectrochemical cell with a scaled-up active area from 0.25 to 25 cm2 based on low-cost and non-critical raw materials was employed to produce green hydrogen by water splitting. It uses a photoanode/membrane/photocathode tandem cell configuration in which a hematite-based photoanode is layered on a fluorine-doped tin oxide glass for the oxygen evolution reaction, CuO is deposited on a hydrophobic gas diffusion layer as the photocathode for the hydrogen evolution reaction and an anion exchange membrane is used as the electrolyte and gas separator. The solid membrane's low hydrogen and oxygen crossover guarantees the operational stability of the tandem photoelectrochemical cell and the efficient separation of water-splitting products. Significant efforts have been focused on scaling up the cell. It has allowed obtaining, for the first time, a 25 cm2 unit cell prototype. Appropriate design approaches have been considered to optimise water/gas management, current collection, gas-tightness and clamping. The adopted architecture allowed for the reduction of the bias-potential from −1.23 V, generally employed to investigate PEC cells, up to −0.6/-0.4 V 20 h-durability tests demonstrated good resistance to corrosion, showing a constant photocurrent. Efficiency at −0.6 V was about 0.2%. Selective hydrogen production was demonstrated by mass spectrometric analysis.

Patterned hydrophobic gas diffusion layers for enhanced water management in polymer electrolyte fuel cells

Flooding of the cathode due to water accumulation is one of the biggest limiting factors in the performance of polymer electrolyte fuel cells (PEFCs). This study therefore attempts to solve this issue by fabricating gas diffusion layers (GDLs) with differently patterned hydrophobic regions. The GDLs in three different patterns (triangular, diamond, and inverted-triangular) were prepared by brushing a Polytetrafluoroethylene (PTFE) solution onto commercial carbon papers through a mask and tested in PEFCs. The patterned GDLs results in superior performance in all cases compared to a uniformly PTFE-treated GDL. Notably, the oxygen transport resistance is significantly reduced, indicating that the water accumulation in the cathode is avoided. This is attributed to the patterned hydrophobicity gradient providing distinct pathways for water and oxygen. The GDL with triangular patterning displays the highest peak power density, due to the fact that the untreated less hydrophobic region is in direct contact with the cathode outlet in this case, facilitating the removal of excess liquid water. Overall, the study confirms that the GDLs with patterned hydrophobicity could be used to enhance the performance of commercial PEFC systems by facilitating water management, potentially leading to improved efficiency and durability.

Thioacetamide Additive Homogenizing Zn Deposition Revealed by In Situ Digital Holography for Advanced Zn Ion Batteries

HighlightsDigital holography can realize the in situ observation of electrode/electrolyte interface and provide dynamic evolution information of the liquid phase of electrode, which is both efficient and effective in investing the interficial electrochemical mechanism and screening electrolyte additives.Thioacetamide electrolyte additive effectively enhances the electrochemical performance of Zn anode by regulating the interficial ion flux to induce dendrite-free Zn deposition and constructing adsorption molecule layers to inhibit side reactions.

In Situ Heterodyne-Detected Second-Harmonic Generation Study of the Influence of Cholesterol on Dye Molecule Adsorption on Lipid Membrane.

Cholesterol plays an essential role in regulating the functionality of biomembranes. This study employed in situ second-harmonic generation (SHG) to investigate the adsorption behavior of the dye molecule 4-(4-(diethylamino)styryl)-N-methyl-pyridinium iodide (D289) on a biomimic membrane composed of 1,2-dipalmitoyl-sn-glycero-3-phospho-(1'-rac-glycerol) (sodium salt) (DPPG) and cholesterol. The time-dependent polarization SHG intensity exhibited an initial rapid increase, followed by a subsequent decline. The initial increased SHG intensity is responsible for the electrostatic interaction-driven adsorption of D289 onto the membrane, while the decrease in the SHG signal results from the broadening of the orientation distribution within the membrane. Heterodyne-detected SHG (HD-SHG) measurements demonstrated that the adsorption of dye molecules influenced the phase of the induced electric field. The interfacial potential Φ(0) as a function of time was measured, and we found that even after reaching a stable Stern layer state, the diffusion layer continued to exhibit a dynamic change. This study offers a comprehensive understanding of the influence of cholesterol on adsorption, reorientation dynamics, and dynamic changes in the reorientation of water in the diffusion layer.

Analytical solutions for viscoelectric effects in electrokinetic nanochannels.

Understanding electrokinetic transport in nanochannels and nanopores is essential for emerging biological and electrochemical applications. The viscoelectric effect is an important mechanism implicated in the increase of local viscosity due to the polarization of a solvent under a strong electric field. However, most analyses of the viscoelectric effect have been limited to numerical analyses. In this work, we present a set of analytical solutions applicable to the physical description of viscoelectric effects in nanochannel electrokinetic systems. To achieve such closed-form solutions, we employ the Debye-Hückel approximation of small diffuse charge layer potentials compared to the thermal potential. We analyze critical parameters, including electroosmotic flow profiles, electroosmotic mobility, flow rate, and channel conductance. We compare and benchmark our analytical solutions with published predictions from numerical models. Importantly, we leverage these analytical solutions to identify essential thermophysical and nondimensional parameters that govern the behavior of these systems. We identify scaling parameters and relations among surface charge density, ionic strength, and nanochannel height.

Lead (II) ions enable the ion-specific effects of monovalent anions on the molecular structure and interactions at silica/aqueous interfaces

HypothesisThe adsorption of heavy metal ions such as Pb(II) onto negatively charged minerals such as silica is expected to alter the structure and the interactions at the silica/aqueous interfaces. Besides the solution pH, the inner-sphere sorption of Pb(II) is expected to regulate the surface charge/potential, hypothesized to control the actions of monovalent anions in the aqueous environment. These complex pictures can be probed directly using surface-sensitive sum-frequency generation (SFG) spectroscopy. ExperimentsThe pH-dependent water structure within the double layer at silica/aqueous interfaces under the influence of different ions was examined using SFG. The recorded SFG spectra were deconvoluted into the Stern layer (SL) and diffuse layer (DL) using the maximum entropy method in conjunction with the electrical double-layer theory. FindingsStandalone monovalent sodium salts do not exhibit ion-specific effects on the silica/aqueous interfaces. However, the mixture of Pb(II) species and each of these salts display profound ion-specific effects on the structure of silica/aqueous interfaces, indicating the role of Pb(II) as an enabler of the ion-specificity of the investigated monovalent anions. The interesting effect arises from a complex interplay between the physical processes (i.e., electrostatic interactions, screening effects, etc.) and chemical processes such as the hydrolysis of Pb(II) ions, ion complexation, protonation and deprotonation of the surface silanol group.

Effects of Inhomogeneous Gas Diffusion Layer Properties on the Transportation Phenomenon and Performances of Proton-Exchange Membrane Fuel Cells.

The encapsulation of the proton-exchange membrane fuel cell (PEMFC) is an essential step of fuel cell stack assembly. The selection of the assembly pressure is very important to the stack performance and life. Based on that, this paper presents a method to describe the internal physical deformation of the gas diffusion layer (GDL) after inhomogeneous pressure by using user-defined functions (UDFs). The results show that the transmission difference caused by the nonuniform GDL deformation can be clearly seen by the UDFs method, and there is an obvious transition of GDL at the interface of the channel and the rib. A three-dimensional single-channel PEMFC model is established, and an optimal assembly pressure range is obtained, between 1.5 and 2.0 MPa. The maximum thermal stress inside the cell occurs in the middle of the membrane electrode assembly and decreases as the assembly pressure increases. Furthermore, the influence of rib-channel ratios is discussed. Compared to the fuel cells with ratios of 2:1, 2:3, and 1:2, the one with 1:1 exhibits the maximum current density and the highest power density.

Pore-scale study of water and mass transport characteristic in anion exchange membrane fuel cells with anisotropic gas diffusion layer

The complicated microporous structure and spatial distribution characteristics of the gas diffusion layer have crucial impacts on the water management of an anion-exchange membrane fuel cell, in which water is produced at the anode and consumed at the cathode. Consequently, a three-dimensional pore network model is developed to numerically simulate hydrogen transport and liquid water removal in the anode gas diffusion layer. Anisotropy is an important property of the gas diffusion layer, and the quasi-static two-phase transport within the anisotropic GDL is investigated from various perspectives. Pore-scale simulations demonstrate that the variation of the relative diffusion coefficient with saturation can be described as g(S)= (1-S)2.3, and the relative permeability varies with saturation in the range of S1.5 and S3. What's more, high anisotropy has a positive effect on both hydrogen and liquid water transport, if the anisotropy parameter is increased from 1 to 1.55, the relative diffusion coefficient and water permeability at all thicknesses are increased by more than 11% and 16%, respectively. However, in practice, high anisotropy is detrimental to the liquid water removal under the rib. Moreover, wettability distribution has a negligible effect on two-phase transport within the highly anisotropic GDL, while the effect of thickness remains significant.

Microstructure and Mechanical Properties of Electrically Assisted Brazing Joints of Dissimilar Aluminum and Steel Alloys

The microstructure and mechanical properties of electrically assisted brazing (EA-brazing) joints of aluminum alloy 6061-t6 (AA6061-t6) and S45C steel are experimentally investigated. During the EA-brazing process, an electric current is directly applied to the cylindrical specimen assembly (S45C and AA6061-t6) and fillers of 88% Al and 12% Si (in the middle of the specimen assembly). The temperature of the specimen assembly rises rapidly to the melting point of the filler and remains nearly constant for a period of time using a pulsed electric current. Two types of EA-brazing joints are fabricated, namely Joint-0s (no temperature holding time) and Joint-12s (12 s temperature holding time). The characteristics of the intermetallic compounds (IMCs) formed at the EA-brazing joint interface are analyzed using scanning electron microscopy and energy dispersive spectrometer. Compared to Joint-0s, the Fe-rich IMCs (FeAl) are observed at the interface of Joint-12s due to the 12 s temperature holding time. In addition, the microstructural analysis shows that the thickness of the diffusion layer increases with increasing temperature holding time. The mechanical properties of the EA-brazing joints are evaluated using bending tests. The results of the mechanical test show that the strength of Joint-12s is higher than that of Joint-0s.