Rate equation theory for the hydrogenation kinetics of Mg-based materials

A uniform solid product layer normally assumed in the shrinking-core model cannot predict the kinetic transition behavior of the H₂ adsorption reactions. In this study, the concept of a uniform solid product layer has been replaced by that of the inward growth of solid products on the solid surface. A rate equation is established to calculate the inward growth of the solid product and was implemented into the shrinking-core model to calculate the H₂ adsorption kinetics for various shapes of Mg-based materials. The prediction accuracy of the developed model is verified from the detailed experimental data. To account for the external gas diffusion around the particle and the intraparticle gas diffusion, an analytical equation is derived using the Thiele modulus method. This model can be used to analyze various kinetic aspects and to analyze the effect of change in the particle microstructure on intraparticle diffusion.     

Validating the efficiency of γ-Al2O3/La0.6Sr0.4Co0.2Fe0.8O3-δ double-layer electrolyte for low temperature solid oxide fuel cell

Perovskite La_0.6Sr_0.4Co_0.2Fe_0.8O_3+δ (LSCF) as a promising cathode material possessed overwhelming electronic conduction along with certain ionic conductivity. Its strong electron conduction capability hinder the application of pure-phase LSCF as electrolyte in semiconductor membrane fuel cell (SMFC). In order to constrain the electron transport and take advantage of the decent ion conduction of LSCF, a thin layer of γ-Al₂O₃ with insulating property was added as an electron barrier layer and combine with LSCF to form a two-layer structure electrolyte. Through adjusting the weight ratio of LSCF/γ-Al₂O₃ to optimize the thickness of double layers, an open circuit voltage of 0.98 V and a maximum power density of 690 mW/cm² was received at 550 °C. At the same time, SEM, EIS and other characterization technology had proven that the LSCF/γ-Al₂O₃ bi-layer electrolyte can work efficiently at low temperature. The advantage of this work is the application of double-layer (γ-Al₂O₃/LSCF) structure electrolyte to instead of mixed material electrolyte in low-temperature solid oxide fuel cells. Structural innovation and the using of insulating materials provided clues for the further development of SMFC.     

Investigation of Ce0.9Gd0.1O2-δ dispersed Sm1.5Sr0.5NiO4+δ: Cathode for intermediate temperature solid oxide fuel cell applications

Dispersion of nanocrystalline (94–350 nm) Ce_0.9Gd_0.1O_2-δ in superfine (260–312 nm) Sm_1.5Sr_0.5NiO_4+δ using modified precipitation technique is established using X-ray powder diffraction, scanning electron microscopy and transmission electron microscopy. Presence of Ce_0.9Gd_0.1O_2-δ grains inhibits grain growth of Sm_1.5Sr_0.5NiO_4+δ, which provides morphological stability (up to 1100 °C). Ce_0.9Gd_0.1O_2-δ concentration dependent behaviours of ionic conductivity, surface exchange rate and electrode polarization resistance (R_p) of composites (determined using electrochemical impedance spectroscopy) are comprehended using percolation model. Three oxygen reduction reaction mechanisms are considered to understand electrochemical performance. Minimum R_p (0.81 Ω cm² at 700 °C) for 70Sm_1.5Sr_0.5NiO_4+δ:30Ce_0.9Gd_0.1O_2-δ is correlated to percolation threshold (optimum (i) electrochemically active sites (ii) oxygen reduction reaction kinetics, (iii) O^2- conductivity and (iv) charge transfer rate). Nano crystallite size of Ce_0.9Gd_0.1O_2-δ is crucial for enhancement in electrochemical performance. Oxygen partial pressure dependent electrochemical impedance spectroscopy studies reveal dominance of coexisting non-charge transfer oxygen adsorption/desorption and bulk O^2- diffusion.     

Efficient fault diagnosis method of PEMFC thermal management system for various current densities

The temperature of a fuel cell has a considerable impact on the saturation of a membrane, electrochemical reaction speed, and durability. So thermal management is considered one of the critical issues in polymer electrolyte membrane fuel cells. Therefore, the reliability of the thermal management system is also crucial for the performance and durability of a fuel cell system. In this work, a methodology for component-level fault diagnosis of polymer electrolyte membrane fuel cell thermal management system for various current densities is proposed. Specifically, this study suggests fault diagnosis using limited data, based on an experimental approach. Normal and five component-level fault states are diagnosed with a support vector machine model using temperature, pressure, and fan control signal data. The effects of training data at different operating current densities on fault diagnosis are analyzed. The effects of data preprocessing method are investigated, and the cause of misdiagnosis is analyzed. On this basis, diagnosis results show that the proposed methodology can realize efficient component-level fault diagnosis using limited data. The diagnosis accuracy is over 92% when the residual basis scaling method is used, and data at the highest operating current density is used to train the support vector machine.     

Effect of fiber orientation on Liquid–Gas flow in the gas diffusion layer of a polymer electrolyte membrane fuel cell

In this study, the lattice Boltzmann method was used to simulate the three-dimensional intrusion process of liquid water in the gas diffusion layer (GDL) of a polymer electrolyte membrane fuel cell (PEMFC). The GDL was reconstructed by the stochastic method and used to investigate fiber orientation's influence on liquid water transport in the GDL of a PEMFC. The fiber orientation can be described by the angle between a single fiber and the in-plane direction; three different samples were simulated for three different fiber orientation ranges. The simulated permeability correlated well with the anisotropic characteristics of reconstructed carbon papers. It was concluded that the fiber orientation had a significant effect on the liquid invasion pattern in the GDL by changing the pore shape and distribution of the GDL. The results indicated that the stochastically reconstructed GDL, taking into account the fiber orientation, better demonstrates the mass transport properties of the GDL.     

Sulphonated (PVDF-co-HFP)-graphene oxide composite polymer electrolyte membrane for HI decomposition by electrolysis in thermochemical iodine-sulphur cycle for hydrogen production

In overall iodine-sulphur (I-S) cycle (Bunsen reaction), HI decomposition is a serious challenge for improvement in H₂ production efficiency. Herein, we are reporting an electrochemical process for HI decomposition and simultaneous H₂ and I₂ production. Commercial Nafion 117 membrane has been generally utilized as a separator, which also showed huge water transport (electro-osmosis), and deterioration in conductivity due to dehydration. We report sulphonated poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-co-HFP) (SCP) and sulphonated graphene oxide (SGO) composite stable and efficient polymer electrolyte membrane (PEM) for HI electrolysis and H₂ production. Different SCP/SGO composite PEMs were prepared and extensively characterized for water content, ion-exchange capacity (IEC), conductivity, and stabilities (mechanical, chemical, and thermal) in comparison with commercial Nafion117 membrane. Most suitable optimized SCP/SGO-30 composite PEM exhibited 6.78 × 10^?2 S cm^?1 conductivity in comparison with 9.60 × 10^?2 S cm^?1 for Nafion® 117. The electro-osmotic flux ofSCP/SGO-30 composite PEM (2.53 × 10^?4 cm s^?1) was also comparatively lower than Nafion® 117 membrane (2.75 × 10^?4 cm s^?1). For HI electrolysis experiments, SCP/SGO-30 composite PEM showed good performance such as 93.4% current efficiency (η), and 0.043 kWh/mol-H₂ power consumption (Ψ). Further, intelligent architecture of SCP/SGO composite PEM, in which hydrophilic SGO was introduced between fluorinated polymer by strong hydrogen bonding, high efficiency and performance make them suitable candidate for electrochemical HI decomposition, and other diversified electrochemical processes.     

Hydrogen production costs of a polymer electrolyte membrane electrolysis powered by a renewable hybrid system

In this work, a novel approach related to the production of hydrogen using a polymer electrolyte membrane electrolysis powered by a renewable hybrid system is proposed. The investigation is carried out by establishing energy balances in the different components constituting the combined renewable system. A mathematical model to predict the production of electricity and hydrogen is proposed. The discrepancies between the numerical results and those from the literature review do not exceed 7%. The results show that the overall efficiency and the capacity factor of the combined renewable system without thermal storage are 20 and 34%, respectively. The levelized cost of hydrogen also is 6.86 US$/kg. The effect of certain physical parameters such as optical efficiency, water electrolysis temperature, unit electrolysis capital cost and solar multiple on the performance of the combined system is investigated. The results show that the performance of hydrogen production is optimal when the solar installation is three times oversized. The results also show that the levelized cost of hydrogen for the optimal sized is 4.07 US$/kg. Finally, the proposed combined system can produce low cost hydrogen and compete with hybrid sulfur thermochemical cycles, conventional photovoltaic installations, concentrated photovoltaic thermal systems and wind farms developed in all regions of the world.     

Effect of grain size on the electrical performance of BaZr0.1Ce0.7Y0.1Yb0.1O3-δ solid electrolytes with addition of NiO

In order to clarify the effect of grain size on the electrical performance of BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_3-δ (BZCYYb) solid electrolytes with addition of NiO, microcrystalline (~1.5?µm) and ultrafine-grained (~280?nm) BZCYYb electrolytes (with 1?wt% NiO) were fabricated by the conventional and two-step sintering method, respectively. The results show that compared with microcrystalline electrolytes, the ultrafine-grained electrolytes have similar grain-interior conductivities, but much lower grain-boundary conductivities, illustrating that the grain boundary is not conducive for ionic transport. As a result, the electrical conductivity of microcrystalline electrolytes (1.9?×?10^?2 S?cm^?1 at 600?°C in wet air) is higher than that of ultrafine-grained electrolytes (1.1?×?10^?2 S?cm^?1 at 600?°C in wet air). In addition, the OCV (open-circuit voltage) values of electrolyte-supported single cells show that the undesired electronic conduction exists in the electrolytes due to the BaY₂NiO₅ impurity formed by the reaction of NiO and BZCYYb. The ultrafine-grained electrolytes show lower OCV values than that of microcrystalline ones, due to the prolonged electronic transport paths. Therefore, large-grained or grain boundary-free microstructure are necessary for improving the electrical performance of BZCYYb electrolytes.     

Recent progress in LiF materials for safe lithium metal anode of rechargeable batteries: Is LiF the key to commercializing Li metal batteries?

The lithium metal battery has attracted considerable attention as the ultimate lithium secondary battery for high energy density. However, safety issues and battery performance deterioration due to the growth of lithium dendrites have hampered the practical use of lithium metal batteries. Recently, lithium fluoride has been considered as a lithium metal protective layer to solve this problem. In this review, firstly, the results of the studies on dendrites and SEI that have been carried out to date are reviewed. Secondly, the results of studies on lithium fluoride are divided into additive, artificial SEI, and other methods and the possibilities of their practical use are discussed. Finally, the significance and limitations of the lithium fluoride studies are summarized, and general conclusions and prospects for recommended research directions to accelerate the commercialization of lithium metal batteries are presented.     

Improved magnetic and electromagnetic absorption properties of xSrFe12O19/(1−x)NiFe2O4 composites

xSrFe₁₂O₁₉/(1−x)NiFe₂O₄ composites (0 ≤ x ≤ 1.0) were synthesized by using a conventional solid-state synthetic route. The results show that magnetic hysteresis loops of the xSrFe₁₂O₁₉/(1−x)NiFe₂O₄ composites are similar to those of individual component ferrites, except for the 0.1SrFe₁₂O₁₉/0.9NiFe₂O₄ and 0.3SrFe₁₂O₁₉/0.7NiFe₂O₄, suggesting that the hard/soft magnetic phases are well exchange-coupled. The saturation magnetization, coercivity, and remanent magnetization of the xSrFe₁₂O₁₉/(1−x)NiFe₂O₄ composites are increased with increasing content of SrFe₁₂O₁₉, with maximal values of 42.1 Am² kg⁻¹, 78.7 kA m⁻¹, 17.2 Am² kg⁻¹, respectively, as the content x is about 0.5. They are higher than those of the individual components, implying that interface coupling is present in the magnetic composites. The coercivity and remanent magnetization of the composites are increased initially with increasing sintering temperature and then show a downward tendency. For the component SrFe₁₂O₁₉ and NiFe₂O₄, the minimum reflection losses are −12.5 dB and −18.3 dB at match thicknesses of 2.5 mm and 2 mm, respectively. Compared with those of the component SrFe₁₂O₁₉ and NiFe₂O₄, the microwave absorption performances of the xSrFe₁₂O₁₉/(1−x)NiFe₂O₄ composites are improved remarkably, especially for the samples of x = 0.3 and x = 0.9. The minimum reflection losses values of the 0.3SrFe₁₂O₁₉/0.7NiFe₂O₄ composite are −31.6 dB (12.7 GHz) and −20.2 dB (13 GHz), while those of the 0.9SrFe₁₂O₁₉/0.1NiFe₂O₄ composites are −23.7 dB (16.3 GHz) and −33.5 dB (15.8 GHz), as the matching thicknesses are 2.5 mm and 2 mm, respectively. Therefore, the xSrFe₁₂O₁₉/(1−x)NiFe₂O₄ composites could be used as potential microwave absorption materials.