In situ synthesis of Al2O3–SiC powders via molten-salt-assisted aluminum/carbothermal reduction method

Al₂O₃–SiC composite powder (ASCP) was successfully synthesized using a novel molten-salt-assisted aluminum/carbothermal reduction (MS-ACTR) method with silica fume, aluminum powder, and carbon black as raw materials; NaCl–KCl was used as the molten salt medium. The effects of the synthesis temperature and salt-reactant ratio on the phase composition and microstructure were investigated. The results showed that the Al₂O₃–SiC content increased with an increase in molten salt temperature, and the salt–reactant ratio in the range of 1.5:1–2.5:1 had an impact on the fabrication of ASCP. The optimum condition for synthesizing ASCP from NaCl–KCl molten salt consisted of maintaining the temperature at 1573 K for 4 h. The chemical reaction thermodynamics and growth mechanism indicate that the molten salt plays an important role in the formation of SiC whiskers by following the vapor-solid growth mode in the MS-ACTR treatment. This study demonstrates that the addition of molten salt as a reaction medium is a promising approach for synthesizing high-melting-point composite powders at low temperatures.     

Raman spectroscopy of SrZrO3 based proton conducting electrolyte: Effect of Y-doping and Sr-nonstoichiometry

The present research describes the results of Raman spectroscopic study of undoped and Y-doped SrZrO₃ having a great potential for application in proton-conducting fuel cells. Effects of yttrium doping and strontium nonstoichiometry on the local environment of cations and vibrational properties of strontium zirconate were investigated. Ceramic samples Sr_yZr_1-xY_xO_3-δ (x = 0, 0.02, 0.05; y = 0.94, 0.98, 1.00) were synthesized via a chemical solution method and sintered at 1650 °C. Microstructure, phase and chemical composition of the samples were characterized by Scanning Electron Microscopy (SEM), X-ray diffraction (XRD) and Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). Analysis of Raman spectra peculiarities upon changes in Sr- and Y- concentrations has shown that yttrium ions can be partitioned over both A- and B-sites in the strontium-deficient zirconates with the dopant concentrations more than 2 at%.     

Single chamber Solid Oxide Fuel Cells selective electrodes: A real chance with brownmillerite-based nanocomposites

In this contribution brownmillerite-based nanocomposite cathode for Single-Chamber Solid Oxide Fuel Cells is developed. These cells can be very attractive especially for small and cheap devices because of the absence of seals. The efficiency of SC-SOFCs is strictly connected to the selectivity of anode and cathode, the bottleneck for this technology. The development of a cathode inert in fuel oxidation is particularly challenging. Our strategy is to start from a catalytically un-active support (CFA = Ca₂FeAl_0.95Mg_0.05O₅) and induce the formation of iron oxide based nanoparticles, expected to activate oxygen. Symmetric (CFA + FeO_x/CGO/CFA + FeO_x) and complete cells (CFA + FeO_x/CGO/Ni-CGO) are studied in air and methane/oxygen 2:1 mixture. The Area Specific Resistance of CFA + FeO_x is less than 1/3 that of CFA. The high selectivity allows to reach an efficiency of 25%; power still needs to be increased but we demonstrated the possibility to develop selective low cost electrodes. The effect of air, methane/oxygen exposure and the heat treatments were carefully investigated.     

Multi-objective optimization of hybrid PEMFC/Li-ion battery propulsion systems for small and medium size ferries

Hybrid Polymer Electrolyte Membrane Fuel Cells/Lithium-ion battery powertrains are a promising solution for zero-local-emissions marine propulsion. The present study aims to optimize the design and operation of such hybrid powertrain for small-size passenger ferries, taking into account the performance degradation of both fuel cells and batteries. A Mixed-Integer Linear-Programming approach and a hierarchical method are adopted to concurrently minimize the fuel cells degradation, the capital expenditure and the operating expenditure, while constraints are included in the model to limit the battery degradation. The results show that the proposed multi-objective optimization can lead to a reduction of fuel cells degradation by up to 65% compared to a cost-minimization only. However, this can imply an increase in the battery capacity by up to 136%. The proposed method has general validity, and it is a useful tool for both preliminary design and choice of the optimal energy management strategy for ships energy systems.     

Investigation of surficial and interfacial properties of BaCo0.4Fe0.4Zr0.1Y0.1O3-δ cathode directly on yttria-stabilized zirconia electrolyte for solid oxide fuel cell

The cobalt/iron-containing perovskites are the most promising cathodes for the intermediate-temperature solid oxide fuel cell (IT-SOFC). However, these cathodes are generally not directly applied on the currently available commercial yttria-stabilized zirconia (YSZ) electrolyte due to the issues of over-firing, harmful reaction and thermal incompatibility. BaCo_0.4Fe_0.4Zr_0.1Y_0.1O_3-δ (BCFZY) which contains both zirconium and yttrium ions can theoretically be more compatible with the YSZ electrolyte. This paper focuses on the surficial and interfacial properties of BCFZY directly prepared with YSZ under different conditions. The surface of BCFZY by the glycine-nitrate process (GNP) can form the nanoparticles in contrast to that by solid-state reaction (SSR). The peak power density of the cell with BCFZY-GNP cathode directly on YSZ electrolyte can reach 1250 mW cm⁻² at 750 °C, which is hardly achieved on the reported traditional cobalt/iron-containing cathodes. It is proved that BCFZY-GNP cathode fired at 900 °C can show more distinct nanoparticles with extensive specific surface area and better BCFZY|YSZ interface, which can promote both oxygen exchange and ion incorporation processes.     

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.     

A polyanionic anthraquinone organic cathode for pure small-molecule organic Li-ion batteries

Sodium 9,10-anthraquinone-2,6-disulfonate (Na₂AQ26DS, 130 mAh g⁻¹) with polyanionic character and two O–Na ionic bonds is used as an organic cathode for Li-ion batteries. Na₂AQ26DS exhibits highly impressive cycle stability in ether electrolytes due to its polyanionic character and the effective suppression of solvent-molecule co-intercalation. In half cells (1–3.9 V vs. Li⁺/Li) using 1 M bis(trifluoromethanesulphonyl)imide lithium salt (LiTFSI) in 1,3-dioxolane/dimethoxyethane (DOL/DME), Na₂AQ26DS delivers a highly stable specific capacity of 123 mAh g⁻¹ at 50 mA g⁻¹ for 900 cycles (6-month test) and realizes ∼69 mAh g⁻¹ for 2800 cycles at 500 mA g⁻¹. In the full cells with the reduced state (Li₄TP) of lithium terephthalate (Li₂TP) as the organic anode, the resulting Li₄TP II Na₂AQ26DS organic lithium-ion batteries (OLIBs) can display a highly stable average discharge capacity of 120 mAh g⁻¹_cathode for 100 cycles at 50 mA g⁻¹ and ∼63 mAh g⁻¹_cathode for 1200 cycles at 500 mA g⁻¹ in 0.2–3.3 V.     

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.