Nano-sized Fe2O3–SO4 solid superacid composite Nafion membranes for direct methanol fuel cells

In this paper, Fe₂O₃–SO₄²⁻/Nafion^® composite membranes were prepared by a solution casting method. The physico-chemical properties of composite membranes were characterized by X-ray diffraction (XRD), SEM–EDX and thermogravimetric analysis (TGA). The water uptake ability, proton conductivity, and methanol permeability of the composite membranes were evaluated and compared with the recast Nafion^® membrane. The results showed that the proton conductivity and the water uptake of the composite membranes were slightly higher than that of the recast Nafion^® membrane. The composite membrane containing 5 wt.% Fe₂O₃–SO₄^2- showed superior ability to suppress methanol crossover, and it further improved the direct methanol fuel cell (DMFC) performances with both 1 M and 5 M methanol feeding, compared with the recast Nafion^® membrane. The preliminary 30 h lifetime test of the DMFC with the composite membrane with 5% Fe₂O₃–SO₄²⁻ indicated that the composite membrane is stable working at the real DMFC operating conditions at least during the test. These results suggest the applicability of the composite membranes in DMFCs.     

ZrO2–SiO2/Nafion composite membrane for polymer electrolyte membrane fuel cells operation at high temperature and low humidity

Recast Nafion^® composite membranes containing ZrO₂–SiO₂ binary oxides with different Zr/Si ratios are investigated for polymer electrolyte membrane fuel cells (PEMFCs) at temperatures above 100 °C. Fine particles of the ZrO₂–SiO₂ binary oxides, same as an inorganic filter, are synthesized from a sodium silicate and a carbonate complex of zirconium by a sol–gel technique. The composite membranes are prepared by blending a 10% (w/w) Nafion^®-water dispersion with the inorganic compound. All composite membranes show higher water uptake than unmodified membranes, and the proton conductivity increases with increasing zirconia content at 80 °C. By contrast, the proton conductivity decreases with zirconia content for the composite membranes containing binary oxides at 120 °C. The composite membranes are tested in a 9-cm² commercial single cell at both 80 °C and 120 °C in humidified H₂/air under different relative humidity (RH) conditions. Composite membrane containing the ZrO₂–SiO₂ binary oxide (Zr/Si = 0.5) give the best performance of 610 mW cm⁻¹ under conditions of 0.6 V, 120 °C, 50% RH and 2 atm.     

Al–Li3AlH6: A novel composite with high activity for hydrogen generation

A novel material for hydrogen generation with high capacity of H₂ generation has been successfully prepared by ball milling the mixture of Al and home-made fresh Li₃AlH₆ powder. Its theoretical capacity of hydrogen released is higher than that of pure Al. Results obtained have shown conversion efficiency of Al–Li₃AlH₆ composite can be close to 100% by increasing the content of Li₃AlH₆. When the content of Li₃AlH₆ is 20 wt%, the maximum hydrogen generation rate and hydrogen yield are 2737.6 mL g⁻¹ min⁻¹ and 1513.1 mL g⁻¹, respectively, at room temperature. By XRD, SEM analyses and reaction heat measurements, it demonstrates that the additive Li₃AlH₆ can provide an additional source of H₂ and an alkaline environment (LiOH) as well as additional heat to promote the Al/H₂O reaction. Therefore, the Al–Li₃AlH₆ composite has a very high activity and high capacity of hydrogen released.     

Catalytic effect of MgFe2O4 on the hydrogen storage properties of Na3AlH6–LiBH4 composite system

The effect of MgFe₂O₄ on the hydrogen storage properties of the composite Na₃AlH₆4LiBH₄ was studied for the first time, where it was found that MgFe₂O₄ addition decreased the onset desorption temperature of Na₃AlH₆4LiBH₄. Hydrogen (～9.5 wt%) was released in three stages and the dehydrogenation temperatures were reduced to 80 °C, 350 °C, and 430 °C for the first, second, and third stage, respectively. The absorption kinetics of Na₃AlH₆4LiBH₄ was also significantly improved due to the catalytic effect of MgFe₂O₄. Using Kissinger analysis, the apparent activation energies of decomposition of the Li₃AlH₆ and NaBH₄ stages in Na₃AlH₆4LiBH₄-10 wt% MgFe₂O₄ were calculated to be 72 and 141 kJ/mol, respectively. These values were considerably lower than the corresponding values for the undoped composite. X-ray diffraction analysis revealed the formation of new products such as MgO and Fe during the heating process. Our results suggest that MgFe₂O₄ enhanced the hydrogen storage properties of Na₃AlH₆4LiBH₄ through the formation of active species, such as MgO and Fe.     

A novel doped CeO2–LaFeO3 composite oxide as both anode and cathode for solid oxide fuel cells

A novel composite oxide Ce(Mn,Fe)O₂-La(Sr)Fe(Mn)O₃ (CFM-LSFM) was synthesized and evaluated as both anode and cathode materials for solid oxide fuel cells. The cell with CFM-LSFM electrodes was fabricated by tape-casting and screen printing technique. The power-generating performance of this cell was comparable to that of the cell with Ni-SSZ anode and LSM-SSZ cathode. During the 120 h long-term test in hydrogen at 800 °C, the performance increased by 8.6% from 256 to 278 mW cm⁻². This was attributed to the decrease of polarization resistance and ohmic resistance during the test. The XRD results showed the presence of Fe, MnO and some unknown second phases after heat-treating the electrode materials in H₂ which may be beneficial to the anode electrochemical process. The gradual decrease of polarization resistance as increasing the current density possibly resulted from the increasing content of water in the anode.     

Nafion/Pd–SiO2 nanofiber composite membranes for direct methanol fuel cell applications

One of the major challenges for direct methanol fuel cells is the problem of methanol crossover. With the aim of solving this problem without adverse effects on the membrane conductivity, Nafion/Palladium–silica nanofiber (N/Pd–SiO₂) composite membranes with various fiber loadings were prepared by a solution casting method. The silica-supported palladium nanofibers had diameters ranging from 100 nm to 200 nm and were synthesized by a facile electro-spinning method. The thermal properties, ionic exchange capacities, water uptake, proton conductivities, methanol permeabilities, chemical structures, and micro-structural morphologies were determined for the prepared membranes. It was found that the transport properties of the membranes were affected by the fiber loading. All of the composite membranes showed higher water uptake and ion exchange capacities compared to commercial Nafion 117 and proved to be thermally stable for use as proton exchange membranes. The composite membranes with optimum fiber content (3 wt%) showed an improved proton conductivity of 0.1292 S cm⁻¹ and a reduced methanol permeability of 8.36 × 10⁻⁷ cm² s⁻¹. In single cell tests, it was observed that, the maximum power density measured with composite membrane is higher than those of commercial Nafion 117.     

High-performance SOFC based on a novel semiconductor-ionic SrFeO3-δ–Ce0.8Sm0.2O2-δ membrane

The semiconductor-ionic composite membrane has been recently developed for a novel solid oxide fuel cell (SOFC), i.e., the semiconductor-ion membrane fuel cell (SIMFC). In this work, the perovskite-type SrFeO_3-δ (SFO) as semiconductor material was composited with ionic conductor Ce_0.8Sm_0.2O_2-δ (SDC) to form the SFO-SDC composite membrane for SIMFCs. The SFO-SDC SIMFCs using the optimized weight ratio of 3:7 SFO-SDC membrane obtained the best performances, 780 mW cm^?2 at 550 °C, compared to 348 mW cm^?2 obtained from the pure SDC electrolyte fuel cell. Introduction of SFO into SDC can extend the triple phase boundary and provide more active sites for accelerating the fuel cell reactions, thus significantly enhanced the cell power output. Moreover, SFO was employed as the cathode, and a higher power output, 907 mW cm^?2 was achieved, suggesting that SFO cathode is more compatible for the SFO-SDC system in SIMFCs. This work provides an attractive strategy for the development of low temperature SOFCs.     

Electroplated Ni–Fe2O3 composite coating for solid oxide fuel cell interconnect application

Ni–Fe₂O₃ composite coating was applied onto ferritic stainless steel using the cost-effective method of electroplating for intermediate temperature solid oxide fuel cell (SOFC) interconnects application. By comparison, the coated and bare steels were evaluated at 800 °C in air corresponding to the cathode environment of SOFC. The oxidation investigations indicated that the oxidation rate of the coated steel was close to that of the bare steel after initially rapid mass gain. The mass gain of the coated steel was higher than that of the bare steel owing to the formation of double-layer oxide structure with an outer layer of (Ni,Fe)₃O₄/NiO atop an inner layer of Cr₂O₃. The area specific resistance (ASR) of the double-layer oxide scale was lower than that of the Cr₂O₃ scale thermally grown on the bare steel.     

B2O3-free SiO2–Al2O3–SrO–La2O3–ZnO–TiO2 glass sealants for intermediate temperature solid oxide fuel cell applications

In this study, the chemical and thermal stabilities of eleven B₂O₃-free SiO₂–Al₂O₃–SrO–La₂O₃–ZnO–TiO₂ glasses were investigated, and the adhesion and sealing properties of the glasses with respect to Gd_0.2Ce_0.8O_2−δ (GDC) electrolyte and SUS 430 stainless steel (SUS430) were evaluated for use in intermediate temperature solid oxide fuel cells (ITSOFCs). It was found that the major crystallites formed in the glasses were initiated during the joining process at 950 °C, and only slight changes were observed in the intensity of crystallite peaks for the glasses subsequently soaked at 700 °C for 200 h. Experiments on the glass sandwiched with GDC electrolyte and SUS430 indicated that the SALSTi11 and SALSZT10 glasses provided good adhesion along the interfaces after heat treatment. According to the results of leakage test, the seals with the SALSTi11 and SALSZT10 glasses at 700 °C for a duration of 500 h showed good thermal stability with low leak rates of 0.007 and 0.003 sccm/cm at 0.5 psi, respectively. This property indicates a highly promising long-term thermal stability qualifying the sealing materials for ITSOFC applications.     

Rehydrogenation and cycle studies of LiBH4–CaH2 composite

Rehydrogenation behavior of 6LiBH₄ + CaH₂ composite with NbF₅ has been studied between 350 and 500 °C after dehydrogenation at 450 °C. The composite exhibits the best rehydrogenation feature at 450 °C in terms of the overall rehydrogenation rate and the amount of absorbed hydrogen. It is found that about 9 wt% hydrogen is absorbed at 450 °C for 12 h. Up to 10 dehydrogenation–hydrogenation cycles have been carried out for the composite. It is demonstrated that 6LiBH₄ + CaH₂ with 15 wt% NbF₅ maintains a reversible hydrogen storage capacity of about 6 wt% at 450 °C after a slight degradation between the 1st and 5th cycles. The addition of NbF₅ seems to improve the cycle properties by retarding microstructural coarsening during cycles.     

Thermophysical properties and devitrification of SrO–La2O3–Al2O3–B2O3–SiO2-based glass sealant for solid oxide fuel/electrolyzer cells

Thermal behaviors and stability of glass/glass–ceramic-based sealant materials are critical issues for high temperature solid oxide fuel/electrolyzer cells. To understand the thermophysical properties and devitrification behavior of SrO–La₂O₃–Al₂O₃–B₂O₃–SiO₂ system, glasses were synthesized by quenching (25 − X)SrO–20La₂O₃–(7 + X)Al₂O₃–40B₂O₃–8SiO₂ oxides, where X was varied from 0.0 mol% to 10.0 mol% at 2.5 mol% interval. Thermal properties were characterized by dilatometry and differential scanning calorimetry (DSC). Microstructural studies were performed by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and X-ray diffraction (XRD). All the compositions have a glass transition temperature greater than 620 °C and a crystallization temperature greater than 826 °C. Also, all the glasses have a coefficient of thermal expansion (CTE) between 9.0 × 10⁻⁶ K⁻¹ and 14.5 × 10⁶ K⁻¹ after the first thermal cycle. La₂O₃ and B₂O₃ contribute to glass devitrification by forming crystalline LaBO₃. Al₂O₃ stabilizes the glasses by suppressing devitrification. Significant improvement in devitrification resistance is observed as X increases from 0.0 mol% to 10.0 mol%.     

SiO2–Al2O3–Y2O3–ZnO glass sealants for intermediate temperature solid oxide fuel cell applications

In this study, eleven alkaline earth metal and B₂O₃-free SiO₂–Al₂O₃–Y₂O₃–ZnO glass sealants were prepared. The thermal stability, adhesion, and sealing properties of the glass systems with respect to SUS430 stainless steel (SUS430) were assessed for use in intermediate temperature solid oxide fuel cells (ITSOFCs). The glass transition points fell in the range of 694 °C and 833 °C, while the glass softening points, varying from 725 °C to 885 °C, decreased linearly with the ZnO/SiO₂ ratio. Among the glasses evaluated, the YAS1-50, YAS4-50, YAS5-50, and YAS5-90 glasses coupled with SUS430 showed fine adhesion and no detectable inter-diffusion across the interface. The coefficient of thermal expansion (CTE) of the YAS5-50 glass escalated from 7.01 to 9.30 × 10⁻⁶/K with 50 wt% Bi_1.5Y_0.5O₃ (BYO) fillers. The leak rates of the composite seals comprising the YAS5-50 glass and 50 wt% BYO fillers were measured at 700 °C after joining at 850 °C. The measurement used helium with a pressure at 1 psi across the glass seals and a slight load of 1.0 psi to minimize compressive seal effect on the glass. It appeared that a low leak rate of 0.052 sccm/cm was obtained and stayed unchanged as the system was soaked at 700 °C for 500 h, indicating a fine thermal stability against the extended duration benefited from the limited crystallization of the YAS5-50 glass. This promising long-term stability qualified the glass for use as SOFC seal.     

Nanostructured palladium–La0.75Sr0.25Cr0.5Mn0.5O3/Y2O3–ZrO2 composite anodes for direct methane and ethanol solid oxide fuel cells

A palladium-impregnated La_0.75Sr_0.25Cr_0.5Mn_0.5O_3−δ/yttria-stabilized zirconia (LSCM/YSZ) composite anode is investigated for the direct utilization of methane and ethanol fuels in solid oxide fuel cells (SOFCs). Impregnation of Pd nanoparticles significantly enhances the electrocatalytic activity of LSCM/YSZ composite anodes for the methane and ethanol electrooxidation reaction. At 800 °C, the maximum power density is increased by two and eight times with methane and ethanol fuels, respectively, for a cell with the Pd-impregnated LSCM/YSZ composite anode, as compared with that using a pure LSCM/YSZ anode. No carbon deposition is observed during the reaction of methane and ethanol fuels on the Pd-impregnated LSCM/YSZ composite anode. The results show the promises of nanostructured Pd-impregnated LSCM/YSZ composites as effective anodes for direct methane and ethanol SOFCs.     

A study on the stability of a NiO–CaO/Al2O3 complex catalyst by La2O3 modification for hydrogen production

This paper details the study of La₂O₃ modifications and their effect on the stability of a NiO–CaO/Al₂O₃ sorption complex catalyst used in the ReSER (reactive sorption enhanced reforming) process of hydrogen production. The La₂O₃-modified NiO–CaO/Al₂O₃ sorption complex catalyst was prepared by isometric impregnation. The microstructure, morphology and reducibility of the La₂O₃-modified sorption complex catalyst were characterized by means of BET, TEM, XRD and TPR. The stability of the catalyst used in the ReSER process was evaluated on a laboratory-scale fixed-bed reactor. Our results showed that modifying the sorption complex catalyst with La₂O₃ improved its stability up to 30 cycles of the ReSER process for hydrogen production, while only seven cycles were obtained without La₂O₃ modification. We showed that the source of the stability improvement that the La₂O₃ in the catalyst not only functioned to restrain the decrease of the support surface area and reduce the sintering of nano-CaCO₃, which could limit the decay of the sorption capacity and stability of the catalyst, but also increased the interaction between nickel oxide and the support, which improved the stability of the catalyst by increasing the dispersion of nickel grains and inhibited the growth of nickel grain size.     

Plasma-reduced Ni/γ–Al2O3 and CeO2–Ni/γ–Al2O3 catalysts for improving dry reforming of propane

Pristine Ni/γ–Al₂O₃ and CeO₂–Ni/γ–Al₂O₃ catalysts were prepared by co-impregnation technique for dry reforming of propane. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) were used to examine the structure and morphology of the catalysts before and after the reforming reactions. The excellent interaction between catalyst active phases was observed in both CeO₂–Ni/γ–Al₂O₃ and Ni/γ–Al₂O₃ stabilized with polyethelene glycol (Ni/γ–Al₂O₃–PEG). Towards C₃H₈ and CO₂ conversion, the CeO₂–Ni/γ–Al₂O₃ and Ni/γ–Al₂O₃–PEG showed improved catalytic activity when compared to the pristine Ni/γ–Al₂O₃ catalyst. Interestingly, high H₂ concentration was achieved with the CeO₂–Ni/γ–Al₂O₃ and high CO concentration with the Ni/γ–Al₂O₃–PEG, which is due to the nanoconfinement of nickel particles within the support and favorable metal-support interaction as a result of plasma reduction. The CeO₂–Ni/γ–Al₂O₃ catalyst exhibited better stability for anti-sintering and coke resistance, thus exhibiting high reactivity and durability in the dry reforming.     

The oxygen-releasing step in the water splitting cycle by MnFe2O4–Na2CO3 system

Investigation of the feasibility of the thermochemical two-step water splitting cycle based on MnFe₂O₄/Na₂CO₃ system is reported. Influence of temperature and carbon dioxide pressure on the oxygen-releasing step was investigated. XRD analysis was applied to obtain phase identification of reacted powders at investigated experimental conditions. Different sodium sub-stoichiometric Na_1−δ(Mn_1/3Fe_2/3)O_2−δ/2 compounds were observed and their structure determined by using Rietveld analysis. Selected experimental conditions permitted to define a T/pCO2$T/p_{{\text{CO}}_{\text{2}}}$ phase diagram, showing different solid phases coexistence regions. Experimental conditions that permit complete regeneration of the initial MnFe₂O₄/Na₂CO₃ mixture were identified (field I in the reported diagram), demonstrating the possibility of full chemical cyclical operation of the system.     

Metal-supported solid oxide fuel cells with in-situ sintered (Bi2O3)0.7(Er2O3)0.3–Ag composite cathode

Metal-supported solid oxide fuel cells (SOFCs) containing porous 430L stainless steel support, Ni-YSZ anode and YSZ electrolyte were fabricated by tape casting, laminating and co-firing in a reduced atmosphere. (Bi₂O₃)_0.7(Er₂O₃)_0.3–Ag composite cathode was applied by screen printing and in-situ sintering. The polarization resistances of the composite cathode were 1.18, 0.48, 0.18, 0.09 Ω cm² at 600, 650, 700 and 750 °C, respectively. A promissing maximum power density of 568 mW cm⁻² at 750 °C was obtained of the single cell. Short-term stability was measured as well.     

Performances of SmBaCoCuO5+δ–Ce0.9Gd0.1O1.95 composite cathodes for intermediate-temperature solid oxide fuel cells

SmBaCoCuO_5+δ–xCe_0.9Gd_0.1O_1.95 (SBCCO–xGDC, x = 10, 30, 50, 60, wt%) composite cathodes have been investigated for their potential utilization in intermediate temperature solid oxide fuel cells (IT-SOFCs). The thermal expansion behavior shows that the thermal expansion coefficient (TEC) values of SBCCO cathode decrease with GDC addition. The TEC of SBCCO–50GDC cathode is 13.1 × 10⁻⁶ K⁻¹ from 30 to 850 °C in air. By means of DC polarization and AC impedance spectroscopy, the electrochemical performance of SBCCO–xGDC composite cathodes on GDC electrolyte is examined. Results indicate that the proper addition of GDC could improve the performance of SBCCO cathode. The optimum content of GDC in the composite cathodes is 50 wt% with the polarization resistance (R_p) of 0.040 Ω cm² at 800 °C. An electrolyte-supported single-cell configuration of SBCCO–50GDC/GDC/Ni–GDC attains a maximum power density of 628 mW cm⁻² at 800 °C. Preliminary results indicate that SBCCO–50GDC is especially promising as a cathode for IT-SOFCs.     

Isothermal reduction of powdery 2CaO·Fe2O3 and CaO·Fe2O3 under H2 atmosphere

Injection of natural gas into the tuyere raceway of a blast furnace (BF) can effectively decrease the use of coke, as well as reduce CO₂ emission. Therefore, the reduction behaviour of sinters, which account for 60% of the raw materials charged into the BF process under H₂, is important for natural gas utilisation. This study used thermogravimetric analysis under H₂ atmosphere to investigate the reduction kinetics of dicalcium ferrite (2CaO·Fe₂O₃, C₂F) and calcium ferrite (CaO·Fe₂O₃, CF), which are the dominant components in fluxed sinters. Results indicated that CF reduction has a larger maximum reduction degree and a higher reaction constant than C₂F. The apparent activation energy of CF is also larger than that of C₂F, thereby illustrating that C₂F reduction proceeds more easily than CF. X–ray diffraction measurements indicated that C₂F is reduced to CaO and Fe in a single step, whereas CF is reduced with four steps in the following order: CaO·FeO·Fe₂O₃, CaO·3FeO·Fe₂O₃, C₂F and Fe. Sharp and ln–ln methods revealed that C₂F reduction is described by 2D Avrami–Erofeev (A–E) equation and that of CF is expressed by 2D A–E equation but tends slightly to 3D A–E equation in the late stage. A–E equations were verified to be consistent with the experimental reduction degree data of C₂F and CF. A kinetics model that links reduction routes to model functions was proposed to describe the powder reduction of C₂F and CF. Comparisons of the reduction behaviours of C₂F or CF by H₂ and CO implied that the reduction rate rises and activation energy declines during the reduction of samples by H₂.     

Methane oxy-steam reforming reaction: Performances of Ru/γ-Al2O3 catalysts loaded on structured cordierite monoliths

The in situ deposition of 1.5 wt.% Ru/γ-Al₂O₃ catalytic layers on cordierite monoliths (400 cpsi, diameter 1 cm, length 1.5 cm), combining Solution Combustion Synthesis (SCS) with Wet Impregnation (WI), was addressed. First of all, the physicochemical properties of the catalyst at powder level were investigated by X-ray Diffraction (XRD), N₂ adsorption (BET), and H₂ chemisorption, while the morphology of final structured catalysts was evaluated by SEM analysis and mechanical strength tests by sonication. The catalytic activity towards methane Oxy-Steam Reforming (OSR) reaction was studied after the choice of the most suitable catalyst load, carrying out tests varying the temperature (500–800 °C), the oxygen-to-carbon ratio (O/C = 0.45–0.75, oxygen as moles), the steam-to-carbon ratio (S/C = 1.0–2.4), and the weight space velocity (WSV = 34,000–400,000 N ml g_cat⁻¹ h⁻¹), in order to identify the optimum operative conditions. The results showed that a total catalytic layer load (active metal plus oxide carrier) equal to 6.5 mg cm⁻² was enough to achieve excellent performances, while no substantial improvements were obtained at higher catalytic layer loads. Moreover, the coated Ru/γ-Al₂O₃ monolith exhibited a good catalytic activity towards the studied reaction also at considerably high WSV values (till 400,000 N ml g_cat⁻¹ h⁻¹).