A novel membrane for DMFC – Na2Ti3O7 Nanotubes/Nafion composite membrane: Performances studies

Systematic experiments have been carried out to study the performance of the novel sodium titanate (Na₂Ti₃O₇) nanotube/Nafion^® composite membrane (5 wt% Na₂Ti₃O₇) in a single direct methanol fuel cell (DMFC) at different operating temperatures, methanol concentrations, air flow rates, methanol flow rates, and cathode humidification temperatures. The experimental results showed that the composite membrane outperform pure Nafion^® membranes with the same thickness, Nafion^®112, under all the operating conditions. Furthermore, under some operating conditions, the new composite membranes even outperform Nafion^®117, a much thicker membrane. These experimental results have proved that the new composite membrane is superior to pure Nafion^® membrane in DMFCs and the addition of Na₂Ti₃O₇ nanotubes into Nafion^® is an effective way to improve membrane performances.     

Performance of composite Nafion/PVA membranes for direct methanol fuel cells

This work has been focused on the characterization of the methanol permeability and fuel cell performance of composite Nafion/PVA membranes in function of their thickness, which ranged from 19 to 97 μm. The composite membranes were made up of Nafion^® polymer deposited between polyvinyl alcohol (PVA) nanofibers. The resistance to methanol permeation of the Nafion/PVA membranes shows a linear variation with the thickness. The separation between apparent and true permeability permits to give an estimated value of 4.0 × 10⁻⁷ cm² s⁻¹ for the intrinsic or true permeability of the bulk phase at the composite membranes. The incorporation of PVA nanofibers causes a remarkable reduction of one order of magnitude in the methanol permeability as compared with pristine Nafion^® membranes. The DMFC performances of membrane-electrode assemblies prepared from Nafion/PVA and pristine Nafion^® membranes were tested at 45, 70 and 95 °C under various methanol concentrations, i.e., 1, 2 and 3 M. The nanocomposite membranes with thicknesses of 19 μm and 47 μm reached power densities of 211 mW cm⁻² and 184 mW cm⁻² at 95 °C and 2 M methanol concentration. These results are comparable to those found for Nafion^® membranes with similar thickness at the same conditions, which were 210 mW cm⁻² and 204 mW cm⁻² respectively. Due to the lower amount of Nafion^® polymer present within the composite membranes, it is suggested a high degree of utilization of Nafion^® as proton conductive material within the Nafion/PVA membranes, and therefore, significant savings in the consumed amount of Nafion^® are potentially able to be achieved. In addition, the reinforcement effect caused by the PVA nanofibers offers the possibility of preparing membranes with very low thickness and good mechanical properties, while on the other hand, pristine Nafion^® membranes are unpractical below a thickness of 50 μm.     

Sol–gel derived sulfonated-silica/Nafion composite membrane for direct methanol fuel cell

Sulfonated-silica/Nafion^® composite membranes were prepared in a sol–gel reaction of (3-Mercaptopropyl)trimethoxysilane (SH-silane) followed by solution casting, and then oxidated using 10 wt% H₂O₂ solution. The chemical and physical properties of the composite membranes were characterized by using FT-IR, XPS, ²⁹Si NMR and SEM analyses. Experimental results indicated that the optimum oxidation condition was 60 °C for 1 h. The performance of the silica–SO₃H/Nafion^® composite membranes was evaluated in terms of methanol permeability, proton conductivity and cell performance. The silica–SO₃H/Nafion^® composite membranes have a higher selectivity (C/P ratio = 26,653) than that of pristine Nafion^® (22,795), perhaps because of their higher proton conductivity and lower methanol permeability. The composite membrane with 0.6 wt% silica–SO₃H/Nafion^® performed better than pristine Nafion^®. The current densities were measured as 62.5 and 70 mA cm⁻² at a potential of 0.2 V with a composite membrane that contained 0 and 0.6 wt% silica–SO₃H, respectively. The cell performance of the DMFC was improved by introducing silica–SO₃H. The composite membrane with 0.6 wt% of silica–SO₃H yielded the maximum power density of 15.18 mW cm⁻². The composite membranes are suitable for DMFC applications with high selectivity.     

Methanol steam reforming in an Al2O3 supported thin Pd-layer membrane reactor over Cu/ZnO/Al2O3 catalyst

In this experimental study, a membrane reactor housing a composite membrane constituted by a thin Pd-layer supported onto Al₂O₃ is utilized to perform methanol steam reforming reaction to produce high-grade hydrogen for PEM fuel cell applications. The influence of various parameters such as temperature, from 280 to 330 °C, and pressure, from 1.5 to 2.5 bar, is analyzed. A commercial Cu/Zn-based catalyst is packed in the annulus of the membrane reactor and the experimental tests are performed at space velocity equal to 18,500 h⁻¹ and H₂O:CH₃OH feed molar ratio equal to 2.5:1. Results in terms of methanol conversion, hydrogen recovery, hydrogen yield and products selectivities are given. As a best result of this work, 85% of methanol conversion and a highly pure hydrogen stream permeated through the membrane with a CO content lower than 10 ppm were reached at 330 °C and 2.5 bar. Furthermore, a comparison between the experimental results obtained in this work and literature data is proposed and discussed.     

Li4Ti5O12/CNTs composite anode material for large capacity and high-rate lithium ion batteries

Li₄Ti₅O₁₂ sub-micro crystallites are synthesized by ball-milling and one-step sintering under different heat treatment temperature from 700 °C to 900 °C. The composite electrode of Li₄Ti₅O₁₂/carbon nanotubes (CNTs) is prepared by mixing powders of Li₄Ti₅O₁₂ and CNTs in different weight ratios. Before mixing, in order to disperse CNTs in Li₄Ti₅O₁₂ particles preferably, the CNTs are cut and dispersed by hyperacoustic shear method and the composite electrodes of low resistance of about 20–30 Ω are obtained. The composite electrodes have steady discharge platform of 1.54 V and large specific capacity, initial discharge capacities are 168, 200, 196, 176 mAh g⁻¹ in different Li₄Ti₅O₁₂:CNTs weight ratios of 94:1, 92:3, 90:5, 88:7 respectively at 0.1 C discharge rate for the Li₄Ti₅O₁₂ synthesized in an optimized heat treatment temperature of 800 °C. In our experimental range, the composite electrode in a CNTs weight ratio of 3:92 shows the best performance under different discharge rate such as the initial capacity is 200 mAh g⁻¹ with discharge capacities retention rate of nearly 100%. Its capacity is about 151 mAh g⁻¹ under 20 C rate discharge condition with excellent high-rate performance. There is almost no decline after 20th cycles under 10 C rate discharging condition.     

High proton-conducting Nafion/–SO3H functionalized mesoporous silica composite membranes

A novel organic–inorganic mesoporous silica (L64 copolymer-templated mesoporous SiO₂), functionalized with perfluoroalkylsulfonic acid groups analogous to that of Nafion^®, was prepared. A condensation reaction between the surface silanol groups of the mesoporous silicas and 1,2,2-trifluoro-2-hydroxy-1-trifluoromethylethane sulfonic acid Beta-sultone was conducted. High proton-conducting Nafion^®/functionalized mesoporous silica composite membranes were prepared via homogeneous dispersive mixing and the solvent casting method. In this investigation, the proton conductivity (σ) of the composite membrane is increased from 0.10 to 0.12 (S cm⁻¹) as the modified mesoporous silica content is increased from 0 to 3 wt%. The methanol permeability of the composite membrane declined as the sulfonic mesoporous silica content increased. The methanol permeability of the composite membrane that contained 3 wt% M–SiO₂–SO₃H was 4.5 × 10⁻⁶ cm² S⁻¹—30% lower than that of pristine Nafion^®. Results of this study demonstrate a significant improvement in the performance of DMFCs.     

Fabrication and investigation of SiO2 supported sulfated zirconia/Nafion self-humidifying membrane for proton exchange membrane fuel cell applications

A self-humidifying composite membrane based on Nafion^® hybrid with SiO₂ supported sulfated zirconia particles (SiO₂–SZ) was fabricated and investigated for fuel cell applications. The bi-functional SiO₂–SZ particles, possessing hygroscopic property and high proton conductivity, were homemade and as the additive incorporated into our composite membrane. X-ray diffraction (XRD) and Fourier infrared spectrum (FT-IR) techniques were employed to characterize the structure of SiO₂–SZ particles. Scanning electronic microscopy (SEM) and energy dispersive spectroscopy (EDS) measurements were conducted to study the morphology of composite membrane. To verify the advantages of Nafion^®/SiO₂–SZ composite membrane, the IEC value, water uptake, proton conductivity, single cell performance and areal resistance were compared with Nafion^®/SiO₂ membrane and recast Nafion^® membrane. The single cell employing our Nafion^®/SiO₂–SZ membrane exhibited the highest peak power density of 0.98 W cm⁻² under dry operation condition in comparison with 0.74 W cm⁻² of Nafion^®/SiO₂ membrane and 0.64 W cm⁻² of recast Nafion^® membrane, respectively. The improved performance was attributed to the introduction of SiO₂–SZ particles, whose high proton conductivity and good water adsorbing/retaining function under dry operation condition, could facilitate proton transfer and water balance in the membrane.     

MWCNTs reinforced Nafion membrane prepared by a novel solution-cast method for PEMFC

An improved solution-cast method is presented to prepare multi-wall carbon nanotubes (MWCNTs)/Nafion^® reinforced membrane with different MWCNTs content (from 1 to 4 wt.%). MWCNTs were oxidized by H₂O₂ and sodium hydroxide (NaOH) was added into the MWCNTs/Nafion^®/N,N-dimethylacetamide (DMAC) solution. The long-term stability of the resulting dispersions was much better than the unmodified dispersions. The as-cast membrane was observed by scanning electron microscope (SEM). The MWCNTs were uniformly dispersed in the Nafion^® resin. The tensile strength and the elongation at break were greatly improved for the reinforced membranes compared to the recast Nafion^® membranes (54 and 27%, respectively). The fuel cell performance of the reinforced membranes with different MWCNTs contents was also tested at 80 °C under fully humidified conditions. By comparing the mechanical properties, proton conductivity and fuel cell performance of the reinforced membranes, we concluded that the content of MWCNTs in the reinforced membranes should not exceed 3 wt.%. The MWCNTs/Nafion^® reinforced membrane with 3 wt.% MWCNTs content showed the best mechanical characteristics and excellent fuel cell performance.     

Photocatalytic water splitting with In-doped H2LaNb2O7 composite oxide semiconductors

The In-doped HLaNb₂O₇ oxide semiconductors synthesized by solid-state reaction followed by an ion-exchange reaction were found to be a novel composite photocatalyst system with enhanced activity for water splitting. Pt was incorporated in the interlayer of In-doped HLaNb₂O₇ by the stepwise intercalation reaction. The In-doped HLaNb₂O₇ powder samples were characterized with X-ray diffraction (XRD) and UV-vis diffuse reflectance spectrometry. The photocatalytic activities of Pt-loaded In-doped HLaNb₂O₇ and individual precursor materials were evaluated by H₂ evolution from aqueous CH₃OH solution under UV light irradiation. It was found that the composite In-doped HLaNb₂O₇ showed a higher H₂ evolution rate in comparison with individual materials. The hydrogen production activity of In-doped HLaNb₂O₇ was greatly enhanced by Pt co-incorporation. The In content in the In-doped HLaNb₂O₇ system was discussed in relation to the photophysical and photocatalytic properties. As In content equal 5 mol%, the HLaNb₂O₇:In/Pt showed a photocatalytic activity of 354 cm³ g⁻¹ hydrogen evolution in 10 vol% methanol solution under irradiation from a 100 W mercury lamp at 333 K for 3 h.     

Use of in situ polymerized phenol-formaldehyde resin to modify a Nafion membrane for the direct methanol fuel cell

Commercial Nafion^®-115 (trademark registered to DuPont) membranes were modified by in situ polymerized phenol formaldehyde resin (PFR) to suppress methanol crossover, and SO₃⁻ groups were introduced to PFR by post-sulfonatation. A series of membranes with different sulfonated phenol formaldehyde resin (sPFR) loadings have been fabricated and investigated. SEM-EDX characterization shows that the PFR was well dispersed throughout the Nafion^® membrane. The composite membranes have a similar or slightly lower proton conductivity compared with a native Nafion^® membrane, but show a significant reduction in methanol crossover (the methanol permeability of sPFR/Nafion^® composite membrane with 2.3 wt.% sPFR loading was 1.5 × 10⁻⁶ cm² s⁻¹, compared with the 2.5 × 10⁻⁶ cm² s⁻¹ for the native Nafion^® membrane). In direct methanol fuel cell (DMFC) evaluation, the membrane electrode assembly (MEA) using a composite membrane with a 2.3 wt.% sPFR loading shows a higher performance than that of a native Nafion^® membrane with 1 M methanol feed, and at higher methanol concentrations (5 M), the composite membrane achieved a 114 mW cm⁻² maximum power density, while the maximum power density of the native Nafion^® was only 78 mW cm⁻².     

Evaluation of Ni/Y2O3/Al2O3 catalysts for hydrogen production by autothermal reforming of methane

Ni/xY₂O₃–Al₂O₃ (x = 5, 10, 15, 20 wt%) catalysts were prepared by sequential impregnation synthesis. The catalytic performance for the autothermal reforming of methane was evaluated and compared with Ni/γ-Al₂O₃ catalyst. The physicochemical properties of catalysts were characterized by X-ray diffraction (XRD), Transmission electron microscope (TEM), X-Ray Photoelectron Spectrometer (XPS), Thermo Gravimetric Analyzer (TGA) and H₂-temperature programmed reduction techniques (TPR). The decrease of nickel particle size and the change of reducibility were found with Y modification. The CH₄ conversion increased with elevating levels of Y₂O₃ from 5% to 10%, then decreased with Y content from 10% to 20%. Ni/xY₂O₃–Al₂O₃ catalysts maintained high activity after 24 h on stream, while Ni/Al₂O₃ had a significant deactivation. The characterization of spent catalysts indicated that the addition of Y retarded Ni sintering and decreased the amount of coke.     

Catalytic effect of Gd2O3 and Nd2O3 on hydrogen desorption behavior of NaAlH4

This study investigated the effect of Nd₂O₃ and Gd₂O₃ as catalyst on hydrogen desorption behavior of NaAlH₄. Pressure-content-temperature (PCT) equipment measurement proved that both two oxides enhanced the dehydrogenation kinetics distinctly and increasing Nd₂O₃ and Gd₂O₃ from 0.5 mol% to 5 mol% caused a similar effect trend that the dehydrogenation amount and average dehydrogenation rate increased firstly and then decreased under the same conditions. 1 mol% Gd₂O₃–NaAlH₄ presented the largest hydrogen desorption amount of 5.94 wt% while 1 mol% Nd₂O₃–NaAlH₄ exerted the fastest dehydrogenation rate. Scanning Electron microscopy (SEM) analysis revealed that Gd₂O₃–NaAlH₄ samples displayed uniform surface morphology that was bulky, uneven and flocculent. The difference of Nd₂O₃–NaAlH₄ was that with the increasing of Nd₂O₃ content, the particles turned more and more big. Compared to dehydrogenation behavior, this phenomenon demonstrated that small particles structure were beneficial to hydrogen desorption. Besides, the further study found that different catalysts and addition amounts had different effects on the microstructure of NaAlH_4.     

Hydrogen production by mechano-chemical reaction of Ti2O3 in water

The purpose of this study is to clarify the physicochemical properties of Ti₂O₃ for hydrogen production. The hydrogen production properties of Ti₂O₃ before and after milling in pure water were investigated in a flat-bottomed reaction vessel made of a Pyrex glass cell which was attached to a closed-gas circulation system under an Ar atmosphere at room temperature using three different types of stirring rod. Ti₂O₃ was found to be a new material for mechano-chemical hydrogen production, although it did not exhibit photocatalysis or mechano-catalysis for hydrogen production.     

In situ crack-healing behavior of Al2O3/SiC composite ceramics undercyclic-fatigue strength

Alumina/silicon carbide (Al₂O₃/SiC) composite ceramics were sintered and subjected to three-point bending. A semicircular surface crack 50–320 µm in diameter was made on each sample. Crack-healing behavior was systematically studied, as a function of cyclic-fatigue strength, crack-healing temperature, healing time, and crack size, and the bending strength of the crack-healed sample from room temperature to 1500 °C were investigated. Four main conclusions were drawn from the present study.

(1)

Crack-healed Al₂O₃/SiC sample exhibited very high cyclic-fatigue limit of 700 MPa.     

Formation and metal-to-insulator transition properties of VO2-ZrV2O7 composite films by polymer-assisted deposition

VO₂-ZrV₂O₇ composite films were prepared on silica glass substrates by polymer-assisted deposition using a V-Zr-O solution. The coexistence of ZrV₂O₇ and VO₂ was confirmed by Raman spectroscopy, glance angle X-ray diffraction, and X-ray photoelectron spectroscopy. The composite films with similar thickness of about 95 nm showed decreased particle sizes and significantly enhanced luminous transmittances (from 32.3% at Zr/V=0 to 53.4% at Zr/V=0.12) with increasing Zr/V rations. The enhancement in the luminous transmittance was ascribed to the absorption-edge changes in the composite films. This feature benefits the application of VO₂ to smart windows.     

Nano Li4Ti5O12–LiMn2O4 batteries with high power capability and improved cycle-life

We report the effects of electrode thickness, cathode particle size and morphology, cathode carbon coating matching ratio and laminate structure on the electrochemical characteristics of nanosized Li₄Ti₅O₁₂–LiMn₂O₄ batteries. We show that a correct adjustment of these parameters resulted in significant improvements in power capability and cycle-life of such devices, making them competitive, low-cost and safe battery chemistry for next generation Li-ion batteries. In addition, Li₄Ti₅O₁₂ reversible specific capacity beyond three Li-ions intercalation is reported.     

Reforming of bioethanol over Ni/Al2O3 and Ni/CeZrO2/Al2O3 catalysts in supercritical water for hydrogen production

Bioethanol was reformed in supercritical water (SCW) at 500 °C and 25 MPa on Ni/Al₂O₃ and Ni/CeZrO₂/Al₂O₃ catalysts to produce high-pressure hydrogen. The results were compared with non-catalytic reactions. Under supercritical water and in a non-catalytic environment, ethanol was reformed to H₂, CO₂ and CH₄ with small amounts of CO and C2 gas and liquid products. The presence of either Ni/Al₂O₃ or Ni/CeZrO₂/Al₂O₃ promoted reactions of ethanol reforming, dehydrogenation and decomposition. Acetaldehyde produced from the decomposition of ethanol was completely decomposed into CH₄ and CO, which underwent a further water-gas shift reaction in SCW. This led to great increases in ethanol conversion and H₂ yield on the catalysts of more than 3-4 times than that of the non-catalytic condition. For the catalytic operation, adding small amounts of oxygen at oxygen to ethanol molar ratio of 0.06 into the feed improved ethanol conversion, at the expense of some H₂ oxidized to water, resulting in a slightly lower H₂ yield. The ceria-zirconia promoted catalyst was more active than the unpromoted catalyst. On the promoted catalyst, complete ethanol conversion was achieved and no coke formation was found. The ceria-zirconia promoter has important roles in improving the decomposition of acetaldehyde, the enhancement of the water-gas shift as well as the methanation reactions to give an extremely low CO yield and a tremendously high H₂/CO ratio. The SCW environment for ethanol reforming caused the transformation of gamma-alumina towards the corundum phase of the alumina support in the Ni/Al₂O₃ catalyst, but this transformation was slowed down by the presence of the ceria-zirconia promoter.     

Basic molten salt process—A new route for synthesis of nanocrystalline Li4Ti5O12-TiO2 anode material for Li-ion batteries using eutectic mixture of LiNO3-LiOH-Li2O2

A nanocrystalline Li₄Ti₅O₁₂-TiO₂ duplex phase has been synthesized by a simple basic molten salt process (BMSP) using an eutectic mixture of LiNO₃-LiOH-Li₂O₂ at 400-500 °C. The microstructure and morphology of the Li₄Ti₅O₁₂-TiO₂ product are characterized by means of X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM). The sample prepared by heat-treating at 300 °C for 3 h (S-1) reveals dense agglomerates of ultra-fine nanocrystalline Li₄Ti₅O₁₂; with heat treatment at 400 °C for 3 h (S-2), there is a duplex crystallite size (fine < 10 nm, and coarse > 20 nm) of Li₄Ti₅O₁₂-TiO₂; at 500 °C for 3 h (S-3), a much coarser and less-dense distribution of lithium titanate (crystallite size ∼15-30 nm) is observed. According to the results of electrochemical testing, the S-2 sample shows initial discharge capacities of 193 mAh g⁻¹ at 0.2 C, 168 mAh g⁻¹ at 0.5 C, 146 mAh g⁻¹ at 1 C, 135 mAh g⁻¹ at 2 C, and 117 mAh g⁻¹ at 5 C. After 100 cycles, the discharge capacity is 138 mAh g⁻¹ at 1 C with a capacity retention of 95%. The S-2 sample yields the best electrochemical performance in terms of charge-discharge capacity and rate capability compared with other samples. Its superior electrochemical performance can be mainly attributed to the duplex crystallite structure, composed of fine (<10 nm) and coarse (>20) nm nanoparticles, where lithium ions can be stored within the grain boundary interfaces between the spinel Li₄Ti₅O₁₂ and the anatase TiO₂.     

Surface modification of LiNi0.5Mn1.5O4 by ZrP2O7 and ZrO2 for lithium-ion batteries

The spinel LiNi_0.5Mn_1.5O₄ has been surface modified separately with 1.0 wt.% ZrO₂ and ZrP₂O₇ for the purpose of improving its cycle performance as a cathode in a 5-V lithium-ion cell. Although the modifications did not change the crystallographic structure of the surface-modified samples, they exhibited better cyclability at elevated temperature (55 °C) compared with pristine LiNi_0.5Mn_1.5O₄. The material that was surface modified with ZrO₂ gave the best cycling performance, only 4% loss of capacity after 150 cycles at 55 °C. Electrochemical impedance spectroscopy demonstrated that the improved performance of the ZrO₂-surface-modified LiNi_0.5Mn_1.5O₄ is due to a small decrease in the charge transfer resistance, indicating limited surface reactivity during cycling. Differential scanning calorimetry showed that the ZrO₂-modified LiNi_0.5Mn_1.5O₄ exhibits lower heat generation and higher onset reaction temperature compared to the pristine material. The excellent cycling and safety performance of the ZrO₂-modified LiNi_0.5Mn_1.5O₄ electrode was found to be due to the protective effect of homogeneous ZrO₂ nano-particles that form on the LiNi_0.5Mn_1.5O₄, as shown by transmission electron microscopy.     

Photocatalytic hydrogen production from aqueous methanol solution with CuO/Al2O3/TiO2 nanocomposite

The photocatalytic hydrogen production from aqueous methanol solution was investigated with ZnO/TiO₂, SnO/TiO₂, CuO/TiO₂, Al₂O₃/TiO₂ and CuO/Al₂O₃/TiO₂ nanocomposites. A mechanical mixing method, followed by the solid-state reaction at elevated temperature, was used for the preparation of nanocomposite photocatalyst. Among these nanocomposite photocatalysts, the maximal photocatalytic hydrogen production was observed with CuO/Al₂O₃/TiO₂ nanocomposites. A variety of components of CuO/Al₂O₃/TiO₂ photocatalysts were tested for the enhancement of H₂ formation. The optimal component was 0.2 wt% CuO/0.3 wt% Al₂O₃/TiO₂. The activity exhibited approximately tenfold enhancement at the optimum loading, compared with that with pure P-25 TiO₂. Nano-sized TiO₂ photocatalytic hydrogen technology has great potential for low-cost, environmentally friendly solar-hydrogen production to support the future hydrogen economy.