Supported bimetallic nanoparticles as anode catalysts for direct methanol fuel cells: A review

Direct methanol fuel cell (DMFC) is an environment friendly energy source that transforms chemical energy of methanol oxidation into electrical energy. The Pt- and non-Pt based bimetallic nanoparticles (BMNPs) with electrocatalyst support materials are employed as anode electrocatalysts for methanol oxidation. These supported BMNPs have drawn prominent consideration due to their incredible physical and chemical properties. This article reviews the advancements in the field of supported BMNPs of varied structures, compositions and morphologies, using innumerable carbonaceous support materials such as carbon black, carbon nanotubes, carbon nanofibers, graphene, mesoporous carbon as well as non-carbonaceous supports like inorganic oxides, graphitic carbon nitride, metal nitrides, conducting polymers and hybrid support materials. The performance of electrocatalysts on the basis of support material, structure, composition and morphology of BMNPs, and pros and cons of various support materials have been discussed.     

Synthesis and characterization of anion exchange membranes for alkaline direct methanol fuel cells

Alkaline fuel cells suggest solution for the problems of low methanol oxidation kinetics and methanol crossover, which are limiting the development of direct methanol fuel cells. In this work, a novel anion exchange membrane, quaternized poly(aryl ether oxadiazole), was prepared through polycondensation, grafting and quaternization. The ionic conductivity of as-synthesized anion exchange membrane can reach up to 2.79 × 10⁻² S/cm at 70 °C. The physical and chemical stability of the anion exchange membranes could also meet the requirement for alkaline direct methanol fuel cells.     

Low temperature decal transfer method for hydrocarbon membrane based membrane electrode assemblies in polymer electrolyte membrane fuel cells

Decal transfer is an effective membrane electrode assembly (MEA) fabrication method known for its low interfacial resistance and suitability for mass processing. Previously decal transfer for hydrocarbon membranes was performed at temperatures above 200 °C. Here a novel low temperature decal transfer (LTD) method for hydrocarbon membranes is introduced. The new method applies a small amount (2.2 mg cm⁻²) of liquid (1-pentanol) onto the membrane separator before decal transfer to lower the T_g of the membrane and achieves complete decal transfer at 110 °C and 6 MPa. Nafion binder amount in the catalyst layer and catalyst layer annealing temperature is controlled to optimize the fuel cell performance. Compared to conventional decal transfer (CDT), the novel LTD method shows enhancement in energy efficiency, simplicity in the process scheme, and improvement in fuel cell performance.     

Effect of the Pt precursor on the morphology and catalytic performance of Pt-impregnated on Pd/C for the oxygen reduction reaction in polymer electrolyte fuel cells

We describe how the morphology and electrocatalytic activity of Pt-Pd with low levels of Pt are dependent on the type of Pt precursor that is used for the impregnation on to Pd/C. When a Pt precursor with a negative charge (H₂PtCl₆) is used in the preparation medium (Pt-Pd/C-H), its electrostatic interaction with the carbon surface results in some Pt nanoparticles being deposited on the carbon separately from the Pd surface. Due to the absence of such an electrostatic interaction with the Pt(NH₃)₄Cl₂ precursor, more selective deposition of Pt can be achieved on the Pd surface (Pt-Pd/C-N). Depending on the morphology, different electrocatalytic performance in oxygen reduction reaction would be observed. Compared to Pt-Pd/C-H, Pt-Pd/C-N shows 180% (half-cell at 0.9 V) and 160% (unit-cell at 0.8 V) enhanced performance, which is comparable to that on Pt/C. It is believed that the interaction between the Pt and the Pd substrate is more extensive in Pt-Pd/C-N than in Pt-Pd/C-H, and this is responsible for the large difference in the catalytic performances between these two catalysts.     

Functionalized carbon nanotube-poly(arylene sulfone) composite membranes for direct methanol fuel cells with enhanced performance

A new type of composite membrane, consisting of functionalized carbon nanotubes (CNTs) and sulfonated poly(arylene sulfone) (sPAS), is prepared for direct methanol fuel cell (DMFC) applications. The CNTs modified with sulfonic acid or PtRu nanopaticles are dispersed within the sPAS matrix by a solution casting method to afford SO₃CNT-sPAS or PtRu/CNT-sPAS composite membranes, respectively. Characterization of the composite membranes reveals that the functionalized CNTs are homogeneously distributed within the sPAS matrix and the composite membranes contain smaller ion clusters than the neat sPAS. The composite membranes exhibit enhanced mechanical properties in terms of tensile strength, strain and toughness, which leads to improvements in ion conductivity and methanol permeability compared with the neat sPAS membrane. In DMFC performance tests, the use of a PtRu/CNT-sPAS membrane yields high power density compared with the neat sPAS membrane, which demonstrates that the improved properties of the composite membranes induce an increase in power density. The strategy for CNT-sPAS composite membranes presented in this work can potentially be extended to other CNT-polymer composite systems.     

A poly (ethylene oxide)/graphene oxide electrolyte membrane for low temperature polymer fuel cells

A novel method to prepare poly (ethylene oxide)/graphene oxide (PEO/GO) composite membrane aimed for the low temperature polymer electrolyte membrane fuel cells without any chemical modification is presented in this work. The membrane thickness is 80 μm with a GO content of 0.5 wt%. And SEM images show the PEO/GO membrane is condensed composite material without structure defects. Small angle XRD results for the membrane samples show that the d-spacing reflection (0 0 1) of GO in PEO matrix is shifted from 2θ = 11° to 4.5° as the PEO molecules intercalated into the GO layers during the membrane preparation process. FTIR tests show the typical -COOH vibration near 1700 cm⁻¹. Tensile tests show the resultant PEO/GO membrane tensile strength of 52.22 MPa and Young's modulus 3.21 GPa, and the fractured elongation was about 5%. The ionic conductivity of this PEO/GO membrane increases from 0.086 to 0.134 S cm⁻¹ when the operation temperature increases from 25 to 60 °C with 100% relative humidity. And further tests show the DC electronic resistance of this membrane is higher than 20 MΩ at room temperature with 100% relative humidity. Polarization curves in a single cell with this membrane give a maximum power density of 53 mW cm⁻² at the operation temperature around 60 °C, without optimizing the catalyst layer composition.     

Effect of ionomer content and relative humidity on polymer electrolyte membrane fuel cell (PEMFC) performance of membrane-electrode assemblies (MEAs) prepared by decal transfer method

Membrane-electrode assemblies (MEAs) were fabricated by the decal transfer method with various Nafion ionomer contents (10–40 wt%) and their single cell performance and electrochemical characteristics were examined in atmospheric air at relative humidities of 25–95%. At high humidity (95%), the MEA performance was the highest with a cathode ionomer content of 30 and 20 wt% at 0.6 and 0.4 V, respectively. The optimum ionomer content of the decal MEAs increased with decreasing humidity, because of the change in the oxygen transport rate (water flooding) and number of active sites (ionic resistance). The concentration overpotential gradually increased with relative humidity up to about 0.4 V at 0.8 A/cm², which was not considered in previous studies using pressurized air and oxygen. The combined effect of the electrochemical active surface area and ionic resistance of the cathodes on the activation overpotential was also investigated, focusing on intermediate and low humidity levels, using a newly developed impedance analysis method.     

Synthesis and characterization of new sulfonated polytriazole proton exchange membrane by click reaction for direct methanol fuel cells (DMFCs)

Sulfonated polytriazole (SPTA) in which the acidic sulfonic acid and basic triazole groups act as physical crosslinking sites within a polymer backbone has been successfully prepared, for use as a proton exchange membrane, using the click reaction. The acid-base interactions of the SPTA membranes leads to the formation of well-dispersed ionic clusters and the random distribution of ion channels with good connectivity resulting in lower methanol permeabilities at ambient temperatures and similar or higher proton conductivities than Nafion 117 at 80 °C in conditions of near zero relative humidity. Proton conductivities (σ) of 0.149 S cm⁻¹ at 80 °C and 9 × 10⁻⁵ S cm⁻¹ in anhydrous conditions together with low methanol permeability (P) at 0.1 × 10⁻⁶ cm² s⁻¹ that are comparable or superior to Nafion 117 (σ_T=80 : 0.151 S cm⁻¹; σ_RH=0 : 3 × 10⁻⁵ S cm⁻¹; P_T=30: 1.31 × 10⁻⁶ cm² s⁻¹) were achieved. Additionally, the selectivity of SPTA is approximately four times higher than that of Nafion 117, thus it may have potential for use in direct methanol fuel cells (DMFCs).     

Synthesis and characterization of polysulfone-containing sulfonated side chains for direct methanol fuel cells

Two series of novel polysulfone-based ionomers containing pendant sulfonic acid groups (designated as PSf-sph-y and PSf-sna-z) have been prepared using commercially available polysulfone and sulfoaryl monomers. The synthesized ionomers have been characterized by nuclear magnetic resonance, differential scanning calorimetry, and thermogravimetric analysis. The thermal characterization data show that these polymers are stable up to 210 °C in acid form and 270 °C in salt form in air. Ion exchange capacity, water uptake, swelling, proton conductivity, and methanol permeability of the membranes have been investigated and compared with those of Nafion 115. The PSf-sna-z membranes bearing highly ionic groups on the flexible side chains show lower water uptake, swelling, and methanol permeability compared to the PSf-sph-y and Nafion 115 membranes. The optimized PSf-sna-58 membrane shows better performance in direct methanol fuel cells (DMFC) than Nafion 115 membranes.     

Novel branched sulfonated poly(ether ether ketone)s membranes for direct methanol fuel cells

In this article, novel branched sulfonated poly(ether ether ketone)s (Br-SPEEK) containing various amounts of 1,3,5-tris(4-fluorobenzoyl)benzene as the branching agent have been successfully prepared. Compared with the traditional linear polymer membranes, the membranes prepared by Br-SPEEK showed improved mechanical strength, excellent dimensional stability and superior oxidative stability with similar proton conductivity. Notably, the Br-SPEEK-10 membrane began to break after 267 min in Fenton's reagent at 80 °C, which was 4 times longer than that of the L-SPEEK. Although the proton conductivity decreased with the addition of the branching agent, satisfying methanol permeability value was observed (down to 6.3 × 10⁻⁷ cm² s⁻¹), which was much lower than Nafion 117 (15.5 × 10⁻⁷ cm² s⁻¹). All the results indicated that the novel branched sulfonated poly(ether ether ketone)s membrane was potential candidate as proton conductive membranes for application in fuel cells.     

Fabrication and properties of poly(vinyl alcohol)-based polymer electrolyte membranes for direct methanol fuel cell applications

A series of poly(vinyl alcohol) (PVA)-based organic–inorganic crosslinked polymer electrolyte membranes with PVA and poly(methacrylic acid-2-acrylamido-2-methyl-1-propanesulfonic acid-vinyltriethoxysilicone) (PMAV) are prepared for direct methanol fuel cell applications. Fourier transform infrared (FTIR) spectroscopy measurements clearly reveal the existence of crosslinking reactions and molecular interactions in PVA–PMAV membranes. The results of TGA show that the PVA–PMAV membranes possess good thermal stability. The uptake behavior, methanol diffusion coefficient, proton conductivity and selectivity of membranes also are investigated as function of PMAV content. The results indicate that the PVA-based organic–inorganic crosslinked membranes are particularly promising to be used as polymer electrolyte membranes due to their excellent methanol barrier property, suitable proton conductivity and high selectivity.     

Polyol synthesis of reduced graphene oxide supported platinum electrocatalysts for fuel cells: Effect of Pt precursor,support oxidation level and pH

In this work, a comprehensive study on the polyol synthesis of platinum supported on reduced graphene oxide (Pt/rGO) catalysts, including both ex-situ and in-situ characterizations of the prepared Pt/rGO catalysts, was performed. The polyol synthesis was studied considering the influence of the platinum precursor, oxidation level of graphite oxide and pH of reaction medium. The as-prepared catalysts were analyzed using thermo-gravimetric (TG) analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and cyclic voltammetry (CV). The best results in terms of platinum particle size and distribution were obtained when the synthesis was performed in acidic medium, using chloroplatinic acid as precursor and using graphene oxide with high oxidation level. The most promising graphene-supported catalyst was used to prepare a polymer electrolyte membrane fuel cell electrode. The membrane electrode assembly (MEA) prepared with graphene-based electrode was compared with a MEA prepared with catalyst based on commercial platinum supported in carbon black (Pt/C). Single cell characterization included polarization curves and in-situ electrochemical impedance spectroscopy (EIS). The graphene-based electrode presented promising albeit unstable electrochemical performance due to water management issues. Additionally, EIS measurements revealed that the MEA made with Pt/rGO catalyst presented a lower mass transport resistance than the commercial Pt/C.     

Performance of passive direct methanol fuel cell with poly(vinyl alcohol)-based polymer electrolyte membranes

Polymer electrolyte membranes (PEMs) were prepared from poly(vinyl alcohol) (PVA) and a modified PVA polyanion containing 2 mol% of 2-methyl-1-propanesulfonic acid (AMPS) groups as a copolymer. The effect of the AMPS content and the crosslinking conditions on the properties of the membranes was investigated in PEMs with various AMPS contents prepared under various crosslinking conditions. The proton conductivity and the permeability of methanol through the PEMs increased with increasing AMPS content, C_AMPS, and with decreasing annealing temperature, T_a, because of the increase in the degree of swelling. The permeability coefficient of methanol through the PEM prepared under the conditions of C_AMPS = 2.0 mol% and T_a 190 °C was approximately 30 times lower than that of Nafion^® 117 under the same measurement conditions. A maximum proton permselectivity of 96 × 10³ S cm⁻³ s, which is defined as the ratio of the proton conductivity to the permeability of methanol, was obtained for this PEM. The permselectivity value is about three times higher than that of Nafion^® 117. A passive air-breathing-type DMFC test cell constructed using the PEM delivered 2.4 mW cm⁻² of maximum power density, P_max, at 2 M methanol concentration, which is smaller than the value obtained with Nafion^® 117. However, at high methanol concentrations (>10 M), the P_max of the PEM decreases slightly to 1.6 mW cm⁻² (at a methanol concentration of 20 M), whereas the P_max of Nafion^® 117 falls to almost zero.     

Cross-linked membranes based on sulfonated poly (ether ether ketone) (SPEEK)/Nafion for direct methanol fuel cells (DMFCs)

A series of cross-linked membranes based on SPEEK/Nafion have been prepared to improve methanol resistance and dimension stability of SPEEK membrane for the usage in the direct methanol fuel cells (DMFCs). Sulfonated diamine monomer is synthesized and used as cross-linker to improve the dispersion of Nafion in the composite membranes and decrease the negative effect of cross-linking on proton conductivity of membranes. FT-IR analysis shows that the cross-linking reaction is performed successfully. The effects of different contents of Nafion on the properties of cross-linked membranes are investigated in detail. All the cross-linked membranes show lower methanol permeability and better dimensional stability compared with the pristine SPEEK membrane. SPEEK-N30 with the 30 wt % Nafion shows a methanol permeability of 0.73 × 10⁻⁶ cm² s⁻¹ and a water uptake of 24.4% at 25 °C, which are lower than those of the pristine membrane. Meanwhile, the proton conductivity of SPEEK-N30 still remains at 0.041 S cm⁻¹ at 25 °C, which is comparable to that of the pristine SPEEK membrane. All the results indicate that these cross-linked membranes based on SPEEK/Nafion show good prospect for the use as proton exchange membranes.     

Fabrication and characterization of poly(vinyl alcohol)/montmorillonite/poly(styrene sulfonic acid) proton-conducting composite membranes for direct methanol fuel cells

A high performance poly(vinyl alcohol)/montmorillonite/poly(styrene sulfonic acid) (PVA/MMT/PSSA) proton-conducting composite membrane was fabricated by a solution casting method. The characteristic properties of these blend composite membranes were investigated by using thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, methanol permeability measurement, and the AC impedance method. The ionic conductivities for the composite membranes are in the order of 10⁻³ S cm⁻¹ at ambient temperature. There are two proton sources used on this novel composite membrane: the modified MMT fillers and PSSA polymer, both materials all contain the -SO₃H group. Therefore, the ionic conductivity was greatly enhanced. The methanol permeabilities of PVA/MMT/PSSA composite membranes is of the order of 10⁻⁷ cm² s⁻¹. It is due to the excellent methanol barrier properties of the PVA polymer. The peak power densities of the air-breathing direct methanol fuel cells (DMFCs) with 1M, 2M, 4M CH₃OH fuels were 14.22, 20.00, and 13.09 mW cm⁻², respectively, at ambient conditions. The direct methanol fuel cell with this composite polymer membrane exhibited good electrochemical performance. The proposed PVA/MMT/PSSA composite membrane is therefore a potential candidate for future applications in DMFC.     

A comparative study of CCM and hot-pressed MEAs for PEM fuel cells

A comparative investigation was performed on PEM fuel cells made with conventional hot-pressed MEAs and catalyst-coated membranes (CCM) under identical conditions of Pt electrolcatalyst loadings. The results showed that cells with a CCM exhibit significantly higher electrochemical performance and power density than those prepared with conventional hot-pressed MEAs. Cyclic voltammetric and impedance studies showed that the MEAs prepared by the CCM method have a higher electrochemical surface area, low cell ohmic resistance and low charge transfer resistance as compared to those prepared with hot-pressed MEAs and the same Pt loading. The results demonstrate that a CCM can enhance the utilization efficiency and improve the catalyst layer and membrane interface of PEM fuel cells.     

In and ex situ characterization of an anion-exchange membrane for alkaline direct methanol fuel cell (ADMFC)

Anion exchange membrane fumasep^® FAA-2 was characterized with ex and in situ methods in order to estimate the membranes’ suitability as an electrolyte for an alkaline direct methanol fuel cell (ADMFC). The interactions of this membrane with water, hydroxyl ions and methanol were studied with both calorimetry and NMR and compared with the widely used proton exchange membrane Nafion^® 115. The results indicate that FAA-2 has a tighter structure and more homogeneous distribution of ionic groups in contrast to the clustered structure of Nafion, moreover, the diffusion of OH⁻ ions through this membrane is clearly slower compared to water molecules. The permeability of methanol through the FAA-2 membrane was found to be an order of magnitude lower than for Nafion. Fuel cell experiments in 1 mol dm⁻³ methanol with FAA-2 resulted in OCV of 0.58 V and maximum power density of 0.32 mW cm⁻². However, even higher current densities were obtained with highly concentrated fuels. This implies that less water is needed for fuel dilution, thereby decreasing the mass of the fuel cell system. In addition, electrochemical impedance spectroscopy for the ADMFC was used to determine ohmic resistance of the cell facilitating the further membrane development.     

Investigating effect of different gas diffusion layers on water droplet characteristics for proton exchange membrane (PEM) fuel cells

In this work, advanced x-ray radiographic techniques available at the Canadian Light Source (CLS) were utilized to study water droplet dynamics in a serpentine flow channel mimicking a proton exchange membrane fuel cell (PEMFC). High spatial and temporal resolution coupled with high energy photons of an x-ray beam provided high-resolution images of water droplets. This technique solved the problem caused by the opaqueness of fuel cell materials including the gas diffusion layer by providing a unique way to study water droplet dynamics at different operating conditions. From the captured images, droplet emergence and formation on porous gas diffusion layers (GDLs) were analyzed. Three commercially available GDLs (Sigracet AA, Sigracet BA, and Sigracet BC) were used and droplet detachment height was found to decrease in the following order AA < BA < BC under the same flow condition. Increasing the superficial gas velocity was found to decrease the droplet detachment height for all GDLs tested. Average droplet cycle for various operating conditions was obtained. It was found that humidified air did not show a difference in droplet dimensions at detachment compared to dry air used at the inlet gas. However, it did show an impact on droplet cycle time, which might be due to condensation.     

A novel cathode structure with double catalyst layers and low Pt loading for proton exchange membrane fuel cells

A novel cathode structure (NCS) was developed, which consisted of an inner and an outer catalyst layer (CL). It showed an improved platinum (Pt) utilization (above 50%), a lowered CL/gas diffusion layer interfacial resistance, and a decreased mass transport polarization compared with the traditional cathode structure (TCS). A hydrogen/air proton exchange membrane fuel cell employing NCS yielded an output power density up to 0.76 W cm⁻² with cathode Pt loading as low as 0.28 mg cm⁻². The enhanced performance of NCS is attributed to synergistic effect of the two catalyst supports in outer CL, which provides abundant pores to relieve water flooding and facilitates heat-induced proton conductor migration from the inner to outer CL, forming a hydrophilic proton conduction network. Moreover, the thin and compact inner CL can meet the demand of rich active sites and catalyst migration toward the regions nearest to the membrane under high current densities.     

Cross-linked poly(vinyl alcohol) and poly(styrene sulfonic acid-co-maleic anhydride)-based semi-interpenetrating network as proton-conducting membranes for direct methanol fuel cells

A series of semi-interpenetrating network (SIPN) membranes was synthesized by using poly(vinyl alcohol) (PVA) with sulfosuccinic acid (SSA) as a cross-linking agent and poly(styrene sulfonic acid-co-maleic acid) (PSSA-MA) as a proton source for direct methanol fuel cell (DMFC) application. A bridge of SSA between PVA molecules not only reinforced the network but also provided extra proton-conducting paths. PSSA-MA chains trapped in the network were the major proton conduction path of the membrane. The SIPN membranes with 80% PSSA-MA (SIPN-80) exhibited a higher proton conductivity value of 2.59 × 10⁻² S cm⁻¹ and very low methanol permeability (4.1 × 10⁻⁷ cm² s⁻¹). More specifically, the SIPN membranes exhibited very high selectivity (proton conductivity/methanol permeability). Membrane characteristics such as water uptake, proton conductivity and methanol permeability were evaluated to determine the effect of PVA molecular weights. The SIPN membranes with higher PVA molecular weight were also evaluated using methanol and oxygen gas in a single cell fuel cell at various temperatures. Power density value of over 100 mW cm⁻² was obtained for SIPN membrane-based membrane electrode assembly at 80 °C and using commercial binary alloy anode catalysts and 2 M methanol.