Research progress of Pt and Pt-based cathode electrocatalysts for proton-exchange membrane fuel cells

Proton-exchange membrane fuel cells (PEMFCs) have been widely used commercially to solve the energy crisis and environmental pollution. The oxygen reduction reaction (ORR) at the cathode is the rate-determining step in PEMFCs. Platinum (Pt) catalysts are used to accelerate the ORR kinetics. Pt's scarcity, high cost, and instability in an acidic environment at high potentials seriously hinder the commercialization of PEMFCs. Therefore, studies should explore electrocatalysts with high catalytic activity, enhanced stability, and low-Pt loading. This review briefly introduces the research progress on Pt and Pt-based ORR electrocatalysts for PEMFCs, including anticorrosion catalyst supports, Pt, and Pt-based alloy electrocatalysts. Advanced preparation technology and material characterization of Pt-based ORR electrocatalysts are necessary to improve the performance and corresponding reaction mechanisms.     

SiO2 stabilized Pt/C cathode catalyst for proton exchange membrane fuel cells

This paper describes the preparation of SiO₂ stabilized Pt/C catalyst (SiO₂/Pt/C) by the hydrolysis of alkoxysilane, and examines the possibility that the SiO₂/Pt/C is used as a durable cathode catalyst for proton exchange membrane fuel cells (PEMFCs). TEM and XRD results revealed that the hydrolysis of alkoxysilane did not significantly change the morphology and crystalline structure of Pt particles. The SiO₂/Pt/C catalyst exhibited higher durability than the Pt/C one, due to the facts that the silica layers covered were beneficial for reducing the Pt aggregation and dissolution as well as increasing the corrosion resistance of supports, although the benefit of silica covering was lower than the case of Pt/CNT catalyst. Also, it was observed that the activity of the SiO₂/Pt/C catalyst for the oxygen reduction reaction was somewhat reduced compared to the Pt/C one after the silica covering. This reduction was partially due to the low oxygen kinetics as revealed by the rotating-disk-electrode measurement. Silica covering by hydrolysis of only 3-aminopropyl trimethoxysilane is able to achieve a good balance between the durability and activity, leading to SiO₂/Pt/C as a promising cathode catalyst for PEMFCs.     

Analytical electron microscopy of proton exchange membrane fuel cells

Microtome sections of proton exchange membrane cells produce a wide range of information ranging from macroscopic distribution of components through specimens in which the detailed distribution of catalyst particles can be observed. Using modern data management practices it is possible to combine information at different scales and correlate processing and performance data. Analytical electron microscopy reveals the compositional variations across used cells at the electrolyte/electrode interface. In particular analytical techniques indicate that sulphur concentrations are likely to diminish at the interface Nafion/anode interface.     

Effect of Ni proportion on the performance of proton exchange membrane fuel cells using PtNi/C electrocatalysts

PtNi/C electrocatalysts were synthesised by borohydride method on functionalised carbon support. Energy-dispersive X-ray spectroscopy, X-ray diffraction, transmission electron microscopy and both cyclic and linear voltammetry were employed to characterise the composition, crystalline structure, morphology and catalytic properties of the PtNi/C electrocatalysts. Different Ni proportions in the PtNi/C electrocatalysts were evaluated in the cathode or anode in a H₂/air proton exchange membrane fuel cells (PEMFC) by polarisation curves. PtNi particles uniformly dispersed with different proportions of metals obtained. The increase of Ni proportion in the electrocatalyst led to materials with higher mass activity values toward the oxygen reduction reaction and a greater electrochemical-active surface area. PtNi/C electrocatalysts in the cathode presented higher mass activity values at high potential in the PEMFC. The best PEMFC performance was obtained with PtNi 13 at.% Ni (cathode) and Pt/C (anode) relative to the Pt/C (cathode and anode) with identical Pt loadings. PtNi/C electrocatalysts in PEMFC may be used as an alternative to Pt/C electrocatalyst.     

Electrostatic spraying of membrane electrode for proton exchange membrane fuel cell

In order to improve the performance of proton exchange membrane fuel cell (PEMFC), the optimization of electrostatic spraying of membrane electrode was conducted. The influence of the spraying voltage on morphology, elemental composition of catalyst layer, and performance of the PEMFC were investigated. The results show that increasing spraying voltage could reduce agglomeration of the carbon-supported platinum particles, leading to more uniform pore distribution. High voltage did not accelerate oxidation of platinum catalyst. A high electrochemical active surface area of 26.18 m²/g_pt was obtained when the platinum-carbon catalyst layer was deposited in cone jet mode. With further increasing spraying voltage, the total ohmic resistance and catalytic activity were changed slightly, whereas the charge transfer resistance was increased. Using the optimized electrostatic spraying parameters (injection rate = 100 μL min⁻¹, spraying voltage = 8.5 kV, and working distance = 12 mm), a peak power density of 1.408 W cm⁻² was obtained with an output voltage of 0.451 V.     

Characterisation of wettability in gas diffusion layer in proton exchange membrane fuel cells

This paper presents a detailed study of the wetting properties of three fuel cell gas diffusion layers (GDLs) having different morphologies and different contents of hydrophobic agent. An internal contact angle to water at temperature representative of PEM fuel cell operating conditions was directly obtained using the Washburn method with 66 ° C water as test liquid. These results show that the surface of the carbon fibres is hydrophilic under fuel cell operating conditions. Surface energy values of the GDL fibres, determined by a combination of the Washburn method and the Owens-Wendt two parameters theory, were found to be low, indicating that GDLs are wet very poorly by most liquids. About 40% of the total surface free energy values was related to a polar component allowing dipole-dipole and hydrogen bonding interactions with water. The origin of this polar character is discussed.     

Ion-beam formation of electrocatalysts for fuel cells with polymer membrane electrolyte

Active layers of electrocatalysts are prepared by the ion-beam assisted deposition (IBAD) of platinum onto carbon-based AVCarb® Carbon Fiber Paper P50 and Toray Carbon Fiber Paper TGP-H-060 T supports and Nafion® N 115 polymer membrane electrolyte in the mode where the deposited metal ions are used as ions assisting the deposition process. Metal deposition and mixing of the deposited layer with the substrate under an accelerating voltage of 10 kV by the same metal ions are carried out from a neutral fraction of metal vapor and the ionized plasma of a pulsed vacuum-arc discharge, respectively. The composition and microstructure of the surface layers obtained are studied by Rutherford backscattering spectrometry (RBS), scanning electron microscopy (SEM), electron-probe microanalysis (EPMA), and X-ray fluorescence (XRF) analysis. The platinum concentration in the layers is (0.5–1.5) × 10¹⁶ at/cm². The prepared electrocatalysts exhibit activity in the process of the electrochemical oxidation of methanol and ethanol, which form the basis for the principle of operation of low temperature fuel cells (direct methanol fuel cells (DMFC) and direct ethanol fuel cells (DEFC)).     

质子交换膜燃料电池中的相关基础性问题

文章介绍了国内外质子交换膜燃料电池的最新进展，特别是在基础研究方面的进展，以促进我国质子交换膜燃料电池的基础研究。     

Fabrication of porous metal fiber sintered sheet as a flow field for proton exchange membrane fuel cell

To improve the diffusion performance of reactive gas, a porous copper fiber sintered sheet (PCFSS) was fabricated and used as the flow field for proton exchange membrane fuel cell (PEMFC). The pressure and flow velocity distribution of the reaction gas in the PCFSS was firstly compared with the serpentine flow field by using the Fluent simulation software. Our results showed that the superiority of PCFSS in the uniformity of gas diffusion was observed. The total resistance of PEMFC with PCFSS in different porosities was obtained. And the advantages of PCFSS in electronic transmission were found by comparing with the serpentine flow field. Besides, the influences of different operating conditions and different porosities of porous flow fields on the performance of PEMFC were experimentally investigated. With the cell temperature of 70 °C as well as the humidification temperature of 60 °C, a PEMFC with PCFSS of 70% porosity exhibited better performance.     

Design of novel SPEEK-based proton exchange membranes by self-assembly method for fuel cells

Fuel cell represents a new energy conversion device, which promises to provide clean source of power. Fuel cell [particularly proton exchange membrane fuel cell and direct methanol fuel cell (DMFC)] is a promising candidate for transportation and portable power source applications. In DMFC, there is a problem of methanol crossover. In order to reduce such a problem, there has been an intensive research activity in the modification of Nafion. In the present investigation, self-assembled membranes were fabricated with sulfonated polyether ether ketone as the core part of the membrane. Aminated polysulfone and sulfonated polysulfone were used as the layers in order to prevent the crossover of methanol. The assembled membranes were characterized by ion exchange capacity, water and methanol absorption, and durability. The methanol permeability and selectivity ratio proved a strong influence on DMFC application. Scanning electron microscopy proved smooth surface, which established strong cohesive force for the polymer chains. Among the synthesized self-assembled membranes, the membrane with two bilayers was the best in terms of power density in DMFC. The membrane electrode assembly with two bilayers showed higher performance (~61.05 mW/cm²) than sulfonated poly(ether ether ketone) and Nafion in DMFC.     

Triazole and triazole derivatives as proton transport facilitators in polymer electrolyte membrane fuel cells

Some basic aspects pertaining to the application of triazole and its derivatives as proton transport facilitators for membranes for high temperature fuel cell operations are investigated. Performance as proton transport facilitators is studied for compounds in their native solid state and as a dopant in a polymer membrane. Some key parameters which influence the proton transport in the system are the proton affinity, pKa or acidity, activation energy and the ease of formation of hydrogen bonding network. Theoretical calculations of the proton affinity of the compounds are presented. The effect of proton affinity of the compound on the activation energies for proton transport is investigated. Proton conductivity is measured for acid doped triazoles in both pellet form (powder triazole mixed with acid) and in composite forms wherein the acid group is contained in a polymer matrix. The effect of formation of a hydrogen bonding network by the triazoles and its impact on the proton conductivity are studied. Also, the effect of ion exchange capacity (IEC) of the host polymeric electrolytes and loading of triazoles in the composites were investigated.     

Effect of gas diffusion layer and membrane properties in an annular proton exchange membrane fuel cell

A complete three-dimensional and single phase computational dynamics model for annular proton exchange membrane (PEM) fuel cell is used to investigate the effect of changing gas diffusion layer and membrane properties on the performances, current density and gas concentration. The proposed model is a full cell model, which includes all the parts of the PEM fuel cell, flow channels, gas diffusion electrodes, catalyst layers and the membrane. Coupled transport and electrochemical kinetics equations are solved in a single domain; therefore no interfacial boundary condition is required at the internal boundaries between cell components. This computational fluid dynamics code is used as the direct problem solver, which is used to simulate the two-dimensional mass, momentum and species transport phenomena as well as the electron- and proton-transfer process taking place in a PEMFC that cannot be investigated experimentally. The results show that by increasing the thickness and decreasing the porosity of GDL the performance of the cell enhances that it is different with planner PEM fuel cell. Also the results show that by decreasing the thickness of the membrane the performance of the cell increases.     

Hybrid Nafion–inorganic oxides membrane doped with heteropolyacids for high temperature operation of proton exchange membrane fuel cell

Performance of the proton exchange membrane fuel cell (PEMFC) with composite Nafion–inorganic additives such as silicon oxide (SiO₂), titanium dioxide (TiO₂), tungsten oxide (WO₃), and SiO₂/phosphotungstic acid (PWA) has been studied for the operation of temperature of above 100 °C. These composite membranes are prepared by the way of blending of the inorganic oxides with Nafion solution by the recasting procedure. The physico-chemical properties studied by means of scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques have proved the uniform and homogeneous distribution of these oxides and the consequent enhancement of crystalline character of these membranes. The thermogravimetry analysis (TGA) results have indicated that the additives TiO₂ and WO₃ have accelerated decomposition of the membrane at an earlier temperature than that of the Nafion membrane. The modified membranes have shown higher uptake of water relative to that of the unmodified membranes. The proton conductivity of the modified membranes, except that of the Nafion/TiO₂, is found to be close to that of the native Nafion membrane at high temperature and at 100% relative humidity (RH), however, it was much higher at low RH. The performance of these modified membranes in the PEMFC operated at 110 °C and 70% RH is better than that of Nafion membrane and is found in the order of Nafion/SiO₂/PWA > Nafion/SiO₂ > Nafion/WO₃ > Nafion/TiO₂.     

Preparation and evaluation of ionomeric membranes based on sulfonated-poly (styrene_isobutylene_styrene) membranes for proton exchange membrane fuel cells (PEMFC)

Sulfonated polystyrene-block-poly-(ethylene-ran-butylene)-block-polystyrene membranes with different sulfonated levels have been prepared and evaluated as proton exchange membrane for polymer electrolyte membrane fuel cell. The polymer was sulfonated by chlorosulfonic acid. Homogeneous membranes were prepared by solvent casting method. Ion exchange capacity, degree of sulfonation, absorption, and solubility of the membranes were studied. The membranes were characterized by Fourier transform infrared, thermogravimetric analyzer, differential scanning calorimetry, and impedance spectroscopy.     

Electrochemical and impedance spectroscopy studies in H2/O2 and methanol/O2 proton exchange membrane fuel cells

This works report results of the structural and the electrochemical characterization of membrane electrode assemblies (MEA) for proton exchange membrane fuel cells (PEMFC) under various cell conditions using different MEA production processes. Electrochemical impedance spectroscopy (EIS) was applied “on-line” (in situ) as a tool for diagnosis concerning the cell performance. MEA with a 25-cm² surface area were prepared using Pt/C and Pt–Ru/C commercial electrocatalysts from E-TEK and Pt–Ru/C electrocatalysts produced by the alcohol reduction process. The catalytic ink was applied directly onto the carbon cloth or, alternatively, onto the Nafion® membrane. Two carbon cloth thicknesses were tested as diffusion layers in the MEA: 0.346 mm (common) and 0.424 mm (ELAT). An increase of the electrocatalytic activity can be obtained by pH control in the alcohol reduction process, possibly due to the better particle dispersion and the smaller particle sizes observed. In addition, a slower current decay in the ohmic region was observed using the thinner carbon cloth. This can be related to a lower resistance of the gas flow through the cloth to the catalytic active layer. Different types of methanol feed were employed in the experiments: by humidification and by evaporation. The results showed that the choice of suitable methods for catalyst preparation as well as for MEA production enhance PEMFC performance.     

Selectivity of anion exchange membrane modified with polyethyleneimine

Previous works have been made on the improvement of selectivity of ion exchange membranes using adsorption of polyelectrolyte on the surface of the materials. The modification of the surface material in the case of an anion exchange membrane concerns the hydrophilic/hydrophobic balance properties and its relationship with the hydration state. Starting from this goal, the AMX membrane has been modified, in this work, by adsorption of polyethyleneimine on its surface. Many conditions of modification of the AMX membrane surface were studied. A factorial experimental design was used for determining the influent parameters on the AMX membrane modification. The results obtained have shown that the initial concentration of polyethyleneimine and the pH of solution were the main influent parameters on the adsorption of polyethyleneimine on the membrane surface. Competitive ion exchange reactions were studied for the modified and the unmodified membrane involving $ {\text{C}}{{\text{l}}^{ - }} $ , $ {\text{NO}}_3^{ - } $ and $ {\text{SO}}_4^{{2 - }} $ ions. All experiments were carried out at constant concentration of 0.3?mol?L^?1 and at 25?°C. Ion exchange isotherms for the binary systems $ \left( {{\text{C}}{{\text{l}}^{ - }}/{\text{NO}}_3^{ - }} \right) $ , $ \left( {{\text{C}}{{\text{l}}^{ - }}/{\text{SO}}_4^{{2 - }}} \right) $ and $ \left( {{\text{NO}}_3^{ - }/{\text{SO}}_4^{{2 - }}} \right) $ were studied. The obtained results show that chloride was the most sorbed and the selectivity order both for the modified membrane and the unmodified one is: $ {\text{Cl}} > {\text{NO}}_3^{ - } > {\text{SO}}_4^{{2 - }} $ , under the experimental conditions. Selectivity coefficients $ {\text{K}}_{{{\text{C}}{{\text{l}}^{ - }}}}^{{{\text{NO}}_3^{ - }}} $ , $ {\text{K}}_{{2{\text{C}}{{\text{l}}^{ - }}}}^{{{\text{SO}}_4^{{2 - }}}} $ and $ {\text{K}}_{{2{\text{NO}}_3^{ - }}}^{{{\text{SO}}_4^{{2 - }}}} $ for the three binary systems and for the two membranes were determined. It was also observed that for the modified membrane the selectivity towards sulfate ion decrease and the modified membrane became more selective towards monovalent anions.     

Surface analysis for catalyst layer (PT/PTFE/C) and diffusion layer (PTFE/C) for proton exchange membrane fuel cells systems (PEMFCs)

X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) studies have been used to analyze the surface of diffusion layer (PTFE/C) and catalyst layer (Pt/C/PTFE) of electrode. Detail analysis of carbon C_1s peak showed that the carbon was of the form of C, C-O, CO, CF, CF₂ and CF₃ with CF₂ is more dominated on the surface compared to CF and CF₃. The oxygen O_1s photoelectron peak showed that the oxygen was of the form of CO and C-O. The platinum was of the form of Pt⁰ with some Pt oxidized to PtO. The scanning electron microscopy was used to observe the dispersion of Teflon in the diffusion layer, the distribution of platinum in the catalyst layer loaded with 0.38 mg Pt/cm² and also the cross section of the membrane electrode assembly. The prepared electrode delivers a superior performance compared with the commercial electrode (E-TEK). The difference in performance between the two electrodes is due to the good localization of the platinum particles.     

Spin-diffusion couples proton relaxation rates for proteins in exchange with a membrane interface

Changes in nuclear spin-lattice relaxation rates that are induced by a freely diffusing paramagnetic relaxation agent are examined for a protein in solution and compared to the case where the protein binds to a membrane. In the solution case, the intramolecular cross-relaxation rates are modest and large differences are observed in the oxygen induced protein–proton relaxation rates. In the case where a dynamic equilibrium between solution and membrane-bound environments is established, the intramolecular ¹H cross-relaxation rates for the protein protons increase dramatically because of the slow reorientational motion in the membrane-bound environment. As a consequence, all protein protons relax with nearly the same spin-lattice relaxation rate constants when bound to the membrane, and site specific relaxation effects of the diffusing paramagnet are suppressed. Slowly reorienting sites or rotationally immobilized sites sampled by observable molecules in vivo will demonstrate similar relaxation leveling effects.