Effects of hot pressing conditions on the performance of Nafion membranes coated by ink-jet printing of Pt/MWCNTs electrocatalyst for PEMFCs

In our previous work, a hydrothermal method was employed to prepare Pt/MWCNTs nanocomposites with 20 wt.% Pt, a low mean Pt nanoparticles size (2.8 nm) and a specific surface area of 99 m² g⁻¹. In this work, the membrane electrode assemblies (MEAs) with hydrothermally synthesized Pt/MWCNTs nanocatalysts were fabricated by catalyst-coated membrane (CCM) method. For this purpose, a commercial HP inkjet printer was used to deposit Pt/MWCNTs ink (as catalyst ink) directly on to the substrate (Nafion membrane or decal substrate) with a loading of 0.2 mg cm⁻² Pt for both the anode and cathode. The effects of hot-pressing conditions on the performance of MEAs were investigated through Taguchi design of experiments method using temperature (100 and 130 °C), pressure (800 and 1000 psi) and time (3 and 5 min) as effective experimental parameters. The compression ratios of MEAs were determined by testing the thicknesses before and after hot-pressing process. The performance of MEAs was characterized by the polarization curves and cyclic voltammetry (CV) and the surface morphologies of the electrodes were observed by scanning electron microscopy (SEM). The results showed that the most appropriate hot-pressing conditions were 800 psi, 100 °C, and 3 min. Electrochemical analysis and physical property examination revealed that the MEA fabricated by CCM method has a better performance compared to the one prepared by conventional decal transfer (DT) method.     

Fabrication and evaluation of membrane electrode assemblies by low-temperature decal methods for direct methanol fuel cells

In this study, a low-temperature decal transfer method is used to fabricate membrane electrode assemblies (MEAs) and the MEAs are tested for application in a direct methanol fuel cell (DMFC). The low-temperature decal transfer uses a carbon-layered decal substrate with a structure of ionomer/catalyst/carbon/substrate to facilitate the transfer of catalyst layers from the decal substrates to the membranes at a temperature as low as 140 °C, and also to prevent the formation of ionomer skin layer that is known to be formed on the surface of the transferred catalyst layer. The DMFC performance of the MEA (with carbon layer) fabricated by the low-temperature decal transfer method is higher than those of MEAs fabricated by the same method without a carbon layer, a conventional high-temperature decal method, and a direct spray-coating method. The improved DMFC performance of the MEA fabricated with carbon layer by the low-temperature decal transfer method can be attributed to the absence of an ionomer skin on the catalyst layer, which can streamline the diffusion of reactants. Furthermore, the intrinsic properties of the MEA fabricated by the low-temperature decal transfer method are elucidated by field-emission scanning electron microscopy (FESEM), electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) techniques, and cathode CO₂ analysis.     

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.     

The effect of the MEA preparation procedure on both ethanol crossover and DEFC performance

In the present work, the changes of Nafion^®-115 membrane porosity in the presence of ethanol aqueous solutions of different concentrations were determined by weighing vacuum-dried and ethanol solution-equilibrated membranes. It was found that membrane porosity increases as ethanol concentration increases. Membrane electrode assemblies (MEAs) have been prepared by following both the conventional and the decal transfer method. The ethanol crossover through these two MEAs was electrochemically quantified by a voltammetric method. A 10 h stability test of direct ethanol fuel cell (DEFC) at a current density of 50 mA cm⁻² was carried out. It was found that the electrode preparation procedure has an obvious effect on ethanol crossover and direct ethanol fuel cell's performance and stability. The single DEFC test results showed that about 15 and 34% of the original peak power density was lost after 10 h of life test for the MEAs prepared by the decal transfer method and the conventional method, respectively. Electrochemical impedance spectrum (EIS) results of the MEAs showed that, in the case of the membrane electrode assembly prepared by the following decal transfer method, the internal cell resistance was almost the same, 0.236 Ω cm² before the life test and 0.239 Ω cm² after 10 h of life test, while the respective values for the membrane electrode assembly by the conventional method are 0.289 and 0.435 Ω cm². It is supposed that the improved cell performance with MEA by the decal transfer method could be resorted to both a better contact between the catalyst layer and the electrolyte membrane and higher catalyst utilization. Furthermore, based on the experimental results, the increased internal cell resistance and the degraded single DEFC performance could be attributed to the delamination of the catalyst layer from the electrolyte membrane.     

Development of a novel decal transfer process for fabrication of high-performance and reliable membrane electrode assemblies for PEMFCs

To improve the performance of a polymer electrolyte membrane fuel cell (PEMFC), various membrane electrode assemblies (MEAs) were fabricated by the decal process. When peeling the decal films away from a Nafion membrane, a novel liquid nitrogen (LN₂) freezing method was employed. The results of a Fourier Transform Infrared (FTIR) analysis of the Nafion membranes demonstrate that this proposed method has no impact on the molecular structure of the Nafion polymer. In addition, the method makes it possible to achieve complete decal transferring under a wide range of hot-pressing pressures and temperatures: 9.8-15.7 MPa and 100-140 °C, respectively. Another approach to optimize the decal technique is to dry catalyst layers under vacuum. Catalyst layers dried under vacuum show better cell performances than atmospherically dried ones. Vacuum drying significantly facilitates the formation of small pores within Pt/C agglomerates on catalyst layers. Third, the use of Additive-A as a commercial dispersant in the catalyst ink has been investigated. From rheological characterizations, including thixotropy and catalyst ink viscosity, it is obvious that the additive plays an important role in elevating the dispersion stability of the ink. In addition, surface images of the catalyst layers revealed that the dispersing agent reduces cracks or fractures within the layers. Although adding Additive-A did not have an effect on the single-cell performance, the MEAs with the dispersant are expected to have better results for a long-term performance test of a single cell.     

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.     

Fabrication of MEA with hydrocarbon based membranes using low temperature decal method for DMFC

The membrane electrode assembly (MEA) with hydrocarbon (HC) based membranes made by a low temperature decal method has been investigated for the direct methanol fuel cells (DMFCs). The conventional low temperature decal (LTD) transfer method (comprised of three layers; viz., carbon, Nafion bonded electrodes and outer ionomer layers over the decal Teflon substrates) meant for the MEAs made of Nafion type membranes is suitably modified to use with hydrocarbon (HC) based membranes. The modification of conventional LTD method is effected by means of modulating the three-layered structure and optimizing other parameters to facilitate complete transfer of catalyst layers onto the HC membranes. The MEAs prepared by the modified LTD method have yielded 21 % higher DMFC performance compared to that of the MEAs produced by conventional LTD method. The structure and electrochemical properties of the MEAs have been analyzed by the field-emission scanning electron microscopy (FE-SEM) and the electrochemical impedance spectroscopy (EIS).     

Development of non-perfluorinated hybrid materials for single-cell proton exchange membrane fuel cells

Development of low temperature fuel cells that operate under 100 °C are needed to reduce the costs, to design a class of hybrid membranes and to construct various structures of membrane-electrode-assembles (MEAs) for proton exchange membrane fuel cells (PEMFC). In this work, PVA/PMA/SiO₂ hybrid composite membranes were synthesized and their conductivities were determined by impedance measurements. We found a maximum conductivity value of 4.2 × 10⁻³ S/cm at 80 °C and 100% relative humidity (RH). A fuel cell test evaluation for various MEAs was conducted by the potentiodynamic analysis and the current density values were determined from the current–voltage (I–V) curves. A maximum current density of 635 mA/cm² was obtained at 80 °C and 100% RH. To the best of our knowledge, this is the first time that a high current density of PVA-based electrolytes for PEMFCs operating at low temperature is reported. The structural characters were examined using of XRD and FTIR methods, and thermal properties were studied using DSC and TGA techniques and the results were discussed (cf. supplementation). The present study revealed that the single cell performance depends mainly on the temperature, relative humidity and chemical compositions of the membranes.     

The influence of the membrane thickness on the performance and durability of PEFC during dynamic aging

The influence of the membrane thickness on the performance and durability of 25 cm² membrane electrode assembly (MEA) toward dynamic aging test was investigated. The tested MEAs consist of chemically stabilized membranes (AQUIVION™) with thicknesses of 30 and 50 μm, electrocatalyst – 46 %Pt/C (Tanaka) with Pt loadings of 0.25 (anode), 0.45 mg cm⁻² (cathode) and gas diffusion layers 25 BC (SGL Group). The applied dynamic aging procedure is repetitive current cycling between 0.12 A cm⁻² for 40 s and 0.6 A cm⁻² for 20 s. The testing conditions were 80 °C, fully saturated hydrogen and air, total pressure of 2.5 atm abs. The aging procedure was regularly interrupted for evaluating the MEAs' “health” via electrochemical methods and mass spectrometry. The carbon support degradation as a function of the electrode potential, current cycling and supplied gas was studied. The effects of the Pt particles agglomeration and Pt physical loss in the active layer of the cathode on the MEAs performance degradation were individually assessed. The effect of the membrane thicknesses on the performance and durability of the PEFC was established. The reasons and stages of MEAs performance degradation were analyzed.     

An efficient decal transfer method using a roll-press to fabricate membrane electrode assemblies for direct methanol fuel cells

This study has focused on the development of a roll-press based decal transfer method to fabricate membrane electrode assemblies (MEAs) for direct methanol fuel cells (DMFCs). This method exhibits an outstanding transfer rate of catalyst layers from substrates to the membrane, despite hot-pressing at a considerably lower pressure and for a much shorter duration than the flat-press based conventional decal method. The MEA produced by a roll-press (R-MEA) delivers an excellent single-cell performance with power densities more than 30% higher than that fabricated using a flat-press (F-MEA). The new method considerably improves catalyst active sites in both electrodes and renders a high cathode porosity. The superior pore structure of the cathode makes the R-MEA more efficient in terms of performance and operation stability under lower air stoichiometries. Moreover, MEAs can be prepared in a continuous mode using this new method due to the unique design of the roll-press. All these advantages demonstrate the superiority of this method over the conventional flat-press decal method and make it suitable for use in the commercial manufacturing of MEAs for direct methanol fuel cells.     

Self-humidifying membrane electrode assembly prepared by adding microcrystalline cellulose in anode catalyst layer as preserve moisture

A novel self-humidifying membrane electrode assemblies (MEAs) with the addition of microcrystalline cellulose (MCC) as a hygroscopic agent into anode catalyst layer was prepared to improve the performance of proton exchange membrane fuel cell (PEMFC) under low humidity conditions. The MEAs were characterized by SEM, contact angles and water uptake measurements. The MEAs with addition of MCC exhibit excellent self-humidifying single cell performance, the cell temperature for self-humidification running is up to 60 °C. As an optimized MEA with 4 wt.％ MCC in its anode catalyst layer, its current density at 0.6 V could be up to 760 mA cm⁻² under 20% of relative humidity, and remains at 680 mA cm⁻² after 22 h long time continuous testing, the attenuation of the current density is only 10%. While the current density of the blank MEA without addition of MCC degraded sharply from 300 mA cm⁻² to 110 mA cm⁻², the attenuation of the current density is high up to 70% within 2 h.     

High platinum utilization in ultra-low Pt loaded PEM fuel cell cathodes prepared by electrospraying

Cathode electrodes for proton exchange membrane fuel cells (PEMFCs) with ultra-low platinum loadings as low as 0.012 mg_Ptcm⁻² have been prepared by the electrospray method. The electrosprayed layers have nanostructured fractal morphologies with dendrites formed by clusters (about 100 nm diameter) of a few single catalyst particles rendering a large exposure surface of the catalyst. Optimization of the control parameters affecting this morphology has allowed us to overcome the state of the art for efficient electrodes prepared by electrospraying. Thus, using these cathodes in membrane electrode assemblies (MEAs), a high platinum utilization in the range 8–10 kW g⁻¹ was obtained for the fuel cell operating at 40 °C and atmospheric pressure. Moreover, a platinum utilization of 20 kW g⁻¹ was attained under more suitable operating conditions (70 °C and 3.4 bar over-pressure). These results substantially improve the performances achieved previously with other low platinum loading electrodes prepared by electrospraying.     

The effects of ionomer content on PEM water electrolyser membrane electrode assembly performance

In this study, the effects of Nafion^® ionomer content in membrane electrode assemblies (MEAs) of polymer electrolyte membrane (PEM) water electrolyser were discussed. The MEAs were prepared with a catalyst coated membrane (CCM) method. The catalysts inks with Nafion ionomer could form uniform coatings deposited on the membrane surfaces. SEM and area EDX mapping demonstrated that anode catalyst coating was uniformly distributed, with a microporous structure. The contents of Nafion ionomer were optimized to 25% for the anode and 20% for cathode. A current density of 1 A cm⁻² was achieved at terminal voltage 1.586 V at 80 °C in a PEMWE single cell, with Nafion 117, Pt/C as cathode, and Ru_0.7Ir_0.3O₂ as anode.     

Proton exchange membrane water electrolysis with short-side-chain Aquivion membrane and IrO2 anode catalyst

A series of three membrane types has been screened for medium temperature solid polymer electrolyte water electrolysis in membrane electrode assemblies coated with 2 mg cm⁻² of iridium oxide as a catalyst for the oxygen evolution reaction, synthesised via a hydrolysis method from the hexachloroiridic acid precursor, and deposited on the membrane either directly by spray deposition or by decal transfer. The short-side-chain perfluorosulfonic acid Aquivion^® ionomer of equivalent weight 870 meq g⁻¹, in membranes of thickness 120 μm, gives higher water electrolysis performance at 120 °C than a composite membrane of Aquivion^® with zirconium phosphate, while a sulfonated ether-linked polybenzimidazole, sulfonated poly-[(1-(4,4′-diphenylether)-5-oxybenzimidazole)-benzimidazole], shows promising performance and no transport limitations up to 2 A cm⁻². The lowest cell voltage was observed at 120 °C for an MEA prepared using spray-coating directly on the Aquivion^® membrane, 1.57 V at 1 A cm⁻².     

Membrane electrode assemblies with low noble metal loadings for hydrogen production from solid polymer electrolyte water electrolysis

High performance membrane electrode assemblies (MEAs) with low noble metal loadings (NMLs) were developed for solid polymer electrolyte (SPE) water electrolysis. The electrochemical and physical characterization of the MEAs was performed by I–V curves, electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM). Even though the total NML was lowered to 0.38 mg cm⁻², it still reached a high performance of 1.633 V at 2 A cm⁻² and 80 °C, with IrO₂ as anode catalyst. The influences of the ionomer content in the anode catalyst layer (CL) and the cell temperature were investigated with the purpose of optimizing the performance. SEM and EIS measurements revealed that the MEA with low NML has very thin porous cathode and anode CLs that get intimate contact with the electrolyte membrane, which makes a reduced mass transport limitation and lower ohmic resistance of the MEA. A short-term water electrolysis operation at 1 A cm⁻² showed that the MEA has good stability: the cell voltage maintained at ∼1.60 V without distinct degradation after 122 h operation at 80 °C and atmospheric pressure.     

An electro-kinetic study of oxygen reduction in polymer electrolyte fuel cells at intermediate temperatures

The oxygen reduction process in polymer electrolyte fuel cells (PEMFCs) was in-situ investigated at intermediate temperatures (80°–130 °C) by using a carbon supported PtCo catalyst and Nafion membrane as electrolyte. To overcome the Nafion dehydration above 100 °C, the experiments were carried out under pressurized conditions. Electro-kinetic parameters such as reaction order and activation energy were determined from the steady-state galvanostatic polarization curves obtained for the PEM single cell. Negative activation energies of 40 kJ mol⁻¹ and 18 kJ mol⁻¹ were observed at 0.9 V and 0.65 V, respectively, in the temperature range 100°–130 °C. This was a consequence of ionomer and membrane dry-out. The ionomer dry-out effect appears to depress reaction kinetics as the temperature increases above 100 °C since the availability of protons at the catalyst–electrolyte interface is linked to the presence of proper water contents. An oxygen reduction reaction of the first order with respect to the oxygen partial pressure was determined at low current densities. Maximum power densities of 990 mW cm⁻² and 780 mW cm⁻² at 100 °C and 110 °C (H₂–O₂) with 100% R.H., were achieved at 3 bars abs.     

Rapid thermal processing of tubular cobalt oxide silica membranes

This work is the first demonstration of rapid thermal processing techniques as applied to metal oxide/silica membranes on tubular geometries. A procedure was developed which combined fast sol–gel synthesis, rapid calcination steps and a thermal annealing stage to reduce the membrane fabrication time by more than two-thirds, from a conventional process taking seven or more days to less than two. A significant aspect of this major development was the use of a pre-hydrolysed silica precursor ethyl silicate 40 (ES40), instead of the generally preferred tetraethyl orthosilicate (TEOS) which eliminated the need for the researcher specific and time consuming sol–gel reaction stages prior to membrane fabrication. As a result, modified-silica membranes containing cobalt oxides could be directly calcined at 600 °C, instead of conventional thermal process which require slow ramping rates of ≤1 °C min⁻¹ to avoid cracking. As-prepared membranes delivered H₂ permeances of 5 × 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ at 450 °C and H₂/N₂ permselectivities of 54. The RTP techniques demonstrated in this work greatly reduced the production time and should both allow researchers to significantly increase their productivity and ultimately reduce the barriers for deployment of inorganic membranes into industrial applications.     

Optimization of catalyst ink composition for the preparation of a membrane electrode assembly in a proton exchange membrane fuel cell using the decal transfer

For low interfacial resistance and feasibility of forming catalyst layer (CL), decal transfer (DT) is considered as one of the most effective methods for preparing a membrane electrode assembly. However, optimization of the catalyst ink composition is necessary, because of the complexity of the CL. Here, 1-propanol is adsorbed onto the CL coated onto the decal, as a swelling agent, for complete transfer of the CL onto Nafion membrane. Using this methodology, flat and complete DT is achieved at the hot-pressing conditions of 60 °C and 5 MPa. For optimization, the solvent-to-carbon ratio (SCR) and Nafion-to-carbon ratio (NCR) are controlled to achieve improved cell performance. In this study, by considering the morphology of CL and the cell performance when CL is annealed at temperatures sufficiently below the boiling point of the solvent, optimized SCR and NCR values of approximately 12.0 and 0.65, respectively, are obtained. In addition, microstructure, thickness and various electrochemical properties of the CLs are examined in detail.     

Alkyl chain modified sulfonated poly(ether sulfone) for fuel cell applications

A new alkyl chain modified sulfonated poly(ether sulfone) (mPES) was synthesized and formed into membranes. The MEAs were tested in the PEMFC and evaluated systematically in the DMFC by varying the methanol concentration from 0.5 to 5.0 M at 60 °C and 70 °C. The synthesized mPES copolymer has been characterized by nuclear magnetic resonance spectroscopy, fourier transform infrared spectroscopy, thermogravimetric analysis, and gel permeation chromatography. The proton conductivity of the resulting membrane is higher than the threshold value of 10⁻² S cm⁻¹ at room temperature for practical PEM fuel cells. The membrane is insoluble in boiling water, thermally stable until 250 °C and shows low methanol permeability. In the H₂/air PEMFC at 70 °C, a current density of 600 mA cm⁻² leads to a potential of 637 mV and 658 mV for 50 μm thick mPES 60 and Nafion NRE 212, respectively. In the DMFC, mPES 60's methanol crossover current density is 4 times lower than that for Nafion NRE 212, leading to higher OCV values and peak power densities. Among all investigated conditions and materials, the highest peak power density of 120 mW cm⁻² was obtained with an mPES 60 based MEA at 70 °C and a methanol feed of 2 M.     

Reinforced short-side-chain Aquivion® membrane for proton exchange membrane water electrolysis

A reinforced short-side-chain per?uorosulfonic acid (PFSA) Aquivion® membrane with equivalent weight (EW) of 980 g/eq and 50 μm thickness produced by Solvay Specialty Polymers was investigated for operation in polymer electrolyte membrane (PEM) water electrolysis. The membrane produced by a dispersion casting process was reinforced by introducing polytetrafluoroethylene (PTFE) fibres in order to enhance mechanical and dimensional stability properties while keeping high conductivity and decreased ohmic drop for operation at high current density. A conventional extruded PFSA Aquivion® membrane with similar EW and thickness was investigated for comparison under similar operating conditions. Membrane-electrode assemblies (MEAs) made of reinforced membranes were tested in a single cell and compared to extruded membranes bared MEAs. All MEAs consisted of home-made unsupported IrRuOx anode and carbon-supported Pt (40%) cathode electrocatalysts. Electrochemical tests showed better water splitting performance for the reinforced Aquivion® based membrane-electrode assembly as compared to the benchmark based MEA. At 90 °C, a current density of 5 Acm^?2 was recorded at 1.8 V (～80% voltage efficiency vs. Higher Heating Value (HHV) with the reinforced Aquivion® membrane. The cell voltage for the reinforced membrane-based cell was about 50 mV lower than the extruded one during a 3500 h durability test. Moreover, lower recoverable losses were observed for the reinforced membrane based MEA during steady-state durability tests and no membrane thinning appeared after prolonged operation.