Performance improvement in direct formic acid fuel cells (DFAFCs) using metal catalyst prepared by dual mode spraying

In the present study, we investigate performance of direct formic acid fuel cells (DFAFCs) consisting of membrane electrode assembly (MEA) prepared by three different catalyst coating methods - direct painting, air spraying and dual mode spraying. For the DFAFC single cell tests, palladium (Pd) and platinum (Pt) are used as anode and cathode catalyst, respectively, and four different formic acid concentrations are provided as a fuel. In the measurements, dual mode spraying shows the best DFAFC performance. To overhaul how difference in coating method influences DFAFC performance, several characterization techniques are utilized. Zeta potential and TEM are used for evaluating anodic Pd particle distribution and its size. Cyclic voltammogram (CV) is measured to calculate electrochemical active surface (EAS) area in anode electrode of the DFAFCs, while charge transfer resistance (R_ct) is estimated by electrochemical impedance spectroscopy (EIS). As a result of the characterizations, Pd prepared by dual mode spraying induces the most uniform particle distribution and the smallest size, the highest EAS area and the lowest R_ct, which are matched with the DFAFC performance result. Conclusively, by adoption of the dual mode spraying, DFAFC can get the maximum power density as high as 240 mW cm⁻² at 5 M formic acid.     

Optimal catalyst layer structure of polymer electrolyte membrane fuel cell

In a membrane electrode assembly (MEA) of polymer electrolyte membrane fuel cells, the structure and morphology of catalyst layers are important to reduce electrochemical resistance and thus obtain high single cell performance. In this study, the catalyst layers fabricated by two catalyst coating methods, spraying method and screen printing method, were characterized by the microscopic images of catalyst layer surface, pore distributions, and electrochemical performances to study the effective MEA fabrication process. For this purpose, a micro-porous layer (MPL) was applied to two different coating methods intending to increase single cell performances by enhancing mass transport. Here, the morphology and structure of catalyst layers were controlled by different catalyst coating methods without varying the ionomer ratio. In particular, MEA fabricated by a screen printing method in a catalyst coated substrate showed uniformly dispersed pores for maximum mass transport. This catalyst layer on micro porous layer resulted in lower ohmic resistance of 0.087 Ω cm² and low mass transport resistance because of enhanced adhesion between catalyst layers and a membrane and improved mass transport of fuel and vapors. Consequently, higher electrochemical performance of current density of 1000 mA cm^-2 at 0.6 V and 1600 mAcm⁻² under 0.5 V came from these low electrochemical resistances comparing the catalyst layer fabricated by a spraying method on membranes because adhesion between catalyst layers and a membrane was much enhanced by screen printing method.     

Highly active screen-printed IrTi4O7 anodes for proton exchange membrane electrolyzers

Electroceramic support materials can help reducing the noble-metal loading of iridium in the membrane electrodes assembly (MEA) of proton exchange membrane (PEM) electrolyzers. Highly active anodes containing Ir-black catalyst and submicronic Ti₄O₇ are manufactured through screen printing technique. Several vehicle solvents, including ethane-1,2-diol; propane-1,2-diol and cyclohexanol are investigated. Suitable functional anodic layer with iridium loading as low as 0.4 mg cm^?2 is obtained. Surface properties of the deposited layers are investigated by atomic force microscopy (AFM). The most homogeneous coating with the highest electronic conductivity is obtained using cyclohexanol. Tests in PEM electrolyzer operating at 1.7 V and 40 °C demonstrate that the CCM with anode coated with cyclohexanol presents a 1.5-fold higher Ir-mass activity than that of the commercial CCM.     

A novel anode catalyst layer with multilayer and pore structure for improving the performance of a direct methanol fuel cell

A novel anode catalyst layer (CL) has been prepared by ultrasonic‐spray process which combines directly spraying method and catalyst‐coated membrane switchover method, and heated‐stereoscopic process has been used to enhance bond force between CLs and proton exchange membrane in this paper. The scanning electron microscopy, electrochemical impedance spectra and polarization curves show that: the anode outer CL with pores and meshwork structure has increased the electrochemical active surface area and retained the transfer of protons and electrons, and the anode inner CL with compact structure has prevented methanol crossover. And the gradient catalysis for methanol electrochemical catalytic oxidation reaction has been achieved. The open circuit voltage has reached 0.697 V, and the performance has increased from 116.8 mW cm^?2 of traditional membrane electrode assembly (MEA) to 202.6 mWcm^?2 of novel MEA at 80°C. Copyright © 2012 John Wiley & Sons, Ltd.     

Pd nanoparticles supported on copper phthalocyanine functionalized carbon nanotubes for enhanced formic acid electrooxidation

The hydrothermal synthesis of a novel Pd electrocatalyst using copper phthalocyanine-3,4′,4″,4′″-tetrasulfonic acid tetrasodium salt (TSCuPc) functionalized multi-walled carbon nanotubes (MWCNTs) composite as catalyst support for Pd nanoparticles is reported. The prepared nanocomposites were characterized by UV–vis absorption spectroscopy, Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, thermogravimetric analysis (TGA), X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and electrochemical tests. It is found that Pd nanoparticles are uniformly deposited on the surface of TSCuPc-MWCNTs, and their dispersion and electrochemical active surface area (ECSA) are significantly improved. Studies of cyclic voltammetry and chronoamperometry demonstrate that the Pd/TSCuPc-MWCNTs exhibits much higher electrocatalytic activity and stability than the Pd/AO-MWCNTs catalyst for formic acid oxidation. This study implies that the as-prepared Pd/TSCuPc-MWCNTs will be a promising candidate as an anode electrocatalyst in direct formic acid fuel cell (DFAFC).     

Effects of Nafion loading in anode catalyst inks on the miniature direct formic acid fuel cell

Nafion, within the anode and cathode catalyst layers, plays a large role in the performance of fuel cells, especially during the operation of the direct formic acid fuel cell (DFAFC). Nafion affects the proton transfer in the catalyst layers of the fuel cell, and studies presented here show the effects of three different Nafion loadings, 10 wt.%, 30 wt.% and 50 wt.%. Short term voltage-current measurements using the three different loadings show that 30 wt.% Nafion loading in the anode shows the best performance in the miniature, passive DFAFC. Nafion also serves as a binder to help hold the catalyst nanoparticles onto the proton exchange membrane (PEM). The DFAFC anode temporarily needs to be regenerated by raising the anode potential to around 0.8 V vs. RHE to oxidize CO bound to the surface, but the Pourbaix diagram predicts that Pd will corrode at these potentials. We found that an anode loading of 30 wt.% Nafion showed the best stability, of the three Nafion loadings chosen, for reducing the amount of loss of electrochemically active area due to high regeneration potentials. Only 58% of the area was lost after 600 potential cycles in formic acid compared to 96 and 99% for 10 wt.% and 50 wt.% loadings, respectively. Lastly we present cyclic voltammetry data that suggest that the Nafion adds to the production of CO during oxidation of formic acid for 12 h at 0.3 V vs. RHE. The resulting data showed that an increase in CO coverage was observed with increasing Nafion content in the anode catalyst layer.     

Effect of rheological properties of catalyst slurry on the structure of catalyst layer in PEMFC

The dispersion process significantly influences the dispersion of catalyst slurry in proton exchange membrane fuel cells (PEMFCs). The particle size distribution and rheological properties of clusters in slurry directly affect the catalyst layer's coating state, surface morphology, and structure. This paper prepared four different catalyst slurries by high shear emulsification, homogenization, ball milling, and ultrasonic methods. The average particle sizes of clusters in slurry were 725, 337, 452, and 1098 nm, respectively. The rheological properties of catalyst slurry prepared by several dispersion processes are different. Amplitude scanning test demonstrates that yield stresses of slurries prepared by shear, homogenization, ball milling, and ultrasonic methods are 0.047, 0.185, 0.133, and 0.136 Pa, respectively. The viscosity of catalyst slurry is the lowest when prepared by the shear method and is the highest when prepared by the ultrasonic method, and the slurry prepared by homogenization and ball milling methods has the best thixotropy. By observing the catalyst layer, the slurry cluster prepared by the homogenization method has small particles, a strong network structure, and good thixotropy, producing a flat catalyst layer and fewer cracks. Electrochemical tests demonstrate that the catalyst layer with the smoothest surface morphology, the smallest cluster particles, and fewer cracks leads to higher polarization performance. The output voltage of the ink prepared by the homogenization method can reach 0.726 V under the condition of 1000 mA cm^?2.     

High-performance anode for Polymer Electrolyte Membrane Fuel Cells by multiple-layer Pt sputter deposition

We investigate the sputtering deposition as a tool for preparing Polymer Electrolyte Membrane Fuel Cell (PEMFC) electrodes with improved performance and catalyst utilization. Anodes of PEMFC with ultra-low loading of Pt (0.05 mg cm⁻²) are developed by alternate sputtering of Pt and painting layers of carbon nanotube ink with Nafion directly on the gas diffusion layer. Sputter depositing alternate layers of Pt on carbon-Nafion layer (CNL) has increased the anode activity over single-layer Pt deposited anode due to improved porosity and the presence of Pt nanoparticles in the inner CNL. Also, we investigated the influence of Nafion content in the CNL. The optimal Nafion content giving less resistance and better performance in an anode is 29 wt.%. This is significantly lower than for standard MEA anodes, indicating sufficient interfacial contact between each CNL. We studied the anodes prepared with 50 wt.% Nafion, which revealed larger ohmic resistance and also, blocks the CNL pores reducing gas permeability. Excellent mass transfer and performance is obtained with three-layer Pt sputter deposited anode with CNL containing 29 wt.% of Nafion.     

Effects of MEA preparation on the performance of a direct methanol fuel cell

The effects of membrane electrode assemblies (MEAs) fabrication methods (spraying and scraping methods) and the hot-pressing pretreatment of anode electrodes on the performance of direct methanol fuel cells (DMFCs) were investigated. The MEA prepared with scraped anode catalyst layer without the hot-pressing pretreatment showed the highest power density of 67 mW cm⁻² at 80 °C and ambient pressure. The scraping method proved to be a little more profitable for improving the cell performance than the spraying method. Atomic force microscopy (AFM) analysis revealed relatively smooth surface of the scraped anode catalyst layer compared with that of sprayed anode catalyst layer. Scanning electron microscopy (SEM) images showed that a suitable number of cracks which were uniformly distributed on the surface of scraped catalyst layer formed a porous structure. It was demonstrated that the surface structure and roughness of the anode catalyst layer had less effect on the performance of the anode electrode in a DMFC. The hot-pressing pretreatment of the anode electrode decreased the performance of the MEA due to the difficulty for electrons and mass transport in the anode electrode, namely the increase of internal cell resistance.     

Applications of graphene nano-sheets as anode diffusion layers in passive direct methanol fuel cells (DMFC)

The diffusion layer is an important structure in the membrane electrode assembly (MEA) of direct methanol fuel cells (DMFCs) that provide a support layer for catalysts, electronic channels, and gas–liquid mass transport channels. In this study, three types of carbon-based materials were used to fabricate anode diffusion layers – carbon black Vulcan^® (CBV), M-15 grade graphene nanosheets (GM-15) and C-500 grade graphene nanosheets (GC-500). The microporous layers of cathodes were constructed with CBV. A carbon-based microporous layer with a 2 mg cm^?2 loading was coated onto a PTFE-pretreated carbon cloth, while a Nafion-117 membrane was applied as the electrolyte to the DMFCs. Pt–Ru black and Pt black were used as anode and cathode electrode catalysts, each with loadings of 8 mg cm^?2 and 4 mg cm^?2, respectively. All tests were conducted using MEAs with active areas of 4 cm² and air was supplied to single cells by passive modes. Surface morphology was studied using scanning electron microscopy (SEM), which produced pictures of complex network formations within the structures. CBV consists of nanosized carbon particles, while both GM-15 and GC-500 are made of stacks of graphene sheets with flaky structures that increase catalyst utilization. Performance tests of the DMFCs were conducted using a potentiostat that generated polarization curves. The highest peak power density of 13.7 mW cm^?2 was obtained by the GC-500 anode diffusion layer using 3 M methanol as fuel. The energy efficiency of the passive DMFCs was approximately 10% with a specific energy of approximately 610 Wh kg^?1, which is higher than that of conventional lithium-ion batteries, portraying the bright future of alternative energy sources for use in power applications for portable devices. The high power densities obtained by both graphene-based materials, GM-15 and GC-500, demonstrate that graphene is a material other than state of the art carbon black that has the potential to be used as a DMFC anode support material.     

Feasibility of ultra-low Pt loading electrodes for high temperature proton exchange membrane fuel cells based in phosphoric acid-doped membrane

Factors as the Pt/C ratio of the catalyst, the binder content of the electrode and the catalyst deposition method were studied within the scope of ultra-low Pt loading electrodes for high temperature proton exchange membrane fuel cells (HT-PEMFCs). The Pt/C ratio of the catalyst allowed to tune the thickness of the catalytic layer and so to minimize the detrimental effect of the phosphoric acid flooding. A membrane electrode assembly (MEA) with 0.05 mg_Ptcm⁻² at anode and 0.1 mg_Ptcm⁻² at cathode (0.150 mg_Ptcm⁻² in total) attained a peak power density of 346 mW cm⁻². It was proven that including a binder in the catalytic layer of ultra-low Pt loading electrodes lowers its performance. Electrospraying-based MEAs with ultra-low Pt loaded electrodes (0.1 mg_Ptcm⁻²) rendered the best (peak power density of 400 mW cm⁻²) compared to conventional methods (spraying or ultrasonic spraying) but with the penalty of a low catalyst deposition rate.     

Optimum compositions of membrane electrode assemblies (MEAs) for direct dimethyl ether fuel cell

We investigated the effects of the compositions of catalyst layers and diffusion layers on performances of the membrane electrode assemblies (MEAs) for direct dimethyl ether fuel cell. The performances of the MEAs with different thicknesses of Nafion membranes were compared in this work. The optimal compositions in the anode are: 20 wt% Nafion content and 3.6 mg cm⁻² Pt loading in the catalyst layer, and 30 wt% PTFE content and 1 mg cm⁻² carbon black loading in the diffusion layer. In the cathode, MEA with 20 wt% Nafion content in the catalyst layer and 30 wt% PTFE content in the diffusion layer presented the optimal performance. The MEA with Nafion 115 membrane displayed the highest maximum power density of 46 mW cm⁻² among the three MEAs with different Nafion membranes. Copyright © 2009 John Wiley & Sons, Ltd.     

PdBi bimetallic catalysts including polyvinylpyrrolidone surfactant inducing excellent formic acid oxidation reaction and direct formic acid fuel cell performance

PdBi bimetallic catalysts are synthesized while their catalytic activity and stability for formic acid oxidation reaction (FAOR) and direct formic acid fuel cell (DFAFC) performance are evaluated. According to investigations, Pd₂Bi₁/C catalyst including low Pd amount promotes oxygen desorption with enhancement in CO poisoning resistance. With that, indirect formic acid oxidation reaction (IFAOR) and its stability are improved. To further improve the FAOR, polyvinylpyrrolidone (PVP) surfactant is contained due to its amphiphilic property reducing Bi aggregation. To determine optimal amount of the PVP, analysis using TEM and XPS is performed and the results are verified by density functional theory (DFT). According to TEM, in 0.22 PVP-Pd₂Bi₁/C catalyst, PdBi has small size (～5 nm) and is well-dispersed with widest E_d- E_F of 3.85 eV, proving the catalyst induces effective CO-poisoning resistance and less Bi aggregation. These results are also compatible with trend in FAOR measured by cyclic voltammogram (CV). Even long-term stability, the catalyst maintains catalytic activity well. The best performance of DFAFC using the catalyst (32.7 mW cm^?2·Pd_g^?1) indicates that 0.22 PVP- Pd₂Bi₁/C is excellent catalyst for FAOR and DFAFC performances.     

Design, fabrication and performance evaluation of a miniature air breathing direct formic acid fuel cell based on printed circuit board technology

A miniature air breathing compact direct formic acid fuel cell (DFAFC), with gold covered printed circuit board (PCB) as current collectors and back boards, is designed, fabricated and evaluated. Effects of formic acid concentration and catalyst loading (anodic palladium loading and cathodic platinum loading) on the cell performance are investigated and optimized fuel concentration and catalyst loading are obtained based on experimental results. A maximum power density of 19.6 mW cm⁻² is achieved at room temperature with passive operational mode when 5.0 M formic acid is fed and 1 mg cm⁻² catalyst at both electrodes is used. The home-made DFAFC also displays good long-term stability at constant current density.     

Fabrication and optimization of LSM infiltrated cathode electrode for anode supported microtubular solid oxide fuel cells

In this study, anode supported microtubular solid oxide fuel cells (SOFCs) with LSM (lanthanum strontium manganite) catalyst infiltrated LSM-YSZ (yttria stabilized zirconia) cathodes are developed to increase the density of triple/three phase boundaries (TPBs) in the cathode, thereby to improve the cell performance. For this purpose, two different porous YSZ layers are formed on the dense YSZ electrolyte, i.e., one is with co-sintering while the other one is not. Incorporation of LSM into these porous YSZ layers is achieved via dip coating of a sol-gel based infiltration solution. The effects of the fabrication method for porous YSZ, LSM solution dwelling time and the thickness of the porous YSZ layer on the cell performance are experimentally investigated and optimized in the given order. A reference cell having a conventional dip coated cathode prepared by mixing the commercial LSM and YSZ powders is also fabricated for comparison. The results show that among the cases considered, the highest peak power density of 0.828 W/cm² can be obtained from the cell, whose single dip coated porous electrolyte layer co-sintered with the dense electrolyte is impregnated with LSM for a dwelling time of 45 min. On the other hand, the peak power density of the reference cell is measured as only 0.558 W/cm². These results reveal that ～50% increase in the maximum cell performance compared to that of the reference cell can be achieved by LSM infiltration after the optimizations.     

Improved PEM fuel cell performance with hydrophobic catalyst layers

Flooding of catalyst layers is one of the major issues, which effects performance of low temperature proton exchange membrane fuel cells (PEMFC). Rendering catalyst layers hydrophobic one may improve the performance of PEMFC depending on Pt percentage in the catalyst and Polytetrafluoroethylene (PTFE) loading on the electrode. In this study, effect of hydrophobicity in catalyst layers on performance has been investigated by comparing performances of membrane electrode assemblies prepared with 48% Pt/C. Ultrasonic coating technique was used to manufacture highly efficient electrodes. Power density at 0.45 V increased by the addition of PTFE, from 0.95 to 1.01 W/cm² with H₂/O₂ feed; while it slightly increased from 0.52 W/cm² to 0.53 W/cm² with H₂/Air feed. Addition of PTFE to catalyst layers while keeping Pt loading constant, enhanced performance providing improved water management. Kinetic activity increased by decreasing Nafion loading from 0.37 mg/cm² to 0.25 mg/cm² while introducing PTFE (0.12 mg/cm²) to the electrode. Electrochemical impedance spectroscopy (EIS) results proved that charge transfer resistance decreased with hydrophobic catalyst layers for H₂/O₂ feed. This is attributed to enhanced water management due to PTFE presence.     

Three-dimensional CFD modeling of a direct formic acid fuel cell

A three-dimensional (3D) with one straight channel computational fluid dynamics (CFD) model is developed by using the ESI-CFD software to investigate the effect of varying operating parameters on the performance of direct formic acid fuel cell (DFAFC) and formic acid crossover from the anode to the cathode side through the membrane. Formic acid concentration (4 M–10 M), temperature (313 K–353 K), anode stoichiometry (1.5–3.0), and cathode stoichiometry (2.0–3.0) are the selected operating parameters in this study. Validation results of the DFAFC are in reasonable agreement with the typical trends reported in the literature on DFAFC performance. Simulation results indicate that formic acid concentration, temperature, anode, and cathode stoichiometry influenced the DFAFC performance and the formic acid crossover. The increments of formic acid concentration or stoichiometric ratio will improve the cell performance; however, the current densities obtained are declining to the increasing temperature. The increase in temperature of the formic acid concentration is found to lead to the decrease in performance. For the formic acid crossover phenomenon, the formic acid crossover flux increases with the increments of formic acid concentration, DFAFC operating temperature, and anode and cathode stoichiometric ratios.     

Real contribution of formic acid in direct formic acid fuel cell: Investigation of origin and guiding for micro structure design

We first experimentally verified the real contribution of formic acid (FA) in the direct formic acid fuel cell (DFAFC). By comparing the cell performance of the fuel cell fueled with FA and methanol, we found that FA not only acts as fuel in the fuel cell, but is also of benefit to proton conducting and triple phase boundary (TPB) building in the anode. Considering the real contribution and the special mass transfer behavior of FA in the fuel cell, the anode was reasonably designed and optimized. Carbon cloth was selected as the optimized anode diffusion layer to achieve quick methanol transfer from fuel reservoir to anode catalyst. The decal method was proved to be the better choice for membrane electrode assembly (MEA) fabrication than the traditional hot pressing because it can result in better TPB building and lowering the FA crossover. DFAFC performed approximately 60% better after these anodic micro structure optimizations.     

Effect of deactivation and reactivation of palladium anode catalyst on performance of direct formic acid fuel cell (DFAFC)

In the present study, degradation and recovery in cell performance of direct formic acid fuel cells (DFAFCs) are investigated. For DFAFC tests, palladium (Pd) and platinum (Pt) are used as anode and cathode catalysts, respectively, and are applied to a Nafion membrane by catalyst-coated membrane (CCM) spraying. As multiple repeated DFAFC operations are performed, the cell performance of DFAFC is steadily degraded. This behavior is ascribed to the electrooxidation of Pd into Pd-OH, which occurs between 0.1 and 0.55 V. To investigate the dependency of the cell performance on the Pd-OH and to evaluate how the cell performance is regenerated, cyclic voltammetry (CV) tests are executed. In CV experiments where the voltages applied to the DFAFC single cell are lower than 0.7 V vs. DHE, the cell performance is further deactivated due to continuous production of Pd-OH. Conversely, in CV experiments where the voltage is higher than 0.9 V vs. DHE, cell performance is reactivated due to redox reactions of Pd-OH into Pd-O and Pd-O into Pd. ATR-FTIR and XPS are used to confirm the transformations of Pd.     

Methanol conditioning for improved performance of formic acid fuel cells

This paper considers the effect of methanol pretreatment on the performance of a direct formic acid fuel cell (DFAFC). We find that conditioning of the cell in methanol results in a substantial increase in current. The current at 60 °C increases from 95 to 320 mA/cm² at 0.3 V. The maximum power density increases from 33 to 119 mW/cm². The cell resistance decreases from 0.37 to 0.32 Ω cm². CO stripping experiments show that the catalyst is not being greatly affected by these changes. Our interpretation of the data is that the anode layer of membrane electrolyte assembly (MEA) undergoes some change during the methanol conditioning. The change improves the performance.