Effects of dissolved iron and chromium on the performance of direct methanol fuel cell

Effects of Fe³⁺ and Cr³⁺ ions on the performance of direct methanol fuel cell were investigated. The results show that the cell performance decreased remarkably when the concentration of Fe³⁺ or Cr³⁺ exceeded 1 × 10⁻⁴ mol L⁻¹. Fe³⁺ displayed a strong negative effect on the catalytic oxidation of methanol, while Cr³⁺ affected the cell performance primarily by exchanging with protons of the membrane/ionomer and resulted in ionic conductivity losses. Complete recovery of the cell performance was not obtained after flushing the cell with deionized water.     

First Principles Analysis of the Electrocatalytic Oxidation of Methanol and Carbon Monoxide

The strong drive to commercialize fuel cells for portable as well as transportation power sources has led to the tremendous growth in fundamental research aimed at elucidating the catalytic paths and kinetics that govern the electrode performance of proton exchange membrane (PEM) fuel cells. Advances in theory over the past decade coupled with the exponential increases in computational speed and memory have enabled theory to become an invaluable partner in elucidating the surface chemistry that controls different catalytic systems. Despite the significant advances in modeling vapor-phase catalytic systems, the widespread use of first principle theoretical calculations in the analysis of electrocatalytic systems has been rather limited due to the complex electrochemical environment. Herein, we describe the development and application of a first-principles-based approach termed the double reference method that can be used to simulate chemistry at an electrified interface. The simulations mimic the half-cell analysis that is currently used to evaluate electrochemical systems experimentally where the potential is set via an external potentiostat. We use this approach to simulate the potential dependence of elementary reaction energies and activation barriers for different electrocatalytic reactions important for the anode of the direct methanol fuel cell. More specifically we examine the potential-dependence for the activation of water and the oxidation of methanol and CO over model Pt and Pt alloy surfaces. The insights from these model systems are subsequently used to test alternative compositions for the development of improved catalytic materials for the anode of the direct methanol fuel cell.     

Electrocatalytic behaviour for oxygen reduction reaction of small nanostructured crystalline bimetallic Pt–M supported catalysts

A 60 wt% Pt–Fe/C and a 60 wt% Pt–Cu/C catalysts with Fe and Cu content of 5 wt% were prepared by using a combination of colloidal and incipient wetness methods; this has allowed synthesis of small nanostructured crystalline bimetallic catalysts with particle size less than 3 nm and with a suitable degree of alloying. These materials were studied in terms of structure, morphology and composition using XRD, XRF and TEM techniques. The electrocatalytic behaviour for ORR of the catalysts was investigated using the rotating disk technique and compared to that of a pure Pt catalyst with similar particle size. No improvement in performance was recorded with the Pt–Cu compared to Pt catalyst, whereas, a promoting effect in enhancing the ORR was observed for the Pt–Fe catalyst both with and without methanol in the oxygen-saturated electrolyte solution.     

负载在预处理后CNT上的Pt氧化甲醇的性能

对多壁碳纳米管(MWCNT)进行了预处理.红外光谱分析证明:预处理后,MWCNT的表面生成了较多的活性官能团.以处理后的MWCNT为载体、乙二醇为还原剂,用交替微波法制备了Pt/CNT催化剂.相比于在10%HF中搅拌和在10%HF与浓HNO_3混合溶液中搅拌,在10%HF中搅拌再用浓HNO_3回流后的MWCNT作为载体制备的Pt/CNT催化剂,粒径为3.76 nm,具有最大的活性面积,对甲醇的氧化性能最好.     

The Influence of Pt Loading,Support and Nafion Content on the Performance of Direct Methanol Fuel Cells: Examined on the Example of the Cathode

Nano‐sized Pt colloids were prepared using the polyol method and supported on Ketjen black EC 600J (KB), Vulcan XC‐72 (VC) and high surface area graphite 300 (HG). The effects of the Nafion ionomer content, and the Pt loading of the cathode catalyst layer as well as the Pt loading on the support on the performance of direct methanol fuel cells (DMFCs), were studied. The membrane electrode assemblies (MEAs) were analysed using current–voltage curves, cyclic voltammetry, electrochemical impedance spectroscopy (EIS) and adsorbed CO stripping voltammetry. Optimum Nafion to carbon (N/C) ratios (N/C being defined as the weight ratio of the Nafion ionomer to the carbon) were determined. The optimum N/C ratios were found to depend on the support as follows, 1.4, 0.7 and 0.5 for Pt/KB, Pt/VC and Pt/HG, respectively and to be independent of the Pt/C loading range of 20–80 wt% tested in this work. The highest DMFC performances, as well as the highest electrochemical active surface areas, and improved gas diffusivities, were achieved using these ratios. For the catalysts prepared in this work, the average Pt crystallite size was found to decrease with increasing surface area of the support for a particular Pt loading. MEAs made using KB as support and the optimal N/C ratio of 1.4 showed the best performances, i.e. higher than the VC and HG supports for any N/C ratio. The highest DMFC performance was observed using 60 wt% Pt on KB cathode electrodes of 1 mg Pt cm^–2 loading and an N/C value of 1.4. For all three supports studied, the 60 wt% Pt on carbon loading resulted in the best DMFC performance. This may be linked to the Pt particle size and catalyst preparation method used in this work. In comparison to literature results, high DMFC performances were achieved using relatively ‘low' Pt and Ru loadings. For example, a maximum power density of >100 mW cm^–2 at 60 °C was observed using a 1 mg Pt cm^–2 cathode loading and a 2 mg PtRu cm^–2 anode loading.     

Improving the water management and cell performance for the passive vapor-feed DMFC fed with neat methanol

A passive vapor-feed direct methanol fuel cell (DMFC) was experimentally investigated to improve its water management and cell performance when neat methanol was directly used. The effects of different water management approaches, including the addition of a water management layer (WML) and a hydrophobic air filter layer (AFL), and the use of thinner membrane on the cell performance, internal resistance, and fuel efficiency were investigated. The transient discharging behavior and long-term stability of the passive vapor-feed DMFC with the optimized water management were also studied. The results showed that by adding a WML and an AFL, or thinning the membrane thickness, the water management capability can be highly improved, not only enhancing the water recovery from the cathode to the anode, leading to a lower internal resistance and better cell performance, but also curbing the methanol crossover, increasing the fuel efficiency. It is also seen from the long-term constant-voltage test that the discharged current varied with the methanol concentration in the tank and the ambient temperature, while no evident permanent performance degradation was encountered after the 150 h test.     

Application of response surface methodology to optimize and investigate the effects of operating conditions on the performance of DMFC

In this study, the response surface methodology (RSM) has been applied to optimize the operating conditions of direct methanol fuel cell (DMFC). A quadratic model was developed through RSM in terms of related independent variable to describe the current as the response. The input data required in this model has been obtained experimentally. For this purpose, an experimental set up for testing of direct methanol fuel cell has been established to investigate the effects of temperature and flow rate parameters on the cell performance. Two different analyses for operating conditions were performed applying the response surface method to obtain the maximum power. These analyses were based on the unlimited and minimum methanol consumptions. Methanol flow rate, oxygen flow rate, methanol temperature, humidification temperature and cell temperature were the main parameters considered that they were varied between 2 and 50 ml/min, 100-1000 ml/min, 30-70 °C, 30 70 °C and 30-80 °C in the analyses respectively. The maximum current under the unlimited and minimum methanol consumptions was found as 1230 mA and 582 mA based on the contour plots and variance analysis.     

Local entropy generation analysis on passive high-concentration DMFCs (direct methanol fuel cell) with different cell structures

In this paper, the local entropy generation analysis has been conducted based on a two-dimensional, two-phase, non-isothermal DMFC (direct methanol fuel cell) model, the entropy generation contributed by the chemical reactions, heat transfer, mass diffusion, and viscous dissipation is investigated. Then, the performance of fuel cells with different methanol barrier layers and electrolyte membranes have been studied based on the local entropy generation analysis. Results indicate that the entropy generation during cell operation is mainly caused by the irreversible electrochemical reactions, and that the entropy generated by mass diffusion and viscous dissipation can be considered negligible. The entropy generated by heat transfer is about two magnitudes less than the entropy generated by the electrochemical reactions in the passive DMFCs operating near room temperature. The overall entropy generation rate in a DMFC can be decreased by increasing the thickness of the methanol barrier layer and decreasing the thickness of the electrolyte membrane.     

1D modeling of a flowing electrolyte-direct methanol fuel cell

In this study, the performance characteristics of a flowing electrolyte-direct methanol fuel cell (FE-DMFC) and a direct methanol fuel cell (DMFC) are evaluated by computer simulations; and results are compared to experimental data found in the literature. Simulations are carried out to assess the effects of the operating parameters on the output parameters; namely, methanol concentration distribution, cell voltage, power density, and electrical efficiency of the cell. The operating parameters studied include the electrolyte flow rate, flowing electrolyte channel thickness, and methanol concentration at the feed stream. In addition, the effect of the circulation of the flowing electrolyte channel outlet stream on the performance is discussed. The results show that the maximum power densities that could be achieved do not significantly differ between these two fuel cells; however the electrical efficiency could be increased by 57% when FE-DMFC is used instead of DMFC.     

Effect of the cathode open ratios on the water management of a passive vapor-feed direct methanol fuel cell fed with neat methanol

A novel approach has been proposed to improve the water management of a passive direct methanol fuel cell (DMFC) fed with neat methanol without increasing its volume or weight. By adopting perforated covers with different open ratios at the cathode, the water management has been significantly improved in a DMFC fed with neat methanol. An optimized cathode open ratio could ensure both the sufficient supply of oxygen and low water loss. While changing the open ratio of anode vaporizer can adjust the methanol crossover rate in a DMFC. Furthermore, the gas mixing layer, added between the anode vaporizer and the anode current collector to increase the mass transfer resistance, can improve the cell performance, decrease the methanol crossover, and increase the fuel efficiency. For the case of a DMFC fed with neat methanol, an anode vaporizer with the open ratio of 12% and a cathode open ratio of 20% produced the highest peak power density, 22.7 mW cm⁻², and high fuel efficiency, 70.1%, at room temperature of 25 ± 1 °C and ambient humidity of 25-50%.