The effect of cell orientations and environmental conditions on the performance of a passive DMFC single cell

A single cell passive air-breathing liquid feed direct methanol fuel cell (DMFC) is designed and fabricated. Furthermore, the effects of cell orientation and environmental conditions such as temperature and relative humidity on the performance of such passive DMFC are tested experimentally. The obtained results indicate that both environmental temperature and relative humidity have significant effects on the performance of fabricated fuel cell. The experimental data contained within this work shows that under lower relative humidity and higher temperature, the passive air-breathing direct methanol fuel cell has higher power output and better performance. According to experimental results, flooding has a vital role on the cell performance in various relative humidity and temperatures. The results also show that cell orientation has a strong effect on the performance of passive DMFC. The best power output and performance were achieved under vertical orientation.     

直接甲醇燃料电池膜及阴极模拟

本文提出一个针对直接甲醇燃料电池膜及阴极的二维、多组分稳态数学模型．模型根据直接甲醇膜燃料电池膜及阴极运行工况特性,考虑质量、动量、组分守恒以及电池中的电化学过程而建立,并应用了计算流体动力学(CFD)技术．模拟结果表明传质对直接甲醇燃料电池的性能影响很大;本文还进行了直接甲醇燃料电池阴极水管理的初步探讨．     

Composites of Proton-Conducting Polymer Electrolyte Membrane in Direct Methanol Fuel Cells

Fuel cells are a replacement for the conventional energy resources. As early as 1839, William Grove discovered the basic operating principle of fuel cells by reversing water electrolysis to generate electricity from hydrogen and oxygen. A Direct Methanol Fuel Cell (DMFC) operates on liquid fuel, which is one of the exciting varieties of fuel cells. There are many problems with DMFCs such as the high cost of electrolyte membranes, high platinum loading, CO poisoning, fuel cross-over, and so on. In this review, research regarding the solution of these problems will be cited and discussed. The electrical performance (in respect to power density) of the composites for the Nafion® and other perfluorinated membranes in DMFC are evaluated. The effect of these modifications on various aspects, such as mobility of protons through the membrane, permeation of hydronium ions, and cross-over of methanol through the membrane leading to the negative potential, have previously been discussed. Therefore, the main focus of this review is on the effect of composites of Nafion® and non-fluorinated membranes on the DMFC 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.     

Direct methanol fuel cells : Methanol crossover and its influence on single DMFC performance

In the present investigation, the methanol crossover rate through Nafion®-115 membrane at different temperatures and different concentrations had been investigated in a fuel cell test apparatus by using gas chromatography analysis. The singledirect methanol fuel cell (DMFC) tests were carried out to investigate the effect of the concentration of methanol aqueous solutions and cell temperature on methanol crossover and consequently, on the open circuit voltage and the cell performance of DMFC. It can be found that the methanol crossover rate through Nafion® membrane increases as methanol concentration and temperature increase. It can also be found that methanol crossover presented a negative effect on the open circuit voltage and the single DMFC performance. Single DMFC test results showed that an improved cell performance was obtained as temperature increased although the methanol crossover rate increased with temperature increment.     

Surface-modified Nafion membrane by trioctylphosphine-stabilized palladium nanoparticles for DMFC applications

Trioctylphosphine (TOP)/Pd composites have been synthesized and used as a methanol-barrier material to modify the surface of Nafion 115. The TOP/Pd composites have been applied to the surface of Nafion instead of being incorporated into the Nafion matrix, to provide the best chance of maintaining the inherent proton conductivity of Nafion. The properties of the TOP/Pd-modified membrane, in terms of its conductivity and methanol permeability, as well as the performance of the membrane electrode assembly (MEA) in direct methanol fuel cell (DMFC), have been analyzed and compared with those of bare Nafion. The DMFC performance of the TOP/Pd-modified membrane is somewhat better than that of the bare Nafion one at methanol concentration of 2 M and significantly better at a high concentration of 5 M. The TOP/Pd-modified membrane is able to operate the DMFC using a high concentration of methanol, which can satisfy the requirement to reduce the reactant volumes for portable applications as well as to achieve high performance. In contrast to bare Nafion, the TOP/Pd-modified membrane with its well-adhering and crack-free modified surface shows effect on reducing the methanol loss.     

High-throughput screening of fuel cell electrocatalysts

The drawbacks of our earlier report of preparing fuel cell catalyst arrays by borohydride reduction of inkjet prepared arrays of metal salts are discussed along with the need for inclusion of state-of-the-art metrics in all array screening. An alternative method for screening of hydrogen/air cathode catalysts, direct methanol fuel cell (DMFC) anode catalysts, and catalyst loading studies is provided. State-of-the-art Johnson Matthey catalysts were used in control experiments to demonstrate the utility of the array fuel cell for high throughput screening of fuel cell catalysts in the 3-4 mg/cm² range. This report lays out hard learned rules for high throughput screening and demonstrates that the array fuel cell can be used for very precise screening of libraries of membrane electrode assembly (MEA) components without the pitfalls discussed in the introduction.     

Ultrasonic radiation to enable improvement of direct methanol fuel cell

To improve DMFC (direct methanol fuel cell) performance, a new method using ultrasonic radiation is proposed and a novel DMFC structure is designed and fabricated in the present paper. Three ultrasonic transducers (piezoelectric transducer, PZT) are integrated in the flow field plate to form the ultrasonic field in the liquid fuel. Ultrasonic frequency, acoustic power, and methanol concentration have been considered as variables in the experiments. With the help of ultrasonic radiation, the maximum output power and limiting current of cell can be independently increased by 30.73% and 40.54%, respectively. The best performance of DMFC is obtained at the condition of ultrasonic radiation (30 kHz and 4 W) fed with 2 M methanol solution, because both its limiting current and output power reach their maximum value simultaneously (222 mA and 33.6 mW, respectively) under this condition. These results conclude that ultrasonic can be an alternative choice for improving the cell performance, and can facilitate a guideline for the optimization of DMFC.     

High-throughput screening of binary catalysts for oxygen electroreduction

A series of Pt based and non-Pt catalysts for proton exchange membrane fuel cell (PEMFC) and direct methanol fuel cell (DMFC) have been evaluated towards oxygen reduction, by high-throughput optical screening. Fluorescein was first used as pH indicator for detecting pH change of the electrolyte in the vicinity of cathode caused by oxygen reduction. Arrays of catalyst spot comprised of binary catalysts and pure Pt were prepared by using robotic micro-dispenser. The analysis of fluorescence images has showed that some of Pt based catalysts including PtBi, PtCu, PtSe, PtTe and PtIr, as well as RuFe, as a non-Pt catalyst, exhibited higher activities and methanol tolerance than pure Pt. Moreover, acceptable stability of these catalysts at high potential in acid environment suits them to the requirements of cathode catalyst in PEMFC or DMFC.     

DMFC两相流及其对传质影响的研究

采用自制的实验系统对液态进料直接甲醇燃料电池(DMFC)阳极交叉指状流道内的两相况功特性进行了可视化实验研究.自制的DMFC单电池带有透明窗口,采用镀金的不锈钢阴极极板和透明的聚碳酸脂阳极流场板,电解质为Nafion117膜.实验过程中燃料电池的进口总管和出口总管是水平的,进口流道和出口流道是竖直的.实验发现,出口流道中典型的两相流流型是泡状流、而出口总管中的典型流型是弹状流.进口流道中的气弹和气柱导致了阳极传质恶化.     

直接甲醇燃料电池反应和组分传递的模型计算

本文建立了直接甲醇燃料电池的二维、单相数学模型来研究电池内各种场的分布情况.模型中考虑了与电化学反应相伴随的、与流体动力学相关的反应与物料传递的耦合过程以及甲醇串流对阴极反应的影响;对阳极和阴极催化层传质过程引入了团聚块模型进行修正.计算了电池内的反应组分浓度分布和局部电流分布以及催化层沿长度方向的局部过电势分布,分析丁催化层内反应的非均匀性.在此基础上考察了对电池流场板结构的改进方案:减小集流板肋条宽度以及在肋条过窄时引入金属泡沫代替电池流场板和扩散层对电池性能的影响,通过对比计算表明两种改进均可以使得催化层反应均匀化,使电池输出性能得到提高,后者效果更佳.     

Non-conventional solid state fuel cells: Materials & technology

Investigation of “Non-conventional material” for fuel cells, such as oxide-salt-ceramic composites and ceria based or perovskite oxides with different dopants, leads to a much lower fuel cell operating temperature compared to conventional high temperature, ∼1000 °C, solid oxide fuel cells (SOFCs), which provides the new possibilities for facilitating SOFC commercialisation. This work is essentially an effort to develop new types of solid oxide ion and proton fuel cells (SOFC and SPFC) at fairly low temperatures, <800 °C, or intermediate temperature, 400 to 800 °C. The conventional high temperature SOFCs using yttria-stabilised zirconia (YSZ) materials, and low temperature SPFCs (<200 °C) using polymer membrane electrolytes have complex material and system problems from either special high temperature requests or expensive technology and reforming systems. This research is intended to provide materials and technology along new routes for so-called non-conventional fuel cell systems, to facilitate solid state fuel cell cmmercialisation. The fuel cell research on these non-conventional systems is promising. This paper, based on recent achievements in research on materials and technology, summaries the developnt of material systems and new fuel cell devices regarding their potential marketability in the near future. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

New solid state fuel cells - green power source for 21st century

The exhaustion of the major fossil energy sources on earth in near future and the serious environmental pollution from the fuel combustion processes in the presently applied technologies are the most important problems of modern society. The sustainable development of mankind requests strongly to develop “green” power devices characterized by high fuel energy conversion efficiency, less pollution to the environment and convenience to use. Fuel cells have been commonly accepted to be a kind of clean, safe and convenient power source with high energy efficiency and are on the verge of revolutionizing the electric power industry by offering better ways to produce electricity and to deliver it to the consumers. Among all the advanced fuel cells being developed, which one might be the better choice for ideal green power generators in the 21st century? The answer is solid state fuel cells, particularly the solid oxide fuel cells(SOFCs) but not in the present stage of development. The new generation of SOFCs will certainly be based on all the results and experiences achieved so far in the fuel cell field and a lot of R & D work has to be performed furthermore. This paper attempts to present the current status of the R & D work on fuel cells, especially SOFCs, new concepts and trends, problems and possible measures which may initiate further discussion. The present article includes the following sub-topics:

The best electric power plants for the 21st Century

R & D on SOFCs: current status, problems and new trends

Intermediate temperature SOFCs - what do we need to do?

Fabrication techniques - soft chemistry routes

What to do for coming up with “green” power plants?

     

Hydrogen energy and solid state fuel cells

This paper discusses hydrogen energy and the methods for production of hydrogen. It also provides a review of various materials which are hydrogen permeable. Previous studies on the proton-conducting ceramics and their properties are summarized. The principle of proton-conducting solid state fuel cell for conversing the energy of hydrogen containing fuel is described with a discussion of the advantages of proton-conducting ceramic fuel cells as compared to oxygen-ionic conducting fuel cells. The paper is concluded with a discussion of the major materials related technical challenges in the development of the proton-conducting ceramic fuel cells. Paper presented at the 97th Xiangshan Science Conference on New Solid State Fuel Cells, Xiangshan, Beijing, China, June 14–17, 1998.     

Reduced methanol crossover and enhanced proton transport in nanocomposite membranes based on clay−CNTs hybrid materials for direct methanol fuel cells

Hybrid nanomaterial based on the combination between a 2D silicate structure of a smectic clay (SWy) and 1D structures of carbon nanotubes has been synthesized and used as additive in the polymer matrix of Nafion for the preparation of electrolyte nanocomposite membranes. The CNTs anchored on the clay’s lamellae were subsequently oxidized and organo-functionalized by sulphonic groups. The hybrid membranes have been tested in direct methanol fuel cells (DMFCs) and studied by NMR spectroscopy (pulse field gradient technique and relaxation times), electrochemical impedance spectroscopy and SEM microscopy. The study of the molecular dynamics of methanol and protons, as well as the tests in the DMFC, shows the effectiveness of these “branched particles” for the reduction of the methanol crossover, whilst ensuring appropriate proton conductivity, especially in conditions of low humidity and high temperature (>100 °C).     

PtCu二元金属催化剂抗CO中毒性能的理论研究

基于密度泛函第一性原理研究了M-graphene(M=Pt,Cu,PtCu;graphene:pristine,Stonewales,Single-vacancy graphene)催化剂的抗CO中毒能力.对于纯Pt和纯Cu吸附在石墨烯上时,Pt的吸附能力最强,吸附结构最稳定.当Pt中掺杂Cu后,PtCu二元金属催化剂在石墨烯上的吸附结构的稳定性进一步增强.通过对M-graphene-CO吸附结构的研究,发现以缺陷石墨烯为载体的金属催化剂的抗CO中毒能力优于以原始石墨烯为载体的同种金属催化剂,PtCu二元金属催化剂抗CO中毒能力明显好于纯Pt和纯Cu的抗毒性.因此,缺陷石墨烯载体以及掺杂Cu的PtCu二元金属催化剂,对于提高催化剂的稳定性和抗CO中毒能力起到了重要的作用.     

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)).     

Oxide anode materials for solid oxide fuel cells

A major advantage of solid oxide fuel cells (SOFCs) over polymer electrolyte membrane (PEM) fuel cells is their tolerance for the type and purity of fuel. This fuel flexibility is due in large part to the high operating temperature of SOFCs, but also relies on the selection and development of appropriate materials — particularly for the anode where the fuel reaction occurs. This paper reviews the oxide materials being investigated as alternatives to the most commonly used nickel–YSZ cermet anodes for SOFCs. The majority of these oxides form the perovskite structure, which provides good flexibility in doping for control of the transport properties. However, oxides that form other crystal structures, such as the cubic fluorite structure, have also shown promise for use as SOFC anodes. In this paper, oxides are compared primarily in terms of their transport properties, but other properties relative to SOFC anode performance are also discussed.     

Sulfonated Aromatic Polymers and Organically Modified Montmorillonite Nanocomposite Membranes for Fuel Cells Applications

Aromatic polymers, such as sulfonated poly(2,6-dimethyl-1,4-phenylene oxide) (SPPO), sulfonated poly(ether ether ketone) (SPEEK), and sulfonated poly(ether sulfone) (SPES), at the optimum degrees of sulfonation (DS), are suggested and evaluated as alternatives to Nafion for direct methanol fuel cells (DMFCs) applications. To reduce the methanol cross-over, which decreases the efficiency of the cell, organically modified montmorillonite nanoclays (OMMT) were added at 1 wt% to the sulfonated matrices with the optimum DS. The X-ray diffraction (XRD) patterns of nanocomposite membranes proved that the nanoclay layers were exfoliated. The proton conductivity and methanol permeability of the membranes, as well as the ion-exchange capacity (IEC), were measured. The selectivity parameter, ratio of proton conductivity to methanol permeability, was identified at 25°C for the nanocomposite membranes and the results were compared with Nafion117. Finally, the DMFC performance tests were investigated at 70°C and 5 M methanol feed for the manufactured nanocomposite polyelectrolyte membranes (PEMs). The SPEEK-based nanocomposite membrane showed the highest maximum power density in comparison with Nafion 117 and SPES and SPPO nanocomposite membranes. The results indicated that the nanocomposite membranes were promising PEMs for DMFC applications.     

Polyelectrolyte Nanocomposite Membranes,Based on Chitosan-phosphotungstic Acid Complex and Montmorillonite for Fuel Cells Applications

A polyelectrolyte complex (PEC) of chitosan and phosphotungstic acid (PWA) was prepared and characterized as a proton-conducting membrane for direct methanol fuel cell (DMFC) applications. Fourier transform infrared spectroscopy showed the presence of stable PWA in PEC. To reduce the methanol permeability, several amounts of montmorilonite (MMT) nanoclays (trade name: Cloisite Na) were introduced to the system. The X-ray diffraction patterns of nanocomposite membranes proved the nanoclay layers were exfoliated in the membranes at loading weights of MMT lower than 3 wt%. Proton conductivity and methanol permeability were measured. According to the selectivity parameter—ratio of proton conductivity to methanol permeability—PEC containing 2 wt% MMT (PEC/2 wt% MMT) was identified as the optimum composition. Finally, DMFC performance tests were investigated at 70°C and 5 M methanol feed and the optimum membrane showed higher maximum power density in comparison with Nafion 117. The results indicated the optimum nanocomposite membrane is a promising polyelectrolyte membrane (PEM) for DMFC applications.