Operation characteristics of portable direct methanol fuel cell stack at sub-zero temperatures using hydrocarbon membrane and high concentration methanol

Cold start and operation of a direct methanol fuel cell (DMFC) are investigated at sub-zero temperatures by using a 10-cell stack. The stack is manufactured with a hydrocarbon membrane to minimize the methanol crossover problem, which can be caused by use of high concentration methanol solutions. The stack is heated up for the cold start and operation only by heat of the exothermic reactions without any heating device and additional insulation means, to examine operation characteristics of the DMFC stack at low temperatures. The concentration of methanol solutions is selected in the range of 3-8 M, considering the freezing points of the solution for corresponding operation temperatures (−5 to −15 °C). Although the DMFC stack undergoes a sharp voltage drop and a significant performance decrease at the initial stage of the frozen condition, the self-heating DMFC are successfully operated at −5 and −10 °C in both constant current or constant voltage modes. The cold start-up time also is nearly independent of the operating modes. In contrast, the stack at −15 °C is barely started up only by a constant voltage mode with some voltage fluctuation. The DMFC stack after the cold operation exhibits the performance loss of about 45%. Such performance loss is mainly caused by degradation of the electrocatalysts.     

Gas evolution and power performance in direct methanol fuel cells

The use of acrylic cells and a CCTV camera for visually investigating the carbon dioxide gas evolution process inside an operating direct methanol fuel cell environment is demonstrated. Also, the effect of operating parameters on the system gas management, using a series of tests with different gas diffusion layer supporting materials, flow bed designs, cell sizes and exhaust manifold configurations, is studied. Carbon dioxide gas management is an important issue obstructing progress in viable direct methanol fuel cell systems development. Gas evolution mechanisms and gas management techniques are discussed and analysed with reference to several video picture and performance data. The data demonstrate that Toray carbon paper is not a suitable material for DMFCs due to its poor gas removal properties. A type carbon cloth shows relatively good gas removal behaviour. Increasing the liquid phase inlet flow rate is beneficial for gas removal. Increasing the current density results in higher gas production and in the formation of gas slugs, especially at low flow rates, which can lead to blocking of the channels and hence deterioration in the cell performance. A new flow bed design, based on a heat exchanger concept, is affective for gas management and gives a more uniform flow distribution in the flow bed channels. Using the results of this study, and the modelling techniques developed by our group, will are able to determine suitable operating conditions for our prototype 0.5kW cell DMFC stack.     

Performance of a direct methanol fuel cell

The performance of a direct methanol fuel cell based on a Nafion® solid polymer electrolyte membrane (SPE) is reported. The fuel cell utilizes a vaporized aqueous methanol fuel at a porous Pt–Ru–carbon catalyst anode. The effect of oxygen pressure, methanol/water vapour temperature and methanol concentration on the cell voltage and power output is described. A problem with the operation of the fuel cell with Nafion® proton conducting membranes is that of methanol crossover from the anode to the cathode through the polymer membrane. This causes a mixed potential at the cathode, can result in cathode flooding and represents a loss in fuel efficiency. To evaluate cell performance mathematical models are developed to predict the cell voltage, current density response of the fuel cell.     

Hydrodynamic modelling of direct methanol liquid feed fuel cell stacks

A model for the liquid feed, direct methanol fuel cell (DMFC), based on the homogeneous two-phase flow theory and mass conservation equation, which describes the hydraulic behaviour of internally manifolded cell stacks, is presented. The model predicts the pressure drop behaviour of the anode side of an individual DMFC cell and is used to determine the channel depth and width for fast and efficient carbon dioxide removal with minimum pressure drop. The model is used to calculate flow distribution through fuel cell stack internal manifolds. The effect of inlet and outlet manifold diameters on flow distribution is also determined. Two types of manifold design are compared, reverse flow and parallel flow. An iterative numerical scheme is used to solve the differential equations for longitudinal momentum and continuity.     

PEM – Fuel Cell System for Residential Applications

Viessmann is developing a PEM fuel cell system for residential applications. The uncharged PEM fuel cell system has a 2 kW electrical and 3 kW thermal power output. The Viessmann Fuel Processor is characterized by a steam‐reformer/burner combination in which the burner supplies the required heat to the steam reformer unit and the burner exhaust gas is used to heat water. Natural gas is used as fuel, which is fed into the reforming reactor after passing an integrated desulphurisation unit. The low temperature (600 °C) fuel processor is designed on the basis of steam reforming technology. For carbon monoxide removal, a single shift reactor and selective methanisation is used with noble metal catalysts on monoliths. In the shift reactor, carbon monoxide is converted into hydrogen by the water gas shift reaction. The low level of carbon monoxide at the outlet of the shift reactor is further reduced, to approximately 20 ppm, downstream in the methanisation reactor, to meet PEM fuel cell requirements. Since both catalysts work at the same temperature (240 °C), there is no requirement for an additional heat exchanger in the fuel processor. Start up time is less than 30 min. In addition, Viessmann has developed a 2 kW class PEFC stack, without humidification. Reformate and dry air are fed straight to the stack. Due to the dry operation, water produced by the cell reaction rapidly diffuses through the electrolyte membrane. This was achieved by optimising the MEA, the gas flow pattern and the operating conditions. The cathode is operated by an air blower.     

Catalytic activation of CO2: Use of secondary CO2 for the production of synthesis gas and for methanol synthesis over copper-based zirconia-containing catalysts

Consumption of fossil fuel resources throughout the industrial era has resulted in an enormous increase in carbon dioxide concentration in the atmosphere. Developed countries have committed to reducing the atmospheric load of greenhouse gases and ratified the Kyoto Protocol. Chemical utilization of carbon dioxide captured from large scale stationary sources is one possible pathway to decrease the rate of emissions. Catalysis plays a crucial role in these carbon dioxide utilization reactions. In this paper, the production of synthesis gas from carbon dioxide-containing secondary gases and carbon dioxide hydrogenation to methanol over copper-based zirconia-containing catalysts have been investigated. Pathways of carbon dioxide utilization are outlined, research done on carbon dioxide hydrogenation over copper-based zirconia-containing catalysts is reviewed, and the challenges of these reactions are reported. It is argued that direct utilization of secondary carbon dioxide from industrial sources can be a significant step toward developing sustainable industrial practices and a critical part in sustainable energy strategies.     

Development and operation of a 150 W air-feed direct methanol fuel cell stack

A five-cell 150 W air-feed direct methanol fuel cell (DMFC) stack was demonstrated. The DMFC cells employed Nafion 117^® as a solid polymer electrolyte membrane and high surface area carbon supported Pt-Ru and Pt catalysts for methanol electrooxidation and oxygen reduction, respectively. Stainless steel-based stack housing and bipolar plates were utilized. Electrodes with a 225 cm² geometrical area were manufactured by a doctor-blade technique. An average power density of about 140 mW cm^–2 was obtained at 110 °C in the presence of 1 M methanol and 3 atm air feed. A small area graphite single cell (5 cm²) based on the same membrane electrode assembly (MEA) gave a power density of 180 mW cm^–2 under similar operating conditions. This difference is ascribed to the larger internal resistance of the stack and to non-homogeneous reactant distribution. A small loss of performance was observed at high current densities after one month of discontinuous stack operation.     

Direct conversion of dimethyl ether in high-temperature polymer electrolyte fuel cells under stationary and dynamic conditions

The behavior of a polybenzimidazole-based high-temperature polymer electrolyte membrane fuel cell using dimethyl ether (DME) as fuel was investigated under stationary and dynamic load conditions. The power density was enhanced significantly with an increase of both operating temperature and anodic water stoichiometry. Likewise, the power density decreased with increasing DME stoichiometry. The characterization of the dynamic operation showed a strong qualitative similarity to low-temperature direct methanol fuel cells. The development of the cell voltage after a spontaneous change of cell current density could be assigned to the electrochemical oxidation of an intermediate species.     

Proton conducting membranes based on sulfonated poly(ether ether ketone)/TiO2 nanocomposites for a direct methanol fuel cell

This paper presents an evaluation of the effects of titanium dioxide nanoparticles in sulfonated poly(ether ether ketone) (SPEEK) with a sulfonation degree of 57%. A series of inorganic/organic hybrid membranes was prepared with a systematic variation of titanium dioxide nanoparticle content. Their water uptake, methanol permeability and proton conductivity as a function of temperature were investigated. The results obtained show that the inorganic oxide network decreases the proton conductivity and water swelling. It is also found that increasing the inorganic oxide content leads to a decrease of methanol permeability. In terms of morphology, the membranes are homogeneous and exhibit good adhesion between inorganic domains and the polymer matrix. The proton conductivity and fuel cell performances of the nanocomposite membranes showed very good prospective in direct methanol fuel cell usages. The properties of the composite membranes are compared with those of standard Nafion membranes. Copyright © 2006 Society of Chemical Industry     

Application of sodium conducting membranes in direct methanol alkaline fuel cells

A study of a direct methanol alkaline fuel cell (DMAFC) operating with sodium conducting membranes is reported. Evaluation of the fuel cell was performed using membrane electrode assemblies incorporating carbon supported platinum catalysts and Nafion^® 117 and 112 membranes. A membrane electrode assembly was also prepared by the direct chemical deposition of platinum into the surface region of the membrane. Evaluation of the chemically deposited assembly showed it to be less active than those based on carbon supported catalysts. SEM &; TEM analysis indicate that this behaviour is due to the low surface area of the chemically deposited catalyst layer. The fuel cell performance with Nafion membranes is reported and is not as good as achieved with hydroxide ion conducting membranes suggesting that Nafion may not be suitable for DMAFC operation.     

Electrochemical and gas evolution characteristics of direct methanol fuel cells with stainless steel mesh flow beds

Carbon dioxide gas management and bipolar plate/(flow bed) design are important to the development of direct methanol fuel cell (DMFC) systems. If the gas produced at the anode is not removed rapidly and efficiently a gradual deterioration in electrical performance can occur. This paper examines the feasibility of using stainless steel mesh materials as flow beds for the DMFC. A flow visualization study, using a high-speed video camera and appropriate computer software, of the anode side, carbon dioxide gas evolution and flow behaviour with flow beds based on stainless steel mesh is reported. The electrochemical behaviour of the direct methanol fuel cell with stainless steel flow beds is also reported. A number of the flow bed designs, based on stainless steel mesh, showed promising behaviour in terms of gas removal characteristics and electrical performance.     

A semi‐empirical cell voltage model for polymer electrolyte/methanol systems: Applicability of the group contribution method

A new group contribution model is established to describe the cell voltage of a direct methanol fuel cell as a function of the current density. The model equation is validated with experimental data over a wide range of methanol concentrations and temperatures. The proposed model focuses on very unfavorable conditions for cell operation, that is, low methanol solution concentrations and relatively low cell temperatures. The proposed group contribution method includes a methanol crossover effect that plays a major role in determining the cell voltage of a direct methanol fuel cell. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

自呼吸式直接甲醇燃料电池性能及其传质特性

针对有效面积为1 cm2的自呼吸式直接甲醇燃料电池（direct methanol fuel cell,DMFC）单电池,阳极采用燃料罐供液,将阴极侧集流体和夹具设计为一体式结构,并用自制的七合一膜电极组件对其进行测试,讨论了催化剂类型、扩散层材料、集流体结构等因素对其性能的影响,分析了电池内部的传质特性,优化了电池特别是其在中高电流密度条件下的性能。实验结果表明：采用Pt黑、Pt-Ru黑催化剂制作的自呼吸式DMFC能强化反应物的传质;采用碳布制作的膜电极更倾向于获得更高的极限电流密度;低电流密度时,因甲醇渗透电池电压随着甲醇浓度的增加而降低,但在中高电流密度下,电池性能随甲醇浓度的增大先升高后降低;平行集流体有利于阴阳极生成物的排出和反应物的传质,因此易获得较高的电池性能。     

Large‐scale DMFC Stack Model: Feed Disturbances and Their Impact on Stack Performance

A highly scalable quasi‐3D model of a large 1‐kW class direct methanol fuel cell stack is developed. The model takes into account in‐plane heat and current transport in the bipolar plates, coupled to the through‐plane transport in the membrane‐electrode assemblies. The electro chemical model is an extension of a Perry–Newman–Cairns model with the Butler–Volmer rate of electrochemical conversion. The stack is ”cut” into a large number of elementary geometrical units and each unit is solved on a separate core using supercomputing resources. The model is used to simulate the regimes of stack operation with methanol flow failures in part of the cell. The results show that the full‐fed domain of the cell takes over part of the load of the starved domain, which homogenizes the distribution of all parameters over the defect cell surface.     

Experimental results on the direct electrochemical oxidation of methanol in PEM fuel cells

The cell performance of direct methanol fuel cells (DMFC) is 0.5 V at 0.5 A cm^–2 under high pressure oxygen operation (3 bar abs.) at 110 °C. However, high oxygen pressure operation at high temperatures is only useful in special market niches. Therefore, our work has now focused on air operation of a DMFC under low pressure (up to 1.5 bar abs.). At present, a power density of more than 100 mW cm^–2 can be achieved at 0.5 V on air operation at 110 °C. These measurements were carried out in single cells with an electrode area of 3 cm² and the air stoichiometry only amounted to 10. The effects of methanol concentration and temperature on the anode performance were studied by pseudo half cell measurements and the results are presented together with their impact on the cell voltage. A cell design with an electrode area of 550 cm², which is appropriate for assembling a DMFC stack, was tested. A three-celled stack based on this design revealed nearly the same power densities as in the small experimental cells at low air excess pressure and the voltage–current curves for the three cells were almost identical. At 110 °C a power output of 165 W at a stack voltage of 1.5 V can be obtained in the air mode.     

Mass transport of direct methanol fuel cell species in sulfonated poly(ether ether ketone) membranes

Homogeneous membranes based on sulfonated poly(ether ether ketone) (sPEEK) with different sulfonation degrees (SD) were prepared and characterized. In order to perform a critical analysis of the SD effect on the polymer barrier and mass transport properties towards direct methanol fuel cell species, proton conductivity, water/methanol pervaporation and nitrogen/oxygen/carbon dioxide pressure rise method experiments are proposed. This procedure allows the evaluation of the individual permeability coefficients in hydrated sPEEK membranes with different sulfonation degrees. Nafion^® 112 was used as reference material. DMFC tests were also performed at 50 °C. It was observed that the proton conductivity and the permeability towards water, methanol, oxygen and carbon dioxide increase with the sPEEK sulfonation degree. In contrast, the SD seems to not affect the nitrogen permeability coefficient. In terms of selectivity, it was observed that the carbon dioxide/oxygen selectivity increases with the sPEEK SD. In contrast, the nitrogen/oxygen selectivity decreases. In terms of barrier properties for preventing the DMFC reactants loss, the polymer electrolyte membrane based on the sulfonated poly(ether ether ketone) with SD lower or equal to 71%, although having slightly lower proton conductivity, presented much better characteristics for fuel cell applications compared with the well known Nafion^® 112. In terms of the DMFC tests of the studied membranes at low temperature, the sPEEK membrane with SD = 71% showed to have similar performance, or even better, as that of Nafion^® 112. However, the highest DMFC overall efficiency was achieved using sPEEK membrane with SD = 52%.     

Application of response surface methodology for optimization of purge gas recycling to an industrial reactor for conversion of CO2 to methanol

Nowadays, by the increasing attention to environment and high rate of fuel production, recycling of purge gas as reactant to a reactor is highly considered. In this study, it is proposed that the purge gases of methanol production unit, which are approximately15.018 t·h~(-1) in the largest methanol production complexes in the world, can be recycled to the reactor and utilized for increasing the production rate. Purge gas streams contain 63% hydrogen,20% carbon monoxide and carbon dioxide as reactants and 17% nitrogen and methane as inert. The recycling effect of beneficial components on methanol production rate has been investigated in this study. Simulation results show that methanol production enhances by recycling just hydrogen, carbon dioxide and carbon monoxide which is an effective configuration among the others. It is named as Desired Recycle Configuration(DRC) in this study. The optimum fraction of returning purge gas is calculated via one dimensional modeling of process and Response Surface Methodology(RSM) is applied to maximize the methanol flow rate and minimize the carbon dioxide flow rate. Simulation results illustrate that methanol flow rate increases by 0.106% in DRC compared to Conventional Recycle Configuration(CRC) which therefore shows the superiority of applying DRC to CRC.     

A study of a microbial fuel cell battery using manure sludge waste

The cell voltage and power performance of a microbial fuel cell utilising waste carbohydrate as a fuel, that does not use a mediator, catalysts or a proton exchange membrane, is reported. Tests were conducted with the cell operated essentially as a battery using manure sludge as fuel and with oxygen reduction in an aqueous solution. Using carbon cloth as both anode and cathode, the cell produced peak power of the order of 5 mW m^?2. The cell performance was not greatly influenced by the quantity of fuel used and required a suitable separation between the cathode, anode and sludge/water interface. Agitation of the sludge did not adversely affect the cell performance, indicating that a continuous fuel cell system could be operated using the manure sludge. Using a platinised carbon cathode doubled the power density to over 10 mW m^?2. The use of nickel as an alternative cathode catalyst was not found to be effective under the conditions of operation of the cell. The cell power performance was found to be consistent and stable over the 3 month duration of the tests, after which point over 95% consumption of carbohydrate was achieved. Examination of the carbon anodes after the tests showed consistent formation of a biofilm on the surface of the fibres. A cell stack design based on multiple pocket anodes containing the fuel sludge has also been demonstrated. Copyright © 2007 Society of Chemical Industry     

Recovery of CO2 from flue gas using an electrochemical membrane

A novel process has been designed for the economic production of very pure carbon dioxide from flue gas. Using a molten carbonate fuel cell stack as an electrically-driven membrane concentrator, a portion of the carbon dioxide in the flue gas, along with some oxygen, is emitted as a product stream. The oxygen is recycled to enrich the flue gas entering the concentrator. Preliminary economics appear favorable, with carbon dioxide produced at $21 per ton, this product is, however, in a binary mixture with oxygen and must be separated for final use, this mixture is suitable for standard means of separation. The cost is sensitive to the cost of electricity and the installed cost of the fuel-cell stack, as can be seen in Table 1. The projected cost, however, is significantly below the typical $70 per ton sales price for carbon dioxide, so that the process could be viable at higher electricity and equipment charges.