Nanostructured Pd barrier for low methanol crossover DMFC

This work reports the successful fabrication of Pd nanostructured proton conducting-fluid blocking barriers on standard perfluorosulfonic acid membranes, able to reduce considerably methanol crossover in Direct Methanol Fuel Cells. The barrier nanostructure and grafting to the underlying membrane was optimized by fine-tuning the deposition conditions. A reduction in methanol crossover up to 50% was achieved, increasing significantly the fuel cell efficiency, admitting a slight power density reduction with respect to a reference cell. The developed barriers hindered methanol transport through the membrane as well as water transport, therefore membrane dehydration can be observed at low current density, if operating conditions are not suitably modified.     

An algebraic semi-empirical model for evaluating fuel crossover fluxes of a DMFC under various operating conditions

In a fuel cell of low temperature, especially a direct methanol fuel cell (DMFC), fuel crossover phenomenon plays a significant role not only in its performance evaluation and analysis, but also in the optimum control under various operating conditions. A quantitative prediction of the fuel crossover flux thus becomes essential. Generally speaking, the theoretical approaches to the issue will be dramatically complex and less practical. On the other hand, experimental schemes are time-consuming and less capable of further analysis and applications. Consequently, a semi-empirical model that incorporates dominant physical parameters and operating variables is proposed in this paper to adequately evaluate the phenomenon of fuel crossover fluxes. It is stated analytically in the form of an algebraic function, in which the fuel concentration, the current density, and the temperature of the fuel cell are considered. It is therefore more suitable for a variety of in-situ applications. In the proposed model, the methanol concentration gradient in the anode backing layer, the anode catalyst layer, and the membrane are analyzed. The transfer behavior of methanol is modeled on the basis of diffusion and electro-osmosis mechanisms. By means of the proposed model, one can obtain a better prediction and a clearer picture of the effects of operating variables and physical parameters on methanol crossover fluxes.     

Nanocatalyst for direct methanol fuel cell (DMFC)

Nanotechnology has recently been applied to direct methanol fuel cells (DMFC), one of the most suitable and promising options for portable devices. With characteristics such as low working temperature, high energy-conversion efficiency and low emission of pollutants, DMFCs may help solve the future energy crisis. However, a significant limitation to DMFC includes slow reaction kinetics, which reduces performance and power output. Recently, research has focused on increasing the performance and activity of catalysts. Catalysts composed of small, metallic particles, such as platinum and ruthenium, supported on nanocarbons or metal oxides are widely used in DMFC. Thus, this paper presents an overview of the development of nanocatalysts for DMFC. Particularly, this review focuses on nanocatalyst structure, catalyst support, and challenges in the synthesis of nanocatalyst. This paper also presents computational approaches for theoretical modeling of nanomaterials such as carbon nanotubes (CNT) through molecular dynamic techniques.     

Modeling of a passive DMFC operating with neat methanol

A mathematical model is developed to simulate the fundamental transport phenomena in a passive direct methanol fuel cell (DMFC) operating with neat methanol. The neat methanol operation is realized by using a ‘pervaporation’ membrane that allows the methanol concentration from the neat methanol in the fuel reservoir to be declined to an appropriate level in the anode catalyst layer (CL). The water required by the methanol oxidation reaction on the anode is passively obtained by diffusion from the cathode through the membrane. The numerical results indicate that the methanol delivery rate from the fuel reservoir to the anode CL is predominately controlled by the pervaporation process. It is also found that under the neat methanol operating condition, water distribution across the membrane electrode assembly is greatly influenced by the membrane thickness, the cathode design, the operating temperature, and the ambient relative humidity.     

Modelling and experimental studies on a direct methanol fuel cell working under low methanol crossover and high methanol concentrations

A number of issues need to be resolved before DMFC can be commercially viable such as the methanol crossover and water crossover which must be minimised in portable DMFCs.     

Non-linear optimization of passive direct methanol fuel cell (DMFC)

The cost associated with a direct methanol fuel cell (DMFC) is the main drawback of its commercialization. To address this issue, the main objective of this study is to minimize the cost of micro DMFCs for portable applications. The model was coupled with a non-linear constrained optimization to determine an optimum design of the DMFC with respect to the design and geometrical parameters of the anode and cathode, including methanol concentration, power density, catalyst loading, etc. Optimization was performed using Matlab to minimize the difference between the power input required and the power optimum via Non-Linear Programming (NLP). The optimum characteristics of DMFC were solved by using an NLP simulation. The outputs were verified by both experimental and modeling results. These dynamic optimization results provided an optimum design parameters for the physical properties of DMFC required to generate the portable application. Lastly, a cost analysis was also considered in this study.     

A mathematical model for simulating methanol permeation and the mixed potential effect in a direct methanol fuel cell

A mathematical model for simulating methanol permeation and the pertinent mixed potential effect in a direct methanol fuel cell (DMFC) is presented. In this model a DMFC is divided into seven compartments namely the anodic flow channel, the anodic diffusion layer, the anodic catalyst layer, the proton exchange membrane (PEM), the cathodic catalyst layer, the cathodic diffusion layer and the cathodic flow channel. All compartments are considered to have finite thickness, and within every one of them a set of governing equations are given to stipulate methanol transport and oxygen transport. For the flow channels, fluid dynamics, which could substantially lower the local methanol concentration within catalyst layers is taken into account. With the knowledge of local concentrations of the species, the electrochemical reaction rates within both catalyst layers can be quantified by a kinetic Tafel expression. For the anodic catalyst layer the local external current generated by methanol oxidation is computed; for the cathodic catalyst layer, in addition to the local external current generated by oxygen reduction, the local internal current as a result of methanol permeation is also computed. With the information of the local internal current, the mixed potential effect, which is responsible for adversely lowering the cell voltage can be analyzed.     

Study of pulsed-current loading of direct methanol fuel cells using a new time-domain model based on bi-functional methanol oxidation kinetics

This work describes a non-linear time-domain model of a direct methanol fuel cell (DMFC) and uses that model to show that pulsed-current loading of a direct methanol fuel cell does not improve average efficiency. Unlike previous system level models, the one presented here is capable of predicting the step response of the fuel cell over its entire voltage range. This improved model is based on bi-functional methanol oxidation reaction kinetics and is derived from a lumped, four-step reaction mechanism. In total, six states are incorporated into the model: three states for intermediate surface adsorbates on the anode electrode, two states for the anode and cathode potentials, and one state for the liquid methanol concentration in the anode compartment. Model parameters were identified using experimental data from a real DMFC. The model was applied to study the steady-state and transient performance of a DMFC with the objective to understand the possibility of improving the efficiency of the DMFC by using periodic current pulses to drive adsorbed CO from the anode catalyst. Our results indicate that the pulsed-current method does indeed boost the average potential of the DMFC by 40 mV; but on the other hand, executing that strategy reduces the overall operating efficiency and does not yield any net benefit.     

A semi-empirical model for efficiency evaluation of a direct methanol fuel cell

Energy density and power density are two of the most significant performance indices of a fuel cell system. Both the indices are closely related to the operating conditions. Energy density, which can be derived from fuel cell efficiency, is especially important to small and portable applications. Generally speaking, power density can be easily obtained by acquiring the voltage and current density of an operating fuel cell. However, for a direct methanol fuel cell (DMFC), it is much more difficult to evaluate its efficiency due to fuel crossover and the complex architecture of fuel circulation. The present paper proposes a semi-empirical model for the efficiency evaluation of a DMFC under various operating conditions. The power density and the efficiency of a DMFC are depicted by explicit functions of operating temperature, fuel concentration and current density. It provides a good prediction and a clear insight into the relationship between the aforementioned performance indices and operating variables. Therefore, information including power density, efficiency, as well as remaining run-time about the status of an operating DMFC can be in situ evaluated and predicted. The resulting model can also serve as an important basis for developing real-time control strategies of a DMFC system.     

A novel design for a flow field configuration, of a direct methanol fuel cell

We proposed and tested a new and novel arrangement for a direct methanol fuel cell consisting of one inlet for a methanol solution and four outlets for oxidant gas (air), in both the anode and cathode flow fields. It utilizes different operating temperatures of 40 °C and 60 °C, and different methanol solution flow rates of 5 ml min⁻¹, 10 ml min⁻¹, and 20 ml min⁻¹. Test results indicate a significant reduction in produced CO₂ gas in the anode flow channels and product water in the cathode flow channels; consequently, cell performance can be greatly improved. Furthermore, methanol crossover can also be avoided and reduced.     

Surface-modified Nafion membrane by oleylamine-stabilized Pd nanoparticles for DMFC applications

The surface of Nafion was modified by applying palladium nanoparticles as methanol barrier materials to decrease methanol crossover and improve the performance of fuel cells. The properties of the Pd-modified membrane, in terms of conductivity, methanol permeability, percentage of liquid uptake as well as the performance of its membrane electrode assembly (MEA) in the direct methanol fuel cell, were analyzed and compared with those using bare Nafion. The modified membrane showed considerable improvement on reducing methanol loss without decreasing proton conductivity. The DMFC performance of modified membrane was superior to that of bare Nafion both at a typical fuel state of 2 M and at high concentration of 5 M, implying that the palladium-modified Nafion can be a good alternative approach for DMFC applications.     

Electron transport in direct methanol fuel cells

A three-dimensional (3D), two-phase, isothermal model of direct methanol fuel cells (DMFCs) was employed to investigate effects of electron transport through the backing layer and the land in bipolar plates. It was found that the electronic resistance of the backing layer, affected by backing layer electronic conductivity, backing layer thickness and flow channel width, played a relatively important role in determining the current density distribution and cell performance. In order to ignore the electron transport effect on the average current density, the minimum electronic conductivity of the backing layer has to be 1000 S m⁻¹, with the relative error in the average current density less than 5%, under the given conditions.     

Characterization and performance evaluation of PtRu/CTiO2 anode electrocatalyst for DMFC applications

In this study, the effect of introduction of titania (TiO₂) material into PtRu/C anode electrocatalyst on the performance of direct methanol fuel cells (DMFCs) was investigated. TiO₂ materials were first synthesized applying a sol–gel method and then incorporated directly into commercial PtRu/C anode electrocatalyst with different TiO₂ weight ratios (5, 15, and 25 wt.%) to improve the performance of the DMFC. For comparison, the anode electrocatalysts with the same TiO₂ weight ratios were also prepared using commercial TiO₂ materials. The performance tests of the DMFCs based on these composite anode electrocatalysts were conducted and their performances were also compared to that of a DMFC based on a traditional anode electrocatalyst (PtRu/C) under various operating conditions. In addition, 4 h short-term stability tests were conducted for all the manufactured DMFCs. The highest power densities were found as 705.12 W/m² and 709.32 W/m² at 80 °C and 1 M for the DMFCs based on PtRu/CTiO₂ anode electrocatalysts containing 5 wt.% of commercial and in-house TiO₂, respectively. The results of the short-term stability tests showed that introduction of 5 wt.% of commercial TiO₂ into commercial PtRu/C anode electrocatalyst improved its stability characteristics significantly.     

Portable DMFC system with methanol sensor-less control

This work develops a prototype 20 W portable DMFC by system integration of stack, condenser, methanol sensor-less control and start-up characteristics. The effects of these key components and control schemes on the performance are also discussed. To expedite the use of portable DMFC in electronic applications, the system utilizes a novel methanol sensor-less control method, providing improved fuel efficiency, durability, miniaturization and cost reduction. The operating characteristics of the DMFC stack are applied to control the fuel ejection time and period, enabling the system to continue operating even when the MEAs of the stack are deteriorated. The portable system is also designed with several features including water balance and quick start-up (in 5 min). Notably, the proposed system using methanol sensor-less control with injection of pure methanol can power the DVD player and notebook PC. The system specific energy and energy density following three days of operation are 362 Wh kg⁻¹ and 335 Wh L⁻¹, respectively, which are better than those of lithium batteries (∼150 Wh kg⁻¹ and ∼250 Wh L⁻). This good energy storage feature demonstrates that the portable DMFC is likely to be valuable in computer, communication and consumer electronic (3C) markets.     

Crosslinked SPEEK/AMPS blend membranes with high proton conductivity and low methanol diffusion coefficient for DMFC applications

The crosslinked sulfonated poly (ether ether ketone)/2-acrylamido-2-methyl-1-propanesulfonic acid (SPEEK/AMPS) blend membranres were prepared and evaluated as proton exchange membranes for direct methanol fuel cell (DMFC) applications. The structure and morphology of SPEEK/AMPS membranes were characterized by FTIR and SEM, respectively. The effects of crosslinking and AMPS content on the performance of membranes were studied and discussed in detail. The proton conductivity and methanol diffusion coefficient of SPEEK/AMPS membranes increased gradually with the increase of AMPS content. Most SPEEK/AMPS membranes exhibited higher proton conductivity than Nafion^® 117 (0.05 S cm⁻¹ at 25 °C). However, all the membranes possessed much lower methanol diffusion coefficient compared with Nafion^® 117 (2.38 × 10⁻⁶ cm² s⁻¹) under the same measuring conditions. Even the methanol diffusion coefficient (8.89 × 10⁻⁷ cm² s⁻¹) of SPEEK/AMPS 30 sample with the highest proton conductivity (0.084 S cm⁻¹ at 25 °C) was only about one third of that of Nafion^® 117. The selectivity of all the SPEEK/AMPS membranes was much higher in comparison with Nafion^® 117 (2.8 × 10⁴ S s cm⁻³). In addition, the SPEEK/AMPS membranes possessed relatively good thermal and hydrolytic stability. These results suggested that the SPEEK/AMPS membranes were particularly promising to be used as proton exchange membranes in DMFCs, and the high proton conductivity, low methanol diffusion coefficient and high selectivity were their primary advantages for DMFC applications.     

Evaluation of silver-coated stainless steel bipolar plates for fuel cell applications

In this study, computer-aided design and manufacturing (CAD/CAM) technology were applied to develop and produce stainless steel bipolar plates for DMFC (direct methanol fuel cell). Effect of surface modification on the cell performance of DMFC was investigated. Surface modifications of the stainless steel bipolar plates were made by the electroless plating method. A DMFC consisting of silver coated stainless steel as anode and uncoated stainless steel as cathode was assembled and evaluated. The methanol crossover rate (R_c) of the proton exchange membrane (PEM) was decreased by about 52.8%, the efficiency (E_f) of DMFC increased about 7.1% and amounts of methanol electro-oxidation at the cathode side (M_co) were decreased by about 28.6%, as compared to uncoated anode polar plates. These measurements were determined by the transient current and mathematical analysis.     

Performance of a direct methanol fuel cell (DMFC) at low temperature: Cathode optimization

The effects of Pt loading, Nafion content in the cathode and membrane–electrode assembly (MEA) preparation techniques (CCS_cathode/CCS_anode and CCM_cathode/CCS_anode) on the performance of MEAs for direct methanol fuel cells (DMFC) were studied. The MEA performance was analyzed with polarization curves, electrochemical impedance spectroscopy and scanning electron microscopy data. It was shown, that the cathode prepared by the catalyst coated membrane (CCM) method forms a mainly microporous and mesoporous structure, whereas the catalyst coated substrate (CCS) method generates macroporosity together with micropores and mesopores. The power density of the CCM_cathode/CCS_anode typed MEAs strongly depends on the CCM-cathode composition: Pt loading and Nafion content in the cathode. Nafion (10.7 wt.%) was found to be an optimum for DMFC performance, and at this composition, the power density gradually increased with the Pt loading up to 6.0 mg cm⁻². At higher Nafion contents, a significant mass transfer limitation at high Pt loadings occurs. Comparing the CCM and CCS methods of the cathode fabrication, the latter revealed a higher power density, which reached 104 mW cm⁻² at 0.4 V and 70 °C owing to the lack of significant mass transfer limitations. This behavior indicates that in addition to Pt loading and Nafion content, the cathode pore structure is critical to DMFC MEA performance.     

Overview on the application of direct methanol fuel cell (DMFC) for portable electronic devices

Technologically advanced human societies require specialized tools and equipment to enable their diverse and mobile activities. Portable electronic devices like laptop, PDA, handphone, etc. are now an essential tool for many people in their daily lives. The rechargeable batteries used to power the portable electronic devices could be improved upon with regards to power density, and there is a crucial need for efficient, renewable and more environmentally friendly power sources. Many researchers have shown that the direct methanol fuel cell (DMFC) is an appropriate alternative to rechargeable battery technology, although many factors must be resolved before it can be commercialized. This paper gives an overview on the possibilities for using the DMFC as portable electronic devices power source along with some views on current and future trends in DMFC development, economic analysis and presents the current problems and solutions by DMFC researchers.     

Efficient electro-oxidation of methanol using PtCo nanocatalysts supported reduced graphene oxide matrix as anode for DMFC

Platinum – cobalt (PtCo) alloy based highly efficient nano electro-catalysts on reduced graphene oxide (rGO) matrix have been synthesized for the electro-oxidation of methanol, by chemical reduction method. Different molar ratio of Pt (IV) and Co (II) ions along with graphene oxide (GO) were reduced using ethylene glycol to obtain PtCo nanoparticles onto rGO sheets (Pt/rGO, PtCo (1:1)/rGO, PtCo (1:5)/rGO, PtCo (1:9)/rGO and PtCo (1:11)/rGO) with 20 wt. % metal and 80 wt. % rGO. The average particle size of PtCo nanoparticles onto rGO support was observed to be 2–5 nm using XRD and TEM analysis. The PtCo (1:9)/rGO nanocomposite catalyst exhibited ～23 times higher anodic current density compare to commercially available Pt/C catalyst (1.68 mA/cm²) for methanol oxidation reaction. The peak power density of 118.4 mW/cm² was obtained for PtCo (1:9)/rGO catalyst in direct methanol fuel cell (DMFC) at 100 °C, 1 bar, and 2 M methanol as anode feed, which is ～3 times higher than that of Pt/C catalyst. The results indicate the potential application of synthesized nanocomposite catalyst in commercial DMFCs.     

A study on the overall efficiency of direct methanol fuel cell by methanol crossover current

This paper was presented to determine the methanol crossover and efficiency of a direct methanol fuel cell (DMFC) under various operating conditions such as cell temperature, methanol concentration, methanol flow rate, cathode flow rate, and cathode backpressure. The methanol crossover measurements were performed by measuring crossover current density at an open circuit using humidified nitrogen instead of air at the cathode and applied voltage with a power supply. The membrane electrode assembly (MEA) with an active area of 5 cm² was composed of a Nafion 117 membrane, a Pt–Ru (4 mg/cm²) anode catalyst, and a Pt (4 mg/cm²) cathode catalyst. It was shown that methanol crossover increased by increasing cell temperature, methanol concentration, methanol flow rate, cathode flow rate and decreasing cathode backpressure. Also, it was revealed that the efficiency of the DMFC was closely related with methanol crossover, and significantly improved as the cell temperature and cathode backpressure increased and methanol concentration decreased.