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.     

An algorithm for sensor-less fuel control of direct methanol fuel cells

We report an algorithm for real-time control of the fuel of a DMFC. The MEA voltage decay coefficients [e₁, e₂], and I-V-T, M′-I-T, and W′-I-T curves (where I is the current, V the voltage, T the temperature, and M′ and W′ the methanol and water consumption rates, respectively) of n fuels with specified methanol concentrations C_M,k (k = 1, 2,…, n) are pre-established and form (I,V,T), (M′,I,T), and (W′,I,T) surfaces for each C_M,k. The in situ measured (I,V,T)_u after voltage decay correction is applied to the n preset (I,V,T) surfaces to estimate C_M,u (the C_M corresponding to (I,V,T)_u) using an interpolation procedure. The C_M,u is then applied to the n preset (M′,I,T) and (W′,I,T) surfaces to estimate cumulated “methanol” and “water” consumed quantities . Thus in a real-time system, the C_M and total quantity of fuel can be controlled using the estimated C_M,u and cumulated “methanol” and “water” consumed quantities.     

A direct methanol fuel cell system to power a humanoid robot

In this study, a direct methanol fuel cell (DMFC) system, which is the first of its kind, has been developed to power a humanoid robot. The DMFC system consists of a stack, a balance of plant (BOP), a power management unit (PMU), and a back-up battery. The stack has 42 unit cells and is able to produce about 400 W at 19.3 V. The robot is 125 cm tall, weighs 56 kg, and consumes 210 W during normal operation. The robot is integrated with the DMFC system that powers the robot in a stable manner for more than 2 h. The power consumption by the robot during various motions is studied, and load sharing between the fuel cell and the back-up battery is also observed. The loss of methanol feed due to crossover and evaporation amounts to 32.0% and the efficiency of the DMFC system in terms of net electric power is 22.0%.     

Exergy analysis of a passive direct methanol fuel cell

An analytical, one-dimensional, steady state model is employed to solve for overpotentials at the catalyst layers along with the liquid water and methanol distributions at the anode, and oxygen transport at the cathode. An iterative method is utilized to calculate the cell temperature at each cell current density. A comprehensive exergy analysis considering all possible species inside the cell during normal operation is presented. The contributions of different types of irreversibilities including overpotentials at the anode and cathode, methanol crossover, contact resistance, and proton conductivity of the membrane are investigated. Of all losses, overpotentials in conjunction with the methanol crossover are considered as the major exergy destruction sources inside the cell during the normal operation. While the exergy losses due to electrochemical reactions are more significant at higher current densities, exergy destruction by methanol crossover at the cathode plays more important role at lower currents. It is also found that the first-law efficiency of a passive direct methanol fuel cell increases as the methanol solution in the tank increases in concentration from 1 M to 3 M. However, this is not the case with the second-law efficiency which is always decreasing as the concentration of the methanol solution in the tank increases.     

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.     

Development of an advanced MEA to use high-concentration methanol fuel in a direct methanol fuel cell system

Despite serious methanol crossover issues in Direct Methanol Fuel Cells (DMFCs), the use of high-concentration methanol fuel is highly demanded to improve the energy density of passive fuel DMFC systems for portable applications. In this paper, the effects of a hydrophobic anode micro-porous layer (MPL) and cathode air humidification are experimentally studied as a function of the methanol-feed concentration. It is found in polarization tests that the anode MPL dramatically influences cell performance, positively under high-concentration methanol-feed but negatively under low-concentration methanol-feed, which indicates that methanol transport in the anode is considerably altered by the presence of the anode MPL. In addition, the experimental data show that cathode air humidification has a beneficial effect on cell performance due to the enhanced backflow of water from the cathode to the anode and the subsequent dilution of the methanol concentration in the anode catalyst layer. Using an advanced membrane electrode assembly (MEA) with the anode MPL and cathode air humidification, we report that the maximum power density of 78 mW/cm² is achieved at a methanol-feed concentration of 8 M and cell operating temperature of 60 °C. This paper illustrates that the anode MPL and cathode air humidification are key factors to successfully operate a DMFC with high-concentration methanol fuel.     

Experimental investigation of current distribution in a direct methanol fuel cell with serpentine flow-fields under various operating conditions

The influences of various operating conditions on the current distribution of a direct methanol fuel cell with flow-fields of serpentine channels are investigated by means of a current-mapping method. The current densities generally deviate more from an even distribution when the cell temperature or flow rate of the cathode reactant is lower, or when the current loaded on the cell or the methanol concentration is higher. In addition, uneven current distributions decrease the cell performance. Relevant mass-transfer phenomena such as water flooding and methanol crossover are discussed. The characteristics of the channel configuration also affect the current density profiles. With a five-line serpentine channel, the current densities are lowered periodically where the flow direction is inverted due to the corner flow effect and the subsequent water accumulation. With a single serpentine channel, on the other hand, the current densities peak periodically where the flow direction is inverted due to enhanced air convection through the gas-diffusion layer.     

Single passive direct methanol fuel cell supplied with pure methanol

A new single passive direct methanol fuel cell (DMFC) supplied with pure methanol is designed, assembled and tested using a pervaporation membrane (PM) to control the methanol transport. The effect of the PM size on the fuel cell performances and the constant current discharge of the fuel cell with one-fueling are studied. The results show that the fuel cell with PM 9 cm² can yield a maximum power density of about 21 mW cm⁻², and a stable performances at a discharge current of 100 mA can last about 45 h. Compared with DMFC supplied with 3 M methanol solution, the energy density provided by this new DMFC has increased about 6 times.     

Counter flow membraneless microfluidic fuel cell

A counter flow membraneless microfluidic fuel cell is presented, where a non-reacting electrolyte separates the reacting streams. In this fuel cell design, vanadium reactants flow through porous carbon electrocatalysts. A sulfuric acid stream is introduced in the gap between the electrodes and diverts the reactants to opposite and independent outlets. This fuel cell differs from other membraneless designs in its ability to maintain a constant separation between the reactants without diffusive mixing.     

Non-isothermal modeling of direct methanol fuel cell

In this work, a two-dimensional, two-phase non-isothermal model is developed for DMFC. The natural convection heat transfer at the out surface of the current collector is considered as the thermal boundary conditions to obtain a more realistic simulation of the DMFC working conditions. The heat and mass transfer, along with the electrochemical reactions occurring in the DMFC are modeled and numerically solved by a self-developed simulation code. The numerical results show that cell performance is enhanced with the increase in the inlet temperature. The distribution of temperature in the DMFC mainly depends on the inlet temperature of the dilute methanol aqueous in the anode side. The mean temperature of MEA and temperature difference in MEA increase with the increase in current density and the profiles show the same trend. With the decrease in MEA thermal conductivity and the increase in the inlet temperature the temperature difference in MEA becomes larger.     

Electrode in direct methanol fuel cells

Nanotechnology has recently generated a lot of attention and high expectations not only in the academic community but also among investors, scientists and researchers in both government and industry sectors. Its unique capability to fabricate new structures at the atomic scale has already produced novel materials and devices with great potential applications in a wide number of fields. Up to now, the electrodes in direct methanol fuel cells (DMFCs) have generally been based on the porous carbon gas diffusion electrodes that are employed in proton exchange membrane fuel cells. Typically, the structure of such electrodes is comprised of a catalyst layer and a diffusion layer, the latter being carbon cloth or carbon paper. It is a challenge to develop an electrode with high surface area, good electrical conductivity and suitable porosity to allow good reactant flux and high stability in the fuel cell environment. This paper presents an overview of electrode structure in general and recent material developments, with particular attention paid to the application of nanotechnology in DMFCs.     

Water and air management systems for a passive direct methanol fuel cell

In this paper water and air management systems were developed for a miniature, passive direct methanol fuel cell (DMFC). The membrane thickness, water management system, air management system and gas diffusion electrodes (GDE) were examined to find their effects on the water balance coefficient, fuel utilization efficiency, energy efficiency and power density. Two membranes were used, Nafion^® 112 and Nafion^® 117. Nafion^® 117 cells had greater water balance coefficients, higher fuel utilization efficiency and greater energy efficiency. A passive water management system which utilizes additional cathode gas diffusion layers (GDL) and a passive air management system which makes use of air filters was developed and tested. Water management was improved with the addition of two additional cathode GDLs. The water balance coefficients were increased from −1.930 to 1.021 for a cell using a 3.0 mol kg⁻¹ solution at a current density of 33 mA cm⁻². The addition of an air filter further increased the water balance coefficient to 1.131. Maximum power density was improved from 20 mW cm⁻² to 25 mW cm⁻² for 3.0 mol kg⁻¹ solutions by upgrading from second to third generation GDEs, obtained from E-TEK. There was no significant difference in water management found between second and third generation GDEs. A fuel utilization efficiency of 63% and energy efficiency of 16% was achieved for a 3.0 mol kg⁻¹ solution with a current density of 66 mA cm⁻² for third generation GDEs.     

Current density measurements in direct methanol fuel cells

The current density in the fuel cell is the direct consequence of reactions taking place over the active surface area. Thus, measurement of its distribution will lead to identification of the location and nature of reactions and will give opportunity to improve the overall efficiency of fuel cells. Within this study, the current density distribution in a direct methanol fuel cell was analyzed by segmenting the current collector into nine sections. Besides, the effect of the different operating parameters such as molarity, flow rate and reactant gas on the current density distribution was analyzed.     

Performance of air-breathing direct methanol fuel cell with anion-exchange membrane

This report details development of an air-breathing direct methanol alkaline fuel cell with an anion-exchange membrane. The commercially available anion-exchange membrane used in the fuel cell was first electrochemically characterized by measuring its ionic conductivity, and showed a promising result of 1.0 × 10⁻¹ S cm⁻¹ in a 5 M KOH solution. A laboratory-scale direct methanol fuel cell using the alkaline membrane was then assembled to demonstrate the feasibility of the system. A high open-circuit voltage of 700 mV was obtained for the air-breathing alkaline membrane direct methanol fuel cell (AMDMFC), a result about 100 mV higher than that obtained for the air-breathing DMFC using a proton exchange membrane. Polarization measurement revealed that the power densities for the AMDMFC are strongly dependent on the methanol concentration and reach a maximum value of 12.8 mW cm⁻² at 0.3 V with a 7 M methanol concentration. A durability test for the air-breathing AMDMFC was performed in chronoamperometry mode (0.3 V), and the decay rate was approximately 0.056 mA cm⁻² h⁻¹ over 160 h of operation. The cell area resistance for the air-breathing AMDMFC was around 1.3 Ω cm² in the open-circuit voltage (OCV) mode and then is stably supported around 0.8 Ω cm² in constant voltage (0.3 V) mode.     

Simplified model for the direct methanol fuel cell anode

A kinetic model for the anode of the direct methanol fuel cell (DMFC) is presented. The model is based on the generally accepted dual site mechanism of methanol oxidation, in aqueous solution, on well characterized Pt–Ru catalyst and it can predict the performance of the electrode as a function of cell temperature, anode potential and methanol concentration. In addition the model also generates data regarding the surface coverage of significant adsorbates involved in methanol oxidation on the dual site catalyst.     

Effect of conditioning method on direct methanol fuel cell performance

We investigated the effect of the conditioning methods on improving the direct methanol fuel cell (DMFC) performance. The DMFC performance after the conditioning was measured using a newly developed single cell having an Ag/Ag₂SO₄ reference electrode, which is not influenced by methanol. As a result, we succeeded in developing an original two-step conditioning method in which the conditioning by fueling H₂ gas is conducted prior to a conventional DMFC conditioning. The anode and cathode characteristics after the two-step conditioning were measured with respect to a reference electrode. Based on the obtained i-E curves, the two-step conditioning is found to improve the methanol oxidation performance at the anode and also suppress the decline of the O₂ reduction performance at the cathode. The high DMFC performance based on the two-step conditioning is well explained by the anode and cathode characteristics.     

Development of optimisation model for direct methanol fuel cells via cell integrated network

A cell network consists of a combination of fuel cells to achieve the targeted power consumption for a specific application. The main objective of this study is to design and optimise direct methanol fuel cell (DMFC) via cell integrated network model targeted for small portable application, such as cell phones and tablets. The target current and voltage was 1400 mA and 3.7 V, respectively, for a 5.18 W of cell network power. The optimisation was performed using 16 cells that were arranged in series with a voltage output of 3.781 V and a current of 1400 mA. The overall active area for the cell network was 128 cm², and the cost of 1 set of cell networks is USD 1400.     

Development of planar air breathing direct methanol fuel cell stacks

In this paper, design criteria and development techniques for planar air breathing direct methanol fuel cell stacks are described in detail. The fuel cell design in this study incorporates a window-frame structure that provides a large open area for more efficient mass transfer and is modular, making it possible to fabricate components separately. The membrane electrode assembly and gas diffusion layers are laminated together to reduce contact resistance, which eliminates the need for heavy hardware. The composite current collector is low cost, has high electrical conductivity and corrosion resistance. In the interest of quick and cost-efficient prototyping, the fabrication techniques were first developed on a single cell with an active area of 1.0 cm². Larger single cells with active areas of 4.5 and 9.0 cm² were fabricated using techniques based on those developed for the smaller single cell. Two four-cell stacks, one with a total active area of 18.0 cm² and the other with 36.0 cm², were fabricated by inter-connecting four identical cells in series. These four-cell stacks are suitable for portable passive power source applications. The performance analysis of single cells as well as stacks is presented. Peak power outputs of 519.0 and 870.0 mW were achieved in the stacks with active areas of 18.0 and 36.0 cm², respectively. The effects of methanol concentration and fuel cell self-heating on the fuel cell performance are emphasized.     

A direct methanol fuel cell system with passive fuel delivery based on liquid surface tension

The existing direct methanol fuel cell (DMFC) systems are fed with a fixed concentration of fuel, which are either a diluted methanol solution or an active fuel delivery driven by an attached active pump. Both approaches limit the power conversion density or degrade the overall efficiency of the DMFC system significantly. Such disadvantages become more severe in small-scale DMFCs, which require a high conversion efficiency and a small physical space suitable for portable electronics. In this paper, passive fuel delivery based on a surface tension driving mechanism was designed and integrated in a laboratory-made prototype to achieve consumption depending on fuel concentration and power-free fuel delivery. Unidirectional methanol-to-water smooth flow is achieved through the capillaries of a Teflon PTFE (polytetrafluoroethylene) membrane based on the difference in liquid surface tension. The prototype was demonstrated to exhibit a better polarization performance and to last for an extended operating time compared to conventional DMFCs. Its high efficiency and load regulation performance were also demonstrated in contrast to an active DMFC supplied with a constant concentration fuel. The fuel delivery driven by the liquid surface tension effect demonstrated here is believed to be more applicable for future small-scale DMFCs for portable electronics.     

Orthogonal flow membraneless fuel cell

This communication reports the development and performance of a membraneless fuel cell that utilizes a convective electrolyte flow orthogonal to the plane of the cell electrodes. The orthogonal flow acts to convect reactants to the electrodes and as a pseudo-membrane between anode and cathode, preventing mixed potentials caused by back diffusion of oxidant onto the anode. The membraneless design allows the cell parameters to be defined by the fuel rather than the membrane. The convective electrolyte flow eliminates the mass transport limited current regime and allows the cell to run under semi-mixed conditions. Power densities as high as 46 mW cm⁻² were achieved with both hydrogen and methanol as fuels. Methanol had a fuel utilization of 42%.