INTERNATIONAL JOURNAL OF ENERGY RESEARCH Int. J. Energy Res.

2009; 33:719727 Published online 13 January 2009 in Wiley InterScience (www.interscience.wiley.com). DOI: 10.1002/er.1507

Effect of anode current collector on the performance of passive direct methanol fuel cells
Qin-Zhi Lai, Ge-Ping Yin,y,z and Zhen-Bo Wang
School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001, China

SUMMARY The effect of anode current collector on the performance of passive direct methanol fuel cell (DMFC) was investigated in this paper. The results revealed that the anode of passive DMFC with perforated current collector was poor at removing the produced CO2 bubbles that blocked the access of fuel to the active sites and thus degraded the cell performance. Moreover, the performances of the passive DMFCs with different parallel current collectors and different methanol concentrations at different temperatures were also tested and compared. The results indicated that the anode parallel current collector with a larger open ratio exhibited the best performance at higher temperatures and lower methanol solution concentrations due to enhanced mass transfer of methanol from the methanol solution reservoir to the gas diffusion layer. However, the passive DMFC with a smaller open ratio of the parallel current collector exhibited the best performance at lower temperatures and higher methanol solution concentrations due to the lower methanol crossover rate. Copyright r 2009 John Wiley & Sons, Ltd.
KEY WORDS:

passive direct methanol fuel cell; current collector; open ratio; methanol concentration; cell temperature

1. INTRODUCTION Over the past decades, the worldwide proliferation of portable electronic devices has created a large and growing demand for energy sources that are compact, lightweight, and powerful. The direct methanol fuel cell (DMFC) has received much attention for its high theoretical energy density, using liquid fuel, employing solid polymer electrolyte, and working at low temperature, and has presented benecial opportunities for use as a

power source for small mobile devices [1,2]. However, these accessorial devices make the fuel cell system complex. Therefore, the passive DMFC with neither liquid pumps nor gas compressors has been proposed and studied. In the passive DMFC, the oxygen diffuses into the cathode side from ambient air without any help of external devices, and the methanol solution stored in the reservoir attaches to the anode current collector and the methanol driven by concentration gradient between the reservoir and anode also diffuses into

*Correspondence to: Ge-Ping Yin, School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001, China. y E-mail: yingphit@hit.edu.cn z Professor. Contract/grant sponsor: Natural Science Foundation of China; contract/grant numbers: 20606007, 50872027 Received 21 October 2008 Revised 19 November 2008 Accepted 24 November 2008

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the anode catalyst layer. Therefore, the passive DMFC can potentially result in higher reliability, lower cost, higher fuel utilization, and higher energy density, which are in favor of mobile equipments in future electronic devices [37]. The key component of a passive DMFC system consists of a methanol solution reservoir, anode current collector, membrane electrode assembly (MEA), and cathode current collector. Liu et al. [8] presented that the optimal concentration of methanol solution in passive DMFC was 4.0 mol L1. Similar opinions about the effect of methanol concentration on the performance of passive DMFC could also be found in the literature [913]. The utilizations of highly concentrated fuel of DMFCs with vapor fed had also been reported [14,15]. Chen et al. reported a suitable MEA for DMFC [16,17] and optimized the ow-elds [7,18]. Lu et al. [19] applied a highly hydrophobic cathode microporous layer (MPL) and a thin membrane to control the water crossover. Thus, the cathode ooding was avoided by facilitating water backow to the anode via hydraulic permeation. Yang et al. [20] presented that the micro DMFC with a parallel ow-eld at the anode and a perforated ow-eld at the cathode performed the best. Jeong et al. [21] presented the open area of cathode and the relative humidity of the atmosphere on the performance of passive air breathing PEMFCs. Chen et al. [22] found that the cell performance was improved with the increase of cathode and anode open ratios, which resulted in the improvement of mass transport of both methanol and oxygen, although the cell operating temperature decreases slightly with the increase of open ratio. The anode current collector is effective on the PEMFC performance and the methanol crossover ux is very important [2325]. In a passive DMFC, the methanol solution stored in the reservoir attaches to the anode current collector, and the methanol driven by the concentration gradient between the reservoir and the anode diffuses into the anode. The anode current collector is to provide channels for methanol fuel to access the MEA surface. Therefore, the anode current collector had a signicant effect on the cell performance. In this paper, we experimentally
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investigated the effect of the parallel current collector and the perforated current collector on the performance of a passive DMFC. We found that the parallel current collector exhibited a better performance than the perforated current collector. Then we focused on studying the effects of the parallel current collector with different open ratios on the cell performance at different methanol concentrations and cell temperatures.

2. EXPERIMENTAL 2.1. MEA fabrication All the electrocatalysts used in this paper were prepared in-house by chemical reduction with formaldehyde of H2PtCl6 and RuCl3 as precursors [26]. The anode catalyst was 40 wt% PtRu (with an atomic ratio of 1:1)/C and the cathode catalyst was 40 wt% Pt/C. The gas diffusion layers (GDLs) for the cathode electrodes were wet-proofed Toray carbon papers coated with the MPLs, which comprised Vulcan XC-72 carbon black and 10 wt% of PTFE. The anode GDLs were the Toray carbon papers coated with the MPLs, which comprised Vulcan XC-72 carbon black and 10 wt% of Naon ionomer (DuPont). The loading of carbon black was 2 mg cm2 for both the anode and the cathode. The catalyst powder and 5 wt% Naon ionomer solution were ultrasonically mixed in isopropyl alcohol to form a homogeneous catalyst ink. Then the catalyst ink was scraped onto the GDLs, and then the electrodes were dried for 2 h in the vacuum oven at 801C. The Naon content in both the anode and the cathode was 20 wt% and the metal loading (PtRu or Pt) was 2.0 mg cm2 in each electrode. Naon 117 polymer membranes (DuPont) were used to fabricate MEAs. Before being applied to the electrodes, the membranes were pretreated in four steps to eliminate the organic and inorganic contaminants. First, membranes were boiled in 3 wt% H2O2 solution followed by washing in the ultra-pure water. Then, they were boiled in 0.5 mol L1 H2SO4 solution. Finally, the membranes were boiled again in the ultra-pure water. Each step took about 1 h. The pretreated Naon 117 membrane was sandwiched between
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the anode and the cathode, and then the assembly was hot pressed under a loading of 100 kg cm2 for 90 s at 1351C. 2.2. Single cell xture The prepared MEA was sandwiched between two graphite plates to form an apparent area of approximately 9 cm2. The graphite plates of the cathode side was machined with many holes for air diffusion and the anode side machined through the graphite plates had channels and large open space for delivering and storing methanol solution, respectively. The oxygen diffused into the cathode side from ambient air without any help of external devices, such as a pump or a fan, and the methanol solution was stored in the reservoir attached to the anode side plate, and the methanol driven by concentration gradient between the reservoir and the anode diffused into the anode. The volume of the methanol reservoir was 10 cm3. The extension area of the bipolar plates served as a current collector, and a heating tape was attached to the extension area to adjust the operating temperature of passive DMFC to a desired value during the experiments. 2.3. Anode current collector design The geometry areas of current collectors are listed in Table I and Figure 1. As can be seen from Figure 1 and Table I, the open ratio of the current collector with perforated ow-elds (perforated current collector) is 50%, and the open ratios of current collectors with parallel ow-elds (parallel current collector-1 to perforated current collector3) are from 35.5 to 68.8%.

2.4. Electrochemical measurements The Fuel Cell Testing System (Arbin Instrument Corp.) connecting with a computer was used to control the conditions of discharge and record the voltagecurrent curves. For each discharging current point along the IV curve, a more than 40-s waiting time was used to obtain the stable voltage. A solution of 1.08.0 mol L1 aqueous methanol driven by the concentration gradient between the reservoir and the anode diffused into the anode. The oxygen diffused into the cathode side from ambient air without any help of external devices. Prior to testing the performance of passive DMFC, the MEA was installed in an active cell xture and activated at 801C for about 24 h. During the activation period, methanol solution of 2.0 mol L1 was fed at a ow rate of 3.0 mL min1, while oxygen was supplied under atmospheric pressure at a ow rate of 200 mL min1.

3. RESULTS AND DISCUSSION Figure 2 shows the performance of passive DMFCs with different anode current collectors. The performance of the passive DMFC with the parallel current collector is better than that with the perforated collector. In the initial discharge process, its performance with the parallel current collector is similar to that with the perforated current collector. However, the performance of the latter evidently decays at higher current densities. This is because the anode of the passive DMFC with the perforated current collector is poor at removing the produced CO2 bubbles that block the access of fuel to the active sites and thus

Table I. The geometry of the anode current collector. Current collector Channel width (mm) Rib width (mm) Aperture (mm) Holescenters distance (mm) Depth (mm) Open area (mm2 ) Effective area (mm2) Open ratio (%) Perforated current collector 4 5 2 452 900 50 Parallel current collector-1 1 2 2 319 899 35.5 Parallel current collector-2 2 2 2 450 900 50 Parallel current collector-3 2 1 2 600 896 68.8

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Int. J. Energy Res. 2009; 33:719727 DOI: 10.1002/er

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Figure 1. Geometry of the anode current collectors: (a) perforated current collector; (b) parallel current collector-1; (c) parallel current collector-2; and (d) parallel current collector-3.

Figure 2. Comparison of the passive DMFC performance among DMFCs with different anode current collectors (2.0 mol L1 methanol solution, cell temperature 301C).
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degrade its performance [20,23]. On the other hand, the passive DMFC with the parallel current collector exhibits the better performance due to the easier removal of CO2 bubbles from the anode. Figure 3 shows that the transient discharging voltage curves of passive DMFCs with different anode current collectors at current density 30 mA cm2 at an ambient temperature and a cell temperature of 301C. The passive DMFC with the parallel anode current collector shows the higher transient discharging voltage. In the initial discharge process, the transient discharging voltage of the passive DMFC with the perforated current collector sharply decays to about 0.26 V, and then slowly decreases with time. The anode of the passive DMFC with the perforated current collector makes against the removing of produced
Int. J. Energy Res. 2009; 33:719727 DOI: 10.1002/er

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Figure 3. Transient discharging voltagetime curves at a current density of 30 mA cm2 with a start from the passive DMFC to be fueled with 2.0 mol L1 methanol solution (10 mL) at passive DMFCs with different anode current collectors (cell temperature 301C).

Figure 4. The effect of different open ratios of the parallel current collector on the performance of the cell with 2.0 mol L1 methanol at 301C.

CO2 bubbles. Therefore, its voltage fastly degrades in the initial discharge process. Moreover, we still study the effects of different parallel current collectors as the parallel current collector exhibited a better performance than the perforated current collector. The effects of different open ratios of the parallel current collectors on the cell performance were investigated using collector-1 (open ratios: 35.5%), collector-2 (open ratios: 50%), and collector-3 (open ratios: 68.8%). Figure 4 shows the polarization curves and the power density curves of passive DMFCs with the parallel current collector at a methanol concentration of 2.0 mol L1. The maximum power density of the passive DMFC with an open ratio of 50% is the highest. However, three parallel current collectors of passive DMFCs exhibit similar performances. Figure 5 shows the polarization curves and the power density curves of passive DMFCs with parallel current collectors at a methanol concentration of 4.0 mol L1. The cell with the parallel current collector with an open ratio of 50% exhibits the best performance. The parallel current collectors with a smaller open ratio (35.5%) and a larger open ratio (68.8%) exhibit the worse cell performances. It is believed that the parallel current collector with a smaller open ratio
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Figure 5. The effect of different open ratios of the parallel current collector on the performance of the cell with 4.0 mol L1 methanol at 301C.

presents a smaller effective contact area between the liquid fuel and the MEA, which results in the degradation of the cell performance. On the other hand, the parallel current collector with a larger open ratio presents a larger effective contact area between the liquid fuel and the MEA. However, rst of all, the internal resistance of the cell increases with the increase of the open ratio of the parallel current collector [26]. Second, the larger methanol permeation area causes a higher methanol crossover rate through the membrane. Figure 6 shows the transient discharging voltage curves of passive DMFCs with different
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Table II. The effect of the open ratio on Faradic efciencies for the passive DMFC under current density (15.0 mA cm2) discharge. Open ratio (%) i (mA) C (mol L1) V (ml) Z (%) 35.5 50 68.8 135 135 135 2 2 2 10 10 10 48.3 44.1 42.0

Figure 6. Transient discharging voltage at a current density of 15 mA cm2 with a start from the passive DMFC to be fueled with 2.0 mol L1 methanol solution (10 mL) at the passive DMFC with different open ratios (air temperature 201C, the passive DMFC temperature 301C).

parallel collectors at a current density of 15 mA cm2. To investigate the fuel utilization, the Faraday efciency (Z) is adopted for the passive DMFC with different open ratios. The Faradic efciency is here dened as a ratio of the actual discharge capacity versus the theoretical capacity of fuel used in the fuel cell. It is believed that the Faraday efciency of the passive DMFC was reduced because of the loss of methanol by crossover and remaining methanol in the reservoir, which cannot be used due to methanol mass transfer limitations. The Faradic efciency can be calculated with the following equation [8]: Z it 100% 6CVF 1

Figure 7. The effect of different open ratios of the parallel current collector on the performance of the cell with 1.0 mol L1 methanol at 301C.

where i (A) is the discharging current, t (s) the time of the discharging process C (mol L1) the methanol concentration, V (L) the methanol solution volume, F (C) the Faraday constant, and Z the Faradic efciency. The Faradic efciencies determined by Equation (1) with different methanol concentrations at a constant current density of 15 mA cm2 are given in Table II. The Faradic efciency decreases from 48.3 to 42.0% when the open ratio increased from 35.5 to 68.8%. The lower Faradic efciency is primarily caused by the higher rate of methanol crossover with a higher open ratio.
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In addition, it can be seen from Figures 4 and 5 that the highest open-circuit voltage (OCV) is obtained with a parallel current collector-1. It is believed that the gradual decrease of OCVs with the increase of open ratio results from the increase of methanol crossover through the Naon 117 membrane. Figure 7 shows that the anode of the passive DMFC with the parallel current collector-3 exhibits the best performance with the methanol concentration of 1.0 mol L1. It is believed that the transfer of fuel molecules into the anode catalyst layer is the main factor affecting the cell performance at a lower methanol concentration. Under such a situation, the parallel current collector with a larger open ratio affords a larger effective contact area between the liquid fuel and the GDL, which improves the mass transfer of methanol from the methanol solution reservoir to the catalyst layer. Therefore, the parallel current collector with a larger open ratio tends to yield
Int. J. Energy Res. 2009; 33:719727 DOI: 10.1002/er

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Figure 8. The effect of different open ratios of the parallel current collector on the performance of the cell with 8.0 mol L1 methanol at 301C.

Figure 9. The effect of different open ratios of the parallel current collector on the performance of the cell with 2.0 mol L1 methanol at 201C.

a better cell performance with a lower methanol solution concentration. Figure 8 shows that the parallel current collector-1 exhibits the best performance with a methanol concentration of 8.0 mol L1. It is believed that when the cell is operating at a higher methanol solution concentration, the methanol transfer rate becomes faster and the lower performance is primarily caused by the higher rate of methanol crossover and excessive water crossover through the membrane with a higher open ratio [27,28]. The experiments were carried out at 20 and 401C with the same methanol concentration as in Figures 9 and 10, respectively. In Figure 9, the anode of the passive DMFC with the parallel current collector-1 exhibits the best performance at a low temperature of 201C. It is believed that there are more methanol molecules in the surface of the anode catalyst layer with a larger open ratio. However, the poor catalytic activity of the anode at a low temperature of 201C leads to a higher methanol crossover rate through the membrane. Therefore, the anode of the passive DMFC with the parallel current collector-1 exhibits the best performance. However, as can be seen from Figure 10, at a higher temperature of 401C, the anode of the passive DMFC with the parallel current collector-3 exhibits the best performance. It is believed that the catalytic activity of the anode catalyst increases with the increase of temperature, and the higher methanol mass transfer rate
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Figure 10. The effect of different open ratios of the parallel current collector on the performance of the cell with 2.0 mol L1 methanol at 401C.

becomes the main factor enhancing the cell performance. On the other hand, the anode of the passive DMFC with smaller open areas means a smaller effective contact area between the liquid fuel and the GDL, which weakens the methanol mass transfer. Therefore, the anode of the passive DMFC with the parallel current collector-3 exhibits the best performance.

4. CONCLUSION The effect of the anode current collector on the performance of the passive DMFC was
Int. J. Energy Res. 2009; 33:719727 DOI: 10.1002/er

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investigated. The experimental results show that the passive DMFCs with the perforated current collector are poor at removing the produced CO2 bubbles, which block the access of fuel to the active sites and thus degrade the cell performance, compared with the parallel current collector. Moreover, the effect of different parallel current collectors with various open ratios on performances of the passive DMFCs at different temperatures and different methanol concentrations is also studied. The passive DMFC equipped with a smaller open ratio (35.5 %) of the parallel current collector exhibits the best performance at a higher methanol solution concentration and a lower temperature as the methanol mass transfer rate becomes relatively fast, and the best performance is primarily caused by the lowest methanol crossover rate with a smaller open ratio. The experiments also reveal that the passive DMFCs equipped with a larger open ratio (68.8%) of the parallel current collector exhibit the best performance at a lower methanol concentration and a higher temperature. The best performance results primarily from the improvement of the mass transfer of methanol to the GDL due to the larger open ratio.

ACKNOWLEDGEMENTS

This work was supported by Natural Science Foundation of China (Nos. 20606007 and 50872027).

REFERENCES 1. Springer TE, Zawodzinski TA, Gottesfeld S. Polymer electrolyte fuel cell model. Journal of the Electrochemical Society 1991; 136:23342342. 2. Fukada S. Analysis of oxygen reduction rate in aproton exchange membrane fuel cell. Energy Conversion and Management 2001; 42:11211131. 3. Heinzel A, Nolte R, Ledjeff-Hey K et al. Membrane fuel cells concepts and system design. Electrochimica Acta 1998; 43:38173820. 4. Rice J, Faghri A. A transient, multi-phase and multicomponent model of a new passive DMFC. International Journal of Heat and Mass Transfer 2006; 49:48044820. 5. Lu GQ, Lim PC, Liu FQ et al. On mass transport in an airbreathing DMFC stack. International Journal of Energy Research 2005; 29:10411050. Copyright r 2009 John Wiley & Sons, Ltd.

6. Yazici MS. Passive air management for cylindrical cartridge fuel cells. Journal of Power Sources 2007; 166:137142. 7. Chen R, Zhao TS. Porous current collectors for passive direct methanol fuel cells. Electrochimica Acta 2007; 52:43174324. 8. Liu JG, Zhao TS, Chen R et al. The effect of methanol concentration on the performance of a passive DMFC. Electrochemistry Communications 2005; 7:288294. 9. Kim D, Cho EA, Hong SA et al. Recent progress in passive direct methanol fuel cells at KIST. Journal of Power Sources 2004; 130:172177. 10. Chu D, Jiang RZ. Effect of operating conditions on energy efciency for a small passive direct methanol fuel cell. Electrochimica Acta 2006; 51:58295835. 11. Kim YJ, Bae B, Scibioh MA et al. Behavioral pattern of a monopolar passive direct methanol fuel cell stack. Journal of Power Sources 2006; 157:253259. 12. Kho BK, Bae B, Scibioh MA et al. On the consequences of methanol crossover in passive air-breathing direct methanol fuel cells. Journal of Power Sources 2005; 142:5055. 13. Hong SA, Ha HY. Performance evaluation of passive DMFC single cells. Journal of Power Sources 2006; 158:12561261. 14. Kim HK. Passive direct methanol fuel cells fed with methanol vapor. Journal of Power Sources 2006; 162:12321235. 15. Guo Z, Faghri A. Vapor feed direct methanol fuel cells with passive thermal-uids management system. Journal of Power Sources 2007; 167:378390. 16. Chen R, Zhao TS. A novel electrode architecture for passive direct methanol fuel cells. Electrochemistry Communications 2007; 9:718724. 17. Shao ZG, Hsing IM, Zhang HM et al. Inuence of anode diffusion layer on the performance of a liquid feed direct methanol fuel cell by AC impedance spectroscopy. International Journal of Energy Research 2006; 30: 12161227. 18. Kazim A, Forges P, Liu HT. Effects of cathode operating conditions on performance of a PEM fuel cell with interdigitated ow elds. International Journal of Energy Research 2003; 27:401414. 19. Lu GQ, Lim PC, Liu FQ et al. On mass transport in an airbreathing DMFC stack. International Journal of Energy Research 2005; 29:10411050. 20. Yang WM, Choub SK, Shu C. Effect of current-collector structure on performance of passive micro direct methanol fuel cell. Journal of Power Sources 2007; 164:549554. 21. Jeong SU, Cho EA, Kim HJ et al. Effects of cathode open area and relative humidity on the performance of airbreathing polymer electrolyte membrane fuel cells. Journal of Power Sources 2006; 158:348353. 22. Chen R, Zhao TS, Yang WW et al. Two-dimensional twophase thermal model for passive direct methanol fuel cells. Journal of Power Sources 2008; 175:276287. 23. Lu GQ, Wang CY. Electrochemical and ow characterization of a direct methanol fuel cell. Journal of Power Sources 2004; 134:3340. 24. Ferng YM, Su A, Lu SM. Experiment and simulation investigations for effects of ow channel patterns on the PEMFC performance. International Journal of Energy Research 2008; 32:1223. Int. J. Energy Res. 2009; 33:719727 DOI: 10.1002/er

EFFECT OF ANODE CURRENT COLLECTOR ON THE PERFORMANCE OF DMFC

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25. Su A, Chiu YC, Weng FB. The impact of ow eld pattern on concentration and performance in PEMFC. International Journal of Energy Research 2005; 29: 409425. 26. Wang ZB, Yin GP, Shi PF. Effects of ozone treatment of carbon support on PtRu/C catalysts performance for direct methanol fuel cell. Carbon 2006; 44:133140.

27. Lu GQ, Liu FQ, Wang CY. Water transport through Naon 112 membrane in DMFCs. Electrochemical and Solid State Letters 2005; 8:A1A4. 28. Liu FQ, Lu GQ, Wang CY. Low crossover of methanol and water through thin membranes in direct methanol fuel cells. Journal of the Electrochemical Society 2006; 153:A543A553.

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Int. J. Energy Res. 2009; 33:719727 DOI: 10.1002/er