Journal of Polymer Research 11: 217224, 2004. 2004 Kluwer Academic Publishers. Printed in the Netherlands.

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Naon/PTFE Composite Membranes for Fuel Cell Applications

T. Leon Yu1,2, , Hsiu-Li Lin1,2 , Kun-Sheng Shen1 , Li-Ning Huang1 , Yu-Chen Chang1,2 , Guo-Bin Jung2 and Jerry C. Huang1
1 Department of 2 Fuel

Chemical Engineering, Yuan Ze University, Nei-Li, Taoyuan, 32026, Taiwan Cell Center, Yuan Ze University, Nei-Li, Taoyuan, 32026, Taiwan ( Author for correspondence; Tel.: +886-3-463880 ext 553; Fax: +886-3-4559373; E-mail: cetlyu@saturn.yzu.edu.tw)

Received 13 September; accepted in revised form 5 February 2004

Key words: composite membrane, fuel cell, Naon, poly(tetrauoroethylene) Abstract The composite membranes were prepared by impregnation of porous poly(tetrauoroethylene) membranes with a 5 wt% Naon solution. Scanning electron microscope micrographs of composite membranes show the surface and cross section of poly(tetrauoroethylene) membranes were covered and lled with Naon resin. Comparison of physical properties and fuel cell performance of composite membranes with those of Naon membranes (DuPont Co) is presented. The composite membrane has better thermal stability and gas barrier property but worse ionic conductivity than Naon membrane. Though the composite membrane has a lower conductivity than Naon membrane, however, owing to the thinner thickness of composite membrane (in thickness of 20 5 m) than Naon-115 (in thickness of 125 m) and Naon-117 (in thickness of 175 m) membranes, the composite membrane has a shorter H+ ion transporting pathway and thus a higher conductance (conductance = conductivity/membrane thickness) than Naon-115 and Naon-117 membranes. Thus the composite membrane has a better fuel cell performance than Naon-117 and Naon-115 membranes. In this report, we show that our composite membrane has a fuel cell performance similar to Naon-112 membrane (in thickness of 50 m). Introduction Peruorosulfonated ionomer (PFSI) membrane is a successful proton exchange membrane (PEM); a fast protonconducting separator fuel cell. The membrane is located between the cathode and anode and transports protons formed near the catalyst at the hydrogen electrode to the oxygen electrode thereby allowing the current to be drawn from the cell. It is generally accepted that PEM fuel cells present an attractive alternative to traditional power sources, due to their high efciency and non-pollution. Proton-conducting polymer electrolyte membranes for high performance PEM fuel cells have to meet the following requirements, especially for electric vehicle applications [1]: (1) low cost materials; (2) high proton conductivities; (3) good water uptakes; (4) low gas permeability; (5) reliable durability. However, the high cost of the cell components impediment to their commercialization. One of the primary contributors to the PEM fuel cells high cost is the PFSI membrane. Recent research reports have shown that cost reduction can be realized by replacing PFSI membrane by a PFSIbased composite membrane [212]. Composite membranes may be prepared by the impregnation of a low cost microporous supporting material with a PFSI solution. The most common PFSI solution and porous membrane for preparing composite membrane are: Naon solution, a registered trademark of E.I. DuPont, and porous polytetrauoroethylene (PTFE) membrane. It is important to note that the composite membranes contain much less of the expensive PFSI resin than the traditional PFSI membranes such as Naon 117 (in thickness of 175 m), Naon-115 (in thickness of 125 m), and Naon-112 (in thickness of 50 m), thus the cost of composite membranes is much lower than that of the traditional PFSI membranes. Naon has a chemical structure with hydrophobic tetrauoride backbone and hydrophilic ionic side chains. It has been reported [13] that Naon polymers aggregate in dilute low alcohol and water solvents and form fringed cylindrical rods structured with ionic side chains surrounding the periphery of rods. These aggregates cause problems for impregnating porous PTFE membranes with Naon solutions, i.e., the pores of PTFE membranes are not fully impregnated by Naon resin, because of the larger sizes of Naon aggregates than pore sizes of PTFE membranes. Thus the efciency of composite membranes as gas barriers of H2 and O2 is not as good as that of Naon membranes. In literature, there were reports [7, 11, 12] that the gas permeability of Naon/PTFE composite membranes was higher than that of Naon membranes. Yeo [14] determined the solubility parameter using the swelling method and showed dual solubility parameters of Naon: one ( = 9.5 (cal/cm3 )1/2 ) is ascribed to the Naon organic backbone part whereas the other ( = 16.8 (cal/cm3 )1/2 ) is attributed to the ionic side chains. The aggregation of Naon molecules in the solvents strongly depends on the dielectric constant and solubility parameter of solvents. In a previous work [15], using dynamic light scattering, we measured the particle sizes distributions of dilute Naon in various low alcohol/water mixture solvents, i.e., methanol/water, ethanol/water, and 2-propanol/water,

218 which had different solubility parameters. The data showed that the particle sizes of Naon molecular aggregates decreased while the solubility parameter of solvent was close to the solubility parameter of Naon backbone ( = 9.5 (cal/cm3)1/2 ). The Naon has the smallest aggregation particles sizes in 2-propanol/water solvent and the largest aggregation particle sizes in methanol/water solvent. In this paper, we report the preparation of Naon/PTFE composite membrane by impregnating a porous PTFE membrane with a modied Naon solution, which, containing solvent, has a better solubility to Naon backbone than the solvent of the received Naon solution. The smaller sizes of Naon aggregation particles cause the Naon molecules to be easily plugged into the micro-pores of PTFE membranes and results in a better gas barrier property for composite membranes than Naon membranes. Comparison of physical properties and fuel cell performance of composite membranes with those of Naon membranes was studied. Besides the cheap cost, we report other advantages of the composite membranes: good thermo-stability and thinner thickness (the thickness of our composite membranes is around 20 m) for fuel cell applications. Although the roomtemperature conductivity of composite membranes is lower than that of Naon membranes, their area resistances are signicantly lower due to their thinness. Thus the composite membrane has a similar fuel cell performance as that of Naon-112 membrane, and a better performance than Naon-115 and Naon-117 membranes. Experimental Materials PTFE membrane, purchased from Yue-Ming-Tai Chemical Ind. Co, Taiwan, with a thickness of 20 5 m, pore sizes of 0.5 0.1 m, and porosity of 85 5% was used as a supporting material of composite membranes. Naon-117 (in thickness of 175 m), Naon-115 (in thickness of 125 m), Naon-112 (in thickness of 50 m) membranes, and Naon solution were purchased from DuPont Co. All the Naon membranes and Naon solution were with SO3 H equivalent weight (EW) of 1100. The Naon solution had a composition of 5 wt% Naon and 95 wt% solvent. The solvent mixture composed of water, propanol, ethanol, methanol, and unspecied mixed ethers [16]. The chemical structure of Naon [1]:

T. Leon Yu et al. Preparation of Naon/PTFE Composite Membranes The solvent of the received Naon solution was evaporated under vacuum at 60 C and the residual Naon resin was mixed with 2-propanol/ water (4/1 wt ratio) mixture solvent to a solution containing 5 wt% of Naon. The newly prepared solution was used to prepare composite membranes. Porous PTFE membranes were mounted on a 12 12 cm2 steel frame and boiled in acetone at 55 C for 1 hr. These pretreated PTFE membranes were then impregnated with a 5 wt% Naon solution for 24 hr. These impregnated membranes were then annealed at 120 C for 30 min (sample # PN-30), 40 min (sample # PN-40), and 50 min (sample # PN50), respectively. After annealing, these membranes were then swollen with distilled water for 24 hr. Finally, the membranes were swollen with 1 N sulfuric acid for 4 hr. Table 1 lists the nal compositions of the composite membranes. Characterizations of Naon/PTFE Composite Membranes The morphology of surface and cross section of composite membranes was studied using a scanning electron microscope (SEM, model JSM-5600, Jeol Co., Japan). The sample surface was coated with gold powder under vacuum before the morphology of membranes was observed. The thermal stability of composite membranes was investigated, using a thermogravimetric analyzer (TGA, DuPont model 910), with sample sizes of 1015 mg, and a heating rate of 10 C/min and a nitrogen ow rate of 145 ml/min. The thermal behavior of composite membranes was studied using a differential scanning calorimeter (DSC, DuPont 910 model). For DSC analysis, a sample with a weight of around 56 mg was quenched to 80 C then heated from 80 C to 450 C with a heating rate of 10 C/min. The mechanical property of the composite membranes was tested, using an Instron testing machine (model 4204), in accordance with JIS-K7127. The tensile strength of the composite membranes was 17.6 1.5 kg/cm2. The ionic conductivity ( ) was calculated from current resistance (R) using an equation = L/(AR), where A is the cross section area of membrane for a resistance measurement and L the length for a resistance measurement, i.e., the thickness of a membrane. R was measured using an ac impedance system (model SA1125B, Solartron Co, UK). A device capable of holding a membrane for R measurement was located between probes. The testing device with a membrane was kept in a thermostat under a relative humility of
Table 1. Final compositions of Naon/PTFE composite membranes Sample # Annealing time (min) at 120 C 30 40 50 PTFE (wt%) 41.4 41.2 42.4 Naon (wt%) 48.4 49.8 49.3 Water (wt%) 10.2 9.0 8.3

PN-30 PN-40 PN-50

where n 6.5 and m

1.

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Figure 1. SEM micrograph (5000) of the surface of porous PTFE membrane.

Figure 2. SEM micrograph (2500) of PN-50 composite membrane: (a) surface; (b) cross section.

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Figure 3. TGA curves of membranes: (A) PN-30; (B) PN-40; (C) PN-50; (D) Naon-117; (E) PTFE. The curves are vertically shifted and separated by 10 wt% in order for easy view.

95% and a temperature of 90 C. The membrane area for R measurement was 3.14 cm2 . Gas permeability of membranes was investigated using an apparatus designed by our laboratory. A device of holding a membrane was located between two vessels, with the volume of vessel-1 of 3000 ml and that of vessel-2 of 200 ml. At the beginning of the gas permeability test, vessel-1 was lled with N2 gas under a pressure of 3 kg/cm2 and vessel-2 was kept under vacuum. The membrane holder was kept at a temperature of 25 C. The gas permeability of the membrane was characterized by measuring the pressure of vessel-2 (P2 ) versus testing time. A membrane with a higher gas permeability (or poor gas barrier) should have a higher P2 increment rate, i.e. higher dP2 /dt. Fuel Cell Performance Test The Naon membranes (i.e. Naon-117, Naon-115, and Naon-112) and PN-30 (20 m thick) composite membrane prepared in our laboratory were used to prepare membrane electrolyte assemblies (MEA). The gas diffusion layer of MEA was a carbon paper (Toray Co, Japan) pretreated with FEP resin (DuPont Co). The Pt/C catalyst content of anode was 0.5 mg/cm2 and that of cathode was 1.0 mg/cm2. The performances of single cells were tested at 70 C using a Globe Tech Computer Cell GT testing system (Electrochem Inc). The anode H2 input ow rate was 100 ml/min, and the cathode O2 input ow rate was 100 ml/min. Results and Disscussion The solubility parameters of methanol, ethanol, and 2propanol are = 14.5 (cal/cm3 )1/2 , = 12.7 (cal/cm3 )1/2 ,

and = 11.8 (cal/cm3 )1/2 , respectively. Thus the solvent of newly prepared Naon/2-propanol/water solution has a better solubility to Naon backbone ( = 9.5 (cal/cm3 )1/2 ) than the solvent of the received Naon solution, which contains a mixture of water, 2-propanol, ethanol, methanol, and unspecied mixtures. SEM Morphology Study Figure 1 is the SEM micrograph of the surface of porous PTFE membrane. This micrograph shows there are bers and knots in the membrane with micro-pores locate among the bers and knots. Figures 2(a) and 2(b) show the SEM micrograph of the surface and cross section of composite (# PN-50) membrane, respectively. As shown in Figures 2(a) and 2(b), the surface and inner part of PTFE membrane are completely covered and lled with Naon resin and no micro-pore is observed in the micrograph of composite membrane, indicating the porous PTFE membrane is well impregnated with Naon resin. TGA Study Figure 3 shows the TGA curves of PTFE, Naon-117, PN-30, PN-40, and PN-50 composite membranes. The onset decomposition temperatures obtained from Figure 3 are: 470, 274, 305, 307, and 310 C for PTFE, Naon-117, PN-30, PN-40, and PN-50, respectively. Since PTFE has an excellent thermal stability, the reinforcement of Naon with PTFE porous matrix improves the thermal stability of membranes. Thus Figure 3 shows that the composite membranes have higher onset decomposition temperatures than Naon-117 membrane.

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Figure 4. DSC curve of pure dried Naon membrane. Full line DSC curve; dashed lines DSC decomposed curves.

Figure 5. DSC curve of wet Naon membrane, which was prepared by swelling the same dried membrane as in Figure 4 with water at room temperature. Full line DSC curve; dashed lines DSC decomposed curves.

DSC Study It has been shown that the morphology of Naon membranes is composed of side chain ionic aggregation clusters, amorphous regions, and crystalline regions [1820]. In order to identify the endotherms of DSC curves of composite membranes, DSC experiments of pure dried Naon membrane and Naon membrane swollen with water were carried out and their DSC curves are shown in Figures 4 and 5, respectively. These membranes were prepared by casting from 10 wt% Naon/ethanol/water solution. The solvent was evaporated at room temperature for 108 hr, then annealed at 120 C for 1 hr (sample of Figure 4), and then the dried membrane was swollen with water at room temperature: the water content was 20.4 wt% (sample of Figure 5). In Figure 5, the shoulder around 120 C and 230 C are the endotherm of water evaporation and melting of crystalline,

respectively. The endotherm peak around 165 C is the dissociation of ionic clusters. In Figure 4, the Naon membrane had no water and the shoulder around 120 C of DSC curve disappeared. The broad endotherm peak is attributed to the dissociation of ionic clusters. Owing to the ionic side chains, the degree of crystallinity of Naon is usually low, no sharp endotherms of crystalline melting and evaporation of water were observed as shown in Figures 4 and 5. The DSC curves of PTFE, Naon, PN-30, PN-40, and PN-50 membranes are shown in Figure 6. Table 2 summarizes the transition temperatures (Tm ) and endotherms ( Hm ) of PTFE, Naon, PN-30, PN-40, and PN-50 membranes shown in Figure 6. In Figure 6, the endotherms of PTFE at Tm1 = 22 C and Tm3 = 328 C correspond to the transition of triclinic unit cell to hexagonal unit cell and the melting of crystalline, respectively [17]. The presence of Naon in the PTFE membrane causes the composite

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Figure 6. DSC curves of membranes: (A) PTFE; (B) PN-30; (C) PN-40; (D) PN-50. Table 2. DSC data of composite membranes Sample # Tm1 ( C) 22 21 22 21 Tm3 ( C) 328 327 328 327 Hm1 (J/g) 14.3 5.3 4.8 6.0 Hm2 (J/g) 90.4 123.1 134.5 Hm3 (J/g) 22.8 11.2 8.3 10.5

PTFE PN-30 PN-40 PN-50

the standard deviations are around 10%. The conductivity of composite membranes is lower than that of Naon-117 membrane, due to the poor conductivity of PTFE membrane. These data also show the conductivity of composite membrane decreases with increasing membrane annealing time at 120 C. Increasing annealing time of composite membranes at 120 C causes an increase in the degree of Naon crystallinity and thus a decrease in the content of water swollen in the composite membranes [1820]. Thus the conductivity of composite membranes decreases with increasing annealing time of composite membrane. Gas Permeability Test The gas permeability tests of PTFE, Naon-117, and PN30 membranes were performed at 25 C and the vessel-2 pressures P2 are plotted against experimental time, t, and shown in Figure 7. The rate of P2 increment, i.e. dP2 /dt, of these membranes decreases in the following sequence: PTFE > Naon-117 > PN-30. These data show that PN-30 composite membrane (it has thickness around 22 5 m) has a slowest rate of P2 increment, indicating the lowest gas permeability thus the best gas barrier membrane in all of these membranes. PTFE membrane has the highest rate of P2 increment and is the worst gas barrier membrane among these membranes, because of its high porosity. Although the thickness Naon-117 membrane (thickness = 175 m) is thicker than that of PN-30, Figure 7 shows that PN-30 has a lower gas permeability than Naon membrane. The Naon-115 and Naon-112 membranes have thinner thickness than Naon-117. The gas permeability of Naon-115

membrane to have one broad endotherm-2, which locates between endotherm-1 (Tm1 ) and endotherm-3 (Tm3 ). The broad melting endotherm between Tm1 and Tm3 corresponds to the evaporation of water swollen in membrane, dissociation of ionic clusters, and the melting of Naon crystalline, and Hm2 of melting endotherm-2 increases with increasing annealing time of composite membranes, indicating increases both in the degree of Naon crystallinity and the degree of phase separation between hydrophobic backbones and hydrophilic ionic side chains while annealing time is increased [1820]. Conductivity Measurements The conductivity of the composite membranes was measured using an ac impedance system at 90 C with a relative humidity of 95%. The conductivities of Naon-117, PN-30, PN-40, and PN-50 membranes are: 1.25102, 1.30103, 6.59 104, and 5.61 104 S cm1 , respectively. The data are the average values of three measurements and

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Figure 7. Gas permeability test of membranes at 25 C. (*) Naon-117; (!) PN-30; (Q) PTFE.

Figure 8. Cell potential versus current density curves of single fuel cells prepared from (a)PN-30, (Q)Naon-112, (2)Naon-115, and (")Naon-117 membranes.

Figure 9. Reliability test of fuel cell prepared from composite membrane.

224 and Naon-112 membranes should be higher than that of Naon-117. Fuel Cell Performance Test In order to evaluate the fuel cell performance of our composite membranes, the PN-30, Naon-117, Naon-115, and Naon-112 membranes were used to prepare MEAs. Figure 8 shows the cell potential versus current density curves of single fuel cells prepared from these membranes. Figure 8 shows the voltages of single fuel cells fall as current density increases. One of the reasons for the fall of the voltage with increasing current density is the so called ohmic loss which comes from the resistance to the ow of ions through the polymer electrolyte membrane [21]. It is found that though the composite membrane has a lower ionic conductivity than Naon-117 membrane, however, owing to the thinner thickness of composite membrane than Naon membranes, the composite membrane has a shorter pathway for transporting H+ ion and thus a lower ohmic loss. The results of Figure 8 show that the composite membrane has a better fuel cell performance than Naon-117 and Naon115 membranes. Our composite membrane has a fuel cell performance similar to Naon-112 membranes. We also carried out the long time durability test of the fuel cell prepared from composite membranes. Figure 9 shows the current density operated at 0.6 V versus the fuel cell operating time. The data show a slow decay of current density with application time. The decay of current density could be due to the water ooding in the gas diffusion layer, which blocks the gas diffusion channel. Thus the gas supply decreases and the current density decreases as fuel cell operating time increases. However after operating for 100 hrs, the current density was still above 650 mA/cm2 , indicating a good quality of the composite membranes.

T. Leon Yu et al. thickness than Naon membranes while they are used in fuel cell applications. The present experimental results reveal that composite membranes have better thermal stability and gas barrier property than Naon membranes. Though the conductivity of composite membrane is lower than that of Naon membranes, the thinner thickness causes the composite membrane to have shorter pathway for transporting H+ ion and thus a better fuel cell performance.

Acknowledgements The authors would like to thank, for the nancial support, the Energy Council, Ministry of Economy of ROC through grants 90-D0122 and 91-D0 122.

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Conclusion In this work, we successfully prepared Naon-PTFE composite membranes by impregnating a very thin porous PTFE membrane with a 5 wt% Naon solution. In the composite membrane, Naon is a solid electrolyte to conduct proton (H+ ion) from one side of the membrane to the other side and PTFE membrane is a supporting matrix with excellent mechanical properties. The high mechanical strength of PTFE matrix allows the composite membranes to have a thinner

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