Novel PEEK Membranes for Fuel Cell Applications Methanol Diffusion Coefficient.

Diffusion coefficients were

determined using an H-cell arrangement. 1M Methanol was placed
Maria Gil 1, Xiangling Ji1, Xianfeng Li2, Hui Na2, J. Eric Hampsey1 on one side of the H-cell and water was placed on the other side.
and Yunfeng Lu1 Magnetic stirrers were used on each compartment to ensure
uniformity. Methanol analyses were done using a Hewlett Packard
(1) Chemical Engineering Department, Tulane University, 300 Lindy GC chromatograph. Peak areas were converted to methanol
Boggs Center, Tulane University, New Orleans, LA 70118, concentration using a calibration curve.
ylu@tulane.edu, (2) Department of Chemistry, Jilin University,
huina@jlu.edu.cn Thermal Stability. The thermal stability of the membranes
was analyzed using a TA instrument SDT 2960 simultaneous DTA-
Introduction TGA. The sample (~10mg) was heated from 25°C to 900°C at a rate
of 10°C/min under a nitrogen atmosphere.
Proton exchange membrane fuel cells (PEMFC) are promising power
sources for vehicles and portable devices [1,2]. Membranes currently
used in PEMFC are perfluorinated polymers such as Dupont
Results and Discussion.
Nafion®. Even though such membranes have demonstrated good
performances and long-term stability, their high cost and methanol
Methanol Diffusion. S-PEEK polymeric membranes prepared
crossover makes them unpractical for large-scale production. Among
from the sulfonated monomer exhibited methanol diffusion
the desired characteristics of a cation-exchange membrane for PEM
coefficients of 3x10-7 to 5x10-8 cm2/s depending on the degree of
fuel cells applications are: high ionic conductivity, minimal
sulfonation of the starting monomer. These values are significantly
water/methanol transport, high resistance to dehydration, low gas
lower than that of Nafion® membranes (2x10-6 cm2/s). Such results
permeability, low swelling, high mechanical strength, high resistance
are expected for S-PEEK membranes and can be attributed to less
to oxidation, reduction and hydrolysis and low cost. Sulfonated
pronounced hydrophilic and hydrophobic domains within the
aromatic polyether ether ketones (S-PEEK) based membranes have
membrane and to a smaller flexibility of the polymer backbone.
been studied due to their good mechanical properties, thermal
These characteristics reduce the hydrodynamic solvent transport
stability and conductivity [3, 4]. In the present study, poly(aryl ether
(water and methanol), which may help reduce the problems
ether ketone) (PEEK) polymeric membranes fabricated from
associated with water and methanol crossover for direct methanol
sulfonated monomer have been evaluated for possible fuel cell
fuel cells [4].
applications. The sulfonated PEEK membranes were characterized
by measuring the ion exchange capacity, water swelling, proton
conductivity, methanol diffusivity and thermal stability.
Conductivity. Proton conductivities at 25°C of the S-PEEK
membranes (shown on Figure 1) are about 13-42 % that of Nafion
Experimental 117 determined in [5]. The conductivity values are acceptable to
obtain good fuel cell performances.
Membrane Preparation. 1.0 g sulfonated PEEK was dissolved
into 30ml DMF. The solution was cast into thin films of 30 µm – 60
µm thickness on a 10 cm x 10 cm glass slide, which was placed into 0.1
an oven at 50oC and dried for 3 days. A dry membrane was peeled
off from the substrate with deionized water, and was submerged into
1.5M H2SO4 solution overnight. Finally, the membranes were rinsed Nafion
with deionized water and dried under vacuum for one day.

Membrane Characterization S-PEEK-3

Conducitivity [S/cm]

Swelling Degree. Membrane samples were equilibrated in

water at 25°C for 24 h. They were then removed from the water,
quickly dry-wiped and immediately weighed. Subsequently, they
were dried at 100°C and again weighed. The swelling degree was
calculated as follows:
S-PEEK-2
SD = mwet/mdry - 1 (1)

Ion-Exchange Capacity (IEC). The IEC was determined

through titration. The membranes in H+ form were immersed in 1M
NaCl solution for 24 h to liberate the H+ ions (the H+ ions in the S-PEEK-1
membrane were replaced by Na+ ions). The H+ ions now in solution
were then titrated with 0.01M NaOH.
0.01
2 2.5 3 3.5 4
Proton Conductivity. The proton conductivity of the fully
hydrated polymer membrane samples was determined by AC (1000/T) [K]
impedance spectroscopy over a frequency range of 1x103 Hz to
1x106 Hz using a Solartron 1260 gain phase analyzer. Figure 1. Proton conductivity of fully hydrated Nafion [4] and S-
PEEK polymeric membranes prepared from sulfonated monomer.

Fuel Chemistry Division Preprints 2003, 48(1), 445

 Thermal stability. The thermal degradation of the S-PEEK
membranes starts in the range of 250-270°C and these values are
similar to the ones obtained for cross linked polyaryl blend
membranes [6]. Three weight loss steps are observed in Figure 2.
The first weight loss step corresponds to water loss. The second
weight loss step is attributed to the splitting-off of sulfonic acid
groups in the PEEK membrane [7]. The third weight loss step
corresponds to sulfonic acid decomposition. According to the
thermal analysis, the S-PEEK membranes are thermally stable within
the temperature range for PEMFC applications.
Conclusions
S-PEEK membranes with 0.7-1.5 mmol/g ion exchange capacity
exhibited a high proton conductivity (> 0.01 S/cm at room
temperature), good thermal stability and methanol diffusion
coefficients significantly lower than that of Nafion® (PEM of choice
for hydrogen/air fuel cells), making S-PEEK membranes a good
alternative to reduce problems associated with high methanol
crossover in direct methanol fuel cells.

0
References

1. Appleby, A.J., Recent developments and applications of the polymer fuel

S-PEEK-1
-10 cell. Philosophical Transactions of the Royal Society of London, Series
A: Mathematical, Physical and Engineering Sciences, 1996. 354(1712):
p. 1681-1693.
-20 S-PEEK-2 2. Shoesmith, J.P., et al., Status of solid polymer fuel cell system
development. Journal of Power Sources, 1994. 49(1-3): p. 129-42.
Weight loss (%)

3. Kreuer, K.D., On the development of proton conducting materials for

-30 technological applications. Solid State Ionics, 1997. 97(1-4): p. 1-15.
4. Kreuer, K.D., On the development of proton conducting polymer
membranes for hydrogen and methanol fuel cells. Journal of Membrane
-40 Science, 2001. 185(1): p. 29-39.
5. Zawodzinski, T.A., Jr., et al., Determination of water diffusion
S-PEEK-3 coefficients in perfluorosulfonate ionomeric membranes. Journal of
-50 Physical Chemistry, 1991. 95(15): p. 6040-4.
6. Kerres, J., et al., Application of different types of polyaryl-blend-
membranes in DMFC. Journal of New Materials for Electrochemical
-60 Systems, 2002. 5(2): p. 97-107.
7. Zaidi, S.M.J., et al., Proton conducting composite membranes from
0 200 400 600 800 1000 polyether ether ketone and heteropolyacids for fuel cell applications.
Temperature (°C) Journal of Membrane Science, 2000. 173(1): p. 17-34.

Figure 2. TGA curves of S-PEEK membranes

Comparison with Nafion® membranes.

S-PEEK polymeric membranes prepared from the sulfonated

monomer show some similarities with Nafion membranes in IEC and
water swelling properties depending on the degree of sulfonation of
the PEEK, see Table 1. The main differences between S-PEEK ad
Nafion® membranes are ionic conductivity and MeOH diffusion
coefficient. Even though the ionic conductivities are lower than that
of Nafion®, they are still suitable for PEMFC applications and the
lower MeOH diffusion coefficients should reduce methanol
crossover in direct methanol fuel cells.

Table 1. Comparison of Nafion and S-PEEK membranes

S-PEEK S-PEEK S-PEEK Nafion®

1 2 3
Ion Exchange
0.712 1.511 1.465 0.91
Capacity (IEC)
Water Swelling
13 37 54 38
(%)
Conductivity at
0.011 0.013 0.035 0.083
25°C (S/cm)
MeOH diffusion
coefficient at 5x10-8 3x10-7 3x10-7 2x10-6
25°C (cm2/s)

Fuel Chemistry Division Preprints 2003, 48(1), 446