Published on Web 03/13/2007

Tuned Polymer Electrolyte Membranes Based on Aromatic

Polyethers for Fuel Cell Applications
Kenji Miyatake, Yohei Chikashige, Eiji Higuchi, and Masahiro Watanabe*
Contribution from the Clean Energy Research Center, UniVersity of Yamanashi, 4 Takeda,
Kofu 400-8510, Japan
Received October 10, 2006; E-mail: m-watanabe@[Link]
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Abstract: Poly(arylene ether sulfone)-based ionomers containing sulfofluorenyl groups have been
synthesized for applications to polymer electrolyte membrane fuel cells (PEMFCs). In order to achieve
high proton conductivity and chemical, mechanical, and dimensional stability, the molecular structure of
the ionomers has been optimized. Tough, flexible, and transparent membranes were obtained from a series
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of modified ionomers containing methyl groups with the ion-exchange capacity (IEC) ranging from 1.32 to
3.26 meq/g. Isopropylidene tetramethylbiphenylene moieties were more effective than the methyl-substituted
fluorenyl groups in giving a high-IEC ionomer membrane with substantial stability to hydrolysis and oxidation.
Dimensional stability was significantly improved for the methyl-substituted ionomer membranes compared
to that of the non-methylated ones. This new ionomer membrane showed comparable proton conductivity
to that of the perfluorinated ionomer membrane (Nafion 112) under a wide range of conditions (80-120 °C
and 20-93% relative humidity (RH)). The highest proton conductivity of 0.3 S/cm was obtained at 80 °C
and 93% RH. Although there is a decline of proton conductivity with time, after 10 000 h the proton
conductivities were still at acceptable levels for fuel cell operation. The membranes retained their strength,
flexibility, and high molecular weight after 10 000 h. Microscopic analyses revealed well-connected ionic
clusters for the high-IEC membrane. A fuel cell operated using the polyether ionomer membrane showed
better performance than that of Nafion at a low humidity of 20% RH and high temperature of 90 °C. Unlike
the other hydrocarbon ionomers, the present membrane showed a lower resistance than expected from its
conductivity, indicating superior water-holding capability at high temperature and low humidity.

Introduction susceptibility to electrophilic sulfonation reactions. A number

of aromatic polymers such as poly(ether ether ketone)s,4 poly-
Ion-conducting polymers are of interest for a variety of
(arylene ether)s,5 polyimides,6 polyphosphazenes,7 poly-
applications, such as sensors, actuators, batteries, and ion-
benzimidazoles,8 polyphenylenes,9 and others10 have been
exchange membranes or resins.1 Particularly, recent progress
sulfonated or doped with mineral acids. Recently, it has been
in the area of polymer electrolyte membrane fuel cells
reported by several research groups that the polymer electrolytes
(PEMFCs) has stimulated considerable interest in proton
containing fluorenyl groups are highly proton conductive.11,12
conductive polymer membranes.2 Perfluorinated sulfonic acid
ionomers such as Nafion have been the most studied as the (4) (a) Jones, D. J.; Rozière, J. J. Membr. Sci. 2001, 185, 41. (b) Kobayashi,
electrolyte membrane for PEMFCs. Although almost a half- T.; Rikukawa, M.; Sanui, K.; Ogata, N. Solid State Ionics 1998, 106, 219.
(5) (a) Wang, F.; Hickner, M.; Ji, Q.; Harrison, W.; Mecham, J.; Zawodzinski,
century has passed since DuPont developed Nafion membranes, T. A.; McGrath, J. E. Macromol. Symp. 2001, 175, 387. (b) Gao, Y.;
they are still state-of-the-art because of their high proton Robertson, G. P.; Guiver, M. D.; Mikhailenko, S. D.; Li, X.; Kaliaguine,
S. Macromolecules 2005, 38, 3237.
conductivity and excellent stability. There is, however, a great (6) (a) Genis, C.; Mercier, R.; Sillion, B.; Cornet, N.; Gebel, G.; Pineri, M.
demand for non-fluorinated alternative membranes in terms of Polymer 2001, 42, 359. (b) Fang, J.; Guo, X.; Harada, S.; Watari, T.;
Tanaka, K.; Kita, H.; Okamoto, K. Macromolecules 2002, 35, 9022. (c)
production cost, environmental friendliness, and high-temper- Miyatake, K.; Zhou, H.; Uchida, H.; Watanabe, M. Chem. Commun. 2003,
368. (d) Asano, N.; Aoki, M.; Suzuki, S.; Miyatake, K.; Uchida, H.;
ature stability.3 Watanabe, M. J. Am. Chem. Soc. 2006, 128, 1762. (e) Miyatake, K.;
One possible approach for this purpose is acid functional- Watanabe, M. J. Mater. Chem. 2006, 16, 4465.
(7) (a) Tang, H.; Pintauro, P. N. J. Appl. Polym. Sci. 2000, 79, 49. (b) Hofmann,
ization of hydrocarbon polymers. Aromatic polymers have been M. A.; Ambler, C. M.; Maher, A. E.; Chalkova, E.; Zhou, X. Y.; Lvov, S.
extensively studied due to their excellent stability and high N.; Allcock, H. R. Macromolecules 2002, 35, 6490.
(8) (a) Wainright, J. S.; Wang, J.-T.; Weng, D.; Savinell, R. F.; Litt, M. J.
Electrochem. Soc. 1995, 142, L121. (b) Xing, B.; Savadogo, O. J. New
(1) Tant, M. R.; Mauritz, K. A.; Wilkes, G. L. Ionomers; Chapman & Hall: Mater. Electrochem. Syst. 1999, 2, 95.
New York, 1997. (9) (a) Kobayashi, T.; Rikukawa, M.; Sanui, K.; Ogata, N. Solid State Ionics
(2) Colomban, P. Proton Conductors; Cambridge University Press: Cambridge, 1998, 106, 219. (b) Fujimoto, H.; Hickner, M. A.; Cornelius, C. J.; Loy,
1992. D. A. Macromolecules 2005, 38, 5010.
(3) (a) Savadogo, O. J. New Mater. Electrochem. Syst. 1998, 1, 47. (b) Hickner, (10) (a) Chen, Y. L.; Meng, Y. Z.; Hay, A. S. Macromolecules 2005, 38, 3564.
M. A.; Ghassemi, H.; Kim, Y. S.; Einsla, B. R.; McGrath, J. E. Chem. (b) Chen, Y. L.; Meng, Y. Z.; Li, X.; Hay, A. S. Macromolecules 2005,
ReV. 2004, 104, 4587. (c) Miyatake, K.; Watanabe, M. Electrochemistry 38, 10007. (c) Zhou, Z.; Dominey, R. N.; Rolland, J. P.; Maynor, B. W.;
2005, 73, 12. Pandya, A. A.; DeSimone, J. M. J. Am. Chem. Soc. 2006, 128, 12963.
10.1021/ja0672526 CCC: $37.00 © 2007 American Chemical Society J. AM. CHEM. SOC. 2007, 129, 3879-3887 9 3879
ARTICLES Miyatake et al.

Scheme 1. Synthesis of a Series of Methyl-Substituted Poly(arylene ether sulfone)s Containing Fluorenyl Groups

Proton conductivity comparable to that of Nafion has been carbon ionomer membrane in an operating fuel cell.14 There
reported for some of these membrane materials; how- were only minor changes as confirmed by IEC, thickness, and
ever, hydrolytic and oxidative stability are still issues to be molecular weight after the fuel cell operation indicating no
addressed. practical degradation. Before the 2a membrane is subjected for
In previous reports, we proposed that pendent acidic groups further evaluation, the heavy dependence of the proton con-
(not attached to the main chain) keep the polymer chain in a ductivity on humidity has to be improved since fuel cells are
hydrophobic environment and contribute to improved stability.11 often operated at low humidity. The challenge is how to increase
Novel sulfonated poly(arylene ether sulfone) ionomers contain- the conductivity without sacrificing hydrolytic, oxidative,
ing fluorenyl groups (2a in Scheme 1) in which sulfonic acid dimensional, and mechanical stability. In this paper, we describe
groups were substituted only at specific (2,7)-positions on our successful approaches to this purpose. Substituent effects
fluorenyl groups were synthesized. The ionomer membranes have been studied in detail to tune the chemical structure for
show high proton conductivity (0.2 S/cm) at 100% RH, low higher IEC ionomers. It turned out that the 2e membrane in
gas permeation, and high hydrolytic and oxidative stability. The
Scheme 1 shows considerably improved properties. Proton
2a membrane with an ion-exchange capacity (IEC) of 1.6 meq/g
conductivity is comparable to that of Nafion at 20-93% RH
was durable for 5000 h in a H2/air fuel cell operated at 80 °C
and 80-120 °C and was at acceptable levels for fuel cell
and 90% RH.13 This is, to the best of our knowledge, one of
the greatest longevities reported for a non-fluorinated hydro- operation for 10 000 h. We have then demonstrated that the
new membrane functions better than Nafion in a fuel cell
(11) (a) Miyatake, K.; Chikashige, Y.; Watanabe, M. Macromolecules 2003, operated at 90 °C and 20% RH.
36, 9691. (b) Chikashige, Y.; Chikyu, Y.; Miyatake, K.; Watanabe, M.
Macromolecules 2005, 38, 7121. (c) Chikashige, Y.; Chikyu, Y.; Miyatake,
K.; Watanabe, M. Macromol. Chem. Phys. 2006, 207, 1334. (13) Aoki, M.; Chikashige, Y.; Miyatake, K.; Uchida, H.; Watanabe, M.
(12) (a) Guo, X.; Fang, J.; Watari, T.; Tanaka, K.; Kita, H.; Okamoto, K. Electrochem. Commun. 2006, 8, 1412.
Macromolecules 2002, 35, 6707. (b) Shang, X.; Tian, S.; Kong, L.; Meng, (14) There have been recent reports on the durability of hydrocarbon-based
Y. Z. J. Membr. Sci. 2005, 266, 94. (c) Liu, B.; Kim, D.-S.; Murphy, J.; ionomer membranes in fuel cells. See, for example: (a) Besse, S.; Capron,
Robertson, G. P.; Guiver, M. D.; Mikhailenko, S.; Kaliaguine, S.; Sun, O.; Diat, O.; Gebel, G.; Jousse, F.; Marsacq, D.; Pineri, M.; Marestin, C.;
Y.-M.; Liu, Y.-L.; Lai, J.-Y. J. Membr. Sci. 2006, 280, 54. (d) Chen, Y.; Mercier, R. J. New Mater. Electrochem. Syst. 2002, 5, 109. (b) Rozière,
Meng, Y. Z.; Wang, S.; Tian, S.; Chen, Y.; Hay, A. S. J. Membr. Sci. J.; Jones, D. J. Annu. ReV. Mater. Res. 2003, 33, 503. (c) Li, Q.; He, R.;
2006, 280, 433. Jensen, J. O.; Bjerrum, N. J. Fuel Cells 2004, 4, 147.

3880 J. AM. CHEM. SOC. 9 VOL. 129, NO. 13, 2007

Tuned Polymer Electrolyte Membranes for Fuel Cells ARTICLES

Experimental Section chloroform/acetone. The resulting product was dried under vacuum at
60 °C for 15 h to give 1b in 63% yield. Using DMBHF instead of
Measurements. 1H (400 MHz) and 13C (100 MHz) NMR experi- MBHF gave polymer 1c in 75% yield.
ments were performed on a Bruker AVANCE 400S spectrometer using
Copolymers 1d-i. The polymerization was carried out in the same
deuterated dimethyl sulfoxide (DMSO-d6) or deuterated chloroform
manner as described for the homopolymers except that biphenol
(CDCl3) as the solvent and tetramethylsilane (TMS) as the internal
comonomer (BPA, BDMPA, DHP, or TMPCB) was also added. The
reference. Molecular weight measurement was performed via gel
molar ratio of BHF to the biphenol monomer was set at 1:1. White
permeation chromatography (Jasco 880-PU) equipped with two Shodex
flaked pure copolymers 1d-i were obtained in 66-85% yield.
KF-805 columns and a Jasco 875 UV detector set at 300 nm. N,N-
Sulfonation. The sulfonation of polymers 1 using a flow reactor
Dimethylformamide containing 0.01 M LiBr was used as the solvent
has been described previously.11c A typical procedure is as follows. A
at a flow rate of 1.0 mL/min. Mw and Mn were calibrated with standard
200 mL syringe was charged with 100 mL of 0.01 M of polymers
polystyrene samples.
1a-i in dichloromethane, and a 100 mL syringe was charged with 30
Materials. 9-Fluorenone (98%, TCI Co., Inc.), 2,6-xylenol (99%, mL of 1.0 M chlorosulfonic acid in dichloromethane. Both syringes
TCI Co., Inc.), thioglycolic acid (80%, TCI Co., Inc.), 3,3′,5,5′- were connected to the reactor via a Teflon tube. Each solution was
tetramethyl-(1,1′-biphenyl)-4,4′-diol (TMP) (98%, Aldrich Co., Inc.), supplied to the reactor simultaneously using a microfeeder. The flow
propyl isocyanate (96%, TCI Co., Inc.), triethylamine (TEA) (98%, rate of the polymer solution and the chlorosulfonic acid solution was
Aldrich Co., Inc.), tetrahydrofuran (THF) (99%, Kanto Chemical Co., set at 10 mL/min and 3 mL/min, respectively. The obtained mixture
Inc.), 9,9′-bis(4-hydroxyphenyl)fluorene (BHF) (98%, TCI Co., Inc.), was poured dropwise into 500 mL of hexane. The resulting product
9,9′-bis(4-hydroxy-3-methylphenyl)fluorene (MBHF) (98%, TCI Co., was washed with hexane and water several times and dried under
Inc.), 4,4′-isopropylidenediphenol (BPA) (99%, Kanto Chemical Co., vacuum at 60 °C for 15 h to obtain a white powder of sulfonated
Inc.), 2,2′-bis(4-hydroxy-3,5-dimethylphenyl)propane (BDMPA) (98%, polymers 2a-i.
TCI Co., Inc.), 4,4′-dihydroxybiphenyl (DHP) (99%, TCI Co., Inc.),
Membrane Preparation. Ionomers 2 (0.35 g) in 12 mL of DMAc
potassium carbonate (99.5%, Kanto Chemical Co., Inc.), toluene
were cast onto a clean, flat glass plate (9 cm × 6 cm). Drying the
(99.5%, Kanto Chemical Co., Inc.), chlorosulfonic acid (99%, Kanto
solution at 60 °C under atmospheric pressure for 15 h gave colorless
Chemical Co., Inc.), and dichloromethane (99.5%, dehydrated, Kanto
and transparent membranes. The membranes were immersed in 1 N
Chemical Co., Inc.) were used as received. 4-Fluorophenyl sulfone
HNO3(aq) for 12 h. The acidification process was repeated three times.
(FPS) (99%, Acros Organics) was purified by crystallization from
The membranes were then washed with deionized water several times
ethanol. N,N-Dimethyl acetamide (DMAc) (99%, Kanto Chemical Co.,
and dried under vacuum at 60 °C for 15 h.
Inc.) was dried over 3A-molecular sieves prior to use. Other chemicals
Ion-Exchange Capacity (IEC). The IEC of the ionomer 2 mem-
were of commercially available grade and used as received.
branes was determined by 1H NMR spectroscopy and titration. In the
9,9′-Bis(4-hydroxy-3,5-dimethylphenyl)fluorene (DMBHF). DM- 1
H NMR technique, changes in the integration ratio for the aromatic
BHF was synthesized according to the method described in the
protons were taken. In the titration method, a piece of ionomer
literature.15 1H NMR (DMSO-d6): δ (ppm) 2.01 (s, 6H), 6.63 (s, 4H),
membrane was equilibrated in a large excess of 0.01 M NaCl(aq) for
7.28 (t, 2H), 7.34 (t, 2H), 7.39 (d, 2H), 7.85 (d, 2H), 8.09 (s, 2H). 13C
15 h. The amount of HCl released from the membrane sample was
NMR (DMSO-d6): δ (ppm) 16.8, 63.6, 120.2, 123.6, 126.0, 127.1,
determined by titration with 0.01 N NaOH(aq) using phenolphthalein
127.4, 136.3, 139.2, 151.8.
as an indicator.
3,3′,5,5′-Tetramethyl-4,4′bis(propylcarbamoyl)biphenol (TMPCB). Oxidative Stability. A small piece of membrane sample with a
TMPCB was synthesized according to a modified method in the thickness of 50 µm was soaked in Fenton’s reagent (3% H2O2 containing
literature.16 A 100 mL, three-neck, round-bottomed flask equipped with 2 ppm FeSO4) at 80 °C for 1 h. The stability was evaluated by changes
a magnetic stirring bar, a gas inlet, and an addition funnel was charged in molecular weight, IEC, weight, and appearance of the test samples.
with TMP (10.0 mmol, 2.423 g), propyl isocyanate (60 mmol, 5 mL),
Hydrolytic Stability. A small piece of membrane sample with a
TEA (0.5 mL), and 50 mL of THF. The mixture was heated at 70 °C
thickness of 50 µm was treated at 140 °C and 100% RH in a pressurized
for 20 h under N2 atmosphere. The mixture was evaporated to dryness
closed vial for 24 h. The stability was evaluated by changes in molecular
to obtain a crude product. The product was purified twice by
weight, IEC, weight, and appearance of the test samples.
crystallization from chloroform/hexane. The resulting product was dried
Mechanical Strength. Tensile testing was performed with a
under vacuum at 50 °C for 15 h to obtain pure TMPCB in 64% yield.
1 Shimadzu universal testing instrument Autograph AGS-J500N equipped
H NMR (DMSO-d6): δ (ppm) 0.90 (t, 6H), 1.49 (m, 4H), 2.16 (s,
with a chamber in which the temperature and the humidity were
12H), 3.05 (q, 4H), 7.33 (s, 4H), 7.79 (t, 2H). 13C NMR (DMSO-d6):
controlled by flowing humidified air with a Toshin Kogyo temperature
δ (ppm) 11.1, 16.0, 22.6, 42.1, 126.4, 130.9, 136.6, 147.6, 153.9.
control unit Bethel-3A. Stress versus strain curves were obtained at a
Homopolymers 1a-c. The polymerization procedure for 1a has been
speed of 10 mm/min for samples cut into a dumbbell shape (DIN-
described previously.11 Polymers 1b and 1c were synthesized as follows.
53504-S3, 35 mm × 6 mm (total) and 12 mm × 2 mm (test area)).
A 200 mL, three-neck, round-bottomed flask equipped with a magnetic
Swelling Degree. The membrane samples were dried at 80 °C under
stirring bar, a N2 inlet, and an addition funnel was charged with MBHF
vacuum for 3 h, and their sizes were quickly measured. Then the dried
(2.0 mmol, 0.757 g), FPS (2.0 mmol, 0.509 g), potassium carbonate
samples were immersed into deionized water at 25 or 50 °C for 3 h.
(5.0 mmol, 0.691 g), toluene (2.0 mL), and 5 mL of DMAc. The mixture
The swelling degree was evaluated by the changes in thickness, area,
was stirred at room temperature for a few minutes and then heated at
and volume between dry and fully hydrated samples.
140 °C for 3 h and at 165 °C for 3 h under N2 atmosphere. Then, 60
Water Uptake and Proton Conductivity. Water uptake and proton
mL of DMAc was added to the mixture to lower the viscosity. The
conductivity of ionomer 2 membranes were measured with a Bel Japan
solution was poured dropwise into 1 L of deionized water to precipitate
solid electrolyte analyzer system MSB-AD-V-FC equipped with a
a white flaked product. The product was washed with hot deionized
chamber, a magnetic suspension balance, and a four-point probe
water and methanol several times and purified by reprecipitation from
conductivity cell. For water uptake measurement, membrane samples
(50-70 mg) were set in a chamber and dried at 80 °C under vacuum
(15) Culbertson, B.; Tiba, M.; Sang, J.; Liu, Y. N. Polym. AdV. Technol. 1999,
10, 275. for 3 h until constant weight as dry material was obtained. The
(16) (a) Wang, Z. Y.; Carvalho, H. N.; Hay, A. S. J. Chem. Soc., Chem. Commun. membrane was then equilibrated with N2 gas at the given temperature
1991, 1221. (b) Miyatake, K.; Oyaizu, K.; Tsuchida, E.; Hay, A. S.
Macromolecules 2001, 34, 2065. (c) Wang, L.; Meng, Y. Z.; Wang, S. J.; and humidity for at least 1 h before the gravimetry was done. For the
Shang, X. Y.; Li, L.; Hay, A. S. Macromolecules 2004, 37, 3151. proton conductivity measurement, membrane samples (1.0 cm wide,

J. AM. CHEM. SOC. 9 VOL. 129, NO. 13, 2007 3881

ARTICLES Miyatake et al.

3.0 cm long, and 50 µm thick) were set in the chamber where the monomers were pure enough for polymerization as confirmed
temperature and the humidity were controlled by flowing humidified by NMR and LC-MS analyses. The parent homopolymers
N2. The membrane was then equilibrated with N2 gas at the set 1a-c and copolymers 1d-i were synthesized by a typical
temperature and humidity for at least 1 h before the measurement. The nucleophilic substitution polycondensation reaction starting from
samples were contacted with two gold wire outer current-carrying
the corresponding biphenol and difluoride monomers (Scheme
electrodes and two gold wire inner potential-detecting electrodes.
1). Polymers 1d and 1e have isopropylidene units derived from
Impedance measurements were made using a Solartron 1255B fre-
quency response analyzer and Solartron SI 1287 potentiostat. The bisphenol A monomers as main chain methylated derivatives,
instrument was used in potentiostatic mode with an ac amplitude of while the others have methyl groups on aromatic groups.
300 mV with the frequency range from 1 to 100 000 Hz. Bisphenol A is an inexpensive and versatile material. All the
STEM Observation. The membranes were stained with silver by polymers 1a-i were soluble in DMAc, DMF, NMP, and
ion exchange of the sulfonic acid groups by immersing them overnight CH2Cl2. As confirmed by GPC analyses, methyl-substituted
in a large excess of 0.5 M AgNO3(aq), rinsed with water, and dried at polymers 1b-i were of high molecular weight (Mw > 2 × 105,
room temperature for 12 h. The stained samples were embedded in Mn > 3 × 104)18 similar to that of the non-methylated 1a and
epoxy resin and sectioned to yield 90 nm thick samples using a Leica gave tough, flexible, and transparent membranes by solution
microtome Ultracut UCT and placed on copper grids. Images were taken casting. As a typical example, the 1H NMR spectrum of 1e is
on a Hitachi HD-2300C scanning transmission electron microscope
shown in Figure 1a in which all the protons are well-assigned
(STEM) using an accelerating voltage of 200 kV.
to the supposed chemical structure. Integration ratios of the
Membrane Electrode Assemblies (MEAs). Gas diffusion electrodes
peaks correspond to the copolymer composition.
with three-layer structure were prepared by the following steps, i.e.,
wet-proofing treatment of a carbon paper (CP), coating of a gas Polymers 1a-i reacted with chlorosulfonic acid in CH2Cl2
diffusion layer (GDL) onto the CP, and coating of a catalyst layer (CL) to give the title sulfonated polymers 2a-i. Since the ionomers
onto the GDL. The GDL was fabricated by coating a slurry consisting are insoluble in CH2Cl2, they precipitated out of the solution
of carbon black (Denki Kagaku Kogyo K. K. Denka black) and PTFE soon after the polymer and chlorosulfonic acid solutions were
dispersions on CP (TGP-H-120, 360 µm, Toray Industries, Inc., wet- mixed. In order to achieve efficient mixing, we have adopted a
proofed with 15 wt % FEP).17 The loading amount of the GDL (Denka flow reactor for the sulfonation reactions as described in a
black + PTFE) was 0.95 mg/cm2. Pt-loaded carbon black (45.8 wt % previous paper.11c By changing the amount of chlorosulfonic
Pt/CB; Tanaka Kikinzoku Kogyo TEC10E50E), 5 wt % Nafion ionomer
acid used in the reaction, the IEC of the ionomers was easily
solution, 2-propanol, and pure water were mixed in a planetary ball-
controlled. Regardless of the number and the positions of methyl
mill. The weight ratio of Nafion to the CB was 0.7. The obtained
catalyst ink was uniformly spread over the GDL. The electrode was substituents, the ionomers are soluble in polar organic solvents
cold-pressed followed by curing at 60 °C overnight and then hot-pressed such as DMSO, DMAc, DMF, and NMP. The ionomers gave
at 130 °C for 3 min at 1.2 MPa. The loading amount of Pt was 0.41 flexible, ductile, and transparent membranes by casting from
mg/cm2 for both the cathode and anode. The electrodes were treated DMAc solution. In the cases of homopolymers 2a-c (IEC <
with 1 N HNO3 before assembling with the electrolyte membrane. 2.5 meq/g) and copolymers 2d-i (IEC < 1.5 meq/g), the 1H
Membrane 2e (IEC ) 2.51 meq/g) or Nafion (DuPont NRE 212) NMR spectra suggested that the sulfonic acid groups were
was sandwiched between two gas diffusion electrodes (geometric active substituted only at 2,7-positions on the side fluorenyl groups.
area ) 3.1 cm2) and hot-pressed at 130 °C for 3 min at 1.0 MPa. The Attempts to obtain higher IEC ionomers under severe sulfonation
membrane/electrode assembly (MEA) was mounted into a circular reaction conditions (e.g., using more concentrated ClSO3H
single test cell holder equipped with a reversible hydrogen reference solution) resulted in main chain sulfonation as well. In the case
electrode (RHE).
of 2e (IEC ) 3.26 meq/g), the 1H NMR spectrum (Figure 1b)
Fuel Cell Operation. All cells were operated at a cell temperature
indicated that most of the fluorenyl groups were sulfonated (x
(TCell) of 90 °C under ambient pressure. Humidified H2 was fed to the
anode at 200 mL/min with the humidification temperature (TAH) of 53
) 1.76 where x is the degree of sulfonation per fluorenyl group)
°C (20% RH) or 90 °C (100% RH). Humidified O2 was fed to the and the arylene protons ortho to ether groups on the main chains
cathode at 100 mL/min with the humidification temperature (TCH) of were also sulfonated to some extent (y + z ) 2.92 where y and
50 °C (18% RH), 53 °C (20% RH), or 80 °C (68% RH). Current- z are the degree of sulfonation per copolymer repeating unit).
voltage (I-V) curves were measured under steady-state conditions. The contribution of each sulfonation to the total IEC was
Ohmic potential drop (IR drop) was measured with a current interrupter determined to be x ) 1.46 meq/g and y + z ) 1.80 meq/g from
(Nikko Keisoku NCPG 1010) by applying a current-off pulse for 100 a combination of titration and 1H NMR spectroscopy. A series
µs to the cell and recording the resulting potential drop with a storage of sulfonated poly(arylene ether sulfone)s with different numbers
oscilloscope (Hitachi VC6023). of methyl substituents at different positions was obtained. The
Results and Discussion ionomers 2a-i subjected to properties investigations are listed
in Table 1 with their molecular weight and IEC values.
Synthesis and Characterization of Monomers, Polymers, Mechanical, Oxidative, and Hydrolytic Stability. The
and Ionomers. In order to prepare a series of poly(arylene mechanical properties of the ionomer membranes were studied
ether sulfone)s having different numbers and/or positions of at 85 °C and 93% RH simulating fuel cell operating conditions
methyl groups, tetramethyl-substituted fluorenylidene biphenol (Table 2). Ionomer 2 membranes showed a maximum stress of
(DMBHF) was synthesized from fluorenone and 2,6-xylenol by 5-23 MPa with the general trend of lower maximum stress for
an acid-catalyzed reaction. Other methyl-substituted monomers the higher IEC membranes. The 2a membrane with an IEC )
were commercially available, while 3,3′,5,5′-tetramethylbiphenol 2.76 meq/g was too weak to hold the weight of the sample clip
was masked with propylcarbamoyl groups to improve its even for a thick sample (100 µm) so that a reliable measurement
reactivity in the nucleophilic substitution polymerization.16 These
(18) Some of the polymers show rather high polydispersity values (>6.0) due
(17) Song, J. M.; Uchida, H.; Watanabe, M. Electrochemistry 2005, 73, 189. to the very high viscosity of the polymerization mixture.

3882 J. AM. CHEM. SOC. 9 VOL. 129, NO. 13, 2007

Tuned Polymer Electrolyte Membranes for Fuel Cells ARTICLES

Figure 1. 1H NMR spectra of (a) 1e, (b) 2e (IEC ) 3.26 meq/g), (c) 2e-100 after a durability test at 100 °C and 80% RH for 10 000 h, and (d) 2e-120 after
a durability test at 120 °C and 40% RH for 10 000 h.
could not be done. Comparison among the higher IEC (>2.5 The oxidative stability of 2a-i membranes was evaluated in
meq/g) membranes revealed that ionomers 2e and 2g having hot Fenton’s reagent for 1 h as an accelerated test. Losses of
methyl groups at the R5 positions are mechanically stronger than IEC, weight, and molecular weight of the membranes after the
the others. The maximum stress of 2e with an IEC ) 3.26 meq/g testing are shown in Table 2 and plotted as a function of IEC
was 8.2 MPa and was comparable to that of the non-methylated in Figure S1 in the Supporting Information. Membranes with
2a with an IEC ) 2.51 meq/g. The 2e and 2g membranes an IEC lower than 1.8 meq/g showed relatively good resistance
showed lower strain than the other membranes with similar IEC to oxidation and endured without dissolving for 1 h, while
values. It is assumed that the methyl groups on the R5 positions membranes with higher IEC dissolved to some extent and lost
restrict the molecular motion of the polymer chains resulting weight. It should be noted that the residual membranes after
in stronger membranes. In contrast, this effect was not distinct the test retained their IEC values as confirmed by titration. The
for the methyl substituents at the R1-R4 positions (compare 2a results are indicative that the oxidative degradation of these
with 2c or 2i) presumably because these methyl groups are ionomers occurs on the main chains rather than the pendent
placed on the bulky and robust fluorenyl groups as the larger
building blocks. The methyl groups at the R1-R4 positions are (19) The effect of methyl groups at R5 positions was further investigated by
thermal analyses. Since the sulfonated polymers decompose before the glass
in the vicinity of hydrophilic and amorphous sulfonated fluo- transition temperature, parent polymers were tested. As shown in Table
renyl groups which could also account for their lesser effective- S1 in the Supporting Information, substitution of methyl groups caused
the Tg increase. This effect was observed for both the R1-R4 and R5
ness than that of the R5 methyl groups.19 positions.

J. AM. CHEM. SOC. 9 VOL. 129, NO. 13, 2007 3883

ARTICLES Miyatake et al.

Table 1. Molecular Weight and Ion-Exchange Capacity (IEC) of

2a-i Membranes
IEC
ionomer Mn (105) Mw (105) Mw/Mn (meq/g)a
2a 2.86 10.24 3.6 1.59
2a 2.06 12.30 6.0 2.51
2a 1.24 11.57 9.3 2.76
2b 2.50 6.22 2.5 2.47
2c 3.53 8.20 2.5 2.27
2d 3.36 6.24 1.9 1.89
2d 3.84 9.70 2.5 2.09
2e 2.19 6.13 2.8 1.32
2e 1.36 5.17 3.8 2.51
2e 0.69 3.11 4.5 3.26
2f 3.50 13.26 3.8 1.84
2f 3.72 12.66 3.4 2.69 Figure 2. Water uptake of ionomer 2 membranes and Nafion 112 at 80
2g 2.03 7.90 3.9 2.36 °C and at 20% and 93% RH.
2g 0.29 2.63 9.1 2.82
2h 1.87 5.53 3.0 2.01 hydrolytic susceptibility was significantly improved for ionomer
2i 2.12 5.85 2.8 1.78
2e membranes. Four methyl groups at the R5 positions ef-
a Determined by titration. fectively protected the neighboring isopropylidene groups from
attack by water. A similar but less effective effect was observed
Table 2. Mechanical, Oxidative, and Hydrolytic Stability of 2a-i
Membranes for ionomer 2b and 2c membranes compared with that of 2a.
From the mechanical, oxidative, and hydrolytic stability stand-
mechanical oxidative stability: hydrolytic stability:
strength decrease in decrease in point, the ionomer 2e membrane containing tetramethyl bis-
IEC max stress strain weight IEC Mw weight IEC Mw phenol A components was the most appropriate chemical
ionomer (meq/g) (MPa) (%) (%) (%) (%) (%) (%) (%) structure for a high-IEC membrane.
2a 1.63 22.5 34 0 0 76 8 7 11 Water Uptake and Swelling Properties. The humidity
2a 2.51 8.4 179 100 a 96 6 1 10 dependence of water uptake was measured for ionomer 2
membranes at 80 °C and at 20% and 93% RH (Figure 2). Two
2a 2.76 a a 100 a 82 6 2 21
2b 2.47 13.1 25 100 a 93 0 0 1
2c 2.27 5.9 88 5 0 78 0 0 0
homopolymers (2a and 2c) and three copolymers (2d, 2e, and
2d 1.89 22.6 94 24 0 66 1 2 17 2f) were chosen as representative examples. As expected, higher
a a
2d 2.09 10.0 291 100 1 2 47 IEC membranes absorbed more water at both humidity condi-
2e 1.32 14.9 75 1 0 75 1 2 0 tions. The tendency was more pronounced at 93% RH than at
2e 2.51 7.0 190 100 a a 3 2 0
2e 3.26 8.2 170 100 a 98 2 12 19 20% RH. Membrane 2e with the highest IEC ) 3.26 meq/g
2f 1.84 8.3 184 8 1 79 0 1 4 showed the highest water uptake of 44 wt % at 93% RH, which
2f 2.69 4.5 317 98 a a 0 0 26
a a
corresponds to 7.5 water molecules per sulfonic acid group (λ).
2g 2.36 10.6 105 100 2 5 10
2h 2.01 8.1 122 3 0 60 2 0 0
The λ value was similar to that of the lower IEC membranes (λ
2i 1.78 5.5 125 0 2 66 1 3 4 ) 7.8 for 2a with IEC ) 2.76 meq/g). Extrapolation of the
a a
Nafion 117 0.89 23.4 332 2 0 1 0 dashed lines in Figure 2 could give smaller λ values for ionomer
a
2 membranes with an IEC of 0.91 meq/g than that of Nafion
Could not be measured.
112. In typical hydrocarbon ionomer membranes,21 λ increases
sulfonic acid groups. It is reasonable to consider that the with IEC due to excess swelling and therefore increased free
oxidative attacks by HO‚ and HOO‚ radicals are electrophilic volume. We then measured the swelling degree of ionomer 2
and occur more likely on the main chain aromatic rings bound membranes in hot water and evaluated the effect of methyl
with electron-donating ether groups.20 The oxidative stability groups.
of ionomer 2 membranes depends on the IEC but not on the Three membranes 2a, 2b, and 2e were subjected to the
number and positions of methyl substituents implying that these swelling tests at 25 and 50 °C in water (Figure 3). All these
ionomers share the same oxidative degradation mechanisms with membranes swelled more at higher temperature, and the
no participation of the methyl groups. differences were larger for higher IEC membranes. It should
The 2a-i membranes were also subjected to severe hydrolytic be noted that membrane 2e (IEC ) 3.26 meq/g) showed much
stability testing at 140 °C and 100% RH for 24 h. All the lower swelling degree in both directions than membrane 2a (IEC
membranes maintained their transparency, flexibility, toughness, ) 2.76 meq/g), despite the former’s higher IEC value. Sup-
and original weight. Membranes with an IEC lower than 2.5 pression of the swelling was remarkable at 50 °C compared to
meq/g showed good stability to hydrolysis without any practical that at 25 °C. Similar to the mechanical and oxidative stability
changes in the IEC and the 1H NMR spectra. Among these, as discussed above, methyl substituents on the R5 positions are
ionomer 2d membranes showed greater Mw loss. A comparison effective for retaining the dimensional stability in water
of their chemical structures led to the assumption that the especially for higher IEC membranes.
hydrolytic degradation of the ionomer membranes commenced Proton Conductivity. The humidity dependence of the proton
on the main chain at the isopropylidene groups and/or at the conductivity was measured for membranes 2a, 2c, 2d, and 2e
vicinity of the hydrophilic sulfonic acid substituents. This with different IEC values at 80, 100, and 120 °C (Figure 4).
The proton conductivity of ionomer 2 membranes with IEC <
(20) (a) Hübner, G.; Roduner, E. J. Mater. Chem. 1999, 9, 409. (b) Panchenko,
A. J. Membr. Sci. 2006, 278, 269. (21) Rozière, J.; Jones, D. J. Annu. ReV. Mater. Res. 2003, 33, 503.

3884 J. AM. CHEM. SOC. 9 VOL. 129, NO. 13, 2007

Tuned Polymer Electrolyte Membranes for Fuel Cells ARTICLES

Figure 3. Swelling degree of 2a, 2b, and 2e membranes in water at 25

and 50 °C.

Figure 5. Temperature dependence of the proton conductivity and water

uptake of 2 and Nafion 112 membranes at (a) 20% RH and (b) 40% RH.

Figure 6. Durability of the proton conductivity of the 2e (IEC ) 3.26

Figure 4. Humidity dependence of the proton conductivity of 2 membranes meq/g) membrane at 100 °C and 80% RH and at 120 °C and 40% RH.
and Nafion 112 at 80, 100, and 120 °C.
wet/dry cyclings during the measurement (several tens of hours)
2.5 meq/g showed great dependence on humidity. For example, without detectable degradation.
the conductivity of 2d (IEC ) 2.09 meq/g) dropped from 6.3 Proton conductivity and water uptake of the ionomer mem-
× 10-2 S/cm (93% RH) to 6.2 × 10-5 S/cm (20% RH) at 80 branes at 20% and 40% RH are plotted as a function of
°C. The conductivity at 20% RH was more than 2 orders of temperature (Figure 5). Water uptake decreased with increasing
magnitude lower than that of Nafion 112. This is typical temperature at both humidities for all the membranes. Due to
behavior for hydrocarbon ionomer membranes due to less the evaporation of water, the number of hydronium ions as the
developed microphase separation and lower acidity than those proton carrier decreases at high temperature resulting in a
of the perfluorinated ionomers.22 Increasing the IEC of ionomer decrease in the proton conductivity for membranes 2a, 2c, and
2 membranes could significantly increase the conductivity at 2d. In contrast, 2e membranes showed proton conductivity less
low humidity. Ionomer 2e (IEC ) 3.26 meq/g) membrane dependent on the temperature. It is considered that the lower
showed 5.6 × 10-3 S/cm proton conductivity at 20% RH and concentration and the higher mobility of the carrier ions
80 °C. The conductivity of the 2e membrane was comparable counteracted each other and resulted in a nearly constant value
to or even higher than that of Nafion 112 at 80-120 °C and of the proton conductivity. This particular behavior, we believe,
20-93% RH. All of the ionomer 2 membranes were durable in is because of well-connected proton transport channels in 2e
membranes (see the next section). Similar behavior was also
(22) Kreuer, K. D. J. Membr. Sci. 2001, 185, 29. observed for Nafion 112.

J. AM. CHEM. SOC. 9 VOL. 129, NO. 13, 2007 3885

ARTICLES Miyatake et al.

Table 3. Property Changes of 2e (IEC ) 3.26 meq/g) Membrane after a 10 000 h Durability Test
contribution to IEC (meq/g) proton conductivity σ (S/cm)
test thickness width Mn Mw IEC x y+z 100 °C 120 °C
ionomer conditions (µm) (cm) (105) (105) (meq/g) (side chain) (main chain) 80% RH 40% RH
2e fresh 78 0.50 0.69 3.11 3.26 1.46 1.80 1.1 × 10-1 2.4 × 10-2
2e-100 100 °C 78 0.50 0.59 2.91 2.16 (1.45)a (1.11)a 5.8 × 10-2
80% RH (2.56)a (1.1 × 10-1)a
2e-120 120 °C 62 0.46 0.78 3.19 1.82 (0.91)a (1.14)a 2.6 × 10-3
40% RH (2.05)a (1.3 × 10-3)a

a Numbers in parentheses are the values after acid treatment.

Since the 2e (IEC ) 3.26 meq/g) membrane showed the most

preferable properties from the viewpoint of stability and proton
conductivity, its longevity was evaluated at 100 °C and 80%
RH (dew point ) 93.8 °C) and 120 °C and 40% RH (dew point
) 93.3 °C) (Figure 6). At 100 °C and 80% RH, the proton
conductivity decreased from 1.1 × 10-1 to 7.2 × 10-2 S/cm
during the first 1000 h of the test and then gradually decreased
to 5.8 × 10-2 S/cm over 10 000 h. At 120 °C and 40% RH, the
conductivity decreased from 2.4 × 10-2 to 2.6 × 10-3 S/cm
over 10 000 h.
After 10 000 h of testing, 2e membranes retained their
strength and flexibility. Property changes of 2e (IEC ) 3.26
meq/g) membranes after the durability test are summarized in
Table 3. It was found that the IECs of the recovered membranes
were lower than that of the fresh 2e membrane: 2.16 meq/g
Figure 7. STEM images of (a) 2a (IEC ) 1.59 meq/g), (b) 2a (IEC )
for 2e-100 and 1.82 meq/g for 2e-120 membranes. After treating 2.51 meq/g), (c) 2e (IEC ) 3.26 meq/g), and (d) Nafion112 membranes.
2e-100 and 2e-120 membranes with 1 N HNO3(aq), the IEC
and proton conductivity recovered to some extent but not to dark areas represent hydrophilic (ionic) domains and the brighter
the original values. Therefore, we conclude that the conductivity areas represent hydrophobic domains. In Figure 7a, the 2a (IEC
decrease was attributed to two major reasons: loss of sulfonic ) 1.63 meq/g) membrane exhibited spherical ionic clusters of
acid groups and the cationic contamination. The latter has been relatively uniform size. These ionic clusters were not connected
derived from the stainless steel tubing used for flowing with each other but were rather isolated. More clusters were
humidified nitrogen and/or from the environment. By analyzing observed for the higher IEC 2a membrane (Figure 7b); however,
the 1H NMR spectra of the membranes (Figure 1, parts c and the situation seemed alike. The connectivity of these ionic
d), we could elucidate from which positions the sulfonic acid clusters was significantly improved in the 2e (IEC ) 3.26 meq/
groups were removed. In both spectra, peaks around 7.3-7.5 g) membrane (Figure 7c) and was similar to that of the Nafion
ppm (nos. 6, 7, and 8) and 7.1-7.2 ppm (no. 5) ascribed to 112 membrane (Figure 7d). It has generally been considered
unsulfonated aromatic protons are larger than those of the fresh that protons migrate as hydronium ions through hydrophilic ionic
2e membrane (Figure 1b). In the 2e-100 membrane, loss of channels of ionomer membranes. The microscopic structure of
sulfonic acid groups was mainly from the main chains; the the 2e membrane is consistent with the above-mentioned proton
contribution of (y + z) to the total IEC decreased from 1.80 to conductivity behavior especially at low-humidity conditions.
1.11 meq/g. This is reasonable when taking into account that PEFC Performance. Fuel cell performance of the 2e (IEC
hydrolytic loss of sulfonic acid groups is a nucleophilic ) 2.51 meq/g, 40 µm thick) membrane was tested and compared
substitution reaction with water and occurs more likely on the to that of Nafion NRE 212 (IEC ) 0.92 meq/g, 50 µm thick).
main chains (at the y position of the aromatic carbons ipso to Proton conductivity and water uptake properties of the tested
the sulfonic acid groups) connected with electron-withdrawing 2e membrane are provided in Figure S3 in the Supporting
sulfone groups. However, under more severe conditions, the Information and highlighted in gray color in Figures 4 and 5.
loss of sulfonic acid groups was detected both from the main Cells were operated at a rather high temperature of 90 °C and
and the side chains (2e-120). The thickness and width of the at three different humidity conditions. High humidity is 100%
membranes did not change for 2e-100 but slightly decreased RH (anode) and 65% RH (cathode), medium humidity is 100%
for 2e-120. Nevertheless, from GPC elution curves of the 2e, RH (anode) and 18% RH (cathode), and low humidity is 20%
2e-100, and 2e-120 membranes (Figure S2 in the Supporting RH for both electrodes. As shown in Figure 8 (high- and
Information), the molecular weight and its distribution remained medium-humidity conditions), the ohmic resistance of the 2e
almost the same after the durability test. cell was lower than that of Nafion (even taking the slight
STEM Observation. In order to investigate hydrophilic/ difference in thickness into account) so that the better I-V
hydrophobic microphase separation and the proton transport performance was obtained at the current density from 0 to 1.0
pathway on the 2 membranes, scanning transmission electron A/cm2. These data also indicate that the contact between the 2e
microscopic (STEM) observations were carried out (Figure 7). membrane and the Nafion-based electrodes was sufficiently
The membranes were stained with silver ions; therefore, the good despite the different nature of each ionomer material.
3886 J. AM. CHEM. SOC. 9 VOL. 129, NO. 13, 2007
Tuned Polymer Electrolyte Membranes for Fuel Cells ARTICLES

fuel cell applications. The parent polyethers 1a-i were sul-

fonated to give the ionomers with an ion-exchange capacity
(IEC) up to 3.26 meq/g. Sulfonic acid groups were introduced
only on the pendent fluorenyl groups with an IEC < 2.5 meq/
g, while the main chains were also sulfonated for the higher
IEC ionomers. The ionomers were high molecular weight (Mw
> 3 × 105, Mn > 3 × 104) and formed tough and flexible
membranes. Hydrolytic and oxidative stability was confirmed
by accelerated tests. Isopropylidene groups in the bisphenol A
copolymer units resulted in lower stabilities, which could be
sufficiently improved by introducing tetramethyl groups on
adjacent phenylene rings. The methylation was likewise effective
in giving high mechanical strength and good dimensional
stability. In contrast, methyl group substitution on fluorenylide
biphenylene units was less effective. Sulfonic acid groups on
the main chains were more susceptible to both hydrolysis and
Figure 8. Steady-state terminal voltage (including IR loss) and ohmic oxidation due to the concurrent electron-withdrawing sulfone
resistance of fuel cells at high- and medium-humidity conditions for 2e (2, and electron-donating ether groups.
4) and Nafion (b, O) membranes, respectively. All cells were operated at
90 °C. The ionomer membranes were highly proton conductive.
Increasing the IEC significantly increased the conductivity at
low humidity. Ionomer 2e membrane with the highest IEC of
3.26 meq/g showed a proton conductivity of 5.6 × 10-3 S/cm
at 80 °C and 20% RH which is comparable to that of the
perfluorinated Nafion membrane. Although there is a decline
of proton conductivity with time, after 10 000 h the proton
conductivities were still at acceptable levels for fuel cell
operation. The membranes retained their strength, flexibility,
and high molecular weight after 10 000 h. In the 2e-100
membrane, most of the sulfonic acid group loss was from the
main chains, while the sulfonic acid groups were detached both
from the main and the side chains in the 2e-120 membrane.
Sulfonic acid groups on the fluorenyl groups were much less
susceptible to the hydrolytic removal, corresponding to the
results of the accelerated tests. Microscopic analyses revealed
that the connectivity of ionic clusters was significantly improved
in the 2e (IEC ) 3.26 meq/g) membrane compared to that of
Figure 9. Steady-state terminal voltage (including IR loss) and ohmic
resistance of fuel cells at low-humidity conditions for 2e (4) and Nafion
the lower IEC membranes and was similar to that of Nafion
(O) membranes. All cells were operated at 90 °C. 112. The newly developed 2e ionomer membrane has proved
better ohmic performance than Nafion in H2/O2 fuel cells at a
The lower resistance of the 2e cell than that of the Nafion high temperature of 90 °C. The advantage of the 2e membrane
cell was also true under low-humidity conditions (Figure 9). was confirmed under low- and high-humidity conditions and is
The inconsistency between cell resistance and proton conductiv- possibly due to its good water-holding capability.
ity (20% RH in Figure S3) is presumably due to the diffusion
of water (produced at the cathode) into the membrane. The 2e Acknowledgment. This work was partly supported by MEXT
membrane is expected to have better water-holding capability Japan through a Grant-in-Aid for Scientific Research (18750167)
at high temperature.11 Unfortunately, the I-V performance did and the fund for Leading Project and by NEDO through the
not reflect much of the ohmic resistance because of inferior Industrial Technology Research Grant Program (02B70007c).
cathode performance of the 2e cell as confirmed by the IR-free
potential shown in Figure S4 in the Supporting Information. Supporting Information Available: Detailed data on the
ionomer’s properties. This material is available free of charge
Conclusions via the Internet at [Link]
The chemical structures of poly(arylene ether sulfone) iono-
mers containing fluorenyl groups (2a-i) have been tuned for JA0672526

J. AM. CHEM. SOC. 9 VOL. 129, NO. 13, 2007 3887