Professional Documents
Culture Documents
Short-Side-Chain Proton Conducting Perfluorosulfonic Acid Ionomers Why They Perform Better in PEM Fuel Cells
Short-Side-Chain Proton Conducting Perfluorosulfonic Acid Ionomers Why They Perform Better in PEM Fuel Cells
Short-Side-Chain Proton Conducting Perfluorosulfonic Acid Ionomers Why They Perform Better in PEM Fuel Cells
com
Received 28 August 2007; received in revised form 2 November 2007; accepted 5 November 2007
Available online 13 November 2007
Abstract
Short-side-chain (SSC) perfluorosulfonic acid ionomers of different ion exchange capacity, IEC, (Dow 840 and Dow 1150) are characterized
with respect to water sorption, transport (proton conductivity, electroosmotic water drag and water diffusion), microstructure and visco-elastic
properties as a function of temperature and degree of hydration. The data are compared to those of Nafion 117 (Nafion 1100), and the implica-
tions for the use of such ionomers as separator materials in direct methanol and hydrogen fuel cells are discussed. For this purpose, a scheme
is used which allows for the simulation of the water distribution and the resulting solvent (water, methanol) fluxes and potential losses across
the membranes under transient and steady state conditions. The lower solvent (water, methanol) transport across Dow 1150 in direct methanol
fuel cells is essentially the result of the reduced swelling. The smaller potential losses across Dow 840 compared to Nafion 117 in hydro-
gen fuel cells is mainly the result of the higher charge carrier concentration. The present comparison demonstrates that combining high IEC
with high mechanical stability, e.g. by increasing crystallinity as in the present case, or by increasing molecular weight, cross-linking or intro-
ducing interacting particles, results in an increase in proton conductivity and lower electroosmotic drag of water. The improved stability is
also anticipated to preserve the morphology of the membrane/electrode interface under conditions at which Nafion 117 starts to show plas-
tic deformation. Hence, this may prove to be a suitable approach to improve membrane performance in both direct methanol and PEM fuel
cells.
© 2007 Elsevier B.V. All rights reserved.
Keywords: Proton conductivity; Water transport; Dow membrane; Hyflon ion; PEM fuel cell; Simulation
0378-7753/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jpowsour.2007.11.011
500 K.D. Kreuer et al. / Journal of Power Sources 178 (2008) 499–509
temperature when compared to Nafion. Although these prop- (EW = 1100 g eq.−1 , thickness ≈120 m) was also included in
erties likely depend on the membrane preparation conditions, this study for comparative purposes. The acronym Nafion 1100
as they due for Nafion (e.g. extrusion versus casting, choice of is used through out to be consistent with nomenclature. Prior to
solvent, thermal post-treatment), the general trends seem to be all measurements, the membranes were preconditioned by leav-
a characteristic of SSC perfluorosulfonic acid ionomers. The ing them in a 1 M aqueous solution of nitric acid at T = 60 ◦ C
comprehensive work of Tant et al. [4,5] on Dow membranes before carefully washing them in double distilled water at the
of different equivalent weight (EW) revealed that some crys- same temperature. This standardization appeared to be essential
tallinity remains even for EWs below 800 g eq.−1 where Nafion for obtaining reproducible results, e.g. drying Nafion severely
membranes are usually amorphous. Moore and Martin related reducing its swelling capability and even leaving standardized
the lower liquid water uptake of the Na+ -form of the SSC Nafion in water at room temperature reduced its water content,
ionomer to its higher crystallinity [6], and work of Eisman [7] while this effect is hardly observable for the Dow membrane
on the acid form already demonstrated, for a given EW (or ion samples.
exchange capacity, IEC), a lower proton conductivity of the SSC
ionomer compared to Nafion. The conductivity of the Dow mem- 2.1. Water hydration isotherms
brane of an EW of 900 g eq−1 was actually found to be similar
to the conductivity of the commonly used Nafion membrane Water hydration isotherms at room temperature were deter-
(EW = 1100 g eq.−1 ), and glass transition temperatures around mined by equilibrating the membrane samples in a desicator
Tg = 165 ◦ C are reported, while that of Nafion was measured to purged with nitrogen gas of predefined relative humidity. Rel-
be Tg = 110 ◦ C. Later Eisman also reported better performance ative humidities were changed from high to low and from low
of the Dow membrane (EW = 800 g eq.−1 , thickness = 130 m) to high values, which resulted into somewhat different degrees
compared to Nafion 117 membrane (EW = 1100 g eq.−1 , thick- of hydration (the observed hysteresis were significantly more
ness = 175 m) [8]. pronounced for Nafion compared to Dow membranes). The
Recently, extensive first principles based molecular-level hydration levels were determined by weighing on an external
modelling studies have been undertaken on the SSC membrane balance and comparing the weight to that of the dried membrane
[9–12]. These investigations on small (i.e. two and three repeat (T = 140 ◦ C, vacuum).
units) oligomeric fragments have shown how the side-chain
separation and the conformations of backbone and side-chain 2.2. Water hydration isobars
effect preferential hydration, connectivity, water binding, and
proton dissociation under minimal hydration conditions (i.e. 1–3 Water hydration isobars were determined by thermo-
H2 O/–SO3 H). gravimetric analysis (TGA) at a water partial pressure
There is, however, no consistent understanding of the well of pH2 O = 105 Pa (1 atm) and temperatures ranging from
established performance improvement of the SSC membrane, T = 105–180 ◦ C. A Mettler AT20 balance was magnetically cou-
and we have therefore decided to carefully study the water sorp- pled (Rubotherm) to the sample, which allowed measurements
tion, transport and visco-elastic properties of four different EW under high humidity conditions without condensation of water in
(nominally 800, 840, 900 and 1150 g eq.−1 ) SSC membranes the balance. Water was injected into the system by a peristaltic
and to discuss the implications on their performance in PEM pump (Ismatec) via a pre-vaporizer in order to avoid fluctua-
fuel cells. We have developed a scheme, for the latter, which tions in the pressure. Heating and cooling rates were both keep
allows us to simulate the water distribution and the result- constant at 0.2 ◦ C min−1 .
ing resistance of membranes under transient and steady state
conditions. 2.3. Swelling
2.4. Small angle X-ray scattering (SAXS) chamber with a constant flow rate using a digital peristaltic
pump (Ismatec). Inside the chamber the membranes (10–20
Small angle X-ray scattering (SAXS) was carried out on a staged slices of membranes with diameter 8 mm and total
home-built camera using an FR591 Nonius rotating Cu anode thickness of 2–4 mm) were placed in a porous cylindrical tube
operating with a fine focus at a 6◦ takeoff angle corresponding to with a gold electrode at the bottom. The second gold electrode
a 0.2 mm × 0.2 mm apparent beam size. The beam was K␣ /K was pressed from the top onto the stack of membranes by a
filtered (wavelength Cu K␣: λ = 1.5418 Å) and focused in hori- screw in order to assure optimum contact. The measured sample
zontal and vertical directions by total reflection from two curved resistance was found to be independent of the contact pressure
Franks mirrors (Ni-coated glass optical flats). Scattering pat- for all stacked-slices sample geometries inferring that there was
terns were recorded with a two-dimensional position-sensitive no significant contribution due to contact resistance.
gas-filled detector. The sample detector distance was placed Specific conductivities were obtained from the high-
at 1 and 3.5 m to explore q values from about q = 0.01 up to frequency intercept of the complex impedance with the real axis
0.3 Å−1 where q is the momentum transfer (q = (4πsin θ/λ)) and and the dimensions of the stacks. The proton conductivity dif-
2θ the total scattering angle. The sample-detector distance was fusion coefficients, Dσ , were obtained from conductivity data σ
calibrated using silver as a standard. The normalization of the using the Nernst–Einstein relation:
scattering data was applied by first measuring the transmission RTσ
with a semi-transparent beam stop, followed by the thickness of Dσ =
F 2 cH +
each sample, and finally using a Lupolen sample as a calibrat-
ing sample [13]. The samples (2 or 3 pieces for a total of about where T, R, and F have their usual meaning. The concentration of
300–500 m thick) were placed in a brass cell between 2 thin protonic charge carriers, cH+ , is readily calculated from the IEC
sheets of Mylar. (assuming full dissociation) and the volume changes associated
with the swelling.
2.5. Dynamic mechanical analysis (DMA)
2.7. Water diffusion coefficients
Dynamic mechanical analysis (DMA) were performed on a
Triton DMA analyzer (Tritec 2000) as a function of temper- Water diffusion coefficients were determined by the pulsed
ature and fixed relative humidity. The temperature and water magnetic field gradient NMR technique using a home built spec-
partial pressure for each measurement were kept constant for trometer [14] operating at a resonance frequency of ν = 50 MHz
at least 1 h. The maximum elongation was 0.01 mm at a fre- and magnetic field gradients of the order G = 10−2 T cm−1 .
quency of 1 Hz (sample dimensions typically in the range of Membrane stacks of defined water contents were sealed into
4 mm × 5 mm × 0.05–0.2 mm). glass tubes positioned within the rf coil. The same spectrometer
was used for the measurement of electroosmotic drag coeffi-
2.6. Proton conductivities cients [15] by passing protonic currents through the samples
using standard carbon electrodes with a Pt loading of 1 mg cm−2 .
Proton conductivities were derived from ac-impedance
spectra of a two-electrode arrangement measured by an HP-ac- 3. Results and discussion
impedance analyzer (4192A LF) in the frequency range from
10 to 10 MHz with an oscillating voltage of 0.1 V. The mea- 3.1. Membrane properties
surements were performed in a closed cell with pre-equilibrated
samples (10–30 stacked slices of each membrane with pre- A general problem in the development of sulfonic acid based
adjusted water content, diameter ∼6 mm, thickness 2–5 mm) ionomers is the trade off between high IEC and acceptable visco-
with gold electrodes. In this way, conductivities as a function of elastic properties: with increased IEC, such ionomers tend to
temperature but for a constant degree of hydration (λ = constant) soften or even dissolve in the presence of water. The com-
have been measured. monly used Nafion with an equivalent weight of 1100 g eq.−1
In-plane conductivities as a function of relative humidity were (0.91 meq. g−1 ) reflects such a compromise. The comparison of
also determined by four-probe impedance measurements. The the hydration isotherms of Nafion 1100 and Dow membranes of
cell consists of two connected compartments, each held at a different equivalent weight at room temperature (Fig. 1) already
different temperature. The cold compartment contained liquid suggests that this compromise may be at a higher IEC for the SSC
water, while the hot chamber hosted the membrane under test. ionomer. Dow 1084, which has about the same IEC as Nafion
The relative humidities were calculated from the ratio of the 1100, shows similar hydration over the whole relative humid-
saturated water vapor pressures at the temperatures of the cold ity range. But in liquid water, the water uptake of Dow 1084 is
and hot compartment. only λ = 12 compared to λ = 20 for Nafion (Fig. 2). Dow 858,
Conductivity measurements in pure water vapor which has an IEC almost 30% higher than Nafion 1100, shows
(pH2 O = 105 Pa) were carried out in a double wall tem- higher hydration especially in the range RH = 70–100%, where
perature controlled glass chamber with an open outlet at the elastic properties of the membranes are mainly determin-
temperatures between T = 110 and 160 ◦ C. Liquid water was ing the water uptake. But in liquid water, the hydration appears
continuously evaporated by a heater and injected into the to be almost identical to that of Nafion 1100 (λ = 22 compared
502 K.D. Kreuer et al. / Journal of Power Sources 178 (2008) 499–509
to λ = 20). But one should keep in mind that the 30% higher
water volume fraction simply reflects the difference in the IEC.
It should also be noted that for all membranes water sorption and
swelling is dependent on the history of the sample, where time,
temperature, and relative humidity are the determining factors.
It is a general observation from this study that these factors are
more pronounced for Nafion than for the Dow membranes.
The increase in swelling with increasing temperature is also
distinctly different for Nafion than for Dow. While swelling of
Nafion 1100 is virtually constant up to about T = 140 ◦ C, where
exaggerated swelling abruptly begins (for a swelling time of
1 h), the swelling of Dow membranes gradually increases with
temperature, especially for Dow 1084 no exaggerated swelling
is observed up to T = 160 ◦ C (Fig. 2).
As pointed out earlier [2–5] this behavior is probably the
consequence of a higher glass transition temperature and crys-
tallinity in the SSC membrane. Even in the SAXS spectrum the
latter is indicated as a broad peak in the range q = 0.03–0.07 Å−1
Fig. 3. (a and b) Small angle X-ray diffraction spectra (SAXS) for Dow 858 and
Dow 1084 membranes, respectively, as a function of the degree of hydration. A
spectrum of Nafion 1100 for selected degrees of hydration is shown for com-
parison. Note that the ionomer peak is more pronounced for Nafion (smaller
width and higher intensity) with a position at lower momentum transfer. (c)
Average hydrophobic/hydrophilic separations (spacing) as obtained from the
position of the ionomer peaks. Note that the data are plotted as a function of
the water volume fraction; all data virtually fall onto one curve for a plot versus
λ = [H2 O]/[–SO3 H] (not shown).
Fig. 6. Room temperature proton conductivity of Dow 858 and Dow 1084 as
a function of λ = [H2 O]/[–SO3 H]. The corresponding data for Nafion 1100 are
shown for comparison.
Fig. 9. Proton conductivity of Dow 858 and Nafion 1100 as a function of relative
humidity RH at T = 80 ◦ C. Fig. 10. Room temperature electroosmotic water drag coefficients measured by
the E-NMR technique for Dow 858, Dow 1078 and Nafion 1100. The data are
very low degrees of hydration. This effect is also confirmed at plotted as a function of the water volume fraction ϕ; all data virtually fall onto
one curve for a plot versus λ = [H2 O]/[–SO3 H] (not shown).
T = 120 ◦ C, where the conductivity of Dow 858 is more than two
times higher than this of Nafion 1100 in the relative humidity
range RH = 20–50% (Fig. 9). This actually suggests different bers of sulfonic acid groups. With respect to applications in fuel
changes of the microstructures with temperature and decreas- cells, it should be mentioned that the water uptake in terms of λ
ing degree of hydration for both types of ionomer. It should be is similar for all three ionomers (Fig. 1), i.e. for a given relative
mentioned at this point that this regime falls right within the humidity the electroosmotic water drag coefficients are similar,
␣-relaxation of Nafion which recently has been assigned to the but the proton conductivity of Dow 858 is about 50% higher
onset of long-range chain/side-chain mobility as a result of the than that of the other two ionomers.
destabilization of the electrostatic network [20,21], which occurs Returning to the visco-elastic instabilities, let us next con-
at a somewhat higher temperature for the Dow membranes, as sider the elastic modulus as a function of temperature (Fig. 11).
will be discussed later. These transitions may allow for confor- In accordance with the generally observed higher morpholog-
mational changes especially in the presence of pressure [22], ical stability of SSC ionomers (e.g. Refs. [4–7]), the strong
which are also expected to affect the proton conductivity (note, decrease in the elastic modulus occurs at about 25–35 ◦ C higher
that conductivities have been recorded by the two point method, temperatures than for Nafion. This decrease corresponds to the
which always requires the application of some pressure to the ␣-relaxation observed in tan δ determined from DMA measure-
electrodes to ensure good electrical contact). ments [20,21], i.e. the onset of structural instabilities allowing
But before further discussing the changes occurring in the for irreversible changes in the conformation of the polymer.
high temperature regime, let us first continue the discussion of Whether such changes actually occur and whether these changes
the transport coefficients by considering the coupling of water
and proton transport (i.e. electroosmotic drag). The room tem-
perature electroosmotic water drag coefficient, K, i.e. the number
of water molecules “dragged” through the ionomer per protonic
charge carrier, are shown in Fig. 10 for Dow 858, Dow 1084
and Nafion 1100. The data for Dow 1084 are restricted to water
volume fractions less than 30% because this morphologically
stable ionomer is difficult to swell beyond this limit. But the
few data are close to the drag coefficients measured for Nafion
1100. This is not surprising considering the similar degrees of
hydrophobic/hydrophilic separation (Fig. 3) and the virtually
identical ion exchange capacities. These two parameters are gen-
erally considered to determine electroosmotic drag, which has
a high hydrodynamic contribution especially at high degrees
of hydration [17]. For Dow 858, the ionomer with the highest
IEC, the electroosmotic drag is slightly lower than for the other
two ionomers for a given water volume fraction (Fig. 10). The
Fig. 11. Real part of the elastic modulus E’ obtained by DMA for Dow 858,
fact that the drag coefficients virtually coincide when plotted as Dow 1084 and Nafion 1100 as a function of temperature and a constant water
a function of λ suggests that the slight differences are mainly pressure of pH2 O = 16 hPa (mbar) (note that this corresponds to a decreasing
determined by the interaction of the water with different num- relative humidity with increasing temperature).
506 K.D. Kreuer et al. / Journal of Power Sources 178 (2008) 499–509
The better performance of low equivalent weight SSC mem- [5] M.R. Tant, K.P. Darst, K.D. Lee, C.W. Martin, Multiphase polymers: blends
branes in hydrogen fuel cells is chiefly the result of the higher and ionomers, in: L.A. Utracki, R.A. Weiss (Eds.), ACS Symposium Series
IEC and more effective solvent permeation from the cathode to 395, ACS, Washington, 1989, pp. 370–400.
[6] R.B. Moore, C.W. Martin, Macromolecules 22 (1989) 3594–3599.
the anode side in the opposite direction of the electroosmotic [7] G.A. Eisman, Proc. 168th Electrochemical Society Meeting 83–13, 1986,
drag. pp. 156–171.
The better morphological stability of SSC membranes [8] G.A. Eisman, J. Power Sources 29 (1990) 389–398.
compared to Nafion is anticipated to be in favor of the mor- [9] S.J. Paddison, J.A. Elliott, J. Phys. Chem. A 109 (2005) 7583–7593.
phological stability of the membrane electrode interfaces. The [10] S.J. Paddison, J.A. Elliott, Phys. Chem. Chem. Phys. 8 (2006) 2193–2203.
[11] S.J. Paddison, J.A. Elliott, Solid State Ionics 177 (2006) 2385–2390.
microstructure of these interfaces is generally optimized, and [12] S.J. Paddison, J.A. Elliott, Solid State Ionics 178 (2007) 561–567.
any morphological change is critical to the performance of both [13] L.B. Shaffer, R.W. Hendricks, J. Appl. Cryst. 7 (1974) 159–163.
DMFCs [27] and hydrogen fuel cells [28,29]. The higher glass [14] T. Dippel, K.D. Kreuer, M. Hampele, A. Rabenau, Recent developments on
transition temperature of SSC ionomers gives stability to the the pulsed field gradient NMR technique for self diffusion coefficient mea-
active layers (i.e. electrolyte/electrode interface) especially at surements on various nuclei, in: Proceedings of XXV Congress Ampère,
Stuttgart, 1990.
high operation temperatures, where Nafion seems to undergo [15] M. Ise, K.D. Kreuer, J. Maier, Solid State Ionics 125 (1999) 213–223.
severe conformational changes. [16] K.D. Kreuer, J. Membr. Sci. 185 (2001) 29–39.
The present comparison demonstrates that combining high [17] K.D. Kreuer, S.J. Paddison, E. Spohr, M. Schuster, Chem. Rev. 104 (2004)
IEC and high mechanical stability (i.e. elastic modulus), e.g. by 4637–4678.
increasing crystallinity as in the present case, or by increasing [18] M. Schuster, K.D. Kreuer, H.T. Andersen, J. Maier, Macromolecules 40
(2007) 598–607.
molecular weight, cross-linking or introducing interacting parti- [19] K.D. Kreuer, W. Weppner, A. Rabenau, Solid State Ionics 3/4 (1981)
cles, is a promising approach to improve membrane performance 353–358.
in both direct methanol and PEM fuel cells. [20] K.A. Page, K.M. Kable, R.B. Moore, Macromolecules 38 (2005)
6472–6484.
Acknowledgements [21] K.A. Page, F.A. Landis, A.K. Phillips, R.B. Moore, Macromolecules 39
(2006) 3939–3946.
[22] M. Casciola, G. Alberti, M. Sganappa, R. Narducci, J. Power Sources 162
The authors thank H. Steininger (BASF Fuel Cell) for proof (2006) 141–145.
reading and the Bundesministerium für Bildung und Forschung [23] F. Bauer, M. Willert-Porada, Solid State Ionics 177 (2006) 2391–2396.
(project DryD under the contract no. 0329567), and the Stiftung [24] K.D. Kreuer, in press.
Energieforschung Baden-Württemberg (A 23305) for financial [25] K.D. Kreuer, Hydrocarbon membranes, in: W. Vielstich, A. Lamm,
H.A. Gasteiger (Eds.), Handbook of Fuel Cells—Fundamentals, Tech-
support. nology and Applications, John Wiley & Sons, Ltd., Chichester, 2003,
pp. 420–435.
References [26] V. Saarinen, K.D. Kreuer, M. Schuster, R. Merkle, J. Maier, Solid State
Ionics 178 (2007) 533–537.
[1] K. Prater, J. Power Sources 29 (1990) 239–250. [27] X. Chen, C. Peng, M.D. You, L. Liu, Y. Zang, Q.B. Fan, Electrochim. Acta
[2] V. Arcella, A. Ghielmi, G. Tommasi, Ann. NY Acad. Sci. 984 (2003) 51 (2006) 4620–4625.
226–244. [28] J. Xie, D.L. Wood, K.L. Moore, P. Atanassov, R.L. Borup, J. Electrochem.
[3] A. Ghielmi, P. Vaccarono, C. Troglia, V. Arcella, J. Power Sources 145 Soc. 152 (2005) A1011–A1020.
(2005) 108–115. [29] X.Y. Huang, R. Solasi, Y. Zou, M. Feshler, K. Reifsnider, D. Con-
[4] M.R. Tant, K.D. Lee, K.P. Darst, C.W. Martin, Polym. Mat. Sci. Eng. 58 dit, S. Burlatsky, T. Madden, J. Poly. Sci. B-Poly. Phys. 44 (2006)
(1988) 1074–1078. 2346–2357.