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Main-chain, statistically sulfonated proton exchange membranes: the relationships of acid concentration and proton mobility to water content and their effect upon proton conductivity{
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Timothy J. Peckham,a Jennifer Schmeisser,{a Marianne Rodgersab and Steven Holdcroft*ab

Received 15th February 2007, Accepted 8th March 2007 First published as an Advance Article on the web 3rd April 2007 DOI: 10.1039/b702339a An in-depth analysis has been developed for proton exchange membranes to examine the effect of acid concentration and effective proton mobility upon proton conductivity as well as their relationship to water content. The analysis was carried out on a series of main-chain, statistically sulfonated polymers with varying ion-exchange capacities. These polymer systems consisted of: sulfonated poly(ether ether ketone) (1), poly(ethylenetetrafluoroethylene-graft-polystyrenesulfonic acid) (2), sulfonated polyimide (3) and BAM1 membrane (4) with Nafion1 (5) as baseline. They represent membranes comprising polyaromatic polymers (1 and 3), one of which is also a rigid-rod polymer (3), vinylic polymers (4) and a vinylic polymer polymerized inside a polymer matrix (2). In order to remove the differences in acid strength for the membranes, proton mobility values at infinite dilution (Xv = 1.0) and 25 uC were calculated and found to be 3.2 (0.4) 6 1023 cm2 s21 V21 (1), 2.9 (0.4) 6 1023 cm2 s21 V21 (2), 1.6 (0.7) 6 1023 cm2 s21 V21 (3) and 2.1 (0.2) 6 1023 cm2 s21 V21 (4). These were then compared with the theoretical value for the mobility of a free proton at infinite dilution. Significant deviations from this value were theorized to be due to possible differences in tortuosity and proximity of acid groups.

1.0 Introduction
Research on proton exchange membrane fuel cells (PEMFCs) has been an area of active interest since the 1960s but more so over the last decade. This has been partially the result of increasing demands from the public for zero-emission vehicles and power sources that lead to the reduction of greenhouse gases. However, the major impetus, particularly for automotive manufacturers, has been government-funded initiatives such as legislation enacted in California to achieve significantly lower automotive emissions,1 the FreedomCar and Fuel Partnership program initiated by the U.S. government through the U.S. Department of Energy (DOE)2 and an initiative by the European Union through the Commission of the European Communities.3 As a key component in PEMFCs, the proton exchange membrane (PEM) and its development have attracted particular interest in commercial, government and academic institutions. Nafion1 membranes have been at the forefront of this development, offering to date the best combination of performance, durability and reliability. Nevertheless, as the technological requirements for automotive and stationary applications are becoming increasingly rigorous,4 there is a
Department of Chemistry, Simon Fraser University, Burnaby, British Columbia, V5A 1S6, Canada b Institute for Fuel Cell Innovation, National Research Council Canada, 3250 East Mall, Vancouver, British Columbia, V6T 1W5, Canada { This paper is part of a Journal of Materials Chemistry theme issue on New Energy Materials. Guest editor: M. Saiful Islam. { Current address: Department of Chemistry and Biochemistry, 273-1 Essex Hall, 401 Sunset Avenue, University of Windsor, Windsor, Ontario N9B 3P4, Canada.
a

growing need for PEMs that have improved properties over those offered by Nafion1 membranes.4,5 As an iterative or random hit and miss approach to membrane development is generally not very effective, a more desirable way to systematically develop new PEMs would be first to obtain a fundamental understanding of the structureproperty relationships for these materials before attempting to design a new PEM. One of the most important properties of a PEM is its ability to provide an ionic path for protons to travel from the anode to the cathode.6 In the case of Nafion1 and the majority of other PEMs, water-saturated channels are believed to form due to the phase separation of the normally hydrophobic polymer backbone from the hydrophilic, bound sulfonic acid groups. Proton conduction is thought to occur through these channels, mediated by the sulfonic acid groups and in conjunction with water that is either closely associated with the acid groups or present as bulk water in the channels.79 If the level of proton transport is insufficient, a resistive (Ohmic) loss will be observed along with a concomitant negative impact upon the performance of the fuel cell.6,10 Factors such as density of acid-containing groups within the membrane, polymer structure and morphology, in combination with water content, have an impact upon the observed level of proton conduction. In order to design new membranes with improved levels of proton conduction, it is therefore important to learn from existing materials exactly how these factors influence proton conductivity. This attempt to better understand the structureproperty relationship for proton conductivity in PEMs has been a core focus of our research1123 on PEMs as well as that of several other groups.2443 Some of this work will be highlighted in the following paragraphs.
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Not surprisingly given its position as a standard for fuel cell research, Nafion1 has been particularly well studied to better understand its structureproperty relationships. The microstructure of this membrane has been extensively analyzed using both small-angle X-ray scattering (SAXS) and small-angle neutron scattering (SANS) with a wide range of polymer-tosolvent ratios as well as using different types of solvents with much of the primary studies having been conducted by Gebel et al.4447 In Nafion1, as with other PEMs, nanoseparation of the hydrophobic and hydrophilic portions of the polymer leads to the formation of interpenetrating domains wherein proton transport occurs via the hydrophilic domains.31,34 In comparing the microstructure of Nafion1 to that of sulfonated poly(ether ether ketone), SPEEK, Kreuer et al. noted that the hydrated channels in Nafion1 are larger and exhibit better connectivity than those in SPEEK. With smaller channels, the protons in SPEEK are in closer proximity to the tethered SO32 groups and thus experience a higher degree of attraction, more so magnified by the stronger basicity of the sulfonate anion in SPEEK relative to the analogous site in Nafion1. Protons in SPEEK, therefore, exhibit lower mobility values. With less connectivity, the mean free path for protons in SPEEK is also longer, thereby further reducing the overall mobility in comparison to the situation in Nafion1. These differences have thus been used to explain the deleterious effect of lower water contents on conductivity in SPEEK whereas the result is not as severe for Nafion1.5 Investigating structureproperty relationships in PEMs has also been a strong focus of the research in our group on fuel cells. The proton conductivity of BAM1 membranes (4), sulfonated styrene-(ethylene-butylene)-styrene triblock copolymers (DAIS-Analytical), ETFE-g-PSSA (2) and N117 (5) were measured and the microstructures analyzed by SAXS.11 Whereas 5 showed clear signs of microphase separation in the form of ionic aggregates, most ionic sites were homogeneously distributed in the case of 2. For 4, there was evidence for some degree of ionic aggregation but with the aggregates widely and homogeneously dispersed, unlike the channel structure observed for 5. Additional TEM studies on 4 confirmed that localization of ionic domains was not as well developed as in the case of 5. Another study comparing the more structured PS-g-PSSA with PS-r-SSA found that the former exhibited significantly higher conductivity values than the latter for a similar degree of ion content.1214 TEM analysis revealed clear signs for microphase separation and a continuous network of ionic channels in PS-g-PSSA whereas PS-r-SSA showed a lack of phase separation. It was thus surmised that the higher conductivity of PS-g-PSSA was due to its more organized microstructure. More recently, our group has investigated systems in which the presence of fluorinated blocks in a sulfonated copolymer has led to varying degrees of microphase separation.16,1820 These systems and others are currently under investigation to try and determine how the morphology of the microphase-separated structure affects proton conductivity. A number of other groups have also been actively involved in studying structureproperty relationships on PEMs. In the interest of space, only a few, more recent examples will be highlighted here. Elabd et al., for example, have studied
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sulfonated poly(styrene-b-isobutylene-b-styrene) and examined the effect of polymer morphology26 and the increased alignment of ionic domains24 on its properties. In the former study, it was found that a 3-fold decrease in transport properties could be achieved by changing the solvent used to cast the membranes from toluene to a tolueneethanol mixture with observable differences in morphology between the two membranes as determined by SAXS measurements. In the latter study, it was found that up to a 6-fold improvement in conductivity could be achieved by aligning the ionic domains perpendicular to the casting plane of the membrane in comparison to the isotropic analogue. Structureproperty relationships in PEMs have also been investigated for sulfonated polyimides (4). Okamoto et al. observed that a microphase-separated structure for polyimides could be achieved by separating the sulfonic acid group from the polymer backbone by means of a short graft chain.42 Improvements in both conductivity and resistance to hydrolysis over main chain-sulfonated polyimides were attributed to the microphase-separated structure. Watanabe et al. also performed a similar study on polyimides with sulfonic acidbearing side chains and observed improvements in proton conductivity.43 Overall, it appears that the general approach in the literature to study the efficiency of proton transport for a series of new materials is to interpret proton conductivity data (as measured by ac impedance spectroscopy) as a function of ion-exchange capacity (IEC) or water uptake. Using supporting data obtained from supplementary analytical techniques (e.g., TEM, XRD), the results are then usually explained and correlated to the connectivity and size of the water-saturated channels that result from the phase separation of the hydrophobic polymer backbone from the hydrophilic sulfonate side chains in order to explain differences observed in proton conductivity between different materials. While useful information can certainly be obtained from this approach, we have found in our group that a more in-depth, systematic analysis of proton conductivity data also provides additional, useful information that could potentially lead to further understanding of proton conduction in PEMs and thus hopefully aid in the design of new materials with improved levels of proton conductivity. In this paper, we would like to report both this method as well as present examples of its application to a number of different sulfonic acid-bearing polymer systems. Generally, it is difficult to compare literature data in a systematic manner as frequently not all the required information is presented. In addition, measurement techniques are not consistent throughout the literature. In order to circumvent these issues, all the data on the PEMs that we present in this paper were obtained in our own laboratory, thereby ensuring that measurements, treatments and data acquisition were kept consistent.

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2.0 Results and discussion

2.1 Approach to proton conductivity data analysis The observed proton conductivity for a PEM is intimately linked to both its water content and its acid content. The approach for the expanded analysis examines in detail the
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relationships amongst these properties as well as a deeper examination of proton conductivity itself. By carrying out this analysis, it was hoped that additional information could be gained from proton conductivity data alone that could complement other techniques (e.g., TEM) currently employed to explain observed trends in proton conductivity. The analysis itself is divided into four sections: a) proton conductivity, b) effective proton mobility, c) acid concentration in the membrane and d) water content. Fig. 1 shows the various component plots for each section. 2.1.1 Proton conductivity. Although both water content and the density of acid groups have an effect upon the conduction of protons through a PEM, only the density of acid groups remains consistent within a membrane, irrespective of the membrane environment. Thus, the relationship between proton conductivity (s) and the density of acid groups (i.e., IEC) at a fixed temperature and humidity is an effective starting point for an analysis. As proton conductivity is also related to water content, however, determining the relationship between water content and proton conductivity is required. Water content of a PEM is commonly described in terms of water uptake (weight% increase for PEM from dry to wet state). Water uptake as a volume percentage, also described as the water volume fraction (Xv),48 is used as a replacement here for water uptake as a weight percentage. Xv is generally a more useful measure that, in addition to indicating how much water a membrane is capable of absorbing, also gives the actual percentage of the volume of the membrane occupied by water. This is particularly useful for membranes with very high water uptakes, as will be seen in the discussion on BAM1 membranes. With extrapolation to Xv = 1.0, use of this factor also potentially shows how close proton conductivity in the membrane approaches that in pure water. As increasing IEC for all PEMs generally leads to an increase in water content, it is also convenient to standardize water content for acid content and thereby permit comparisons between PEMs with different IEC values. This factor, l (moles of water per mole of acid), will also be used in the analysis.

2.1.2 Proton mobility. Mobility is defined as the rate of transport of a species under an applied electric field (cm2 s21 V21). Upon examination of the general definition of electrical conductivity, se, it can seen that it is simply a function of the quantity of charge carriers in a given volume, g, and the mobility of those charge carriers, me (eqn (1)): se = geme (1)

This general relationship is easily extended to ionic systems where the transference number of an ion is equal to one (eqn (2)): s = Fai|Zi|m (2)

where s is the specific conductivity of the ion, F is Faradays constant, ai is the activity of the ion, and Zi is the charge on the ion. The activity, ai, itself can be defined by the following equation: ai = fiCi (3)

where fi describes the degree of dissociation of the ion and Ci is the analytical concentration of the ion. This relationship is applicable for an estimation of proton mobility from proton conductivity in PEMs as the negatively charged SO32 counter-ions are tethered to the backbone, thus resulting in a transference number of one for the positively charged protons (eqn (4)): sH+ = F[H+]mH+ (4)

In fact, a more correct description of eqn (3) is to replace [H+] with the activity value for H+. This requires accurate knowledge of the activity coefficient of H+, which is concentration dependent and an unattainable value in these systems. The activity, as previously shown in eqn (3), is related to f, the degree of dissociation (dependent upon both the pKa of the acid group and the water content of the PEM) and is thus a factor in the mobility of the proton. In fact, proton mobility in the aqueous phase of a PEM does not fall into the

Fig. 1

Analysis of proton conductivity data.

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classical view of mobility of free ions in solution. For example, strong binding of a proton to the tethered anion (or anions) as it traverses the membrane should be considered as an impediment to its mobility. Hence, the calculated proton mobility is an effective mobility that includes the uncertainties of the activity coefficient(s) for H+. In the extreme, if all the acid groups in the membrane remain undissociated, the effective mobility value is zero. The titration measurement, however, measures the concentration of SO3H groups in the membrane rather than an actual free proton concentration, thus combining both bound and unbound protons (eqn (5)): SO3H = SO32 + H+ (5)

distances between SO32 in A in comparison to the shorter distances between SO32 groups in B. Therefore, it might be expected that this would lead to a lower proton mobility in A in comparison to B.5,49,50 The effective proton mobility, m9H+, as derived from the proton conductivity data using eqn (6), therefore, incorporates terms that relate to acid dissociation (eqn (5)), tortuosity (Fig. 2) and spatial proximity of neighbouring acid groups (Fig. 3). sH+ = F[SO3H]m9H+ (6)

Given that the analytical acid concentration, rather than proton concentration, is the quantity measured by titration, we have substituted acid concentration for proton concentration into the equation for proton conductivity as seen in eqn (6). Calculation of proton mobility, therefore, allows a normalized proton conductivity to be determined; i.e., acid concentration effects are removed. By doing this, it is possible to view the relative contributions of both proton mobility and acid concentration (itself consisting of contributions from both acid and water contents) to the experimentally measured proton conductivity. In addition to the effect dissociation and tethered anionic groups have on mobility, there are additional effects that further remove the mobility of protons in a PEM from the classical picture. One of these relates to the connectivity and effective mean-free path for protons. This is schematically illustrated in Fig. 2 in which A is characterized as having a more tortuous conduction pathway, with a series of dead ends, compared to the conduction pathway in B which is more linear. The supposition, therefore, is that proton mobility will be effectively greater in B relative to A. In fact, Kreuer has previously invoked these concepts of smaller conduction channels and dead ends in order to explain the lower proton mobility in SPEEK compared to Nafion1.5 The distance between acid groups may also play a role in the mobility of protonspores having different distances between acidic groups are shown schematically in Fig. 3. As the protonbearing, positively charged species (e.g., H3O+, H2O5+ and/or H4O9+ ions)34 are transported between the negatively charged, tethered SO32 groups, it may be expected that it will be more difficult for a proton to be transported over the larger

Calculations based on perfluorinated triflic acid (as a small molecule analogue for 5) and the hydrocarbon-based p-toluenesulfonic acid (as a small molecule analogue of 1) with pKa values of 26 and 22 respectively51 suggest that dissociation of the proton occurs when l = 3, forming a hydronium ion.52 However, it has also been calculated that complete separation of the proton-bearing species from the tethered SO32 anion does not occur for l , 6.53 In the case of the PEMs examined in this study, the samples were allowed to equilibrate in water. Thus, all possessed a l value 10 and relatively complete dissociation may be assumed for all the membranes. However, calculations comparing triflic acid and p-toluenesulfonic acid suggest that a greater separation distance between the hydrated proton and the sulfonate group exists in the triflic acid case due to its greater acidity.52 At the theoretical infinite dilution limit (i.e., Xv = 1.0), it is reasonable to assume that differences in acid strengths might have a minimal effect on m9H+ at Xv = 1.0. If the only significant contributing factor for a series of given PEMs is the acid strength, this effect should be removed at infinite dilution. All things being equal, the effective proton mobility of PEMs at Xv = 1.0 should be equivalent to the theoretical mobility value for a single, free proton at infinite dilution (3.6 6 1023 cm2 s21 V21).54 If, however, there are also other contributing factors such as tortuosity,55 different pore sizes and/or dead end channels, these manifest themselves as a deviation for proton mobility of the PEM at Xv = 1.0. If this information could then be attributed to the chemical structures of the membranes, the resultant structure property relationships could then be potentially exploited to design new PEMs with increased values of proton conductivity. 2.1.3 Acid concentration. Acid concentration is determined as shown in eqn (7): SO3 H~ moles of SO3 H Vwet membrane (7)

Fig. 2 Connectivity of aqueous domains in PEMs (white = aqueous domains) where the degree of tortuosity of proton conduction pathway is greater in A than in B.

Fig. 3 Spatial proximity of neighbouring acid groups within an aqueous channel where the distance between acid groups is greater in A than in B.

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where SO3H refers to bound sulfonic acid moieties in the PEM, moles of SO3H = IEC 6 dry mass of polymer and Vwet is the wet volume of the polymer. Although these two latter parameters are determined experimentally, the value of [SO3H] represents the overall concentration of protons in the membrane without distinguishing between those protons that are mostly associated with the sulfonic acid groups and those that are fully dissociated and thus mainly present in the bulk water. Nevertheless, as acid concentration (see eqn (4) and (6)) has an important influence on proton conductivity, it is of interest to note how this parameter itself is affected by changes in acid and water content. Hence, [SO3H] is plotted as a function of IEC, Xv and l and this will show whether acid concentration remains constant or whether it varies (e.g., at high IEC values, water uptake may be very high, leading to an overall dilution of available acid sites, thus having a detrimental effect upon proton conductivity). 2.1.4 Water content. Water content was examined both as a volume percentage (Xv) and as a ratio of moles of water to moles of sulfonic acid (l). These were determined as per eqn (8) and eqn (9) respectively: Water content vol%~Xv ~ Vwater Vwet membrane (8)

As water content tends to vary as a function of acid content, both Xv and l are plotted as a function of IEC and allow for a determination of whether water content increases steadily as a function of acid content or whether there are any sudden, sharp increases. In the latter case, this is a sign of increased swelling and is an important point to note due to the strong effect it will have upon [SO3H] and, hence, upon proton conductivity. Another important plot is to see how l varies as a function of Xv. In common with determining how water content varies as a function of acid content, this plot also will show if swelling occurs at a consistent rate (l increases steadily as a function of Xv) or there are sudden increases (l increases suddenly as a function of Xv). There is also a third case where swelling is very limited (i.e. l remains the same over a wide range of Xv). Finally, a plot of l as a function of Xv also permits relative comparisons between different PEMs and will show whether certain membranes are able to achieve a given l value at lower Xv values than for other membranes. 2.2 Approach to proton conductivity data analysis: application examples In order to demonstrate the usefulness of this approach, four different PEM systems were chosen and compared against the standard, Nafion1 N117 (IEC = 0.91 mmol g21). They are: i) sulfonated poly(ether ether ketone), SPEEK (1); ii) poly(ethylenetetrafluoroethylene-graft-styrene sulfonic acid), ETFE-gPSSA (2); iii) linear sulfonated polyimide, sPI (3); (iv) substituted, sulfonated poly(trifluorostyrene), BAM1 membrane (4). The structures for these systems can be seen in Fig. 4. For each of the four systems (i.e., not including Nafion1), samples with a minimum of three different IEC values were

l~

moles H2 O moles SO3 H

(9)

In the case of eqn (5), the volume of water was calculated by considering all of the water in the membrane as bulk water (rather than a combination of bulk and bound or nonfreezable water) and assuming a water density of 1 g mL21.48

Fig. 4

PEM systems used in this study: SPEEK (1), ETFE-g-PSSA (2), sPI (3), BAM1 membrane (4) and Nafion1 membrane (5).

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used. In addition, the sulfonic acid groups were statistically distributed and attached directly to the main chain of the polymer (vs. a sulfonic acid-bearing side group). The polymer systems were synthesized via step-growth polymerization (1 and 3) or chain-growth polymerization (2, 4 and 5). The analyses of each system (with the analogous results for Nafion1 N117 (5) shown for comparison) are discussed in the following sections. As previously mentioned, in order to ensure consistency for all the data collected, all samples were tested under identical conditions in our laboratory. 2.2.1 Proton conductivity as a function of acid and water content. The plot shown in Fig. 5 (sH+ vs. IEC) is the one most frequently used to present the results of proton conductivity studies on new membranes. A linear relationship is often observed for sH+ as a function of acid content (i.e., IEC). This can be seen in the results for our study for both 1 (conductivity values consistent with literature results)56 and 2 as well as to some degree for 3 and at lower IEC values in the case of 4. Within this range of IEC values, the acid content in these systems is sufficiently high to have reached the percolation threshold; i.e., the point at which there is a sufficiently high enough degree of connectivity between ionic domains for the transport of protons and water through the membrane. Comparing 1 with the baseline, 5, this percolation threshold is reached at a considerably lower IEC value for 5 versus 1 as evidenced by the high conductivity value of 5. As the sulfonic acid groups in 5 are separated from the polymer backbone via a flexible spacer unit, microphase separation of the hydrophilic portion of the polymer from its hydrophobic portion is more readily achieved than in the case of the main chain sulfonated 1. Therefore, this enables 5 to form broad, continuous channels for proton transport through the membrane. In the case of 1, the channels are more narrow with a greater number of discontinuities, thereby leading to less effective proton transport, as previously reported by Kreuer.5 Beyond the percolation threshold, the trend generally observed for the majority of PEMs is an increase in sH+ with increasing IEC. This is normally assumed to be a result of an increasing concentration of sulfonic acid groups and increased water content, water being necessary to ensure the protons are

Fig. 6

Proton conductivity of 15 as a function of l.

sufficiently dissociated for mobility. By analyzing the proton conductivity behaviour of 1 as a function of water content, however, a linear trend is not observed. Instead, sH+ appears to be reaching a maximum with increasing water content. This can be seen clearly in Fig. 6 (sH+ vs. l) and even more clearly in Fig. 7 (sH+ vs. Xv). In addition, it can be seen that 5 exhibits a similar degree of conductivity to 1 for the same water content (virtually identical values in Fig. 6 and slightly higher for 5 in Fig. 7). Moreover, it can be seen from Fig. 10 (later) that 5 (Xv = 0.41, l = 19.6) is able to achieve a higher l value as a function of Xv in comparison to 1 (Xv = 0.40, l = 14.7). Of all the PEMs examined here, 2 displays the highest average IEC value (2.65 meq g21) and exhibits the highest proton conductivity (0.20 S cm21). Although this is significantly higher than the value observed for 5, an extrapolation of the data to lower IEC values suggests that a sample of 2 with an IEC value equivalent to that of 5 would display a similar conductivity value. In comparison to 1, 2 displays significantly higher conductivity values over the IEC range 2.02.6 meq g21 (e.g., sH+ = 0.17 S cm21 at IEC y 2.5 meq g21 versus sH+ = 0.12 S cm21 for 1). Also, in contrast to 1, the data for 2 do not appear to be approaching a maximum in the case of sH+ vs. IEC, sH+ vs. l and sH+ vs. Xv (Fig. 57 respectively). However,

Fig. 5

Proton conductivity of 15 as a function of IEC.

Fig. 7 Proton conductivity of 15 as a function of Xv.

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Fig. 8 l of 15 as a function of IEC.

Fig. 10 l of 15 as a function of Xv.

given the more limited data set available for 2, it is unclear whether this is reflective of a definite trend or not. The higher conductivity values for 2 in comparison to 1 are achieved for similar l values (Fig. 6) and Xv (Fig. 7). An explanation for this observation can be found in section 2.2.2. The relationship between water content, l and Xv, and IEC can be more easily seen in Fig. 8 and 9. At IEC , 2.4 meq g21, 2 possesses both greater l and Xv values for a given IEC than 1. However, this begins to change at IEC y 2.5; the l values for 1 and 2 at IEC = 2.45 meq g21 are both y24 whereas the respective Xv values are 0.53 and 0.62.57 Also, whereas at IEC = 2.56, 1 possess a significantly higher l value in comparison to 2 (42 and 24, respectively), both 1 and 2 have almost the same Xv value (0.66 and 0.63, respectively). This means that the wet volume of 2, given the same approximate volume of water (e.g., at IEC = 2.45 meq g21, both polymers have l y 24 and assuming that water has the same density in both membranes), is smaller than for the wet volume of 1. This is most likely due to a higher density of 2 in comparison to 1.58 There also does not appear to be any change in the amount of water taken up as function of IEC for 2 whereas significantly higher amounts of water are being absorbed by 1 at IEC . 2.5 meq g21 versus the initial trend over the range of IEC = 2.02.5; i.e., the amount of swelling exhibited by 2 appears to

Fig. 9 Xv of 15 as a function of IEC.

be considerably smaller than observed for 1. This difference in swelling behaviour can be seen in the plot of l vs. Xv (Fig. 10): whereas a linear extrapolation of the data for 2 suggests similar l values would be found over the Xv range of 0.30.5, the l values for 1 are much higher than those for 2 when Xv . 0.5. Given the differences in the chemical structures of 1 and 2, the presence of a preformed matrix in 2 (wherein there are crystalline regions that do not swell, thereby acting as physical cross-links) and the chemical cross-linking that may occur during the irradiation grafting process used to obtain 2, it is perhaps not surprising that 2 is unable to swell as easily as 1. PEMs designated as 3 are prepared from sulfonated polyimides in which the polymer assumes a linear backbone. Derivatives of 3 with an angled backbone have been previously reported by our group59 and a more detailed analysis of the proton conductivity results for this system will be reported at a later date. Structurally, 3 is more similar to 1 than to 2 or 4. Thus, as might be expected on this basis, the conductivity data for 3 exhibits similar behaviour to that of 1; i.e., at IEC , 2.5 meq g21, lower conductivity values are generally seem in comparison to 2 or 4. At IEC . 2.5 meq g21, 3 continues to exhibit lower conductivity values than the other PEMs with the exception of 4. More information about the conductivity behaviour of 3 can be gained by examining its relation to water content. As a function of water content (Fig. 6 and 7), the proton conductivity of 3 does not exhibit any apparent sign of approaching a maximum as in the case of 1. Examining the water content as a function of IEC (Fig. 8 and 9), it can be seen that 1 and 3 have similar Xv and l values until IEC y 2.3 meq g21 at which point the value for 1 increases to a much higher value than seen for 3. The latter system does exhibit a similar water content at IEC = 2.7 meq g21 (Xv = 0.62) that 1 exhibits at IEC = 2.6 meq g21 (Xv = 0.62). However, given that 3 does not appear to show signs of a significant increase in Xv as a function of IEC (Fig. 9) as does 1, it is likely that at the same IEC (i.e. 2.7 meq g21), 1 would actually exhibit a significantly higher Xv value in comparison to 3. It thus appears that, like 2, 3 experiences less swelling in water than does 1 even at higher IEC values. This can be clearly seen in Fig. 8 and 10 where it can be seen that the value of l in the case of 3 remains
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relatively consistent across a wide range of IEC and Xv. Such behaviour is in sharp contrast to 1, 2 and 4 for which l is continually increasing as a function of IEC and Xv. BAM1 membrane (4) is an experimental, a,b,b-trifluorostyrene-based copolymer developed by Ballard Advanced Materials, consisting of a perfluorinated polymer backbone with the sulfonic acid groups bound to the benzene ring.60 Structurally, it is more similar to 2 than any of the other PEMs examined in this study although it does not possess either the macrophase separation or the potential cross-linking of 2. Therefore, in some respects, 4 might be anticipated to display some similarities in its conductivity behaviour to that of 2. However, in contrast to both 1 and 2 where conductivity was always seen to be increasing as a function of IEC, Fig. 5 clearly shows that conductivity of 4 reaches a maximum around IEC = 2.0 meq g21 and then decreases rapidly such that at IEC = 2.2 meq g21, the observed value is 30% lower than seen at IEC = 2.0 meq g21. This significant decrease in sH+ as a function of increasing Xv and l is also clearly visible in Fig. 6 and 7, respectively. PEM 4 can also be seen to exhibit similar conductivity values to 1 at Xv y 0.6 and over the range of l y 1030 but significantly lower than observed for 2. In sharp contrast to any of the other PEMs, however, 4 exhibits much higher water contents as observed in Fig. 8 and 9. Even at IEC = 2.2 meq g21, 4 has already achieved Xv = 0.82 and l = 76 whereas 1 only achieves Xv = 0.66 and l = 42 even at IEC = 2.6 meq g21 and 2 reaches Xv = 0.73 and l = 29 at the considerably higher IEC value of 3.3 meq g21. It appears clear that 4 absorbs significantly larger amounts of water than either 1 or 2 at high IEC values. Relating these data to the discussion on the water contents of 1 vs. 2, 4 appears to be moving towards the opposite extreme in comparison to 2; i.e., 4 appears to be able to swell more easily than 1. This higher degree of swelling is probably related to a more flexible backbone for 4 in comparison to 1 as well as the absence of a matrix polymer and/or cross-linking that are present in 2. Furthermore, 4 is able to hold a high water content (e.g., Xv = 0.85 at IEC = 2.5 meq g21) without completely losing its mechanical integrity (i.e., the sample will return to its original dimensions upon drying to ambient conditions) or dissolving. Nevertheless, it can be seen that higher water content does not necessarily lead to higher conductivity values, the reasons for which will be discussed in the following section. 2.2.2 Proton mobility and acid concentration as a function of acid and water content. Additional information can be gleaned from examining the conductivity results in greater detail for the studied polymer systems. The effective proton mobility for 1 is seen to increase steadily over the IEC range until IEC . 2.5 meq g21 at which point m9H+ exhibits an even greater increase. The increase in m9H+ could be due to at least two factors: a) increasing water content leading to increased dissociation of the protons from the SO32 groups; b) increasing water content changes the size and shape of the hydrophilic channels through which proton transport occurs, thereby leading to higher m9H+ values. As water content generally increases with increasing IEC, the observed trend in m9H+ would thus generally be expected.
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At a first approximation, [SO3H] might similarly be expected to increase with increasing IEC since this also means that there are a greater number of sulfonic acid groups available. However, as can be seen in Fig. 14 (later), [SO3H] of 1 actually decreases with increasing IEC (for IEC . 2 meq g21). When the water content of 1 as a function of IEC is taken into account (Fig. 8 and 9), the explanation for this observation becomes apparent. Water content increases as a function of IEC with an even larger increase seen where IEC . 2.5 meq g21. Although higher water content enables greater dissociation of protons and hence higher mobility, the effect on [SO3H] of a significant increase in water content is a dilution of the available sulfonic acid groups and thus a decrease in the observed values of [SO3H]. One parameter for PEMs such as 1 that is frequently altered in the hope of achieving greater levels of conductivity is the IEC. Given the clear effect of water content on proton mobility and concentration and hence on the observed value of conductivity, however, it is important to study the effect that water content has on the available iterations of a PEM and then attempt to extrapolate this information to determine whether significantly higher IEC PEMs of that polymer system would be a worthwhile undertaking. Looking at the available data for 1, it was already previously noted that it appears that conductivity is approaching a maximum as a function of l. As m9H+ is increasing while [SO3H] is decreasing as a function of l (see Fig. 12 and 15 respectively, later), it would therefore appear that a balance is achieved for conductivity as a function of water content. In other words, water content must achieve a level at which proton dissociation is sufficiently high enough for good mobility and yet there must be not too much water because this leads to dilution of those protons. For the series of 1 that were available for this study, conductivity is still increasing as a function of IEC and though, based on the data in Fig. 6, a maximum conductivity appears to exist, there is no definite indication that higher water content would actually lead to lower proton conductivity unlike the situation observed in the case of 4. Although a higher conductivity is generally a desirable quantity in a PEM, achieving this via an increase in IEC may not be necessarily the best method. Higher IEC values are generally accompanied by increases in water content. Given that mechanical stability is also a requirement of a good PEM for FC applications, too much water can lead to large and undesirable volume changes during humidification/dehumidification cycles under FC operating conditions. In Fig. 8 and 9, both Xv and l are seen to increase as a function of IEC, more sharply for IEC . 2.5 meq g21. It should be noted that 1 is known to exhibit poor chemical stability in water at sulfonation levels greater than 70% and temperatures greater than 50 uC (i.e., within the typical PEMFC operating temperature range).61,62 Even if the stability of the polymer could be increased (e.g., via cross-linking), the data in this study suggest that 1 at sulfonation levels in excess of those obtained with our samples (i.e. .95%) will undergo considerable swelling and thus, in this respect, would be unsuitable for application in a PEMFC. In common with 1, 2 also shows a trend towards increasing mobility with increasing IEC, Xv and l values (Fig. 1113) as
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Fig. 11 Effective proton mobility of 15 as a function of IEC.

Fig. 13 Effective proton mobility of 15 as a function of Xv.

well as decreasing [SO3H] with increasing IEC, Xv and l (Fig. 1416 respectively). These observed behaviours are most likely due to the same reasons discussed for 1; i.e., increasing water content leads to increasing proton mobility but also to dilution of available acid sites. In comparison though, 1 has a considerably higher m9H+ value (1.67 6 1023 cm2 s21 V21) at IEC = 2.56 meq g21 (Fig. 11) whereas the analogous value for 2 is only 1.18 6 1023 cm2 s21 V21 even though both membranes have similar water contents at this IEC (Xv = 0.67 and 0.63 for 1 and 2 respectively). In contrast, however, 1 exhibits a lower value for proton conductivity (0.14 S cm21 vs. 0.17 S cm21 for 2 at IEC = 2.56 meq g21). This situation arises due to dilution of the protons as evidenced by the higher l value of 1 (42 vs. 24 for 2) and also its considerably lower [SO3H] (0.88 M for 1 vs. 1.46 M for 2). The higher effective acid concentration of 2 is likely due to its restricted swelling which limits the amount of water that the membrane can uptake and thus helps mitigate against dilution of protons. On the other hand, 2 also benefits from an uptake of water that is sufficient to maintain a high enough proton mobility and, therefore, leads to a higher level of conductivity for 2 relative to 1. Of the PEMs used in this study, 3 exhibits some of the lowest m9H+ values as a function of IEC. For example, while the

Fig. 14 Acid content of 15 as a function of IEC.

respective m9H+ values for 2 and 4 at IEC y 2.0 meq g21 are 8.47 6 1024 cm2 s21 V21 and 1.30 6 1023 cm2 s21 V21 respectively, the corresponding value for 3 is 6.01 6 1024 cm2 s21 V21. Only the value for 1 (2.56 6 1024 cm2 s21 V21) is lower. However, at higher IEC (2.62.7 meq g21), proton mobility for 1 increases to 1.66 6 1023 cm2 s21 V21 whereas little change is observed in the case

Fig. 12 Effective proton mobility of 15 as a function of l.

Fig. 15 Acid content of 15 as a function of l.

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Table 1 Calculated proton mobility values at infinite dilution (Xv = 1.0) Polymer 1 2 3 4 m9H+ at Xv = 1.0/1023 cm2 s21 V21 3.2 2.9 1.6 2.1 0.4 0.4 0.7 0.2

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Fig. 16 Acid content of 15 as a function of Xv.

of 3 (m9H+ = 8.33 6 1024 cm2 s21 V21). As the mobility of the protons in a PEM is directly related to the degree of dissociation from the bound SO32 counter-ions and the degree of dissociation is directly related to water content, this result can be interpreted as a result of the restricted swelling of these PEMs. With l values remaining, for the most part, in the region of y1520 water molecules per sulfonic acid group in the case of 3, the mobility of the protons is similarly kept below y8.3 6 1024 cm2 s21 V21. The restricted water uptake of 3, however, does have the added benefit that the available protons are not dilutedhence the conductivity values of 3 are more dependent upon [SO3H] than for the other PEMs. As was shown earlier, 4 at high IEC levels is capable of absorbing enormous amounts of water without dissolving. However, this ability to absorb greater amounts of water does not appear to be an advantage as the conductivity of 4 actually starts to decrease beyond IEC = 2.0 meq g21. The effect of this high water content on the contributing factors to sH+ can be seen in the plots of m9H+ vs. IEC, m9H+ vs. l, m9H+ vs. Xv, [SO3H] vs. IEC, [SO3H] vs. l and [SO3H] vs. Xv as shown in Fig. 1116, respectively. At IEC y 2.5 meq g21, m9H+ values for 4 (1.75 6 1023 cm2 s21 V21) are higher than for either 1 (1.67 6 1023 cm2 s21 V21) or 2 (1.19 6 1023 cm2 s21 V21). However, acid concentrations are considerably lower in the case of 4 (0.56 M) versus either 1 (0.88 M) or 2 (1.28 M), as would be expected based on the very high l value (85) for 4, thereby leading to lower conductivity values at IEC . 2.0 meq g21 than might be anticipated based on the results from 1 and 2. Thus, 4 is a good example of how increasing IEC for a given PEM can actually lead to lower conductivity values due to the ability of the polymer to absorb excessive volumes of water, resulting in the dilution of the available protons. 2.2.3 Proton mobility at infinite dilution. In order to remove the effect of the different acid strengths for 14 from m9H+, the effective proton mobility was calculated for 14 at Xv = 1.0 by performing linear regressions for the data in Fig. 13 (plots of m9H+ vs. Xv). The calculated infinite m9H+ values can be seen in Table 1. In all cases except 3, the data appeared to be relatively linear (R2 . 0.98). For 3, the correlation of the data to
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linearity was somewhat low (R2 = 0.89) and this is reflected in the high standard deviation (44%) for the calculated m9H+ value at infinite dilution (cf. standard deviations for 1, 2 and 4 average y12%). Nevertheless, for the sake of comparison and keeping the large standard deviation in mind, this value for 3 will still be used for comparison with those calculated for the other membranes. For 1, the linear regression analysis gives value of 3.2 6 1023 cm2 s21 V21 at 25 uC for m9H+ at Xv = 1.0. This mobility value is similar, within y10%, to the calculated mobility of a free proton in water at infinite dilution of 3.63 6 1023 cm2 s21 V21 at 25 uC.54 The slightly lower value in the case of 1 might be due to the immobility of the bound SO32 counter-ion, thus restricting the mobility of the proton. However, the standard deviation for this value brings the calculated value at Xv = 1.0 for 1 to the calculated mobility of a proton at infinite dilution and thus, for 1, there do not appear to be any significant contributions due to tortuosity or proximity of acid groups. A similar approach to determine the mobility of protons at Xv = 1.0 was carried out by Kreuer for Nafion1 and sulfonated poly(ether ether ketone ketone) (SPEEKK) membranes.5,30,34 In his study, proton conductivity measurements were carried out on an SPEEKK sample with a 70% degree of sulfonation and where varying levels of water content were achieved by varying relative humidity. This differs from our study in which the proton conductivity values of our samples with varying IEC values and hence varying water contents were measured in the fully wet state (i.e., membrane was immersed in water prior to measurement). In both studies, the resultant values for proton mobility at Xv = 1.0 determined for this type of polymer were within y10% of the calculated mobility of a free proton at infinite dilution. However, whereas the value for m9H+ at Xv obtained from our study is lower than 3.6 6 1023 cm2 s21 V21, the value derived by Kreuer is higher (estimated to be y3.8 6 1023 cm2 s21 V21 from the literature extrapolation to Xv = 1.0 plot of proton diffusion rate vs. Xv).5,63 The different values for m9H+ at Xv = 1.0 from the two studies may be in part due to the different methods employed. Although we have not to date carried out a similar study (i.e., proton conductivity as a function of relative humidity) for 1, this study has been done for polymers 2 and 4. These results will be reported in a subsequent publication, thus enabling a comparison of the two methods for obtaining a value of m9H+ at Xv = 1.0. In contrast to the value for 1, the theoretical maximum mobility for 2 is 2.9 6 1023 cm2 s21 V21. This is lower than both estimated values for 1 as well as the calculated mobility of a proton in water at infinite dilution. In the case of the
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comparison with 1, the standard deviation range suggests that the differences are not significant but in the case of 2 versus the mobility of a proton in water at infinite dilution, the standard deviation for 2 still predicts a lower value. As was theorized for 1, this may be due in part to the bound SO32 groups restricting the mobility of the protons. This effect could be potentially further magnified by the potentially cross-linked nature of 2, leading to increased tortuosity and thereby decreasing the overall mobility of the protons. For 3, the calculated value for m9H+ value at Xv = 1.0 was found to be approximately 1.6 6 1023 cm2 V21 s21. This is the lowest calculated value for m9H+ at Xv = 1.0 for all of the studied PEMs, even when taking the large standard deviation of the value into account. Again, as previously discussed for 1 and 2, this is probably due in part to the bound sulfonate counter-ions. Also, this observed result potentially arises due to the restrictions imposed on the protons due to the relative inflexibility of the polymer backbone in comparison to 1 and 4. In the case of 2, cross-linking is potentially present in the hydrophobic region of the membrane and hence possibly does not have as much influence on proton mobility, as does a relatively inflexible polymer where the sulfonic acid groups are present on the polymer backbone. In the case of 4, the estimated value for m9H+ at Xv = 1.0 is 2.1 6 1023 cm2 s21 V21. This value is lower than the range observed for 1 and 2 ((2.93.2) 6 1023 cm2 V21 s21) and considerably lower than the theoretical value for a free proton at infinite dilution (3.6 6 1023 cm2 V21 s21). In common with the previous examples, this deviation from the theoretical value at infinite dilution may be partially explained by the restriction imposed on the protons by the bound anionic SO32 groups. However, the explanation used for the lower m9H+ value at Xv = 1.0 of 2 in comparison to 1 cannot be applied at 4 as it seems very unlikely that there are any potential cross-links present in 4. Furthermore, given that 4 appears to swell in the presence of water even more readily than does 1, it may have been anticipated that this PEM would more closely approach the infinite dilution value than either 1 or 2. At this point, it is not clear what the nature of the tortuosity and/or proximity of acid groups might be in the case of 4 to cause the observed low value.

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found to be significantly lower. The differences in mobility at infinite dilution were considered as being potentially a consequence of the different chemical structures for these systems that give rise to different levels of tortuosity and proximity of acid groups. In comparing the sulfonated derivatives of an aromatic polymer (1), a polyaromatic rigid rod polymer (3), a vinylic polymer (4) and a vinylic polymer polymerized inside a preformed matrix (2), the preformed PEM (2) possesses higher Xv and, therefore, higher [SO3H] at higher IEC but at the cost of lower m9H+ values. In contrast, 1 and 4 swell excessively at higher IEC such that [SO3H] is diluted although m9H+ values are higher. Overall, m9H+ values loosely vary linearly with Xv over the range 0.3 A 1.0, and linearly with l over the range 10 A 30. Subsequent publications will detail results of this analysis as applied to other PEM systems (e.g., block copolymers and side-chain sulfonated polymers) as well as PEMs in which ion content is fixed and water content is varied as a function of relative humidity.

4.0 Experimental
4.1 Membranes As received Nafion1 117 (Du Pont) (5) and BAM1 membrane (4) (supplied by Ballard Advanced Materials) were used in this work. Nafion1 membrane was supplied as a single sulfonic acid content polymer whereas a five membrane series of BAM1 membrane was supplied with a wide range of sulfonic acid contents. Dry BAM1 membranes were first hydrated in Milli-Q (18 MV) water (Millipore Systems) for 24 hours, protonated by submersing in 0.5 M H2SO4 for 48 hours at room temperature, and subsequently rinsed and stored in Milli-Q water for at least 24 hours prior to use. Impurities in Nafion were cleaned by boiling in a 3 vol% H2O2 solution for 2 hours, boiling in Milli-Q H2O for two hours, boiling in 0.5 M H2SO4 for two hours and finally boiling in Milli-Q H2O for 2 hours. Nafion1 membranes were stored in Milli-Q water prior to use. The synthesis and preparation of sulfonated linear polyimide membranes (4) has been described previously.59 Radiation-grafted ETFE-g-PSSA membranes (2) were provided by K. Lovell and co-workers (Cranfield University, UK). A detailed description of the synthesis of ETFE-g-PSSA membranes is described elsewhere.64 SPEEK was obtained from PEEK (Victrex, Mn y 110 000) using a literature procedure.62 4.2 Water content analysis Circles (8.48 mm diameter) were cut from fully hydrated sheets and soaked in Milli-Q water for a minimum of 12 hours prior to use. Wet weights, Wwet, were obtained after blotting with a Kimwipe to remove surface water. This was carried out on as short a time scale as possible (,30 s) to avoid water loss to the atmosphere. Dry weights, Wdry, were obtained after membranes were vacuum (1 mmHg) dried to constant weight (0.0005 g) at 80 uC and cooled in a desiccator. For all samples, constant weight was achieved after drying for 2 hours. Membrane volumes were obtained for both wet, Vwet, and dry, Vdry, samples by measuring diameter, d, with a caliper
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3.0 Conclusion
A more in-depth analysis of the proton conductivity data has been developed and provided additional information on the observed proton conductivity behaviour for a series of mainchain, statistically sulfonated PEMs. The analysis has shown the strong links between conductivity and the combination of acid and water content. In addition, it has been shown that at least in the case of one polymer system (4), higher ion content actually leads to lower values for proton conductivity due to very high water uptakes and a resultant dilution of available protons. In order to remove the effect of differing acid strengths of the PEMs, values for proton mobility at infinite dilution (Xv = 1.0) have also been estimated for 14. Whereas the calculated value for 1 and 2 are close or within error identical to the value for the mobility of a free proton at infinite dilution, the corresponding values for 3 and 4 were
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(0.1 mm) and thickness, h, with a micrometer (0.001 mm) and applying the following relationship (eqn (10)): Volume = 0.25pd2h
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(10)

Membrane water content was calculated as a weight percentage (eqn (11)): Water Content wt%~ 4.3 Ion exchange capacity Ion exchange capacity (milliequivalents per dry gram of polymer), IEC, is used to describe sulfonic acid content. It was determined using a direct titration method. Circular samples were cut and placed in 2 M HCl and stirred for 12 hours. The membrane was then transferred to a new beaker containing Milli-Q water and stirred for 30 minutes, after which the water was decanted and replaced with fresh water and stirred for another 30 minutes. This process was repeated two more times. The acidified membranes were then immersed in 50 mL of NaCl (2.0 M) solution for 2 hours, with occasional agitation, and titrated with standardized NaOH (0.025 M) to the phenolphthalein endpoint. After titration the membranes were placed for 1 hour in 0.1 M HCl, rinsed with distilled water and dried under vacuum (1 mmHg) at 80 uC to a constant weight. The ion exchange capacity was calculated as follows (eqn (12)): IEC mmol SO3 H g{1 ~ vol: NaOH, mL|conc: NaOH, M dry wt: of membrane, g 4.4 Proton conductivity Proton conductivity was measured using AC impedance spectroscopy with a Solartron 1260 frequency response analyzer (FRA) employing a transverse two-electrode configuration. Rectangular samples (y1 6 2 cm) of hydrated membranes were cut to the required dimensions (length, L, and width, W, measured using a calliper, 0.1 mm, and thickness, h, using a micrometer, 0.001 mm). To ensure complete protonation samples were soaked in 0.5 M H2SO4 for 24 hours followed by soaking in Milli-Q water for a minimum of 12 hours prior to use. Samples were removed from water, blotted with a Kimwipe to remove surface water, and laid across two Pt electrodes (0.5 6 1 cm) 1 cm apart fixed in place by attaching to an inert Teflon block (2 6 2 cm). Another Teflon block was placed on top and four nylon screws were used to hold the probe together during measurement. Both blocks have identical 1 6 1 cm holes cut out of the centre to allow for membrane equilibration with the atmosphere where necessary (see Fig. 17). Two wires fitted with alligator clips connected the probe to the FRA and ionic resistance was measured by applying a 100 mV sinusoidal AC voltage between the two platinum electrodes over a 10 MHz100 Hz frequency range and measuring the AC resistance (i.e., impedance). Probe assembly was carried out on as short a time scale as possible (,1 min) to
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Wwet {Wdry Wdry

(11)

Fig. 17 Pt/Teflon1 conductivity probe.

(12)

keep the samples from losing water to the atmosphere before completion of the measurement. Data were analyzed using Zplot software (Scribner) and a detailed explanation of the analysis (using BAM1 membranes as examples) is included in the next section. Fig. 18 shows typical complex-plane plots of the imaginary impedance (Z0) versus real impedance (Z9) for 5 BAM1 membranes of various sulfonic acid contents (IEC 1.36, 1.86, 1.96, 2.20, 2.46 mmol g21). Nafion1 is included for comparison. A series of semi-circles is the result where the size of the semi-circle varies with IEC and membrane dimensions. The complex-plane plot for BAM1 membrane (IEC = 2.46) (Fig. 19) is highlighted as an example of how ionic resistance was abstracted from the impedance data. Fitting was performed by non-linear least squares regression to a Randles equivalent circuit model. It consists of the membrane capacitance, Cm, acting in parallel with the membrane ionic resistance, Rm. A contact resistance, Rc, arising from the membrane/electrode interface acts in series with the above. In essence, the data can be approximated by taking the difference between the high frequency and low frequency x-intercepts, i.e., semi-circle diameter. All BAM1 membrane complex-plane plots fit near perfect semi-circles indicating that the Randles equivalent circuit model was a reasonable choice for this system. The low values of contact resistance measured, Rc, compared to that of

Fig. 18 Complex-plane plots obtained by AC impedance spectroscopy for BAM1 membranes with various IEC values.

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Table 3 Polymer 1

Summary of data for Fig. 516 IECa lb Xv sH+c 0.038 0.066 0.098 0.12 0.14 0.15 0.17 0.20 0.057 0.12 0.14 0.10 0.095 0.014 0.059 0.11 0.093 c S cm21. m9H+d [SO3H]e

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Fig. 19 Complex-plane plot for BAM1 membrane (IEC = 2.46).

1.99 13 0.35 2.14 15 0.40 2.30 19 0.49 2.45 24 0.53 2.56 42 0.66 2 2.13 22 0.58 2.56 24 0.63 3.27 29 0.73 3 1.36 14 0.29 1.85 24 0.55 1.96 31 0.62 2.20 76 0.82 2.46 84 0.85 4 1.77 15 0.29 1.95 24 0.42 2.70 26 0.62 5 0.91 20 0.41 a mmol g21. b mol H2O mol21 SO3H. e mol L21.

0.26 1.52 0.45 1.52 0.73 1.40 1.02 1.22 1.67 0.88 0.85 1.78 1.19 1.46 1.59 1.28 0.50 1.19 0.97 1.27 1.30 1.12 1.74 0.60 1.74 0.56 0.14 1.12 0.61 0.94 0.83 1.41 0.87 1.11 d 1023 cm2 s21 V21.

membrane resistance (,1%) indicate that there is sufficient contact between the Pt electrodes and membrane surface. The ionic resistance was used to calculate proton conductivity, sH+, according to the following relationship (eqn (13)): sHz ~ L Rm A (13)

where N = number of data points and where Sxx and Syy are defined as follows by eqn (18) and (19) respectively: Sxx = S(xi 2 x )2 Syy = S(yi 2 y )2 (18) (19)

where L is the spacing between the Pt electrodes (1.0 cm), A is the cross-sectional area of the membrane (W 6 h), and Rm is the ionic resistance of the membrane. 4.5 Linear regression analysis Linear regression analyses for m9H+ as a function of Xv were performed using Microsoft1 Excel1 2004 for Mac Version 11.3 to fit the data to eqn (14): y = mx + b (14)

The results of the regression analysis can be found in Table 2. A summary of all the data used in Fig. 516 can be found in Table 3.

Acknowledgements
We would like to thank Mr Keith Lovell and Dr Jackie Horsfall of Cranfield University for providing the samples of ETFE-g-PSSA (2) and Dr Ana Siu for determining its conductivity data. We are also grateful to Ballard Advanced Materials for providing the samples of BAM1 membrane (4) used for our conductivity studies. Finally, we would like to thank the Natural Sciences and Engineering Research Council of Canada for providing the funding for this project.

where y = m9H+, x = Xv, m = slope of line and b = y-intercept. Standard deviations for the residuals (sy), m (sm) and b (sb) were determined using eqn (15), (16) and (17) respectively: r Syy {m2 Sxx sy ~ (15) N {2 v u 1 u P 2 sb ~sy u t xi N { P x2
i

References
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(16)

sm ~sy

.p Sxx

(17)

Table 2 Results of linear regression analysis (m9H+ as a function of Xv) for 14 m/cm2 s21 Polymer V21 1 2 3 4 4.6 4.8 2.0 2.3 6 6 6 6 1023 1023 1023 1023 s.d./cm2 s21 b/cm2 s21 V21 V2 1 3 4 7 2 6 6 6 6 1024 1024 1024 1024 21.4 6 1023 21.9 6 1023 24 6 1024 22 6 1024 s.d./cm2 s21 V2 1 R2 2 3 3 1 6 6 6 6 1024 1024 1024 1024 0.984 0.991 0.890 0.985

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