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Selectivity of Direct Methanol Fuel Cell Membranes

Article  in  Membranes · November 2015

DOI: 10.3390/membranes5040793

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Membranes 2015, 5, 793-809; doi:10.3390/membranes5040793
OPEN ACCESS

membranes
ISSN 2077-0375
www.mdpi.com/journal/membranes
Article

Selectivity of Direct Methanol Fuel Cell Membranes

Antonino S. Aricò 1,*, David Sebastian 1, Michael Schuster 2, Bernd Bauer 2, Claudia D’Urso 1,
Francesco Lufrano 1 and Vincenzo Baglio 1

1
CNR-ITAE Institute for Advanced Energy Technologies “N. Giordano”,
Via Salita S. Lucia sopra Contesse 5, Messina 98126, Italy; E-Mails: [email protected] (D.S.);
[email protected] (C.D.U.); [email protected] (F.L.); [email protected] (V.B.)
2
FuMA-Tech Gesellschaft für funktionelle Membranen und Anlagentechnologie mbH, Carl-Benz-
Strasse 4, Bietigheim-Bissingen D-74321, Germany; E-Mails: [email protected] (M.S.);
[email protected] (B.B.)

* Author to whom correspondence should be addressed; E-Mail: [email protected];

Tel.: +39-090-624237; Fax: +39-090-624247.

Academic Editor: Bruno Scrosati

Received: 21 October 2015 / Accepted: 17 November 2015 / Published: 24 November 2015

Abstract: Sulfonic acid-functionalized polymer electrolyte membranes alternative to

Nafion® were developed. These were hydrocarbon systems, such as blend sulfonated
polyetheretherketone (s-PEEK), new generation perfluorosulfonic acid (PFSA) systems,
and composite zirconium phosphate–PFSA polymers. The membranes varied in terms of
composition, equivalent weight, thickness, and filler and were investigated with regard to
their methanol permeation characteristics and proton conductivity for application in direct
methanol fuel cells. The behavior of the membrane electrode assemblies (MEA) was
investigated in fuel cell with the aim to individuate a correlation between membrane
characteristics and their performance in a direct methanol fuel cell (DMFC). The power
density of the DMFC at 60 °C increased according to a square root-like function of the
membrane selectivity. This was defined as the reciprocal of the product between area specific
resistance and crossover. The power density achieved at 60 °C for the most promising s-
PEEK-based membrane-electrode assembly (MEA) was higher than the benchmark Nafion®
115-based MEA (77 mW·cm−2 vs. 64 mW·cm−2). This result was due to a lower methanol
crossover (47 mA·cm−2 equivalent current density for s-PEEK vs. 120 mA·cm−2 for Nafion®
115 at 60 °C as recorded at OCV with 2 M methanol) and a suitable area specific resistance
(0.15 Ohm cm2 for s-PEEK vs. 0.22 Ohm cm2 for Nafion® 115).
Membranes 2015, 5 794

Keywords: proton exchange polymer electrolyte membranes; direct methanol fuel cells;
methanol crossover; proton conductivity; membrane selectivity; fuel cell performance

1. Introduction

Direct methanol fuel cells (DMFCs) based on solid protonic electrolytes and operating at low
temperatures (up to 90 °C) are widely considered for application in portable power sources, remote
energy generation, and auxiliary power units (APU) in both stationary and mobile applications [1,2].
The specific advantages of such systems over the competing technologies are related to their simplicity
of operation, high energy density, lightweight, compactness, and fast refilling properties. DMFCs utilize
methanol as liquid fuel to deliver continuous power; in this regard, they have fewer constraints than
hydrogen-fueled fuel cells in terms of fuel handling, refueling, and fuel storage processes. However,
there are still specific drawbacks for DMFCs in terms of high cost and low performance, and the stability
needs to be improved [2,3]. The main objective of the research in the field of direct methanol fuel cells [3–7]
is to develop cost-effective catalysts and membranes with enhanced properties in order to reduce stack
costs and improve performance and durability. Concerning the membrane, the main purpose of the
developmental activities is to provide enhanced conductivity at a reduced methanol crossover [8]. In
principle, the conductivity of the state-of-the-art Nafion® membrane, which is in the range of 0.1 S·cm−1,
appears very appropriate for DMFC devices but the methanol permeability for this polymer electrolyte
is unfortunately also significant, especially under open circuit conditions [3,9].
Both methanol crossover and conductivity increase in hydrophilic membranes with the membrane
hydration level (λ). Thus, an enhancement of one of these properties will have a significant impact on
the other. Methanol has high interaction with polymer chains and high solubility in water, and its permeation
easily occurs through the hydrophilic water channels inside the membrane. A network of widely distributed
and interconnected ionic domains that, under proper hydration, give rise to water channels, is essential
to achieve a high proton conduction in these membranes. Perfluorinated membranes containing sulfonic
acid functionalities, such as Nafion®, are, at present, the best performing systems at temperatures lower
than 90 °C. This is due to a proper combination of proton conductivity, mechanical and hydrolytic
stability, as well as good interface properties. The sulfonic acid groups are characterized by a high level
of dissociation in the presence of suitable water contents. Membrane ionic conductivity is essentially
promoted by proton diffusion through the vehicle mechanism [10–13]; according to this mechanism,
protons are transported by water molecules.
Reduction of methanol crossover can be achieved by using cross-linking procedures or adding
nanosized inorganic fillers inside the membrane to increase the tortuosity path as well as by tuning
the ion exchange capacity (IEC) [2,14].
Another approach considers the variation of the chemical properties of the polymer network
surrounding the ionic groups to modulate the degree of dissociation as well as the degree of
interpenetrated networks [15–17].
These approaches can reduce the level of methanol permeation permeability while keeping the proton
conductivity at suitable levels. This allows us to achieve both convenient fuel utilization and appropriate
Membranes 2015, 5 795

power density since the lower the methanol permeation the smaller are the effects related to the
occurrence of a mixed potential at the cathode [1]. Accordingly, the cathode is less polarized in the
presence of lower methanol permeation. This corresponds to lower overpotentials for the oxygen reduction
reaction [18,19]. This strategy is further assisted by using methanol-tolerant cathode electro-
catalysts with high activity for oxygen reduction [18,19].
It is considered that the occurrence of ionic conductivity better than 50 mS·cm−1 and methanol
crossover lower than 5 × 10−6 mol·cm−2·min−1 for a membrane with a thickness lower than 100 µm in
the presence of low overpotentials for anode/cathode reactions (<0.3 V at 100 mA·cm−2) may result in
an appropriate performance (>50 mW·cm−2 at 60 °C) in the presence of moderate catalyst loading
(1–2 mg·cm−2). A suitable level of power density together with a proper fuel utilization are the main pre-
requisites for fuel cells to compete with batteries in portable power systems and to find application as
alternative power generators in auxiliary power units. In this regard, a more in-depth understanding of
the influence of membrane properties on the performance of DMFCs is necessary.
The present work was addressed to study the effect of varying membranes properties such as methanol
permeability, thickness, and proton conduction on the behavior of direct methanol fuel cells. The
investigated membranes were essentially perfluorinated systems and aromatic hydrocarbon polymers,
such as polyetheretherketone (PEEK), functionalized with sulfonic acid groups. These polymer electrolytes
were varied in terms of equivalent weight, composition, filler content, thickness,
cross-linking to modulate the proton conductivity, and methanol permeability with the aim to investigate
their influence on the DMFC performance.

2. Results and Discussion

2.1. Membrane Characteristics

Proton exchange membranes based on hydrocarbon and perfluorosulfonic acid-type polymers

were developed. Various compositions (nature of polymer backbone, presence or absence of an inorganic
component or cross-linking), polymer equivalent weight (EW), and membrane thickness have been
explored. FuMA-Tech developed a range of low IEC (high EW) membranes designed for low methanol
crossover that were based upon long side chain (Fumion) PFSA blends [20,21]. The nominal EWs of
these membranes were 1400, 1800, and 2300 g/mol. Another series of FuMA-Tech PFSA membranes
incorporated a stabilizer (labeled as FX) to mitigate radical attack. FuMA-Tech also prepared blend
membranes of various thicknesses based upon sulfonated polyetheretherketone, with only 30 µm thickness
in one case (E-730) [12,22]. Another approach at FuMA-Tech was dealing with composite membranes
based on a PFSA polymer where zirconium phosphate nanoparticles were integrated into the PFSA
polymer matrix. These composite membranes based on zirconium phosphate (ZrP = Zr(HPO4)2·H2O)
and perfluorosulfonic acid polymer (PFSA) are labeled as fumapem® FZP. Inclusion of ZrP into a PFSA
matrix is known to increase mechanical stability at elevated temperatures [23,24]. Furthermore, the
presence of layered ZrP nanoparticles in the PFSA polymer matrix may also reduce methanol
crossover [23,25]. This approach allowed the continuous production of composite membranes using the
standard production procedure for membranes at FuMA-Tech where the ZrP nanoparticles were formed
in situ during the casting process.
Membranes 2015, 5 796

The main properties of the most promising membranes in comparison to Nafion 115 are discussed
in detail in the following. Among the long side chain (Fumion), PFSA blends with nominal EWs
of 1400, 1800, and 2300, the F-1850 (EW = 1800) membrane provided promising conductivity values
of 47 mS/cm at 60 °C and 84 mS/cm at 100 °C (measured at 95% RH).
The high-EW PFSA membranes named fumapem® F-1850 (FuMA-Tech) had an EW = 1800 g/mol
and a thickness of 50 µm. This was selected as the best compromise between area resistance, methanol
permeation, fuel cell performance, mechanical strength, processability, handleability, and material cost.
A key features of the fumapem® 1850 was a reduced area resistance while maintaining methanol
permeability lower than Nafion® 115. This resulted in a better DMFC performance than Nafion® 115 at
60 °C. However, most important is the fact that fumapem® F-1850 has the potential to reduce the cost
of materials by a factor of 4 compared to Nafion® 115. FuMA-Tech also prepared blend membranes of
various thicknesses based upon sulfonated polyetheretherketone. The E-730 membrane, even at only 30
µm in thickness, had a reasonably low methanol crossover, and therefore good fuel utilization and high
power density.
Ex situ characterization data of fumapem® F-1850 and E-730 membranes are shown in Table 1 in
comparison to Nafion® 115. This table also includes the FZP960 and FX7050 membranes to provide
a dataset of the properties of the most promising membranes for each composition.

Table 1. Ex situ characterization data of the most promising Fumatech membranes for each
category compared to Nafion® 115.
Membrane Acronym F-1850 E-730 FZP-960 FX-7050 N-115
Unit
Polymer Type PFSA sPEEK PFSA-ZrP PFSA Cross-Linked PFSA
Filler content – – – 10% – –
EW (theoretical) g/mol 1800 740 950 7000 1100
IEC (exp.) mmol/g 0.50 1.35 0.83 0.63 0.9
Thickness (dry) µm 50 30 60 50 125
Solvent uptake in MeOH at 25 °C Wt % 30 38 115 33 54
Length increase Δl in MeOH at 25 °C % 18 10 46 8 31
Conductivity in H2O at T = 25 °C mS·cm−1 58 16 23 56 62

Conductivity, swelling, and methanol uptake varied significantly in these membranes as a

consequence of different chemistry and equivalent weight.
Three composite membranes containing ZrP (FZP-960, FZP-990 and FZP-9110) with equivalent
weight 950 g/mol and thicknesses of 60, 90, and 110 µm were prepared. Ex situ conductivity
measurements in water at room temperature of ZrP-PFSA composite membranes (FZP series) showed
conductivities between 40 and 70 mS·cm−1 after activation, close to standard PFSA membranes. Without
activation, all fumapem® FZP membranes showed a conductivity around 10 mS·cm−1. The conductivity
of FZP9110 was 68 mS·cm−1; this favorably compared to that observed for Nafion, 62 mS·cm−1, under
similar conditions. However, no significant reduction of the swelling behavior in methanol at high
concentrations was observed for this series of membranes, rather a slight increase compared to Nafion®
115. An approach was devoted to prepare a PFSA ionomer containing a chemical/mechanical stabilizer,
mainly intended to reduce swelling in methanol. Membranes with different amounts of stabilizer were
produced; these membranes are labeled as fumapem® FX (stabilized PFSA). Overall, the addition of a
Membranes 2015, 5 797

stabilizer obviously had a weakening effect on the membrane mechanical properties when treated with
methanol solution; however, by increasing the amount of stabilizer, the membrane swelling in methanol
was again reduced. Unfortunately, increasing the amount of stabilizer meant that the conductivity
decreased. For DMFC testing, fumapem® FX-7050 was selected for this series because it showed the
lowest swelling in methanol but still sufficiently high conductivity. The FX-7050 consisted of an
equivalent weight of 7000 and had a thickness of 50 µm.

2.2. Electrochemical Properties

The membranes were investigated at CNR-ITAE in DMFC, at different temperatures, to get insights
into their practical applications. The membranes were characterized in terms of polarization behavior
under fuel cell conditions, cell resistance during operation (by ac-impedance spectroscopy), analysis of
the equivalent methanol crossover current density, and compared to the benchmark Nafion® 115 benchmark
membrane. Catalyst loading was 2 mg PtRu·cm−2 at the anode and 1 mg Pt·cm−2 at the cathode.
The crossover of methanol was determined using two methods. One method concerned the analysis
of the exhaust gas at the cathode side of the DMFC single cell under open circuit voltage (OCV). The
CO2 produced by the oxidation of the methanol permeated to the cathode was analyzed using an
online micro-gas chromatograph; the second approach consisted of a linear sweep voltammetry of the
DMFC operating in a driven-mode with the cathode fed with inert gas [26]. In the latter case, methanol
permeated to the cathode was completely oxidized at high electrochemical potentials (>0.9 V). Both
methods provided consistent results. Methanol concentrations of 1, 2, and 5 M were investigated. In both
procedures, sampled aliquots of the condensed cathode stream were analyzed in a bench
gas-chromatograph equipped with a flame ionization detector. Only traces of unreacted methanol were
detected in the condensed stream from the cathode.
As is well known, methanol crossover decreases with the operating current density [2,3]. In our analysis,
we have preferred to measure methanol crossover under OCV since this condition corresponds to the
maximum conversion of permeated methanol to CO2 at the cathode due to the high electrochemical potential.
Figure 1 provides a comparison of methanol crossover values for some of the investigated membranes
and the commercial Nafion® 115 in the presence of 1 and 5 M methanol. This measurement was carried
out by analyzing the CO2 at the cathode using the online gas chromatograph. The crossover increased in
the order E-730 < F-1850 < Nafion®-115.
In general, crossover values are affected by methanol uptake, permeability and membrane thickness.
However, thick membranes can result in high cell resistances, and this leads to performance losses.
The polarization and power density (P.D.) curves, obtained at 60° and 90 °C for various MEAs based
on different membranes, are reported in Figures 2 and 3. From these curves, it appears that the MEA
based on s-PEEK (E-730) is the best performing one for operation in the low temperature range. At low
temperatures, the performance obtained with the E-730 membrane was higher than that achieved with
Nafion® 115 membrane and similar to the fumapem® F-1850.
Membranes 2015, 5 798

Figure 1. Methanol crossover for selected membranes under different operating conditions
of temperature and methanol concentration; crossover was here determined at open circuit
voltage (OCV) during normal DMFC operation by measuring the CO2 evolved at the cathode
using an in-line chromatograph.

Figure 2. Polarization and power density curves for different membranes in MEAs at
60 °C, 2 M methanol.
Membranes 2015, 5 799

Figure 3. Polarization and power density curves for the different membranes in MEAs
at 90 °C, 2 M methanol.

The main results in terms of performance, crossover, and area-specific resistance recorded at 60 °C
and 90 °C are summarized in Table 2. All data in Table 2 are for DMFC operation with 2 M methanol
and the reported crossover measurements were carried out in this case by linear sweep voltammetry with
the DMFC cell operating in the driven mode.
The E-730 membrane showed better performance than Nafion® at 60 °C (77 vs. 64 mW·cm−2) as a
result of the much lower methanol crossover (48 vs. 110 mA·cm−2 equivalent current density). The thin
F-1850 membrane, characterized by an equivalent weight of 1800, performed much better than the
F-18120 characterized by same EW but had a larger thickness (50 µm vs. 120 µm). The membrane with
similar chemistry e.g., the F-2350 with 50 µm thickness, but having larger EW, i.e., 2300, exhibited
lower performance. If we compare at 60 °C the power density of the most promising PFSA membrane,
i.e., F-1850, to the Nafion® 115 benchmark, it clearly appears that a performance increase of about 15%
is achieved for the FUMATECH membrane. This enhanced performance is essentially due to the lower
methanol crossover. At 60 °C, methanol crossover for the F-1850 was less than half that of Nafion®
despite the fact that the F-1850 membrane was much thinner. The maximum power densities of 74 and
77 mW·cm−2 at 60 °C for the F-1850 and E-730 were quite promising considering the reasonably low
catalyst loading.
At 90 °C, Nafion® 115 performed better than the other membranes in terms of peak power density.
This can be interpreted by the fact that at high temperatures, the poisoning effect caused on
the cathode by methanol crossover is less dramatic since at 90 °C methanol species are not strongly
adsorbed on the electrode surface [27]. This provides a better capability to the O2 molecules to compete
for adsorption on the cathode surface. Under these conditions, the excellent interfacial properties of
Nafion® play a significant role. However, the effect of crossover is still relevant for Nafion®, especially
at low current densities.
Membranes 2015, 5 800

Table 2. Electrochemical characteristics of the membranes in DMFC (2M CH3OH).

Membrane
E-730 E-750 F-1850 F-18120 F-2350 FZP-960 FZP-990 FZP-9110 FX-7050 Nafion® 115
Acronym Units
Polymer Type s-PEEK s-PEEK PFSA PFSA PFSA PFSA-ZrP PFSA-ZrP PFSA-ZrP PFSA Cross-Linked PFSA
Equivalent weight g/mol 700 700 1800 1800 2300 950 950 950 7000 1100
thickness µm 30 50 50 120 50 60 90 110 50 125
−2
mW·cm
Max. Power density 77 17 74 36 50 64 32 35 42 64
@ 60 °C
Ω cm2
Rs (EIS) 0.20 0.62 0.20 0.50 0.31 0.085 0.29 0.33 0.13 0.17
@ 60 °C
mA·cm−2
Crossover current 48 106 120 100 88 128 135 208 186 195
@ 60 °C
mW·cm−2
Max. Power density 145 42 116 64 80 129 55 84 67 167
@ 90 °C
Ω cm2
Rs (EIS) 0.14 0.23 0.16 0.38 0.34 0.06 0.21 0.24 0.12 0.14
@ 90 °C
mA·cm−2
Crossover current 74 185 193 123 121 153 162 245 260 380
@ 90 °C
Membranes 2015, 5 801

From this survey, it appears that thin membranes, both bare and composite ones, are better performing
than the thicker ones in the same series. The membrane based on s-PEEK, 30 µm in thickness (E-730),
provides higher performance and more moderate methanol crossover than the membrane based on the
same polymer with 50 µm in thickness (E-750) characterized by a larger cell resistance. The same
behavior was recorded with the 50-µm membrane based on PSFA (F-1850) compared to the thicker
F-18120 (120 µm). The three composite membranes containing Zr-phosphate appeared less promising,
similarly to the cross-linked FX-7050 membrane containing the stabilizer.
The membrane based on s-PEEK (E-730) was the best performing one for operation in the low
temperature range. At 60 °C, the performance for the E-730 membrane was better than that obtained
with Nafion® 115 membrane and slightly better than the fumapem® F-1850 (see Table 2).

2.3. Membrane Selectivity

To better understand the combined effect of membrane conductivity, thickness, and methanol
permeation, we have here calculated the membrane selectivity, s, as the reciprocal of the product of
the area-specific resistance (series resistance), Rs, multiplied by the crossover equivalent current
density, Icrossover:
s = 1/(Rs·Icrooss-over), (1)
where s ≡ S·mA−1; Rs ≡ Ohm cm2 and Icrossover ≡ mA·cm−2; S ≡ Siemens.
The area-specific resistance or series resistance was measured in situ using ac-impedance spectroscopy;
this parameter includes both the contributions of membrane conductivity and thickness:
Rs = t/σ, (2)
where Rs is the series resistance (ohm cm2); t is the thickness (cm) and σ is the conductivity
(ohm−1·cm−1 or S·cm−1).
By analyzing the data obtained at 60 °C in terms of performance (peak power density, mW·cm−2) vs.
membrane selectivity, a steep increase of performance with selectivity is observed for low values of
selectivity, whereas the trend is less steep when the selectivity of the membrane further increases
(Figure 4). In principle, the performance should approach a plateau for very high selectivity values, e.g.,
for membranes with low area0specific resistance and very low crossover. In the investigated range, ionic
conductivity appears sufficiently high and membrane thickness reasonably low for DMFC applications,
whereas methanol crossover should be further decreased. The observed trend would suggest an increase
of performance with selectivity according to a square root function. In the presence of very small
methanol permeability, the anode characteristics should dominate the cell performance, providing that
the membrane is characterized by suitable area-specific resistance. Thus, the membrane selectivity
(defined as indicated above) appears to be a key parameter to guide the development of DMFC
membranes for portable and APU applications. In particular, the area-specific resistance, Rs (high
frequency intercepts in the Nyquist plot) includes the contributions of both membrane thickness and
proton conductivity. Thus, the selectivity parameter here defined resumes the contribution of the most
important membrane features: crossover, conductivity, and thickness.
Membranes 2015, 5 802

90

Max power density @ 60°C / mW cm-2

80 E-730
F-1850
70 Nafion115
FZP-960
60
F-2350
50
FZP-9110 FX-7050
40
30 F-18120 FZP-990
20
E-750
10
0
0.000 0.020 0.040 0.060 0.080 0.100 0.120
Membrane selectivity / S mA-1

Figure 4. Performance vs. selectivity for MEAs equipped with different membranes at
60 °C (2 M MeOH).

It should be pointed out that this analysis covers different families of membranes such as low-EW
PFSA (Nafion®), high-EW PFSA, sPEEK, composite PFSA membranes with inorganic fillers, cross-linked
membranes, etc. Since the interface characteristics also play a relevant role, some data scattering is
observed for this relationship. The best interface properties should occur for Nafion 115 membrane since
the catalytic layers contain an ionomer of the same chemical composition. The Nafion ionomer
dispersion was kept constant in the various MEAs.
At low temperature conditions (60 °C), the electrode–electrolyte interface probably plays a minor
role provided that MEAs are assembled using the same procedure.
An appropriate regression of the performance data recorded at 60 °C gives a square root relationship
between power density and selectivity, as reported below:
P.D. = k s0.5. (3)
At 60 °C, P.D. ≈ 260 s0.5.
Thus the power density can be estimated, for this series of MEAs, from the square root function of
the selectivity and a multiplication factor being P.D. ≡ mW·cm−2, s ≡ Ohm−1·mA−1 and the multiplication
factor: k ≡ V·mA1.5·Ohm0.5·cm−2.
Less evident is the trend at 90 °C (Figure 5). In this case, there are just two groups of membranes:
one having low selectivity and showing very low or very high power density; and a second group with
just two membranes having high selectivity and high power density. The square root function cannot be
used to fit the data at 90 °C with such large scatter. It is reasonable to consider that, since at 90 °C the
effect of cathode poisoning by methanol crossover is less relevant (the selectivity parameter includes the
crossover effect), the effect of the quality of the electrode–electrolyte interface plays
a major role in determining the performance [14,27]. This is quite clear for Nafion® since the ionomer
dispersion used in the electrodes was of the same composition as in the membrane, whereas, for the other
membranes, there may be less compatibility with the Nafion® ionomer in the electrodes.
Membranes 2015, 5 803

180

Max power density @ 90°C / mW cm-2

Nafion115
160
140
E-730
F-1850
120 FZP-960
100
FZP-9110 F-2350
80
F-18120 FX-7050
60
FZP-990
40 E-750
20
0
0.000 0.020 0.040 0.060 0.080 0.100 0.120
Membrane selectivity / S mA-1

Figure 5. Performance vs. selectivity for MEAs equipped with different membranes at
90 °C (2 M MeOH).

Ac-impedance spectra for selected membranes, recorded in the galvanostatic mode i.e., at a current
density of 75 mA·cm−2, are shown in Figure 6. This current density corresponds to the region where
activation phenomena and methanol crossover play a relevant role. Two overlapping semi-circles
are evident. The ac-impedance profile of the DMFC cell is similar to that generally reported in the
literature [28,29]. In previous studies, the semicircle at low frequencies was in good part associated to
the cathode poisoning by methanol crossover [28,29]. Thus, it can be underlined that under such
conditions the total impedance is significantly affected by the crossover of methanol. At higher current
densities, the poisoning effect of the crossover decreases whereas series resistance (high frequency
intercept on the x-axis), mainly associated with the membrane conductivity and thickness, remains
almost constant. However, the contribution of the series resistance to the total impedance increases as
the current density increases because of the decrease of the polarization resistance (the difference
between the low and high frequency intercept on the x-axis) [28]. Ac-impedance analysis indicates that
the effect of cathode poisoning by methanol crossover is more significant than the series resistance in a
relevant portion of the polarization curve corresponding to high voltage efficiency for most of the
membrane systems investigated here. The situation is different for membranes with low conductivity
(e.g., E-750), especially at high current densities. The overall results clearly show that the membrane
selectivity is one of the main parameters determining the peak power density of DMFCs in the low
temperature range (60 °C).

Figure 6. Ac-impedance plots for selected MEAs equipped with different membranes at
60 °C (2 M MeOH, 75 mA·cm−2).
Membranes 2015, 5 804

3. Experimental Section

Long side chain (Fumion®) PFSA blends with 1800 and 2300 equivalent weight (e.g., fumapem®
F-1850, F-18120, and F-2350), hydrocarbon membranes based on sPEEK (e.g., fumapem® E-730 and
E-750), composite membranes based on zirconium phosphate (ZrP = Zr(HPO4)2·H2O) and perfluorosulfonic
acid polymer (e.g., fumapem® FZP 960 and FZP 990), and cross-linked PFSA membranes (e.g., FX-7050)
were prepared at Fumatech using procedures reported elsewhere [20–23,30,31]. The main characteristics of
these Fumatech membranes in terms of composition, equivalent weight, and preparation methods are
reported in Figure 7.
All the membranes were prepared by solvent casting or extrusion.
Solvent uptake, proton conductivity, and other relevant membrane properties were determined.
Ex situ conductivity was measured in-plane using a four-electrode setup with the membrane in
demineralized water at 25 °C. The cell was connected to an ac-impedance spectrometer. Dimensional
swelling was determined from the increase in membrane dimension (x, y, z directions) on immersion (4
h) in water and methanol. For IEC determination, a treatment of the membrane sample with 0.1 M NaCl
at room temperature was carried out followed by 12 h titration of solution with 0.1 M NaOH. Solvent
uptake of the various membrane samples was carried out by immersing the sample in the solvent at 25 °C
for 1 h followed by removal of solvent from surface by tissue paper and weighting the dry sample in a
vacuum over P2O5 at 50 °C to get a measure of the dry weight.

PFSA  Nafion® 115 / 117

EW = 1100 g/mol extrusion
extrusion

PFSA 
EW = 950 g/mol fumapem® F‐9120 fumapem® FZP‐960

PFSA blend 
EW = 1800 g/mol fumapem® F‐1850 fumapem® FZP‐1840 casting

sPEEK
fumapem® E‐730 fumapem® EZP
EW = 730 g/mol

ZrP composite

Figure 7. Fumatech membranes varying in terms of equivalent weight and preparation

procedures for DMFC applications.

The developed membranes were integrated in membrane–electrode assemblies and investigated in a

direct methanol fuel cell in terms of performance and methanol crossover. The same electrodes were
Membranes 2015, 5 805

used in all experiments. The electrodes consisted of catalytic layers based on 15 wt % Nafion ionomer
(Ion Power, 5 wt % solution, 1100 EW) and 85 wt % catalyst, and commercial backing layers
(E-TEK). A Pt−Ru/C catalyst (1:1 atomic ratio) was used as the anode catalyst; a Pt/C catalyst was used
at the cathode for all MEAs. The same catalyst loading was used for all MEAs. The loadings were 2 mg
(Pt + Ru) cm−2 for the anode and 1 mg·cm−2 Pt for the cathode.
Regarding MEA fabrication, the type of lamination procedure is generally strongly dependent on
the glass transition temperature of the membrane; thus, inappropriate hot pressing procedures may affect
the comparison of membrane characteristics. Lamination at high temperature and pressure may also
affect the crossover characteristics of the membrane by causing membrane thinning and/or penetration
of the catalytic layer inside the membrane during compression.
To assess the different membranes and to compare their behavior to Nafion® in a context where their
properties are not affected by the lamination procedure, MEAs have been assembled in situ. The
compression was kept constant for all the MEAs at 15 kg·cm−2. No thermal treatment was carried out
during the MEA assembling. The recorded performance may be thus lower under these assembling
conditions, but the aim of this analysis was essentially to provide a comparison of the membrane
characteristics in MEAs. These polymer electrolytes have been investigated in direct methanol fuel cells both
at low (60 °C) and high (90 °C) temperatures and compared to the benchmark Nafion® 115 membrane.
The MEAs were tested in a 5-cm2 single cell using a DMFC test station (Fuel Cell Technologies).
The cell was also connected to an Autolab PGSTAT 302 Potentiostat/Galvanostat (Metrohm) equipped
with a FRA impedance module. For polarization curves, a 2 M methanol solution was fed at the anode
with a flow rate of 3 mL·min−1, whereas the oxidant was fed at the cathode under atmospheric pressure
(100 mL·min−1). Area-specific resistance was measured by electrochemical impedance spectroscopy
(EIS) from the high frequency intercept on the real axis of the Nyquist plot. Ac-impedance spectra were
recorded in the galvanostatic mode at 75 mA·cm−2 at 60 and 90 °C.
Methanol crossover for different concentrations of 1, 2, or 5 M (3 mL·min−1) and temperatures of
30°, 60°, or 90 °C, was determined by chromatographic analysis and electrochemical methods. The
exhaust gas at the cathode side of a 5 cm2 DMFC single cell operating under open circuit voltage (OCV)
was analyzed by using an online micro-gas chromatograph (Varian). The CO2 produced by the oxidation
of methanol, permeated to the cathode, was determined. Methanol crossover was also determined
electrochemically with the DMFC operating in the driven mode and using CH3OH (3 mL·min−1) at the
anode side and He (100 cm3·min−1) at the cathode. The methanol permeating the MEA was oxidized at
cathode (Pt catalyst) generating a positive current, which reached a plateau when all methanol was
converted to CO2 under steady state conditions [26]. The crossover measurements were carried out by
using the linear sweep voltammetry (LSV) mode with a voltage scan rate of
2 mVs−1 and in the voltage range from 0 to 0.95 V. A Metrohm Autolab instrument was used for
performing the linear sweep voltammetry.

4. Conclusions

FuMA-Tech developed a new generation of fluorinated membranes for DMFC application. Several
of these systems had ion exchange capacities of 0.4 and 0.5 meq/g, which corresponded formally to
equivalent weights of 1800 and 2300 g/mol, respectively. These values were significantly different
Membranes 2015, 5 806

from those of standard PFSA membranes e.g., Nafion® 115, of equivalent weight 1100 g/mol and
IEC 0.91 meq/g. These blend membranes were formulated to limit methanol crossover, while the cast
membrane thickness of 30–50 µm allowed us to reduce the membrane area resistance compared to
Nafion® 115, with a thickness of 125 µm, and to decrease material cost. Sulfonated polyetheretherketone
membranes and composite membranes with zirconium phosphate were also developed at FuMA-Tech.
A square root-like relationship between DMFC power density and membrane selectivity (reciprocal
of the product between the area-specific resistance and the crossover) was observed at 60 °C. This
relationship can provide a guideline to predict DMFC performance from basic membrane characteristics
in the presence of similar catalyst-loading, mechanical, and interfacial properties.
As discussed above, the selectivity is related to the intrinsic membrane properties. Thus, determination
of membrane selectivity does not necessarily require to carry tests in DMFCs. Selectivity can be determined
from conductivity, thickness, and methanol permeation characteristics. According to our evidence,
membrane selectivity can give an indication of DMFC performance at low temperatures, provided that
the electrode properties are known. This is a good opportunity for membrane developers
who do not have an experimental DMFC setup or are not involved in electrochemistry to develop new
polymeric membranes for methanol fuel cells and get an estimation of the performance achievable in
DMFC under conditions that are relevant for portable applications.
The achievement of proton conductivity for the developed membranes in the range of 50 mS/cm,
in addition to having satisfactory properties with respect to methanol permeation, hydrolytic, and mechanical
degradation, provided a set of polymer electrolyte materials with enhanced characteristics for methanol
fuel cells. This enabled an increase in DMFC performance (power density) with respect to the reference
state-of-the-art Nafion® membrane at 60 °C.
The FuMA-Tech E-730 s-PEEK membrane provided similar or higher power density than Nafion®
in the 60–90 °C range and lower crossover despite the much lower thickness resulting in a better fuel
utilization and higher energy density, and lower polymer cost. Among the most promising membranes,
sulfonated polyetheretherketone E-730 showed several advantages compared to Nafion® in terms of
power density (about 77 mW·cm−2 as compared to 64 mW·cm−2 at 60 °C on a low catalyst loading basis),
lower methanol (2M) crossover (47 mA·cm−2 for E-730 vs. 120 mA·cm−2 equivalent current density for
Nafion® 115 at 60 °C) and suitable area-specific resistance (0.15 Ohm cm2 for E-730 vs. 0.22 Ohm cm2
for Nafion® 115). The significantly lower polymer cost for E-730 compared to Nafion® also provides
interesting perspectives for DMFC application. E-730 consists of a cheap hydrocarbon membrane
(PEEK) and no fluorine chemistry is involved. This is obtained by a cost-effective process instead of the
perfluorinated Nafion®. The lower cost is also associated with the much lower amount of polymer used
in the cell due to the lower thickness. Another Fumatech membrane, a perfluorinated-type, F-1850, was also
promising and potentially can cover a wide range of operating temperatures. This membrane is also
reasonably cheap even if based on PFSA; it already provides a cost advantage over non-blended PFSA
(Nafion®, etc.). In particular, the F1850 provided a proton conductivity of 46 mS·cm−1 at 60 °C.
ZrP-PFSA composite membranes showed conductivities between 40 and 70 mS·cm−1 but large methanol
crossover. From the above results, it is deduced that the developed cost-effective polymer electrolytes
can provide a performance comparable to or better than Nafion®, especially at low temperatures, and
better fuel utilization in DMFCs.
Membranes 2015, 5 807

Acknowledgments

The authors acknowledge the financial support of the EU through the DURAMET Project 278054.
The research leading to these results has received funding from the European Community’s Seventh
Framework Program (FP7/2011–2014) for the Fuel Cells and Hydrogen Joint Technology Initiative
under grant agreement DURAMET No. 278054.

Author Contributions

A.S. Aricò conceived and designed the experiments and wrote the manuscript; D. Sebastian, C.
D’Urso carried out the physico-chemical and electrochemical experiments and data analysis;
M. Schuster, B. Bauer, carried out membrane preparation and characterization; F. Lufrano, V. Baglio
assisted at experimental researches, data analysis, and in writing the manuscript. All authors discussed
the results, and participated to data interpretation and manuscript revision.

Conflicts of Interest

The authors declare no conflict of interest.

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