Increasing The Ion Conductivity by Modification of Anion Exchange Membranes For Alkaline Fuel Cells

ECS Transactions, 86 (13) 629-642 (2018)
10.1149/08613.0629ecst ©The Electrochemical Society
Increasing the Ion Conductivity by Modification of Anion Exchange Membranes for

Alkaline Fuel Cells
J. Leppina, C. Clarkb, J. Behnkena, C. Harmsa, A. Dycka

a
DLR Institute of Networked Energy Systems, Carl-von-Ossietzky-Str. 15,
26129 Oldenburg, Germany
b
University of Southampton, University Road
Southampton SO17 1BJ , United Kingdom
Optimisation of anion exchange membranes provides a high potential

for overcoming remaining challenges of alkaline fuel cells. The
modification of the polymer structure by incorporation of additives
allows a specific adaption of membrane properties such as ion
conductivity. Glucose, ortho-dichlorobenzene (ODB) and silica
particles were tested as additives to modify a commercially available
membrane. An optimised amount of additive was crucial to obtain a
mechanical stable membrane. The morphology of the modified
membranes was studied by scanning electron microscopy showing a
porous structure for the ODB modified membrane. Electrochemical
impedance spectroscopy measurements, over a wide range of
temperatures, resulted in increased ion conductivity for all cases.
Finally, thermogravimetric analysis coupled to a GC/MS system gave
proof of the incorporation of glucose in the membrane. These findings
will encourage us to use modified membranes in the preparation and
testing of single cells for the alkaline fuel cell.
Introduction
Anion exchange membrane (AEM) based fuel cells have received increasing attention due to
their ability of using a non-precious metal catalyst (1) as well as non-fluorinated polymers in
the membrane (2) leading to cost advantages in comparison to commercially available proton
exchange membrane fuel cells (PEMFC). Also, in respect to their beginning-of-life
performance AEMFC are starting to approach the performance of PEMFC systems (2, 3).
However, there are still remaining challenges for the development of commercial AEMFC
systems including high degradation rates, complex water management and low CO2-tolerance
(2-4). There are different strategies to overcome these limitations such as optimisation of the
operating parameters and development of improved AEM materials (3).
The principal focus in the development of AEMs is to increase the ion conductivity. An
increased number of conducting groups in the membranes polymer structure leads to an
increased conductivity. However, this strategy usually also facilitates an increasing water
uptake and therefore decrease in the mechanical strength (5). Therefore, the water uptake
capabilities along with the chemical, thermal, and mechanical stability have to be balanced.
Many developed AEMs showed poor dimensional stability due to strong swelling and
brittleness of the membrane after drying (6, 7). Furthermore, chemical degradation through
nucleophilic attack of hydroxide ions is also known to have an effect on the long-term
stability of alkaline membranes (7-10). In particular, the amount of water present related to
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the hydroxide concentration has been depicted as critical for the AEM stability (11). On the
other hand, the water is needed as a reactant in the oxygen reduction reaction and for the ion
transport through the membrane. It is assumed that the main transport via the Grotthus
mechanism and the hydroxide ion diffuses through the hydrogen bonded network of water
molecules (12). Thus, a proper water management is important for the stability as well as for a
high performance of AEMFC originating from a high ion conductivity of the membranes.
Apart from the development of new AEM materials, there are several promising methods
reported in literature to manipulate AEM properties by the modification of the membrane
structure. Membrane optimisation strategies include chemical crosslinking (13, 14),
mechanical reinforcement (15) and the addition of various additives (16). One possibility is
the modification of the AEM structure through pore formers utilising additives. Previous
reports have shown success with the use of glucose or ortho-dichlorobenzene (ODB) as
porogens for either polybenzimidazole or Nafion® respectively (17, 18). Inorganic particles
can be incorporated into the membrane structures which are subsequently dissolved resulting
in a mesoporous network (19).
Thus, pores are formed at the membrane surface or inside the membrane leading to an
improved catalyst membrane interface and enhanced water flux, respectively (18-20). So far,
most of these studies have been conducted with proton exchange membranes. Nevertheless,
for AEMFC applications also KOH-doped porous PBI membranes (21) as well as pore filled
anion exchange membranes (6) are reported.
In this contribution, AEMs are modified with the goal of achieving high ion conductivity
without sacrificing their physical and chemical properties. It has been considered that the
formation of pores leads to an improved water balance in the membrane, which is essential
during AEMFC operation because of possible dry out at the cathode and flooding at the anode
side (4). Further, an enhanced transport and higher mobility of anions during AEMFC
operation is expected. A commercially available anion exchange polymer and different types
of additives were applied to develop AEMs. The relevant properties of these modified AEM
were studied and also compared with a commercially available AEM. Ion conductivity was
measured as a function of temperature by using electrochemical impedance spectroscopy
(EIS). The thermal decomposition of the modified membranes and the released substances in
the degradation steps were studied with a thermogravimetric system coupled to a GC/MS
system. For future research, the modified membranes will be used for the preparation of
single cell alkaline electrolyte membrane fuel cells.
Experimental
Materials
The commercial alkaline polymer FUMION® (FUMATECH BWT GmbH) in bromide

form was used for the preparation of the modified membranes. The polymer was shredded and
dissolved in ethanol (absolute; Sigma Aldrich) and in dimethyl sulfoxide (DMSO)
(anhydrous, ≥99.9 %; Sigma Aldrich) to obtain an ionomer solution, respectively As
reference, a commercial membrane FUMAPEM® FAA-3-50 (FUMATECH BWT GmbH)
with the same polymer structure as FUMION® was used. The membrane had a thickness of
50 µm and was ion exchanged from bromide to carbonate for 24 h in 1 M sodium carbonate.
The water uptake was specified by the manufacturer as 23 wt% in Cl- / Br- form and 40 wt%
in OH- form and the ion exchange capacity (IEC) is 2.02 meq g-1 (in Cl- / Br- form) (22, 23).
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Preparation of modified membranes
Modified glucose membrane. The commercial polymer was dissolved in dimethyl

sulfoxide (DMSO) (anhydrous, ≥99.9 %; Sigma Aldrich). A 10 wt% solution was stirred for 2
hours and glucose (D-(+)-Glucose ≥99.5 %, Sigma Aldrich) was added and stirred for
additional 24 hours at room temperature.
Modified LUDOX® AS-40 membrane. The commercial polymer was dissolved in

dimethyl sulfoxide (DMSO) (anhydrous, ≥99.9 %; Sigma Aldrich). A 10 wt% solution was
stirred and LUDOX® AS-40 colloidal silica (40 wt% dispersion in H2O, Sigma Aldrich) was
added and stirred for additional 24 hours at room temperature.
Both of the solutions (LUDOX® AS-40 and glucose modified suspension) were cast with
an Easycoater (Coatema®) on a glass plate at 80 °C and the relative humidity (RH) was
controlled to be around 20 %. After casting the membranes were dried in a vacuum furnace at
40 °C and 50 mbar for 48 h, there the membranes were turned after 24 hours. The thicknesses
of the membranes were between 20 and 200 µm. Finally, the membranes were washed in
deionised water and ion exchanged into carbonate by soaking in 1 M Na2CO3 solution for
24 h for further analysis.
Modified ODB membrane. The commercial polymer was dissolved in ethanol (absolute;
Sigma Aldrich) another one in DMSO (anhydrous, ≥99.9 %; Sigma Aldrich). A 10 wt%
solution was stirred for 1 hours and 1,2-dichlorobenzene (ODB) (Sigma Aldrich) was added
and stirred for additional 24 hours at room temperature. The solution had a cloudy, light
brown colour before the membrane was casted. The solution was cast with an Easycoater
(Coatema®) on a glass plate at 40 °C and the RH was controlled to be around 30 %. The upper
side of the membrane was dried slowly in a vacuum furnace (50 mbar) by increasing the
temperature from 40 to 80 °C after casting. After 24 hours, the membrane was turned and the
second side was dried again at 80 °C for 24 hours. Resulting thicknesses of the membranes
were between 50 - 70 µm. Finally, membranes were washed in deionised water and ion
exchanged into carbonate by soaking in 1 M Na2CO3 solution for 24 hours for further
analysis.
Cross section analysis of modified membranes
Scanning Electron Microscope (SEM) images were taken using a Zeiss Neon 40 EsB. The
electron source was a Wolfram Wire/LaB6-Crystal with beam energy of 20 kV. The detector
was an EBSD-Detector. Membranes were prepared by freezing in liquid nitrogen and
breaking them afterwards.
Ion conductivity measurement of modified membranes
A ion conductivity analysis was performed with a Greenlight Innovation G100 test bench
equipped with a Solartron Analytical Energylab XM potentiostat. The fuel cell hardware used
was a QuinTech FC-05-02 5 cm2 with a serpentine flow field and the ion conductivity cell
was a Quintech CdC BT112. The membranes were conditioned at 50 °C, 60 °C and 70 °C at
95 % RH and a synthetic air (N2 + O2) gas flow of 1 l min-1 for 3 hours, respectively.
Afterwards impedance was measured using a 4-electrode set up. The in-plane ion conductivity
σ is calculated from the membrane resistance (equation 1)
σ = L / W*R*T [1]
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where L is the distance between the voltage sense electrodes, W the width, R the resistance
and T the thickness of the membrane.
Thermogravimetric analysis coupled with gas chromatography and mass spectrometer (TGA-
GC/MS)
For the thermal analysis a TGA-GC/MS system (Pyris 1 Thermogravimetric Analyser,

Perkin Elmer) was used. The samples were held for 1 min at 30 °C, heated from 30 °C to
850 °C at a rate of 20 °C min-1 and held for 1 min at 850 °C under a helium flow of
40 ml min-1. Relating to the minima of DTG curves (Differential thermogravimetry, first
derivative of the thermogravimetry curve), the degradation steps were analysed by the GC/MS
system (Clarus 600 Gas Chromatographer and Clarus 600T Mass Spectrometer, Perkin
Elmer). For this, the valve was opened for 30 seconds to the GC in the minima of the DGT
curve and the gases were separated on the column and then analysed in the MS. The time was
calculated with the help of the constant heating rate. If the valve was permanently open, the
peaks would overlap and no assignment of degradation products is possible. The GC column
had a temperature of 30 °C during the measurement. The coupling between the TGA and
GC/MS allows the collection of degradation products for each decomposition step and a
separation of them on the column of the gas chromatograph. Through the swafer (a specially
shaped valve) between the TGA and the GC small amounts can be concentrated. The mass
spectrum allows the analysis of the corresponding molecules ionised by electron ionisation.
Results and Discussion
In order to increase the ion conductivity by a better water management of AEM, pore
formers were used which act in different physical principles. The glucose was used as a “hard
template” pore former. The organic material is introduced into the network of the casted
membrane and subsequently washed out. As glucose is removed, pores are formed in the
membrane. Li et al. also reported on the positive effect of glucose in the preparation of porous
polybenzimidazoles (PBI) for PEMFC (17). Similar studies by Weber et al. on PBI for
PEMFC have shown the use of inorganic silica particles to produce homogenous mesoporous
membranes (19). LUDOX® AS-40 is a suspension of inorganic silica particles with a defined
particle size of around 22 nm and works on a similar principle than glucose as a “hard
template”. After mixing with the polymer solution the particles dissolve in alkaline solutions
as silica is unstable at high pH values. Accordingly, particles are washed out of the membrane
leaving pores in the AEM structure. The use of ODB as a “soft template” was described by
Henkensmeier et al. for Nafion® membranes. In this case, pores are formed by the different
vapour pressures, mixing ratios and densities of the organic solvents and the polymer (18, 20).
All these examples have been applied to PEMFC materials.
Here, the method of pore forming was adapted with a commercial alkaline polymer. The
goal is to form pores to optimize the water uptake capabilities of the membrane, since water is
on the one hand a reactant in the oxygen reduction reaction and on the other hand it enhances
the ion conductivity in the membrane (Grotthus mechanism). Further, the additional water
reservoir inside the pores could support the water balance during flooding (water migrates
into the open space of the pores) and during drying events (water migrates backwards) due to
the osmotic pressure (24).
Therefore, different additives were introduced to the AEM structure and the influence on
the properties of alkaline membranes, especially their ion conductivity, was investigated. For
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aforementioned reasons, glucose, ODB and LUDOX® AS-40 were used as additives. It was
possible to manufacture membranes with all types of additives with the alkaline based
polymer. Furthermore, membranes with different ratios of additive to polymer were produced.
Depending on the additive, different limits for the addition and the subsequent casting of
stable membranes were observed. At very low concentrations of ODB no film-forming
membranes could be achieved. In another approach, the formation of smaller pores by mixing
DMSO and ODB was studied. However, due to a too small difference in the boiling points no
pores were formed. At very high concentrations of OBD also no film-forming membranes can
be produced, since they cannot be detached from the glass plate. The best results were
achieved within a range of 1.0 to 15.0 wt%, above these concentrations the membranes
became very jelly and unusable because of an open pore structure. In the attempt to increase
the concentration of LUDOX® AS-40, it was found that the inorganic particles were
distributed unevenly in the membrane and there were several inhomogeneous phases by
casting at room temperature. Therefore, membranes were very vesicular and unstable.
Functional membranes could be achieved at low concentrations of 0.5 to 1.0 wt%. At higher
concentrations, the particulate form agglomerates in the membrane and distribute
inhomogeneous.
In the modifications with glucose, a series of various concentrations could be tested. The
suspension became highly viscous at higher concentration of glucose and it was difficult to
cast membranes without creating bubbles. At concentrations exceeding the polymer content,
the membranes became gel-like and vesicular and thus unusable. For membranes below this
limit film formation became possible and they could easily be peeled off the glass plate. In
general, it was found that membranes with glucose have a strong water uptake (data not
shown), which limited further investigations of the concentration variation. A selection of the
most promising membranes, which were flexible after drying and showed no cracks or other
discoloration are shown in Table I. Further characterization of these samples will be discussed
in the following passages.
TABLE I. Composition of modified membranes

Sample name Additive Weight percentage of Solvent
additive
UNMOD / / DMSO
MOD_GLU_2.7% Glucose 2.7 % DMSO
MOD_GLU_8.3% Glucose 8.3 % DMSO
MOD_LUD_0.5% LUDOX® AS-40 0.5 % DMSO
MOD_LUD_1.0% LUDOX® AS-40 1.0 % DMSO
MOD_ODB_3.0% ODB 3.0% DMSO
MOD_ODB_15.0% ODB 15.0 % Ethanol
First, the cross sections of the membranes were examined by SEM imaging. The focus
was on the pore formation of the membranes. Figure 1a-d show an example for each
membrane type.
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Figure 1. SEM picture of cross section of modified membrane with a) ODB using ethanol
(MOD_ODB_15.0%), b) ODB using DMSO (MOD_ODB_3.0%), c) MOD_LUD_0.5% with
LUDOX® AS-40 and d) MOD_GLU_8.3% with glucose.
The investigations of the cross-sections clearly showed that only the membrane with
ODB had large pores (Figure 1a). The porosity is very high with an open structure of around
3 - 5 µm in diameter. The pore sizes were independent from the ODB concentration (data not
shown). Also, formation of smaller pores by mixing DMSO and ODB was tested, but boiling
points were too similar, so that no pores were formed (Figure 1b). In Figure 1c the SEM
image of modified membrane with LUDOX® AS-40 is shown. It is supposed that the
concentration of LUDOX® AS-40 was insufficient to form pores. The maximum
concentration was 1.0 wt% since above this value an inhomogeneous distribution of the
additive was observed. Possibly, the silica particles were washed out without having a
significant effect on the morphology the polymer after the casting. The membranes with
glucose showed also no pores in the cross section (Figure 1d). In contrast to the PBI
membranes in the work of Li et al., the glucose seems not to act as a pore-forming agent here.
Instead, glucose might interact with the membrane or rather with its functional groups.
Since no pore formation in the alkaline polymer was observed by SEM, TGA-GC/MS
was used to prove whether the additives were still present in the membranes. In Figure 2 the
TGA and DTG curves of the modified and unmodified membranes are shown. While in the
left graph the weight loss is plotted against the applied temperature, the right graph present
the first derivative of the weight loss against the applied temperature. The main
decomposition steps are colour-coded and labelled with A, B and C in both graphs and show
the same measurements only in different representations.
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Figure 2. TGA (left) and DTG (right) curve of the modified and unmodified membranes.
The unmodified membrane showed three main decomposition steps at 275 °C (B), 375 °C
(C) and 450 °C and small degradation steps at 80 °C, 210 ° and 230 °C (A). The first two
main degradation steps (section B and C) belong to the degradation of the functional groups,
bromide counter ions and the organic side groups. The investigations with the commercial
material showed that in the smaller regions (section A with 120 - 220 °C) the side chains
degrade by the release of carbonate which is the present counter ion. Compared to the
unmodified membranes, the thermogram showed that the modified membranes degrade much
earlier. In the case of the MOD_GLU_8.3%, degradation already begins at 60 °C with a small
step. This can be assigned to the evaporation of water from the membrane found in the related
mass spectra during the measurements. The first major degradation step (A) is in the range of
120 - 220 °C, visible in Figure 2, left. The second degradation step (B) starts at 240 °C and
ends at 330 °C with the exception of the ODB modified membrane MOD_ODB_15.0%. A
smaller degradation step appeared at 330 - 390 °C in the DTG curves for the unmodified as
well as the modified membranes. Within the thermogram itself, only for the LUDOX® AS-40
modified membrane MOD_LUD_1.0% is it hardly recognisable. The last degradation step
around 450 °C is the decomposition of the polymer chains which is the same for all samples.
It is also very noticeable that the MOD_LUD_1.0% and MOD_GLU_8.3% membrane have a
very similar behaviour.
For the investigation of the additives only the ranges up to 400 °C are relevant. The
resulting degradation products were examined for each degradation step with the GC/MS
system. For this, the valve was opened for 30 seconds to the GC in the minima of the DGT
curve and the gases were separated on the column and then analysed in the MS. Figure 3
shows the chromatogram of MOD_GLU_8.3% as an example. The other chromatograms have
shown a similar form with only different opening times for the valve between TGA and
GC/MS depending on the minimum of the DTG curve. The chromatogram is color-coded and
labelled according to the degradation steps in TGA with yellow for the first step (A) at 120 -
220 °C, green for the second step (B) at 240 °C - 330 °C and blue for the third step (C) at
330 - 390 °C.
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Figure 3. Chromatogram of the glucose modified membrane MOD_GLU_8.3% with color-

coded and labelled degradation steps.
The first peak in all steps is an artefact of switching the valves and the following peaks
belong to the samples. This first peak with the subsequent MS has been ignored in the
analysis, since this belongs to the composition of air. It can be clearly seen for the individual
areas that there was a separation of molecules in time, which means that various components
of the membrane were degraded in the different temperature ranges. The evaluation of the
GC/MS measurement will be only once graphically explained at the second degradation step
(Figure 3B). The respective results of all steps and the overall results are shown in Table II.
The first step of degradation was similar for all samples, because here the inserted counter ion
carbonate with its corresponding functional group degraded. A more detailed chromatogram
of the second degradation step is shown in Figure 4, since there the additives degraded. The
associated mass spectra showed a splitting into three peaks for retention times of 14.3 min
(BI), 14.4 min (BII) and 15.8 min (BIII) (Figure 5).
Figure 4. Second degradation step of the chromatogram of MOD_GLU_8.3%.
Figure 5. Associated mass spectra of Section B of the chromatogram of MOD_GLU_8.3%.
This degradation step occurred at 240 °C - 330 °C in the TGA and showed in the mass
spectra a two-part decomposition (BI and BII) of the organic side chains with the functional
group and the bromide counter ion with m/z values of 28/29, 39/40 and 55/57 at BI and m/z
values of 18, 42, 57/58/59, 79/81 and 94/96 at BII. More important is the mass spectrum of
the last peak BIII at 15.8 min, which was not observed for the other samples. The m/z values
of 31, 43, 57 and 73 indicate that there is a small amount of glucose (in the form of its
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decomposition products as alcohols and ketones). Furthermore, organic side chains are also
released with m/z values of 28/29, 39/40 and 55/57 at BIII.
TABLE II. Mass spectra at different retention times of the degradation steps in accordance to DTG curves
Sample name Retention m/z values Assignment
time
[min]
1st Degradation step MOD_GLU_8.3% 9.3 18, 28/29, 31/32 Organic side-chain based
120 - 220 °C 39/40, 55/57 groups and carbonate
A 9.4 18, 27/28, 31, 79/81, Organobromide side-chain
94/96 based groups
MOD_LUD_1.0% 9.4 18, 27/28, 31/32 Organic side-chain based
39/40, 55/56 groups and carbonate
MOD_ODB_15.0% 7.8 18, 28/29, 31/32 Organic side-chain based
39/41, 55/56 groups and carbonate
10.3 28, 79/81, 93/94/96 Organobromide side-chain
based groups
nd
2 Degradation MOD_GLU_8.3%e 14.3 28/29, 39/40, 55/57 Organic side-chain based
step groups
240 °C - 330 °C 14.4 18, 42, 57/58/59, Organobromide side-chain
B 79/81, 94/96 based groups
15.8 27/28, 31, 39/41, Glucose, acetic acid
43/44, 57, 72/73
MOD_LUD_1.0% 14.0 28/29, 39/40, 55/57 Organic side-chain based
groups
14.2 28/29, 42, 58/59, Organobromide side-chain
79/81, 94/96 based groups
14.7 42, 58, 101 Organic / ammonium
compounds of the polymer
MOD_ODB_15.0% - - -
3rd Degradation MOD_GLU_8.3%e 18.2 27/28/29, 32, 39/40, Organic side-chain based
step 55/56/57 groups
330 - 390 °C 18.3 28/30, 41/42, 58/59, Organic bromide side-chain
79/81, 94/96 based groups
C 19.5 58, 101 Organic / ammonium
20.9 27/29, 39/41, 56/58, Organic groups of the

79/81, 94/96, 136 polymer
23.3 58, 101 Organic / ammonium
24.7 27/29, 39/41, 56/57, Organic groups of the

79/81, 93, 136 polymer
MOD_LUD_1.0% 19.2 42, 58, 101 Organic / ammonium
20.5 27/29, 39/41, 56/57, Organobromide side-chain

79/81, 93, 136 based groups
MOD_ODB_15.0% 18.2 28/30, 40/41/43, Organic groups of the
79/81, 94/96 polymer
21.5 28, 42, 57, 70, 85 Organic side-chain based
groups
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Table II summarizes all results of the three degradation steps of the TGA measurement. In
the first step, the analysis of the mass spectra showed the corresponding ratios for the
exchanged counter ions (carbonate), but also minor amounts of initially present counter ions
(bromide) in combination with some parts of the organic functional groups. This can be seen
by the separation of two peaks in the DTG curve and is most prominent in the DTG curve of
the MOD_ODB_15.0% membrane. The mass spectra of the second and third degradation
steps have shown different degradation products of the side chains and the functional groups
for all the modified membranes as well as the counter ion bromide that is still in the
membrane. In general, for the LUDOX® AS-40 and the ODB modified membranes no
molecules were found that indicate the additives. This clearly shows the complete dissolution
of LUDOX® AS-40 and the evaporation of ODB. Only for the glucose modified membrane
some fragment of the additive could be found indicating that glucose was washed out
incompletely. It can be concluded that none of the additives seems to have a negative
influence on the functional groups, since the degradation levels are at temperatures similar to
those of the commercial membrane.
For the ion conductivity measurements all membranes were ion exchanged into the
carbonate form. The measured ion conductivities were lower compared to membranes in the
hydroxide from, but hydroxide tends to be exchanged by carbonate during the preparation and
measurement of the samples resulting in unstable values (3, 25, 26). This is avoided by direct
utilization of the carbonate form. Ion conductivity measurements of the membrane samples by
EIS showed an increased ion conductivity with an increase of the temperature as it is known
from literature (Figure 6) (27). The modifications with different additives resulted in different
effects on the membrane ion conductivities. In order to compare the effect on the ion
conductivity, an unmodified membrane was treated as the modified membranes and
investigated.
Figure 6. Measurements of the in-plane ion conductivity of modified membranes at 50 °C,

60 °C and 70 °C and 95 % RH in carbonate form A) membranes modified with glucose; B)
membranes modified with LUDOX® AS-40, and C) membranes modified with ODB, always
in comparison to the unmodified membrane (UNMOD).
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Compared to the unmodified one, all modified membranes showed higher ion
conductivities. The ion conductivity of the MOD_GLU_8.3% is the highest with a value of
43 mS cm-1 at 70 °C. In general, the ion conductivities of the membranes modified with
glucose showed the best results despite the fact that no visible pores were formed in the
membranes. On the other hand, the membranes treated with LUDOX® AS-40 showed only a
minor change in the ion conductivity. For the membranes modified with ODB the ion
conductivity was dependent on the solvent in the polymer solution for the casting. For
MOD_ODB_15.0% (Ethanol) values of 7 mS cm-1 at 70 °C and for MOD_ODB_3.0%
(DMSO) values of 26 mS cm-1 at 70 °C were achieved. The open-pore membranes had a
lower conductivity than the membranes without pores.
Although an increase of the ion conductivity of the ODB membranes can be attributed to
the larger surface area and the associated improved water management, there is no direct
correlation between the extent of porosity of the membranes and the ion conductivity. The
completely porous membrane (MOD_ODB_15.0%) does not show a large increase in
conductivity compared to the commercial one. The membrane MOD_ODB_3.0% has a higher
ion conductivity but it decrease at higher temperature. It seems like the ODB has an influence
on the morphology of the membrane during the casting and the drying process. Evaporation of
ODB from the membrane will maybe result in a different structure, even if no pores have
formed. The decrease at higher temperature might be explained by degradation or a loss of
mechanical strength. The best results were achieved with the glucose-modified membranes.
These showed indeed no pores in the SEM images but residues of glucose could be detected
with the help of the TGA-GC/MS. Li et al. showed the pore-forming properties of glucose as
a porogen for polybenzimidazole polymer (17). There, the membrane is doped with
phosphoric acid, which is necessary for the ion conductivity in HT-PEMFC in contrast to
water in AEMFC. Pores with a maximum size of 1 µm were observed and also its ion
conductivity increased with a higher doping level with phosphoric acid in the porous structure
(17). This porosity was not observed with the alkaline polymer, which may depend on the
different conditions during membrane casting and different solvents used. It is assumed that in
the alkaline polymer hydrophobic and hydrophilic regions exist (2, 12). Since the glucose
could still be detected, but no pores were formed, it is believed that it has an influence on the
ion conductivity. Due to the polar character of the hydroxide groups, it will accumulate in the
hydrophilic regions, where the functional groups are responsible for the ion conductivity.
Therefore it might be a possibility that the morphology has changed due to the presence of
glucose by forming larger hydrophilic regions and thereby improving water transport and ion
mobility through the membrane.The oxidation of glucose in alkaline media is also exploited
in direct glucose alkaline fuel cell. However, this oxidation is achieved here catalytically. It
could be that there are interactions between glucose and hydroxide. The oxidation of glucose
in alkaline media is also exploited in direct glucose alkaline fuel cell. However, this oxidation
is achieved here catalytically (28). Therefore, remains to be established whether a reaction
between the functional groups and glucose is possible without catalyst in the membrane.
While for the glucose modified membranes the pore formation is dependent on reaction
conditions, the advantage of using "hard templates" lies primarily in the defined particle size
of the used additives. Therefore, defined pore sizes can be achieved. Weber et al. showed this
for mesoporous polybenzimidazoles . However, the silica nanoparticles (also LUDOX® AS-
40) were already mixed during the synthesis of the polymer with the monomers, which than
formed a network within the polymer. It was shown that mixtures of polymer and silica with a
ratio of up to 1:1 were possible. The associated Transmission electron microscope (TEM) images
and nitrogen absorption measurements showed an increasing diameter of the pores with an
increased concentration (19). In the present work, LUDOX® AS-40 was mixed with the
polymer. The maximum achieved mixing percentage was 2.5% (based on the solid contents),
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since higher ratios led to a separation of the suspension into two phases. Further, no pore
formation was visible in the SEM images. The incomplete dissolution of the particles has
been refuted since no residues could be detected by thermal analysis. Also, only minor
differences were observed for the ion conductivity compared to the commercial material. It
can be rather assumed that the polymer structure rearranged after the silica particles were
washed out without having a significant influence on the membrane structure by the particles..
In case of the solvent evaporation method with ODB it was shown that porous structures
can be produced in the commercial alkaline polymer. Investigations with this method on
Nafion® membranes were carried out by Henkensmeier et al. (18, 20)(16, 18). There, porous
structures formed on the surface of the cast membrane while the bulk membrane remained
dense as well as an open pore structure (20)(18). The ion conductivity for the alkaline
membrane in this work showed an increase compared to the commercial membrane. This may
be due to the larger surface area generated and the pores could be filled with water, which
could improve the water management and thus the mobility of ions. The same has been
demonstrated by Henkensmeier et al. for porous Nafion® membrane electrode assemblies.
Thus, the maximum power density of the MEAs improved with increasing ODB content (18).
The different concentrations incorporated into the alkaline polymer showed a limitation for
higher concentrations. While with Nafion® a porous structure could still be achieved, no film-
forming membrane could be obtained in the case of the alkaline material at higher
concentrations. The generated pores were in the complete membrane by using ethanol while
none were generated in the use of DMSO. This is probably related to the different densities
and viscosities of the polymers used as well as to the miscibility of the solvents and the
polymer. The influence of ODB / DMSO on the morphology of the polymer during drying
process has not been investigated yet. However, this approach shows good tendencies for
further investigations since the ion conductivity increased also without development of large
pores. Thus, other solvent mixtures could be tested here to affect the distribution of pores
within the bulk or additional polymers can be applied to the surface of the membrane.
Conclusion
The goal of this study was to increase the ion conductivity of alkaline membranes without
changing the number of functional groups. Specific additives have been used to form pores in
the membrane to increase the ion mobility and support the transport mechanism by an
optimized water uptake. This should result in an improved mobility of the anions. As
additives LUDOX® AS-40, ODB and glucose were used. All of them should act as pore
formers in different ways. It was shown by SEM images that only for one ODB membrane
visible pores were formed. The resulting surface enlargement improved the ion conductivity.
However, since this is an open-pored structure, application of this modified AEM in fuel cells
is only possible to a limited extent, since reactant crossover could be possible. In future
development this will be circumvented by creating pores only in the middle of the membrane.
The use of inorganic particles (LUDOX® AS-40) did not show a big influence. Here,
neither pores in the cross section could be shown nor a significant increase of the ion
conductivity. The best results were achieved with the glucose-modified membranes
MOD_GLU_8.3% although these AEM showed also no pores. Here, an ion conductivity of
43 mS cm-1 could be achieved at 70 °C, which is an improvement of 38 mS cm-1compared to
the commercial alkaline polymer. The thermogravimetric analysis showed that glucose is still
present in the membrane. However, this did not affect the thermal stability in the range below
100 °C. In summary, pore formation was only observed for the membrane
MOD_ODB_15.0% and no correlation between the ion conductivity and the porosity was
640
observed. Instead, it seems that the conductivity depends more on the nature of the specific
additive. The additives used in the associated casting process of the membrane seem to have
an influence on the morphology.
Acknowledgments
We thank the German Federal Ministry of Education as parts of this work was
supported through the project NEMEZU „Neue edelmetallfreie Membran-Elektroden-
Einheiten für Brennstoffzellen der Zukunft“ (grant number 03SF0497E).
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Increasing The Ion Conductivity by Modification of Anion Exchange Membranes For Alkaline Fuel Cells

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Increasing The Ion Conductivity by Modification of Anion Exchange Membranes For Alkaline Fuel Cells

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ECS Transactions, 86 (13) 629-642 (2018)

10.1149/08613.0629ecst ©The Electrochemical Society

Increasing the Ion Conductivity by Modification of Anion Exchange Membranes for

J. Leppina, C. Clarkb, J. Behnkena, C. Harmsa, A. Dycka

Optimisation of anion exchange membranes provides a high potential

The commercial alkaline polymer FUMION® (FUMATECH BWT GmbH) in bromide

Preparation of modified membranes

Modified glucose membrane. The commercial polymer was dissolved in dimethyl

Modified LUDOX® AS-40 membrane. The commercial polymer was dissolved in

Cross section analysis of modified membranes

Ion conductivity measurement of modified membranes

For the thermal analysis a TGA-GC/MS system (Pyris 1 Thermogravimetric Analyser,

Results and Discussion

TABLE I. Composition of modified membranes

Figure 3. Chromatogram of the glucose modified membrane MOD_GLU_8.3% with color-

Figure 4. Second degradation step of the chromatogram of MOD_GLU_8.3%.

Figure 5. Associated mass spectra of Section B of the chromatogram of MOD_GLU_8.3%.

20.9 27/29, 39/41, 56/58, Organic groups of the

24.7 27/29, 39/41, 56/57, Organic groups of the

20.5 27/29, 39/41, 56/57, Organobromide side-chain

Figure 6. Measurements of the in-plane ion conductivity of modified membranes at 50 °C,

1. M. Mamlouk, S. M. S. Kumar, P. Gouerec and K. Scott, J. Power Sources, 196, 7594

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