pubs.acs.

org/JPCC Article

Water Content and Ionic Conductivity of Thin Films of Different

Anionic Forms of Anion Conducting Ionomers
Udit N. Shrivastava, Avital Zhegur-Khais, Maria Bass, Sapir Willdorf-Cohen, Viatcheslav Freger,
Dario R. Dekel, and Kunal Karan*
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ABSTRACT: Typically, in polymer electrolyte-based electro-

chemical devices such as electrolyzers and fuel cells, ionomers in
Downloaded via UNIV OF CALGARY on February 18, 2021 at 03:30:50 (UTC).

the catalyst layers are present as ultrathin films coating the

electrochemically active component. Acidic ionomer thin films
have been extensively characterized over the past decade, yet there
are few reports on the alkaline ionomer thin films. Here, we
present a study on anion-exchange ionomers; specifically, we
investigate the water content and conductivity of fluoride,
bromide, and carbonate forms of 50 nm thick FAA3 and PPO
ionomer thin films at 30 °C and 0−90% RH. A thermodynamic
analysis was performed to compute the Gibbs free energy of
anionic interaction with water to discuss the impact of anion type on the anionic mobility. Structural analysis using GISAXS was
performed on the anion-exchange ionomer thin films. Furthermore, conductivity and water content relationships between FAA3 thin
films and membranes and between FAA3 and PPO thin films were compared and discussed in terms of structure and ion clustering.

1. INTRODUCTION of micrometers thick) separating the anode and the cathode

Typical polymer electrolytes are ionic polymers wherein one of and as a critical component of catalyst layers (CLs) where it
the ions is tethered to or is part of the polymer chain while its ensures ion transport to the electrochemical interface.23 In the
counterion is mobile. The membranes of these materials, CL, the ionomer is thought to be present as an ultrathin film
depending on the type of the mobile ion, are classified as coating the catalysts, akin to that in the CL of proton-
anion-exchange membranes or cation-exchange membranes. conducting polymer electrolyte fuel cells.24,25 Water diffusivity
Anion-exchange membranes (AEMs) found their initial in the membrane and CL ionomer is of high importance to
achieve effective water management.17−21,26 For example, the
application in filtration and separation technologies.1−4
low ionic conductivity of alkaline ionomers in the cathode
Recently, they have attracted much attention for their potential
catalyst layer and high water uptake lead to low catalyst
use in fuel cells and other electrochemical energy storage and
utilization.22,27 A high level of water causes flooding at both
conversion devices such as redox flow batteries and electro-
electrodes leading to severe reactant transport resistance.21,28,29
lyzers.4−7 Unlike proton-exchange membrane fuel cells
Furthermore, owing to the low activity of non-PGM catalysts
(PEMFCs), where precious group metal (PGM)-based
compared to Pt catalysts, AEMFC CLs (∼100 μm) are much
catalysts are necessary for high cell performance, the alkaline
thicker than the Pt-based CLs of PEMFCs (5−10 μm) because
environment in the AEM fuel cells (AEMFCs) permits the use
large amounts of non-PGM catalyst are needed to attain
of non-PGM catalysts such as silver or metal-free catalysts for
sufficiently high current density (>1 A/cm2). Ionic transport in
the cathodic oxygen reduction reaction. This offers AEMFCs a
such thick CLs can become a limiting factor. Thus, a
tremendous potential for breaking the cost barriers that hinder
fundamental understanding of ionic transport within the CL
the commercialization of fuel cells.8−12 The resurgent interest
becomes of critical importance for the optimization of AEMFC
in AEMFCs and the resulting major strides have already led to
CL.
the attainment of impressive performance.11
Nonetheless, for further improvement in performance and
durability, there is a need for enhanced ionic conductivity and Received: May 12, 2020
chemical stability, improved water management, mitigation of Revised: August 25, 2020
carbonation effect, and optimized catalyst layer design to Published: August 25, 2020
deliver high-performance, highly stable AEMFCs.13−22 All of
these issues are linked directly or indirectly to the ionomer
materialwhich is employed as an electrolyte membrane (tens

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In PEMFCs, the ionomers in CLs are known to exist as 4−
10 nm thin films covering the Pt/C catalysts.30 CLs of
AEMFCs are expected to have a microstructure similar to
those of PEMFCs, where ionomer film coats the carbon
support decorated with the catalyst31 although the thickness of
these films is a matter of speculation at present. There is now
abundant evidence of suppression of water content32−35 and
conductivity36−38 of ultrathin (<50 nm) perfluorosulfonic acid
(PFSA) ionomer films confined to a substrate compared to
their membrane form.32−34,37 In one of our prior studies, the
suppression of proton conductivity was found to be correlated
to reduced water content.24,34 Similar data for AEI thin films
are not available. Only a very few studies have reported water
content in alkaline ionomer thin films.39,40 However, to date,
the ionic conductivity of ultrathin AEI films of thickness
relevant to CLs has not been reported.
A few studies have reported an anion transport mechanism
in terms of anion−cation interaction and morphology for the
membrane form of AEI.41−45 For instance, Kreuer et al.
measured water content, diffusivity, and conductivity of the
FAA3 membrane in different ionic forms (including F−, Br−,
and HCO3−).44 In another study, extensive analysis on the
thermodynamics of ion transport for different cation types
using isothermal titration calorimetry has demonstrated that
the interaction between counterion and cation has a substantial
impact on the ionic conductivity of AEMs.45 Both studies have
confirmed that the thermodynamics of anion−cation inter-
action impacts the mobility of ions.
In thin-film form, the contribution of ion mobility and
ionomer morphology to the ionic conductivity becomes more
important for several reasons including46−48 (a) the control of
morphology by either the confinement effect or interfacial
interaction with the substrate or both and (b) the low water
content, which may adversely affect the ionic mobility
dependent on the state of water, i.e., bound, exchanged, and
free. Both of these factors lead to an increased tortuosity and a
suppressed ionic mobility and, in turn, highly suppressed
conductivity.49−52
This work examines the water content and conductivity of
50 nm thin films of two different AEIspoly(phenylene
oxide) (PPO) with ion exchange capacity (IEC) ∼ 3.7 and
commercial FAA3 with IEC ∼ 2 on SiO2 substrateeach one
with three different counterions (F−, Br−, and HCO3−). To the
best of our knowledge, this type of study which focuses on the
investigation of hydration, conduction, and their inter-
relationship for AEIs thin films is being reported for the first
time. The structure of PPO is shown in Scheme 1. The full
chemical structure of commercial FAA3 is unknown; however,
it is composed of poly(phenylene oxide) backbone without a
side chain, functionalized with quaternary ammonium
Scheme 1. Chemical Structure of PPO (X = Br, F, HCO3)
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cations.44,53 First, anion-dependent hydration characteristics
of the alkaline thin film are discussed in terms of the Gibbs free
energy. The relationship between the water content and
conductivity of different counterion types along with the
morphological information from grazing-incidence small-angle
X-ray scattering (GISAXS) is discussed as well to shed light on
ionic transport mechanisms in AEI thin films.
2. EXPERIMENTAL SECTION
2.1. Ionomer Preparation and Dispersion. FAA3 in Br−
form was purchased from FumaTech (Germany). Anion-
conducting PPO polymer was synthesized by functionalizing
the brominated poly(2, 6-dimethyl-1, 4-phenylene oxide)
(BPPO) (48% phenyl bromination and 52% benzyl bromina-
tion purchased from Tianwei Membrane Co. Ltd. (Shandong,
China)) with triethylamine (TEA) Menshutkin reaction.54 N-
Methyl- pyrrolidone (NMP) was added to a round-bottom
flask (25 mL), BPPO (0.5 g) was slowly added, and the
solution was stirred until completely dissolved. TEA, at 1:1.2
molar ratio between amine and polymer, was added dropwise
to the solution which was further stirred for 16 h at room
temperature. The dark brown colored polymer solution was
cast onto a clean glass plate and dried at 60 °C for 24 h.
Afterward, the membrane was thoroughly washed in milli-Q
deionized water (DIW, 18.2 MΩ) to remove any residue of
TEA.
For conversion to bicarbonate or fluoride ionic forms, the
bulk FAA3 and PPO polymers were immersed in an excess
amount of a corresponding salt solution (1 M KHCO3 or 1 M
NaF) for 48 h. Subsequently, they were thoroughly washed in
milli-Q deionized water (DIW, 18.2 MΩ) for 48 h to remove
the excess salt. Finally, the polymers were dried in an oven at
60 °C. To determine the ion exchange capacity of all the AEIs
a Metrohm titrator was used, and the method described in a
previous work was implemented.55
2.2. Water Content of Ionomer Thin Films. For swelling
measurements, 50 nm thick ionomer thin-film samples were
fabricated by spin-coating ionomer dispersions on 300 nm
thick thermal oxide on Si wafer. A custom-designed environ-
mental cell to control both temperature and RH was adapted
into the M2000 (JA Wollam Inc., USA) ellipsometer stage.56
The temperature was controlled using electrical heaters.
Humidified clean air was flown into the cell to control RHs
which were monitored using sensors (SHT75, Sensirion,
USA). Humidity was controlled within 1% and temperature
within 1 °C. The film was maintained at a given RH for 20 min
or until a steady response from the ellipsometer was
determined. The optical properties and film expansion due
to water content were determined by fitting a B-Spline model
to the ionomer film. The film expansion (ΔL = Lwet,RH − Ldry)
was converted to water content expressed in terms of water
content using eq 1.
ΔL ρw
λ= ·EW·
Ldry ρionomer . M w (1)
λ is water content representing the number of water molecules
per mobile ion (e.g., F−, Br−, or HCO3−), EW is the equivalent
weight of ionomer (500 for FAA and 270 for PPO), ρw is the
density of water (g/cm3), ρionomer is the density of ionomer (g/
cm3), and Mw is the molecular weight of water.
2.3. Conductivity Measurement. Anion conductivity of
ionomer thin films was determined by impedance spectroscopy
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using an interdigitated array (IDA) of Au electrodes following
the method and setup previously employed to measure the
conductivity of Nafion thin films.37,38 The design of IDA is
shown in Figure S1 of the Supporting Information. Before the
ionomer films were spin-coated, IDAs were rinsed multiple
times with acetone and isopropyl alcohol and placed in an
ultraviolet cleaner for 30 min. Next, ∼1.2 wt % of FAA3 and
PPO ionomer dispersions in methanol was used to spin-coat
on IDA at 5000 rpm for 30 s to achieve ∼50 nm thin films.
AEI-coated IDAs were kept in a vacuum oven for 24 h at 40
°C. The thickness of the ionomer film was measured at
multiple points using an ellipsometer (Model M2000; JA
Woollam Inc., USA). AEI-coated IDAs were placed in a
temperature and humidity cell to maintain humidity from 20%
to 90% RH at 30 °C. Microprobes (Signatone INC., California,
USA) were used to make contacts with IDAs which were
connected to a Biologic SP200 potentiostat/galvanostat
(Biologic, France) with an electrochemical impedance spec-
troscopy (EIS) option to carry out impedance measurements
over the 7 MHz−1 Hz range. A sample of Nyquist impedance
is shown in Figure S2 of the Supporting Information.
Impedance spectra were fitted with equivalent circuits reported
in refs 37 and 38 to estimate thin-film resistance (R in Ω)
which was then used to compute conductivity (σ in S/cm)
using eq 2.
d
σ=
R × (L) × (N − 1) × w (2)
where d is the gap between electrodes (100 μm), L is the dry
thickness of the film (∼50 nm), N is the number of electrodes,
and w is the width of the electrode (8 mm).
2.4. Samples for GISAXS Measurements. Ionomer thin
films of about 50 nm thickness were prepared by spin-coating
1.5% (w/w) polymers solutions in methanol on bare Si wafers
with a native hydrophilic oxide layer using a WS-650HZ-
23NPP spin-coater (Laurell). X-ray reflectivity was used to
confirm the thickness of thin films (see the Supporting
Information). A selected number of samples were also
prepared on hydrophobic Si wafers in order to ensure their
stability at a higher RH. The hydrophobic Si wafers were
prepared by silanization with octadecyl tricholorosilane (OTS)
vapor as follows. The wafers were first cleaned by sonication in
DIW for 5 min followed by washing in 2% sodium dodecyl
sulfate (SDS) solution for 30 min; then the wafers were
thoroughly rinsed with DIW, dried with nitrogen, and
ozonated for 20 min in UV/ozone (ProCleaner, BioForce
Nanosciences). Immediately thereafter the samples were
placed to a desiccator along with an open bottle containing
5 mL of OTS; the desiccator was evacuated and left closed
overnight. The clean OTS-treated hydrophobic wafers showed
a water contact angle 105 ± 1° (KRUSS VSA100) using a 5 μL
sessile drop.
2.5. GISAXS and X-ray Reflectivity. GISAXS experiments
were performed at the high-energy beamline for buried
interface structure and materials processing ID31 at the
ESRFEuropean Synchrotron Radiation Facility, Grenoble,
France. The X-ray beam from a cpmU14 undulator was
parallelized by the first CRL transfocator and monochromi-
tized by a bent Laue−Laue monochromator. A second CRL
transfocator focuses the beam onto the sample position with a
5 × 20 μm2 spot size. The XRR spectra were acquired with a
MAXIPIX CdTe detector and the GISAXS data with a Pilatus3
X CdTe 2 M detector. To avoid excessive radiation damage the
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samples were laterally displaced by 0.5 mm between XRR and
GISAXS scans. XRR allowed verification of the film thickness
based on the spacing of Kiessig fringes,57 which was within a
few percent of the thickness obtained by ellipsometry. GISAXS
spectra were recorded for a series of 20 incidence angles in the
range 0−0.1°, which was below, near, and slightly above the
critical angle.58,59 Before measurements, the samples were
stabilized inside a closed humidity chamber with Kapton
windows maintained at a RH of 88 ± 2% for about 1.5−2 h.
Background scattering for the closed chamber was measured
using a horizontal beam passing through the chamber windows
above the sample. 2D GISAXS scattering intensity maps were
constructed using the dedicated MATLAB software provided
by ID31.
3. RESULTS AND DISCUSSION
3.1. Hydration of Different Anionic Forms of FAA3
Thin Films. Figure 1 compares the water content of different
Figure 1. Water content (estimated from swelling) at 25 °C as a
function of relative humidity for different anionic forms of FAA3
ionomer.
anion forms of FAA3 thin films determined via eq 1 from
swelling measurements using ellipsometry. An example of
ellipsometry data fitted with the B-spline model is shown in
Figure S1 of the Supporting Information. The Br− form of
FAA3 ionomer thin film exhibited the least hydration, the F−
form the highest, and the HCO3− form a hydration level
between the two halides. These results are consistent with the
findings reported for the (thick) FAA3 membrane.44
The hydration of the ionomers is in part governed by the
affinity of water for the cation/anion ion-pair at low RH and
energy to dissociate the ions, i.e., cationic quaternary
ammonium (QA) and the mobile anion, at high RH.60 The
degree of affinity of water toward the anion and cation of an
ion-pair influences the hydration characteristics under drier
conditions. The Hofmeister series suggests that large anions
such as Br− and HCO3− and large cations such as QA+ exhibit
weak interaction with water whereas small anions such as F−
and OH− and cations such H+ and Li+ strongly interact with
water.61,62 In addition, as per Pearson’s HSAB (hard and soft
acid−base) theory, where large anions and cations tend to
form condensates, it is expected that ion-pairs of QA+Br− and
QA+HCO3− tend to form stronger ion condensates than QA+
F−.63 Thus, it can be expected that the QA+F− ion-pair and its
condensate would dissociate upon hydration more easily than
QA+Br− and QA+HCO3− ion-pairs and their condensates.
Further insights into the hydration behavior can be gained
by comparing Gibbs energy change upon hydration.64,65
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Equation 3 is the change in the Gibbs energy of the water and
QA−X (where X = Br−, HCO3−, and F−) from their pure (or
unmixed) state to the state of mixture.
i y
ΔG = RT jjj− λd ln a w + λ ln a w zzz
k {
aw
∫0
(3)
where ΔG is the Gibbs free energy change (kJ/mol), aw is the
water activity, R is the universal gas constant, and T is the
temperature. It is effectively the free energy of mixing of
condensed water and nonhydrated QA+X− ion-pair. The first
term on the right-hand side represents the Gibbs free energy
change of the QA−X ion-pair in the dry state to that in the
hydrated state of the mixture, and the second term is the Gibbs
free energy change for pure water to that in the mixture of
(QA−X)−water. The absorption of water implies that the total
Gibbs energy change is negative. Comparison of the Gibbs free
energy change of hydration for different anionic forms can
provide insight into the interaction of water with ion/ion-pair.
It is instructive to consider the various stages of ion-pair
hydration−reverse order of depiction (Figure 2) as presented
in the review reported by Marcus and Hefter, in which they
consider the formation of ion-pairs from corresponding
hydrated ions.66
Figure 2. Depiction of ion-pair types in a salt solution: (a) solvent-
separated ion-pair, (b) solvent-shared ion-pair, and (c) contact ion-
pair. Adapted from Marcus and Hefter.66
At low water content, a contact pair exists, and it evolves
into “solvent-shared” and “solvent-separated” ion-pair struc-
tures, as water content increases. At a higher hydration level,
the complete dissociation of ion-pair occurs, and the solvation
shell around ions may be formed.67 Often, the terms “solvation
number” or “hydration number” are used interchangeably to
discuss the effect of water on the ion-pair bonding.68 For the
sake of clarity, we use the definition of solvation number as the
number of water molecules required to fully hydrate an ion-
pair or dissociate an ion-pair. The solvation number has been
reported for various cations and anions; among halides,
fluoride has the highest solvation number (λ of 6−7).69 In
the presence of QA+, the solvation number of 3−4 water
molecules for bromide has been reported.70,71 No such
information is available for bicarbonates. However, a MD
simulation study has shown that at a hydration level of up to λ
equal to 4, QA+HCO3− do not dissociate.60 In the contact pair
regime (λ < anion solvation number), the enthalpic term of
hydration Gibbs energy would arise from the exothermic effect
of mobile water attaining a less energetic state of sorbed water.
For our experiments, the comparison between three forms can
be done for λ of 2 or less and between F− and HCO3− forms
for λ up to 4. Under these conditions, the contact ion-pair is
expected to exist, and the enthalpic effects must dominate the
water sorption on an ion-pair. The change in entropy is
predominantly due to a change in the state of water in the
mobile state to a restricted mobility state and should be similar
for all ionomer forms for λ of 2 or 4. MD simulation and X-ray
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studies on QA+Br− and QA+HCO3− point to a higher affinity
of water toward Br− and HCO3− rather than QA+.60,70,71
Similar preferential affinity of water for F− compared to that for
QA+ can be expected. Accordingly, the observed differences in
calculated Gibbs energy change are reflective of the enthalpy
change associated with water−anion (X = F− > HCO3− > Br−)
interactions. From the trends, it is obvious that at a given λ, the
Gibbs free energy change increases in the order of F− >
HCO3− > Br− (see Figure 3), indicating stronger affinity of
water to F− followed by HCO3− and then Br−.
Figure 3. Gibbs energy change of hydration of different anionic forms
of the FAA3 ionomer. Inset shows the change in Gibbs free energy at
λ ∼ 2.
3.2. Conductivity of Different Anionic Forms of FAA3
Thin Films. 3.2.1. Comparison of Thin-Film Conductivity for
Different Anionic Forms of FAA3. Anion conductivities of
FAA3 thin films for the three anion forms are compared in
Figure 4a. Possibly due to the very low conductivity below 40%
RH, the FAA3−Br sample did not yield reasonable spectra
which can be fitted with a model; therefore, conductivity was
not measured for FAA3−Br at 20% RH. An example of
impedance data fitted with the model is shown in Figure S2 of
the Supporting Information. As expected, conductivity
increases with an increase in relative humidity, regardless of
the counteranion.72 FAA3−F shows the highest conductivity at
a given RH, followed by FAA3−HCO3 and then FAA3−Br. It
also follows the trend of water content at a given RH (Figure
1). For example, at 80% RH, λ for the F− form is 5.7 and the
corresponding conductivity is 1.9 mS cm−1, λ for the HCO3
form is 2.9 and the corresponding conductivity is 0.68 mS
cm−1, and for the Br− form λ is 1.8 and the corresponding
conductivity is 3.4 mS cm−1, consistent with previously
reported conductivity measurements.73 It is well-known that
the conductivity is dependent on λ, and thus differences in
conductivity at a given RH are governed by the water content.
For a meaningful comparison, it is important to compare the
conductivity of these ionomers at a given λ (see Figure 4b).
The low water content by the Br− form limits the
comparison for all forms to an ion-pair with two water
molecules. At λ ∼ 1.2−2, the conductivity of the FAA3−Br
form is almost two times higher than that of the FAA3−HCO3
form but an order of magnitude higher than that of FAA3−F.
Since conductivity is compared at similar λs for the same
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Figure 4. Conductivity for different anionic forms of FAA3 thin film as a function of (a) relative humidity and (b) water content.
ionomer type, the difference among conductivities must arise
from local mobilities of ions and not due to the differences in
the water content itself. Conductivities of different FAA3
anionic forms are compared at λs below the solvation number
of the respective ions. When the λ is below the solvation
number, it can be expected that the anion must be closely
paired with the cation and, thereby, must exist in the bound
state. The water is expected to be sorbed to the ion-pair but
less strongly. Considering the untethered anion to be strongly
bound to the tethered cation, the conductivity at such low
water content may be attributed to arise from the mobility of
the OH− of water. At λ ∼ 2, the ion-dependent conductivity
increases in reverse order of ion-dependent ΔG (see inset of
Figure 3). Higher ΔG implies higher energy of water
interaction or water sorption. This observation supports the
idea that the strength of water−anion interaction which is
expected to affect water (or OH−) mobility determines the
ionic conductivity. Further insight can be garnered from
examining the hydrogen bond strength. In the Jones−Dole
equation (see eq 4 below) which correlates the viscosity of the
solution to the ion concentration, the value of the coefficient B
directly correlates with hydrogen bond strength:
η membranes, the conductivity at similar λ was found to decrease
= 1 + AC1/2 + BC
ηo (4)
where η is the viscosity of solution at a condition, η0 is the
viscosity of the solvent, C is solute concentration, the
coefficient A pertains to charge−charge interaction, and the
coefficient B depends on solute−solvent interaction. From
Table 1, notably the value of coefficient B is much higher for
fluoride than bicarbonate and bromide ions which indicates
that fluorine is an ionic kosmotrope, and bicarbonate and
bromine are ionic chaotropes.61 Kosmotropes tend to create
dense water structure by strengthening the hydrogen network
and thus may reduce the mobility of protons and hydroxyl ions
whereas chaotropes tend to create low-density water structure
Table 1. Comparison of Coeffient B in the Jone−Dole
Equation76,77
ions coefficient B in the Jone−Dole equation
F 0.127
Br −0.033
HCO3 −0.33
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and thus have no effect on the mobility of protons and
hydroxyl ions. A previous solid-state NMR study on 10 and
160 nm thick Nafion films showed that at λ < 2 water
associates strongly with H+ ion.46 At λs < 7, fluoride strongly
interacts with water and has a significant effect on restructuring
the hydrogen network74,75 and thus reduces the OH− mobility,
whereas Br and HCO3 are loosely associated with water, which
may not affect OH− mobility as much. To provide further
insight into the effect of counteranion on OH− mobility, the
conductivity measurement of the OH− form of the ionomer
film would be useful. However, such measurements are not
trivial and require a specialized setup14 to avoid rapid
carbonation of hydroxyls upon ambient air exposure and are
out of the scope of the present work.
3.2.2. Comparison between Thin-Film and Membrane
Conductivity. Figure 5a presents a conductivity comparison of
ionomer thin films and membranes for different anionic forms.
The membrane conductivity data were obtained from previous
work by Kreuer and colleagues.44 Interestingly, the con-
ductivity of FAA3 thin films shows an opposite trend with
respect to ionic forms compared to that of membranes.44 For
with the increasing size of ion. On the other hand, the
conductivity of thin films decreases in the order of Br > HCO3
> F for the FAA3 ionomer. Marino et al. claimed that the
conductivity of the ionomer at similar λ decreases with the
increasing size of the ion and is related to the degree of
dissociation of ion condensates or ion-pairs.44 For example, in
membranes, at λ ∼ 3 the conductivity of the F form is an order
of magnitude higher than that of the Br form,44 which is
opposite to the trend for thin films observed in the present
study. A key observation that emerges from Figure 5a is that
the conductivities of thin films are higher than the
conductivities of the membrane in all forms. This is contrary
to Nafion ionomers, for which the conductivity of thin films
has been found to be suppressed compared to that of thicker
films or membranes.34 The F− form of thin film up to λ∼ 3
displays an order of magnitude higher conductivity than
membrane; however, as λ increases the conductivity of the
membrane approaches the conductivity of the thin film.
Although low water content in thin films does not allow direct
comparison at the same λ, it is evident from Figure 5a that the
conductivities of Br and HCO3 forms in thin films would be
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Figure 5. (a) Conductivity of different anionic forms of the FAA ionomer thin film and membrane. (b) Ratio of tortuosity of the membrane to that
of the thin film of the F form of the FAA ionomer as a function of water content. The dotted line is to guide the eye.
Figure 6. Comparison of different anionic forms of PPO and FAA3 at 30 °C and different RHs: (a) water content and (b) conductivity.
much higher than the conductivities of membranes in the same
form if conductivity data were to be extrapolated to λ > 5.
In principle, the molar conductivity (σm) for a polymer
electrolyte can be expressed as a function of ionic mobility
(μion) and concentration (Cion) and structural factors such as
the volume fraction of ion-conducting phase (ϕw) and
tortuosity (τ) (see eq 5).
σm = Cionμion ϕw /τ (5)
As an alternative to (ϕw/τ), a Bruggeman type correlation
(ϕwn) could also be considered, where n is equal to 1.5. An
attempt to fit the conductivity−water volume fraction data
yielded n equal to 4 with deviation at higher water content (see
fitting in the Supporting Information). Thus, further discussion
on structural factor influences on conductivity is presented in
terms of the (ϕw/τ) effect. As the water content or water
volume fraction (ϕw) increases, the connectivity between
water-rich regions changes and the pathway for water-mediated
ion transport is expected to become less tortuous. In other
words, the tortuosity will change with water content. In
addition to these structural factors, both the mobile ion
concentration78 and ionic mobility44 will change with a change
in water content. However, at the same λ, Cion should be
similar for a particular ion form of the membrane and thin film,
and ϕw should be the same as well because λ is essentially
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derived from the volume fraction of water within the polymer.
Therefore, the difference in conductivity arises from differ-
ences in τ and μion. Due to the confinement, the orientation
and the size of the domain in the thin film are expected to be
different from those of the membrane.33 Since the size of the
domain weakly affects μion,79 the only remaining factor τ
relating to the orientation of domains can be considered to be
primarily responsible for the difference in the conductivity of
membranes and thin films.
The σ−λ data for the F form of thin films and membranes
can be compared at a wide range of λ. However, due to the
limited water content of the Br and HCO3 forms of FAA3 thin
films, the Br and HCO3 forms of thin films and membranes
cannot be compared directly. Thus, we compare the ratio of τ
for the F form of the membrane to that of the thin film in
Figure 5b. It can be noted that the tortuosity ratio decreases
sharply from λ of 3 to λ of 8 and then onward gradually and
becoming similar at higher λ. It must be recognized that the
conductivity for the thin films was determined from the
interdigitated electrodes and represents the conductivity in the
in-plane direction whereas membrane conductivity was
measured in the through-plane direction.
Several studies on cationic ionomer thin films suggest that
both confinement effects and the interaction of ionomer with
the substrate control its local structure and, thereby, its
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The Journal of Physical Chemistry C
properties such as a thickness-dependent elastic modulus and
water content as well as substrate-dependent ionic con-
ductivity.34,35,56,80−82 However, there is a major difference
between the flexible fluorocarbon backbone of Nafion and the
less flexible aromatic backbone. Nagao et al. reported higher
conductivity of the proton-conducting sulfonated polyimide
thin-film form than the bulk form, and they identified it as
mainly due to the confinement-led aligned network of the
domains.83 Therefore, unlike the Nafion ionomer wherein the
conductivity in thin films has been found to be suppressed
compared to the bulk membrane, the enhancement of
conductivity for the FAA3 thin film compared to the bulk
membrane would imply improved connectivity due to the
aligned network of the conducting domains. We speculate that
the aromatic backbone of the ionomer may align the plane of
ring structures parallel to the substrate thereby providing facile
in-plane long-range transport of ions.
3.3. Comparison of FAA3 with PPO. Now, we compare
the water content and conductivity of two different AEIs with a
similar backboneFAA3 and PPO. The equivalent weight
(EW) for PPO is nearly half that of FAA3 and FAA3 does not
have a side chain; therefore, we expect EW and molecular
structure related differences in conductivity and water content
for both ionomers.
Similar to the FAA3 ionomer, the water content of PPO in
the F form is greater than in the Br form, and for the same
anionic form, PPO films exhibit higher water content than
FAA3 films at the same RH (see Figure 6a). At the same RH,
the conductivity of PPO−Br is much lower than that of PPO−
F (Figure 6b). Comparing the PPO and FAA conductivities, it
can be noted that the conductivity of PPO−F at all the RHs is
higher than for FAA3−F, but the conductivity of PPO−Br is
somewhat similar to the conductivity of FAA3−Br. The model
fits of ellipsometry and impedance data for PPO are available
in Figures S3 and S4 of the Supporting Informaton.
Again, to discuss the conductivity mechanism, the
conductivities are normalized to the volume fraction of water
(σ/ε) for both ionomers and presented as a function of λs (see
Figure 7). Similar to FAA3, the F form of PPO shows highly
suppressed conductivity compared to the Br form of PPO. At
similar λ, the F forms of FAA3 and PPO showed similar
Figure 7. Conductivity vs water content compared for different
anionic forms of PPO and FAA3 ionomers.
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conductivity, but the Br forms of FAA exhibited much higher
conductivity than the same forms of PPO. According to eq 5,
σ/ε is a function of the concentration of conducting species,
mobility, and tortuosity. At similar λ values, the concentration
of the conducting species within an ionomer must be similar;
therefore, as explained in the earlier section 3.2.1, the lower
conductivity of PPO−F than PPO−Br is mainly due to the
ionic mobilities. Surprisingly, σ/ε of PPO−F is similar to that
of FAA−F, but σ/ε of PPO−Br is much smaller than that of
FAA−Br. At similar λs the concentration of ionic species must
be similar; however, given that the volume fraction of water in
PPO is higher than in FAA3 ,a more established network of
water, i.e., less tortuous pathways in PPO than FAA3, is
expected, which in theory should be more conducive to the ion
transport; however, observation from Figure 7 confirms
otherwise.
We had carried out GISAXS measurements to gain some
insight into the phase-segregated morphology. It was expected
that anisotropy of the ringlike feature corresponding to the
amorphous ionomer peak of these ionomers could be
indicative of a preferential orientation of the conducting
channels.59,84 Unfortunately, this peak, corresponding to Q-
values 0.05−0.1 A−1 for FAA3, could not be resolved in
GISAXS spectra44 (see the Supporting Information). Appa-
rently, either the electron density contrast was insufficient in
the examined AEM polymers or the microphase separation in
the present hydrocarbon materials was not as strong as in
perfluourinated Nafion. Indeed, SAXS data reported by Marino
and Kreuer indicate that the ionomer peak in FAA3 was far less
pronounced than in PEM materials such as Nafion.44 In the
absence of both nanomorphology from GISAXS and the exact
molecular structure of FAA3, we can only speculate about the
structural effects on conductivity.
Within a polymer chain, if the distance between ion-pairs is
shorter than the Bjerrum length (a function of the dielectric
constant of the solvent and the temperature) the ion-pair is
expected to form a cluster or a condensate.85 First, since PPO
has a lower equivalent weight than FAA3, it is plausible to
assume that the gap between the ion-pair in PPO is smaller
than that in FAA3 which makes PPO more susceptible to form
intrachain ion-condensates in MeOH medium which are likely
to exist in film form. Second, PPO has more ionic groups
within a polymer chain, so upon vacuum dehydration, PPO has
a higher degree of forming the interchain ionic clusters through
chain−chain interaction. Hence, we hypothesize that in both
F− and Br− forms, PPO tend to form more ionic clusters than
FAA3. Since fluoride is more strongly hydrated, the ions within
these clusters are weaker and may dissociate upon water
absorption; however, hydrophobic bromide may form more
tightly packed clusters that may persist. Therefore, the F forms
of both PPO and FAA3 show similar conductivity at similar λ.
While strong and unbreakable bromide ion clusters in PPO−Br
must have, on average, less hydrated microstructure than
FAA3−Br and thereby more tortuous conducting phase in
PPO−Br than FAA3−Br, they must be responsible for the
suppressed conductivity in PPO−Br as compared to FAA3−
Br. Further, it would be instructive to study the effect of IEC
on water uptake and the conductivity of ionomers without
modifying the structure of ionomers to understand the impact
of IEC on AEI properties.
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J. Phys. Chem. C 2020, 124, 23469−23478
The Journal of Physical Chemistry C
4. CONCLUSIONS
In this study, the humidity-dependent ion conductivity and
water content for thin films of different ionic forms of two
different alkaline exchange ionomers (AEIs)FAA3 and PPO
ionomer on SiO2 substrateare reported. This is the first
study to report conductivity data for ultrathin films of AEIs and
to correlate it to water content. From the computed Gibbs free
energy of hydration for ionomer thin films, it is revealed that
the fluoride form has highest affinity to water, followed by
bromide and bicarbonate forms. From the Gibbs free energy,
water content, and conductivity data analyses, it is found that
at low λs, ionic conductivity is strongly dependent on ionic
mobility which is governed by the energy of interaction (Gibbs
free energy) between anion and water molecules. At similar λ,
owing to the alignment of FAA3 ionomer thin films, the
tortuosity of thin films is much lower than the tortuosity of the
membrane; thus, the conductivity of all the ion forms of FAA3
thin films is much greater than the corresponding form of
membranes. In addition, the water content and conductivity
relationship for fluoride and bromide forms of FAA3 and PPO
were compared. At similar λ, fluoride forms of PPO show
similar conductivity to FAA3 thin films. The conductivity of
the bromide form of PPO is more suppressed than tht of
FAA3, which is attributed to the aggravated clustering in PPO.
Note that this work reports AEI thin-film property on SiO2
substrate which is not a catalyst support in the fuel cell and
electrolyzers. It is known that substrate−polymer interactions
can induce structural changes manifesting in substrate-
dependent properties of polymers. Accordingly, any extrap-
olation of the results from the present study to ionomer films
on different substrates must be done with caution. A separate
future study needs to be conducted on polymer films on a
versatile substrate such as carbon.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.jpcc.0c04278.
Examples of model fidelity fitted to the raw ellipsometry
data (psi and delta) obtained to compute thin-film
swelling; examples of model fidelity fitted to the raw
electrochemical impedance spectra to compute thin-film
ionic resistance; examples of XRR data and GISAXS
spectra; example of conductivity−water volume fraction
data fitted with a trend line (PDF)
■
AUTHOR INFORMATION
Corresponding Author
Kunal Karan − Department of Chemical and Petroleum
Engineering, University of Calgary, Calgary AB-T2N-1N4,
Canada; orcid.org/0000-0001-5432-8050;
Email: kkaran@ucalgary.ca
Authors
Udit N. Shrivastava − Department of Chemical and Petroleum
Engineering, University of Calgary, Calgary AB-T2N-1N4,
Canada
Avital Zhegur-Khais − The Wolfson Department of Chemical
Engineering, Technion−Israel Institute of Technology, Haifa
3200003, Israel
Maria Bass − The Wolfson Department of Chemical Engineering
and The Nancy & Stephen Grand Technion Energy Program
23476
pubs.acs.org/JPCC Article
(GTEP), Technion−Israel Institute of Technology, Haifa
3200003, Israel
Sapir Willdorf-Cohen − The Wolfson Department of Chemical
Engineering, Technion−Israel Institute of Technology, Haifa
3200003, Israel
Viatcheslav Freger − The Wolfson Department of Chemical
Engineering and The Nancy & Stephen Grand Technion Energy
Program (GTEP), Technion−Israel Institute of Technology,
Haifa 3200003, Israel; orcid.org/0000-0001-8067-052X
Dario R. Dekel − The Wolfson Department of Chemical
Engineering and The Nancy & Stephen Grand Technion Energy
Program (GTEP), Technion−Israel Institute of Technology,
Haifa 3200003, Israel; orcid.org/0000-0002-8610-0808
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jpcc.0c04278
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The collaboration research was enabled by the UCalgary GRI−
Technion Isreal Institute of Technology partnership program
through support from UCalagry Canada First Research
Excellence Fund (CFREF). K.K. and U.N.S. also acknowledge
funding from the Natural Sciences and Engineering Council of
Canada (NSERC). The work was partially funded by the
Nancy & Stephen Grand Technion Energy Program (GTEP);
by the European Union’s Horizon 2020 research and
innovation program (grant No. 721065); by the Israel Science
Foundation (ISF) (grant No. 1481/17); by the Ministry of
National Infrastructure, Energy and Water Resources of Israel
(grant No. 3-13671); by the Melvyn & Carolyn Miller Fund
for Innovation; and by the Planning & Budgeting Committee/
ISRAEL Council for Higher Education (CHE) and Fuel
Choice Initiative (Prime Minister Office of ISRAEL), within
the framework of “Israel National Research Center for
Electrochemical Propulsion (INREP)”. The authors thank
Veijo Honkimäki and Maria Valeria Blanco for assistance
during GISAXS and XRR measurements at the ID31 beamline
at ESFR.
■
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