Power D 22 04425 - R2

Journal of Power Sources
Ether-free sulfonated poly(fluorene biphenyl indole) membranes and ionomer binders

for proton exchange membrane fuel cells
--Manuscript Draft--
Manuscript Number: POWER-D-22-04425R2
Article Type: Research Paper
Keywords: fuel cell; proton exchange membrane; Ionomer binder; Chemical stability; Ether-free
Corresponding Author: Dukjoon Kim, PhD

Sungkyunkwan University
Suwon, KOREA, REPUBLIC OF
First Author: Thuc Vu Dong
Order of Authors: Thuc Vu Dong
Vo Dinh Cong Tinh
Dukjoon Kim
Abstract: Because of the vulnerability of ether bonds to oxidative radicals, the ether-free polymer
electrolytes were synthesized to prepare chemically more stable proton exchange
membranes for long time durable fuel cell application. Here, we presented a series of
ether-free sulfonated poly(fluorene biphenyl indole)s (SPFBI) synthesized by a feasible
and cost-effective process. Owing to the ether-free structure, SPFBI membranes
displayed great chemical stability comparable to the commercial Pemion membranes
from Fenton’s test. SPFBI membranes exhibited high proton conductivity up to 0.1956
S cm -1 at 80 o C under the limited swelling ratio lower than 16.5%. Consequently,
while the SPFBI-0.4 membrane showed the excellent cell performance reaching the
maximum power density of 365 mW cm -2 , it also played a decent role as an ionomer
binder for both SPFBI and Nafion membranes. In open circuit voltage stability test, the
membrane electrode assemblies using SPFBI-0.2 membrane sustained more than 620
h without any severe defects at 90 o C under low relative humidity of 30%,
outweighing the Nafion counterpart. This study provides a remarkable approach for
optimizing the ether-free hydrocarbon-based polymer structure for the application of
both polymer electrolyte membrane and ionomer binder with high proton conductivity
and chemical stability.
Suggested Reviewers: Simon Thiele

University of Freiburg Department of Microsystems Engineering
simon.thiele@imtek.de
Byungchan Bae
Korea Institute of Energy Research
bcbae@kier.re.kr
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Cover Letter
School of Chemical Engineering

Sungkyunkwan University
Suwon 16419, Republic of Korea
Tel: +82-31-290-7240 Fax: +82-31-290-7272
http://chemeng.skku.edu/
September, 2022
Dear Editor:
We are pleased to submit the paper entitled, “Ether-free sulfonated poly(fluorene biphenyl indole)
membranes and ionomer binders for proton exchange membrane fuel cells” by Vu Dong Thuc, Vo Dinh
Cong Tinh and Dukjoon Kim to Journal of Power Sources.
Fabrication of chemically stable membranes is crucial to extend the lifetime of polymer electrolyte
membrane fuel cells. Therefore, ether bonds that exist in many hydrocarbon-based proton exchange
membranes (PEMs) have raised concerns about oxidative stability, since those bonds are vulnerable to radical
attacks. In this work, we rationally designed a novel ether-free polymer, named sulfonated poly(fluorene
biphenyl indole) (SPFBI), consisting of a rigid polyaromatic main chain and long sulfonated alkyl side chains.
Accordingly, a series of SPFBI polymers were synthesized by a facile and cost-effective process using
superacid-catalyzed polymerization. Thanks to the decent solubility of SPFBI in alcohol and water mixture,
the polymers were employed to prepare both PEM and ionomer binder for fuel cell tests. In general, SPFBI
PEMs possessed high oxidative stability in comparison to Pemion and other reported PEMs. They also
exhibited excellent proton conductivities along with a limited swelling ratio, resulting in the enhanced fuel
cell performance of SPFBI membranes, compared to that of Nafion membrane. The open circuit voltage
stability test demonstrated superior long-term in-situ stability of SPFBI-0.2 PEM that remained intact after
over 620 h test. On the other hand, SPFBI-0.4 ionomer binder provides decent cell performances and did not
affect the stability of the cell. This study provides the possibility of developing ether-free PEMs with
excellent properties as well as merits further improvement of hydrocarbon ionomer binders for fuel cell
applications.
Ethics Statement
This work has not been published previously (except in the form of an abstract or as part of a published
lecture or academic thesis), and it is not under consideration for publication elsewhere. Also, its publication
is approved by all authors and tacitly or explicitly by the responsible authorities where the work was carried
out. If accepted, it will not be published elsewhere in the same form, in English or in any other language,
without the written consent of the Publisher.
Thank you for your consideration. We look forward to hearing a positive response from you.
Sincerely yours,
Dukjoon Kim
Ph.D., Professor, SKKU Fellow
Executive Director of Korea Polymer Society
National Research Laboratory, School of Chemical Engineering, Sungkyunkwan University
Suwon, 16419, Republic of Korea
[Email] djkim@skku.edu; [Phone] +82-10-3017-7250

Response to Reviewers
RESPONSE TO EDITOR’S COMMENT
Manuscript Number: POWER-D-22-04425R1
Title: Ether-free sulfonated poly(fluorene biphenyl indole) membranes and ionomer binders for
proton exchange membrane fuel cells.
The authors appreciate reviewers’ positive comments which recommend the publication of our
work in Journal of Power Sources. We also thank Editor for the comment on the format of Nyquist
plots:
Editor: the EIS Nyquist plots shall be traced on orthonormal sets of axes and parametered in
frequency as detailed in [https://doi.org/10.1016/j.jpowsour.2019.227635].
Response: Based on the comment and the practical guide, we modified the Nyquist plots in Fig.
6b, Fig 7d, e and f. In detail, all Nyquist plots were changed to be orthonormal (same length on
the x and y axes for 0.1 Ω cm2). To parameterize the graphs in frequency, we added the label and
a curved arrow to indicate the frequency range, as shown below:
Fig.6:
has changed to
Fig.7:
has changed to:

Previously rejected submission: Response to Editor/Reviewer
comments (Marked with highlighted changes)
Ether-free sulfonated poly(fluorene biphenyl indole) membranes and ionomer binders for
proton exchange membrane fuel cells
Vu Dong Thuca, Vo Dinh Cong Tinha, Dukjoon Kima*

a
School of Chemical Engineering, Sungkyunkwan University, 2066 Seobu-ro, Jangan-gu,
Suwon, Gyeonggi 16419, Republic of Korea

*
Email: djkim@skku.edu
Abstract
Because of the vulnerability of ether bonds to oxidative radicals, the ether-free polymer
electrolytes are synthesized to prepare chemically more stable proton exchange membranes for
long time durable fuel cell application. Here, we present a series of ether-free sulfonated
poly(fluorene biphenyl indole)s (SPFBI) synthesized by a feasible and cost-effective process.
Owing to the ether-free structure, SPFBI membranes display great chemical stability comparable
to the commercial Pemion membranes from Fenton’s test. SPFBI membranes exhibit high proton
conductivity up to 0.1956 S cm-1 at 80 oC under the limited swelling ratio lower than 16.5%.
Consequently, while the SPFBI-0.4 membrane shows the excellent cell performance reaching the
maximum power density of 365 mW cm-2, it also plays a decent role as an ionomer binder for both
SPFBI and Nafion membranes. In open circuit voltage stability test, the membrane electrode
assemblies using SPFBI-0.2 membrane can sustain more than 620 h without any severe defects at
90 oC under low relative humidity of 30%, outweighing the Nafion counterpart. This study
provides a remarkable approach for optimizing the ether-free hydrocarbon-based polymer
structure for the application of both polymer electrolyte membrane and ionomer binder with high
proton conductivity and chemical stability.
1
Keywords: Fuel cell; Proton exchange membrane; Ionomer binder; Chemical stability; Ether-free
1. Introduction.
To satisfy the growing demand for the green energy with no harm to the environment,
proton-exchange membrane fuel cell (PEMFC) has been recognized as one of the promising
electrochemical energy sources due to its eco-friendliness and high energy density [1–4]. As a key
component of PEMFC, proton-exchange membrane (PEM) needs to fulfill various requirements,
such as high mechanical and chemical stability and low gas crossover in addition to high proton
conductivity [5,6]. While many attempts have been launched to fabricate high-quality PEMs with
enhanced properties so far, the perfluorosulfonic acid-based membranes including Nafion are the
most successful and popular PEMs for commercial applications. Nafion possesses good
mechanical and oxidative stability as well as a decent proton conductivity in humidified conditions
due to the formation of ion clusters by well-separated hydrophobic and hydrophilic phases [4,7,8].
Despite those advantages, Nafion has major drawbacks, including high gas permeability, poor
water retention, and high cost [6,9]. Because of the perfluorinated backbone structure, Nafion also
causes environmental concerns in its disposal process [10,11].
In order to replace the perfluorinated polymers with cost and disposal ineffectiveness,
hydrocarbon-based polymers with acidic functional groups have been developed. Those generally
consist of the hydrophobic aromatic backbones functionalized with the proton-conducting moieties
such as sulfonic acid or phosphonic acid groups statistically distributed. Depending on the polymer
designs, these acid groups can be either directly attached to the polymer backbone [12,13], or
located on the long alkyl chains grafted onto the polymer backbone [14,15]. Therefore, similar to
the perfluorinated polymer membranes, the phase-separated hydrophilic domains in hydrocarbon-
2
based PEMs allow the construction of interconnected water channels to facilitate the proton
transport. With many attempts to improve membrane properties, the hydrocarbon-based PEMs
currently not only exhibit high proton conductivity and cell performance [16–18], but also offer
cost reduction compared to perfluorinated PEMs.
Despite the aforementioned advantages, several limitations of hydrocarbon-based PEMs
hinder their commercialization. A major concern is about their chemical stability, since the
polymer structure typically contains more reactive functional groups and thus possesses less
oxidative resistance than Nafion composed of an inert Teflon-like backbone [19,20]. In such
polymer structures, the ether bond is the most commonly encountered heteroatom bond in the main
chain, usually resulting from the polymerization reaction to link monomer molecules together
[14,21]. Unfortunately, ether groups are very prone to attacking of ·OH radicals continuously
generated from the formation of reactive oxygen species and fuel crossover during the cell
operation [22,23]. The low oxidative stability of ether group is because the oxygen in ether
increases the electron density of neighboring aryl rings via the electron-donating effect and thus
weakens the resistance against oxidative species [1,24,25]. Since the ether groups do not have
crucial role in PEM properties, their elimination from the polymer structure can be considered an
attractive way to enhance the chemical stability of PEMs. Accordingly, many studies have been
conducted to synthesize ether-free PEMs. For instance, Miyake et al. reported a flexible
polyphenylene PEM (SPP-QP) with excellent flexibility and stability [26]. Pemion is also a
commercially available ether-free hydrocarbon-based PEM [27,28]. The synthetic process of
polymer electrolytes without ether linkages is usually quite complicated with the requirement of
costly metallic catalysts [27–29]. The superacid-catalyzed polymerization reaction was employed
as a good method, characterized by a short reaction time without the requirement of heating and
3
expensive catalysts [30,31]. This method has been widely used to synthesize ether-free polymers
for anion exchange membrane (AEM) [32,33], but just a few publications have been reported for
PEMs [34,35]. As the ether-free PEMs synthesized from the previous studies showed only
mediocre properties without profound investigation of chemical stability enhancement, it is
difficult to draw the potential of its methodological effectiveness.
In this work, the synthesis and characterization of sulfonated poly(fluorene biphenyl indole)
(SPFBI) are reported as a novel ether-free polymer electrolyte with improved PEM properties.
Compared to the previous ether-free polymers synthesized by superacid-catalyzed reaction, this
polymer structure was rationally designed from common monomers to establish the mechanically
robust rigid aromatic backbone grafted with long sulfonated alkyl chains to improve proton
conductivity. The synthetic procedure of SPFBI involves two main steps, starting from the
synthesis of poly(fluorene biphenyl indole) (PFBI) from isatin, biphenyl, and fluorene under
superacid conditions [31]. In the second step, the sulfonated alkyl groups were grafted to PFBI
backbone using 1,3-propane sultone and tetrabutylammonium bromide catalyst under basic
conditions [36,37]. By varying the monomer ratios, a series of SPFBI PEMs with different sulfonic
acid contents were prepared for an intensive investigation on proton conductivity, oxidative
stability, and PEMFC performance. Additionally, the solubility of SPFBI in isopropanol and water
mixture allowed its utilization as the ionomer binder for the preparation of catalyst ink in
membrane electrode assembly (MEA) process.
2. Experimental Section.
2.1. Materials.
Fluorene, isatin, trifluoroacetic acid (TFA), trifluoromethanesulfonic acid (TFSA), 1,3
4
propane sultone (99.0%) and tetrabutylammonium bromide (TBAB) were purchased from Tokyo
Chemical Industry (TCI, Japan). Biphenyl, iron(II) sulfate heptahydrate (FeSO4.7H2O) and
hydrogen peroxide (H2O2) solution were obtained from Sigma-Aldrich (Milwaukee, WI, USA).
Nafion alcohol-based dispersion (5 wt%, EW1100) was supplied from Chemours (Wilmington,
DE, USA), as well as platinum (nominally 40% on carbon black) (Pt/C) was provided by Alfa
Aesar (Ward Hill, MA, USA) to prepare MEAs. Other common solvents (99.5% purity) were
obtained from Samchun Chemicals (Korea).
2.2. Synthesis of poly(fluorene biphenyl indole) (PFBI).
The synthetic process of PFBI is briefly represented in Scheme 1. In detail, isatin (150
mmol) was added to a three-neck round bottom flask, along with a total of 150 mmol of two other
monomers (biphenyl and fluorene). The ratio of biphenyl and fluorene was varied to control the
sulfonation degree of the final polymer product. Then, 15 mL of dichloromethane (CH2Cl2) was
poured into the flask to dissolve the monomers under magnetic stirring. Subsequently, TFA (10
mL) and TFSA (15 mL) were dropwise added, and the mixture was stirred and kept at 0-5 oC for
12 h. After the reaction was finished, the dark purple mixture was slowly poured into methanol to
obtain PFBI precipitation. The polymer was washed with methanol and water several times, and
then dried in a vacuum oven at 80 oC for 24 h. It is designated as PFBI-x, where x represents the
proportion of fluorene over the total amount of biphenyl + fluorene used for the synthesis. The
yield of the PFBI synthetic process was about 93-96%. 1H NMR (300 MHz, DMSO-d6): 10.78
ppm (Hi), 7.73 ppm (Hb), 7.55 ppm (Hc), 7.21 – 7.31 ppm (Hd,e,g), 6.93 – 7.19 ppm (Hf,h) and 3.74
ppm (Ha).
5
2.3. Synthesis of sulfonated poly(fluorene biphenyl indole) (SPFBI).
The second step in Scheme 1 illustrates the synthetic procedure of SPFBI. For each
synthesis, 3 g of PFBI and 0.116 g of TBAB were simultaneously dissolved in 70 mL of dimethyl
sulfoxide (DMSO) at 60 oC and then poured into a three-neck round bottom flask. Next, nitrogen
gas was continuously supplied into the flask to remove the oxygen, and 4 mL of 50 wt% KOH
was slowly added to the polymer solution by syringe, followed by adding an excess amount of 1,3-
propane sultone. The reaction mixture was stirred at 60 oC for 6 h, under a nitrogen atmosphere.
Afterward, the product was precipitated by dropwise adding into methanol, and then washed with
water and isopropyl alcohol (IPA) in sequence and dried. The obtained polymer is named SPFBI-
x, where x refers to the PFBI-x precursor. The yield of the sulfonation process is 85-88 %. 1H
NMR (300 MHz, DMSO-d6): 7.55 – 7.61 ppm (Hb,c), 7.21 – 7.40 ppm (Hd,e,g), 7.07 – 7.19 ppm
(Hf,h), 3.83 ppm (Hi), 2.34 – 2.46 ppm (Ha,l) and 1.89 ppm (Hk).
6
Scheme 1. Two-step synthetic process of SPFBI-x.
2.4. Preparation of membrane and catalyst ink.
To prepare the SPFBI membrane, 0.3 g of SPFBI was completely dissolved in DMSO at
60 oC, and then the polymer solution was poured into a petri dish and placed in a vacuum oven at
80 oC for 24 h. After that, the polymer membrane was peeled off to be immersed in 1 M H2SO4
solution for 24 h to convert the sulfonated groups to H+ form. Finally, the membrane was washed
with deionized water for 24 h. For membrane comparison, Nafion PEMs were prepared by casting
method. Nafion alcohol-based dispersion (5 wt%) was poured into a flat petri dish, then dried at
7
80 oC for 24 h. The formed film was peeled off from the dish to obtain a Nafion pristine membrane.
The thickness of all fabricated membranes in this work was controlled within a range of 80-90 µm.
For catalyst ink preparation, 5 wt% solution of SPFBI-0.4 was prepared in-house by
acidifying the polymer solid in 1 M H2SO4 solution. After rinsing it with water, it was dissolved
in a mixture of IPA and water (4:6 w/w). For comparison, the preparation of catalyst ink using
SPFBI-0.4 ionomer followed a similar procedure as that of Nafion ionomer. Pt/C catalyst was
mixed with deionized water, IPA, and 5 wt% polymer solution (Nafion or SPFBI-0.4) and
subsequently ultra-sonicated to obtain a colloidal catalyst slurry. In all catalyst ink solutions, the
ionomer binder:catalyst mass ratio was fixed at 1:4.
2.5. Characterizations.
Chemical structure. To confirm the synthesis of the polymers, the proton nuclear
magnetic resonance (1H NMR) spectra were obtained by a Varian Oxford 300 MHz NMR
spectrometer (CA, USA) using DMSO-d6 as a solvent to dissolve polymer samples. The standard
chemical shift of DMSO-d6 is determined at 2.50 ppm.
Intrinsic viscosity. The intrinsic viscosity ([η]) of SPFBI was determined by a method
using a Ubbelohde viscometer. The polymers were dissolved in DMSO to obtain solutions with
five different concentrations, and the efflux time of each solution was recorded at 20 oC. By
drawing a plot of reduced viscosity versus concentration, we obtained [η] at the y-intercept value.
Solubility testing. The solubility of polymers was measured in various common organic
solvents, water and a mixture of IPA and water (4:6 w/w). The tests were performed at room
temperature and 60 oC (only for solvents with a high boiling point). The polymer was considered
insoluble in a certain solvent if it cannot be dissolved in both room and elevated temperatures.
8
Membrane hydration properties and IEC. The water uptake (WU) and swelling ratio
(SR) of SPFBI membranes were measured using the weight and length change of membrane
samples in fully dry and wet states at different temperatures. The membrane was dried at 80 oC for
48 h, and then cut into a 1 x 3 cm rectangular piece to measure the mass (md) and length (ld) of the
dry sample. Next, the sample was immersed in deionized water for 48 h under stirring. After that,
the sample was removed, the excess water on the membrane surface was wiped off with tissue
papers to measure the mass and length of the membrane at wet state (mw and lw). The test was
repeated 3 times for each sample to obtain the average value of WU and SR according to the
following equations:
𝑊𝑈(%) = (𝑚𝑤 − 𝑚𝑑 )/𝑚𝑑 × 100 (1)
𝑆𝑅(%) = (𝑙𝑤 − 𝑙𝑑 )/𝑙𝑑 × 100 (2)
The experimental ion exchange capacity (IECex) was measured by acid-base titration
method. A dry membrane sample with the mass m (g) was submerged in standard NaOH solution
with the known concentration and volume (CNaOH, VNaOH) for 48 h. The base solution after
removing the membrane was titrated with standard HCl solution (CHCl, VHCl) to determine IECex
from equation (3):

𝐶𝑁𝑎𝑂𝐻 𝑉𝑁𝑎𝑂𝐻 − 𝐶𝐻𝐶𝑙 𝑉𝐻𝐶𝑙
𝐼𝐸𝐶𝑒𝑥 (meg g −1 ) = × 1000 (3)
𝑚
For comparison, the theoretical ion exchange capacity (IECtheo) was also calculated from
the chemical structure of SPFBI, based on the number of acid groups and the theoretical molecular
weight of the repeating unit of polymer.
Thermal and mechanical properties. The thermal stability of the membrane in proton
form was investigated by thermogravimetric analysis (TGA) using a Seiko Exstar 6000 instrument
(Seiko Instruments, Japan). The temperature range was set from 100 to 700 oC at the heating rate
9
of 10 oC min-1 under nitrogen atmosphere. In terms of mechanical property, both dry and hydrated
membranes were cut into a 1 x 5 cm rectangular piece to measure their tensile stress vs. strain
behavior using a universal tensile machine (UTM, Model 5565, Lloyd, Fareham, UK) with a 250
N load cell.
Proton conductivity. Proton conductivity (σ, S cm-1) was measured in in-plane dimension
by an electrochemical workstation (ZIVE SP2, Wonatech, Korea) connected with a four-probe
single cell (Bekktech LLC, Loveland, CO, USA). Each membrane was cut into a 1 x 3 cm shape
to place inside the cell, and the test was repeated three times at 95% relative humidity (RH). The
testing temperature varied from 30 to 80 oC and the oxygen gas rate was 500 mL min-1. The proton
conductivity of the membranes was calculated from equation (4):
𝜎 (𝑆 𝑐𝑚−1 ) = 𝑙/(𝑅 × 𝑡 × 𝑤) (4)
where l is the distance between electrodes (cm), R is sample resistance (Ω), t and w are sample
thickness (cm) and width (cm), respectively.
Oxidative stability. Fenton’s reagent (an aqueous solution containing 3 wt% H2O2 and 3
ppm Fe2+) was used to study the oxidative stability of SPFBI membranes. The membrane sample
was dried, weighed, and then immersed in the Fenton solution at 80 oC for 1 to 5 h. After the test,
the sample was gently washed with water and dried in a vacuum oven at 80 oC. The residual weight
(RW) of the sample was calculated from the before-test weight (mb) and after-test weight (ma) of
the sample, using equation (5):
𝑅𝑊 (%) = (𝑚𝑎 /𝑚𝑏 ) × 100 (5)
After the test, the proton conductivity of the treated membrane was measured following
the aforementioned procedure. Moreover, the chemical structure of the membrane sample was
analyzed using Fourier-transform infrared (FT-IR) spectroscopy (Nicolet iS20, Thermo Scientific,
10
Waltham, MA, USA).
Catalyst particle size. The catalyst ink was prepared as described in Section 2.4, and then
IPA was added to dilute the ink two-fold. Subsequently, the resultant solution was ultra-sonicated
for 30 min and the particle size of the catalyst was identified by employing a dynamic light
scattering (DLS) analyzer (ELS-Z2000, Photal Otsuka Electronics, Japan).
PEMFC tests. Membrane electrode assembly (MEA) was prepared by spraying catalyst
ink onto both sides of the PEM surface. A vacuum plate controller system (CNL Energy, Korea)
and a metal mask were used to maintain the flatness of the membrane, and the temperature was
kept at 60 oC to completely remove moisture and solvents during the spraying process. The Pt
loading was fixed at 0.4 mg cm-2 on an active area of 5 cm2 for each side of the membrane. Next,
the MEA was assembled with two gas diffusion layers (GDL, SGL GDL 39BB, CNL Energy,
Korea, thickness ~325 µm) and then sealed with two Teflon gaskets. The formed stack was inserted
between two graphite plates of the cell test unit in a PEMFC station (CNL Energy, Korea) for in-
situ fuel cell tests.
The PEMFC performance tests were conduct at 80 oC and 100% RH. Fully humidified
hydrogen and oxygen gases were supplied at anode and cathode, respectively, at the same flow
rate of 300 mL min-1. This flow rate corresponds to the stoichiometry values of hydrogen (λH2) and
oxygen (λO2) of 8.6 and 17.2, respectively, at 1000 mA cm-2. Electrochemical impedance
spectroscopy (EIS) measurements were carried out at cell conditions as the cell performance test
by connecting the fuel cell stack with ZIVE SP2 electrochemical workstation (Wonatech, Korea).
The EIS tests used the potentiostatic mode in the frequency range of 0.1 Hz – 100 kHz at the
potential amplitude of 6 mV. Nyquist plots were constructed and fitted by ZIVE Smart Manager
software.
11
In-situ open-circuit voltage (OCV) test of MEAs was carried out at 90 oC and 30% RH to
accelerate the degradation of MEA. The hydrogen and oxygen gas inlet rates were the same at 300
mL min-1. The MEA stability was demonstrated, as the OCV decays as a function of operation
time.
3. Results and discussion.
3.1. Polymer properties.
In the present study, we synthesized a series of ether-free SPFBI by a simple two-step
procedure: the polymerization under superacid-catalyzed condition to form PFBI without ether
groups, followed by the sulfonation reaction between PFBI and 1,3-propane sultone in an alkaline
solution. As described in section 2.2. and 2.3, the synthetic process of SFPBI has its remarkable
advantages: facile and short synthesis time and heating requirement of no more than 60 oC. Three
SPFBI samples, SPFBI-0.2, 0.3 and 0.4 with different sulfonation degrees, were synthesized by
simply adjusting the fluorene/biphenyl feed ratio to fabricate PEMs.
The chemical structures of PFBI and SPFBI were confirmed by 1H NMR spectra in Fig. 1.
The SPFBI consists of a hydrophobic poly(phenylene indole) backbone grafted with long alkyl
sulfonated side chains. In terms of the polymer backbone, fluorene was rationally employed as a
monomer along with biphenyl to increase and regulate the sulfonation degree of the final product.
Fluorene has a higher rotation energy barrier than biphenyl because the carbon C9 restricts the
movement of phenyl rings, and thus fluorene molecule is more planar than biphenyl, resulting in
higher reactivity towards the electrophilic substitution reaction [38]. Therefore, the use of fluorene
is also expected to improve the molecular weight and rigidity of polymer backbone, which is
beneficial for physicochemical properties of SPFBI PEMs. As a result, SPFBI-0.2, 0.3 and 0.4
12
showed different intrinsic viscosities ([η]). The [η] value of SPFBI-0.2 was 5.35 dL g-1, lower than
6.18 and 6.36 dL g-1 of SPFBI-0.3 and SPFBI-0.4, respectively. The difference of [η] implies the
increase of polymer molecular weight (MW) from SPFBI-0.2 to 0.4, based on the relationship
between [η] and MW in the Mark–Houwink–Sakurada relationship [39]. This result might
correspond to the increase of fluorene segment in polymer structure from 0.2 to 0.4 which
improves the polymerization reactivity.
Fig. 1. 1H NMR spectra of (a) PFBI-0.4 and (b) SPFBI-0.4.
The solubility of polymers in common solvents is summarized in Table S1. When we
increased the fluorene content to 0.5, SPFBI-0.5 became so hydrophilic that it was dissolved in
water. Hence, the maximum fluorene ratio was fixed at 0.4, ensuring that the membrane can retain
and operate in fuel cell environments. Although the SPFBI with a lower sulfonation degree was
insoluble in individual water and IPA, it was surprising that it showed a decent solubility in a
mixture of IPA and water even at the ambient condition. The dissolution of SPFBI in IPA and water
mixture resulted in a light yellow and transparent solution (Fig. S1). When the solubility of this
polymer was further investigated in various IPA:H2O ratios (Table S2), the highest solubility was
13
exhibited at 4:6 w/w IPA:water mixture. The decent solubility in a mixture of those solvents
indicates that the polarity of the mixture is more suitable for SPFBI, and thus it allows the
utilization of the alcohol-based SPFBI solution as an ionomer binder. Because IPA and water are
easier to remove by heating after spraying catalyst onto a PEM, this alcohol-based polymer
solution is quite promising for the catalyst ink preparation compared to other attempts that
prepared the hydrocarbon ionomer solution in DMSO or dimethylacetamide [40,41]. In this study,
we used not only Nafion but also SPFBI as an ionomer binder to test the PEMFC performance for
comparison.
3.2. Physicochemical properties of membrane.
When the SPFBI membrane with H+ form was obtained after casting and ion-exchange in
acidic solution, it appeared as a yellow and transparent thin film. The thermal stability of the
membranes was studied by thermogravimetric analysis (TGA), as shown in Fig. 2a. All
membranes were thermally stable until the first significant degradation from 200 oC, and they
exhibited 28 – 30 % weight loss at 700 oC. The weight loss behavior of SPFBI membranes was
more clearly demonstrated by differential thermogravimetric (DTG) curves in Fig. 2b. In general,
the degradation behaviors of the membranes were similar to one another, illustrating two main
stages corresponding to two peaks in DTG - the thermal decomposition of sulfonic acid groups in
alkyl side chains (from 200 to around 425 oC) and the disintegration of the polymer main chain
(from 475 oC) [5,42]. The magnitude of DTG peaks was different among three membranes,
indicating more or less sulfonic acid group degradation compared to the backbone degradation.
This result was well consistent with the difference in sulfonation degree among the three polymers.
Overall, the high decomposition temperature of the membranes demonstrates that the thermal
14
stability of SPFBI PEMs satisfies the practical operation requirement of PEMFCs.
Fig. 2. (a) TGA curves and (b) DTG curves of SPFBI membranes in nitrogen atmosphere.
Ion exchange capacity (IEC) is a key parameter to evaluate the hydration properties and
proton-conducting ability of PEMs. For SPFBI membranes, we determined IEC values from both
polymer structure based theoretical and the acid-base titration-based experimental methods. As
listed in Table S3, the experimental IEC values followed a consistent order with theoretical ones,
and as the higher sulfonic acid content increased IEC, the SPFBI-0.4 membrane exhibited the
highest value of 3.25.
The water uptake of SPFBI membranes was gravimetrically measured in the temperature
range of 30 – 80 oC as presented in Fig. 3a. In general, water uptake behavior of SPFBI membranes
followed two major trends. Firstly, the water uptake of all membranes increased with temperature,
because higher temperature increases polymer free volume and polymer - water interaction [43].
Secondly, the sulfonic acid groups enhanced the hydrophilicity of PEMs, allowing the membrane
to absorb more water. As a result, the SPFBI-0.4 membrane showed the highest water uptake of
46.03 % compared to 41.69 % of SPFBI-0.2 at 80 oC. It is worth mentioning that the increase of
water content from 30 to 80 oC was not significant (less than 10 %), due to the rigidity of SPFBI
15
backbone and high intrinsic viscosity as described [38]. Notably, SPFBI membranes synthesized
in this study exhibited relatively low water uptake compared to other PEMs, taking into account
very high IEC values that often lead to an excessive water content of PEM[27,44].
Fig. 3b shows the swelling ratio of SPFBI membranes. Similar to the water uptake behavior,
the membranes were more swollen at higher temperatures and higher sulfonation degrees. For
instance, while the swelling ratio of SPFBI-0.4 was 13.98 % at 30 oC, it was 16.12 % at 80 oC.
Moreover, taking the benefits from limited water uptake, the membranes were dimensionally quite
stable, showing the swelling ratio lower than 14 % at 30 oC. These relatively low water uptake and
swelling ratios of SPFBI membranes compared with the previously reported hydrocarbon
membranes [12,14,21], indicate a remarkable advantage of their dimensional stability for PEMFC
applications.
Fig. 3. (a) Water uptake, (b) swelling ratio of SPFBI membranes at different temperatures, (c), (d)
16
stress-strain curves of the membranes at fully hydrated and dry forms, respectively.
Mechanical properties of SPFBI membranes were analyzed by UTM and the resulting
stress-strain behavior is depicted in Fig. 3c and 3d. With increasing sulfonation degree, the
membrane became more flexible in the hydrated state and thus the maximum tensile strength
decreased (from 35.4 MPa of SPFBI-0.2 to around 30 MPa of SPFBI-0.4 membrane), while the
elongation at break opposingly increased (from 24.2 % of SPFBI-0.2 to 29.6 % of SPFBI-0.4
membrane). Despite the highest intrinsic viscosity, the SPFBI-0.4 membrane was less rigid under
humidified conditions than other membranes because of the plasticizing effect of high water uptake.
To remove the effect of hydration, we also conducted the mechanical property test for dry
membranes. As expected, the tensile strength of membranes increased following the order 0.2 <
0.3 < 0.4, which is a different trend from the fully humidified test results. In the dry state, the
higher content of fluorene backbone contributes to the mechanical durability of the membranes,
even though it was outweighed by the effect of water uptake in the hydrated state. Due to the
highest tensile strength under humidified conditions, SPFBI-0.2 PEM was considered for use in
long-term stability test, as described later in this study.
3.3. Proton conductivity.
The proton conductivity of SPFBI membranes was measured in-plane at 95% RH and
temperatures between 30 and 80 oC, as depicted in Fig. 4a. We also measured the conductivity of
Nafion membrane for comparison. In general, as the hopping and/or vehicle movement of protons
is thermally activated in more hydrated state of the membranes, the proton conductivity of all
membranes gradually increased with temperature. Also, the membranes with higher IEC showed
17
higher proton conductivity; for instance, the SPFBI-0.4 membrane with the highest IEC exhibited
the highest proton conductivity of 0.121 S cm-1 at 30 oC and 0.1956 S cm-1 at 80 oC. This result
supports the positive effect of high sulfonic acid content on the proton conduction. Notably, the
SPFBI-0.3 and SPFBI-0.4 membranes outperformed the Nafion membrane in terms of proton
conductivity, and even the SPFBI-0.2 membrane reached a proton conductivity from 0.063 to
0.105 S cm-1, which is comparable to that of Nafion membrane.
Fig. 4. (a) Proton conductivity of Nafion and SPFBI membranes at different temperatures, (b) the
corresponding Arrhenius plots of SPFBI membranes, (c) comparison of proton conductivity
correlating with IEC value and in-plane swelling ratio for various reported PEMs (details of test
18
conditions are summarized in Table 1).
To obtain more intensive information on the proton conduction behavior of SPFBI PEMs,
the activation energy (Ea) was calculated from the Arrhenius plots relating ln σ and T-1 (Fig. 4b).
As the gradual decrease in Ea was observed from 9.87 kJ mol-1 of SPFBI-0.2 to 8.67 kJ mol-1 of
SPFBI-0.4, it demonstrates that protons are more feasibly transported when the sulfonic acid
density increases. This activation energy behavior implies that the proton conduction behavior in
SPFBI membranes complies with the well-known Grotthuss and vehicular mechanisms [45].
Because the water uptake increased with the sulfonation degree as described, the expanded ionic
cluster dimension provided lower energy barriers for proton transport. Besides, the large amount
of sulfonic acids are beneficial for proton conduction via Grotthuss mechanism by shortening the
distance between acid groups for proton hopping [46,47]. In summary, as the increase of sulfonic
acid density reduces the energy barrier of proton-transfer pathways, the SPFBI-0.4 membrane
showed the highest conductivity. For comparison, we summarized the proton conductivity of the
0.4 membrane and various commercial and lab-synthesized hydrocarbon-based PEMs as a
function of swelling ratio and IEC as three-dimensionally illustrated in Fig. 4c. Table 1 provides
a more detailed comparison, including test results, test conditions, and polymer types. In general,
the SPFBI-0.4 membrane illustrated an excellent proton conductivity under relatively low swelling
when it was placed alongside the non-composite PEMs such as Nafion and Pemion.
Table 1. Summary of proton conductivity, IECex and swelling ratio of SPFBI-04 membrane and
some typical commercial and lab-synthesized PEMs.
19
IECex In-plane SRb
PEM σa (S cm-1) Polymer type Ref.
(meq g-1) (%)
SPFBI-0.4 0.196 ± 0.005 3.25 ± 0.31 16.12 ± 0.16 Ether-free This work
Nafion 0.121 ±0.007 0.92 ± 0.24 6.74 ± 0.09 Perfluorinated This work
Pemion
~ 0.265 3.28 ± 0.06 44.87c Ether-free [27]
(sPPN-H+)
Pemion
~ 0.170 3.19 ± 0.05 33.3c Ether-free [27]
(sPPB-H+)
SPPBP 40 0.162 2.45 10.8 Ether-free [48]
SIPiP 0.0975 2.50 11.5 Ether-free [49]
SPAES160 ~ 0.150 2.10 ± 0.24 19.57 Ether-containing [14]
SPEEK 0.170 1.654 51.3d Ether-containing [50]
SPFAE 0.1507 1.62 5.2 Ether-containing [51]
a
Measured at 80 oC, RH varies from 90 – 100%
b
Measured at 80 oC in water
c
Mathematically calculated from reported area swelling ratios, assuming that the sample shape
was square.
d
Measured at 60 oC and 100% RH
3.4. Oxidative stability.
The oxidative stability of SPFBI membranes was investigated by subjecting the membrane
samples to Fentons’s test where the chemical degradation of membrane was stimulated by •OH
radical generation. The membranes were treated with Fenton’s solution (3 wt% H2O2, 3 ppm Fe2+)
for 1 h and 5 h. During the test, membrane samples were gradually dissolved in the solution due
to polymer decomposition under ·OH radical bombardment. The residual weights of the samples
were determined and listed in Table 2, indicating how much the membrane retained after the test.
While the SPFBI-0.2 sample exhibited the highest residual weight of 98.95 % after 1 h and 43.33%
after 5 h, the SPFBI sample lost 5.73% and 81.73% of its original weight after 1 h and 5 h treatment,
20
respectively. For all samples, no significant mass loss and visual changes were observable after
the exposure for 1 h. As the oxidative stability of the membrane decreased with increasing
sulfonation degree, the ether-free phenylene backbone might be less prone to radical attack than
highly reactive -SO3H groups as reported in several studies [14,27,52]. To more precisely evaluate
the oxidative stability of SPFBI membranes, their Fenton’s test results were compared with those
of other hydrocarbon PEMs obtained under similar test conditions in Table S4 and S5. For 1 h test,
the stability of all SPFBI PEMs surpasses that of the common ether-containing hydrocarbon PEMs
even under harsher conditions. Even though Pemion illustrated better oxidative stability than
SPFBI PEMs for 1 h test, their residual weight difference was not significant. For 5 h test, although
the stability of PEMs varied with the sulfonation degree, SPFBI PEMs showed quite good
oxidative stability that could compete with Pemion, a state-of-the-art ether-free PEM. It is
necessary to mention that these 5 h Fenton’s test results under the similar experimental conditions
have been barely reported for other hydrocarbon PEMs because it often led to the entire
decomposition of membrane samples [46]. The improved chemical stability of this ether-free
SPFBI membrane compared to the ether-containing PEMs can be explained by the different bond
dissociation energy between aryl-aryl (C6H5-C6H5) segment (476 ± 6 kJ mol-1) and aryl-ether-aryl
(C6H5-O-C6H5) segments (355 ± 6 kJ mol-1)[53]. More importantly, the ether group creates
vulnerable sites on the neighboring aromatic rings due to the electron-donating effect [1,25,54], as
illustrated in Fig. S2. The attack of the oxidative radicals on those sites leads to the cleavage and
scission of the polymer backbone, resulting in poor chemical stability of the polymer membrane
in Fenton’s test.
Table 2. Residual weights of SPFBI samples after 1 h and 5 h Fenton’s test.
21
Sample RW(%) (1 h) RW(%) (5 h)
SPFBI-0.2 98.85 ± 1.25 43.33 ± 2.39

SPFBI-0.3 95.00 ± 0.52 29.07 ± 3.05
SPFBI-0.4 94.27 ± 0.40 18.27 ± 3.56
The proton conductivity test and FT-IR were employed to analyze the after-treatment
membrane samples. Because all membrane samples were almost intact after 1 h treatment, it was
available to measure the proton conductivity of SPFBI membranes with and without 1 h exposure
with Fenton’s solution for comparison (Fig. 5a). Despite slight conductivity losses due to the
chemical degradation, the membranes still exhibited a decent proton conductivity at various
temperatures, implying that most of the polymer structure and membrane morphology were not
significantly damaged. The recovered pieces of samples were also assessed by Fourier-transform
infrared (FT-IR) spectroscopy (Fig. 5b-d). For all samples, there were no serious changes in the
chemical structure after Fenton’s treatment. The IR bands originating from -SO3H groups in the
pristine membranes still can be clearly observed in the spectra of the membranes after treatment
for both 1 h and 5 h.
22
Fig. 5. (a) Proton conductivity of SPFBI membranes before and after 1 h Fenton’s test; FT-IR
spectra of (b) SPFBI-0.2, (c) SPFBI-0.3 and (d) SPFBI-0.4 membrane before and after 1 h and 5
h Fenton’s test.
3.5. PEMFC performance.
Compared with many other hydrocarbon polymers used to prepare PEMs, it was discovered
that SPFBIs have a decent solubility in a mixture of IPA and water, as previously presented. As
this behavior has been rarely reported from the hydrocarbon-based polymers for PEMs, this unique
solubility property of SPFBI was more detail exploited for its application as an ionomer binder as
well as PEM. As presented, SPFBI-0.4 showed the highest proton conductivity, compared to
SPFBI-0.2 and SPFBI-0.3 PEMs. When the size of particles agglomerated in catalyst ink was
analyzed using the dynamic light scattering (DLS) method, SPFBI-0.4 was more compatible with
23
Pt/C catalyst than the other two SPFBI samples (Fig. S3) [55]. Accordingly, taking into account
both membrane and ionomer properties, SPFBI-0.4 was chosen to prepare the ionomer solution,
along with the conventional Nafion ionomer as a reference. Using these ionomer binders, we
fabricated MEAs consisting of SPFBI and Nafion membranes for PEMFC operation.
Fig. 6. (a) H2/O2 fuel cell performances of different MEAs using Nafion ionomer binder, (b)
corresponding Nyquist plots of MEAs using Nafion ionomer binder. (Test conditions: 80 oC, 100%
RH, and gas inlet rate of 300 mL min-1 at both anode and cathode).
First, we compared the cell performance of MEAs of SPFBI and Nafion PEMs fabricated
using the same ionomer binder. Fig. 6a shows the polarization curves of MEAs using the Nafion
binder at 80 oC under the fully humidified H2/O2 supply. As the thickness of membranes was
controlled by casting process, its difference among membranes was less than 3 µm as shown in
Table 3 to minimize its effect on cell performance. While the maximum power density of SPFBI-
0.2 MEA was quite similar to that of Nafion MEA, that of SPFBI-0.3 and SPFBI-0.4 MEAs
exhibited higher maximum power densities of 346 and 365 mW cm-2, respectively. This
performance improvement can be attributed to the superior proton conductivity of SPFBI
membranes. To further understand the effect of types of PEMs on PEMFC performance, the
24
electrochemical impedance spectroscopy (EIS) measurements were performed to obtain the
corresponding Nyquist plots for each MEA, as shown in Fig. 6b. All MEAs showed a semicircular
pattern of Nyquist plots, in which the high-frequency intercept (left intersection of the real axis)
provided the electrolyte resistance (Rel), and the semicircle diameter provided the charge-transfer
resistance (Rct) of MEA [56]. It can be seen that the differences in Rct among MEAs were small
because of the utilization of the same catalyst and ionomer binder for all MEAs. On the other hand,
the Rel values of MEAs varied quite a lot, following the order of SPFBI-0.4 < SPFBI-0.3 < Nafion
< SPFBI-0.2, which is in compliance with the cell performance results. These results demonstrate
the benefit of SPFBI PEMs that reduce the membrane resistance and thus lead to the enhancement
of cell performance.
25
Fig. 7. Comparison of H2/O2 cell performance of the MEAs fabricated with different PEMs and
ionomer: (a) Nafion membrane, (b) SPFBI-0.2 membrane, (c) SPFBI-0.4 membrane. The
corresponding Nyquist plots for (d) Nafion membrane, (e) SPFBI-0.2 membrane and (f) SPFBI-
0.4 membrane. (Test conditions: 80 oC, 100% RH, and gas inlet rates of 300 mL min-1 at both anode
and cathode).
26
Table 3. Summary of power density and EIS for SPFBI and Nafion MEAs.
Membrane Electrode Assembly (MEA)

Maximum power
Rel (Ω cm2) Rct (Ω cm2)
density (mW cm-2)
Thickness
Membrane Ionomer binder
(µm)
Nafion 318 0.17373 0.39523

Nafion 90
SPFBI-0.4 294 0.18020 0.45080
Nafion 321 0.18121 0.43527
SPFBI-0.2 88
SPFBI-0.4 296 0.18682 0.48073
Nafion 346 0.13311 0.44089
SPFBI-0.3 87
SPFBI-0.4 - - -
Nafion 365 0.12421 0.43427
SPFBI-0.4 87
SPFBI-0.4 346 0.11330 0.47170
Next, PEMFC performance tests for Nafion, SPFBI-0.2 and SPFBI-0.4 MEAs using the
SPFBI-0.4 ionomer were also conducted. Their polarization curves were depicted along with those
of MEAs using the Nafion ionomer (Fig. 7a-c) and the corresponding EIS spectra (Fig. 7d-f) for
comparison. Additionally, some important experimental results including the maximum power
density, Rel and Rct, are summarized in Table 3. For all membranes, SPFBI-0.4 ionomer still
achieved decent cell performances, even though the Nafion ionomer showed better performances
with a 5 – 8% higher maximum power density. A similar conclusion can be drawn from the
comparison of Nyquist plots for MEAs fabricated with different ionomers. In each EIS curve,
although Rel was not significantly varied because the same types of PEMs were employed, Rct
increased when SPFBI-0.4 ionomer was used instead of Nafion. For instance, the MEA fabricated
using Nafion ionomer and Nafion PEM exhibited Rct of 0.39523 Ω cm2, which was lower than that
27
of the MEA using SPFBI-0.4 ionomer and Nafion PEM, 0.45080 Ω cm2. This difference probably
stems from the difference in proton transport in the catalyst layer affected by ionomer [8,55], as
the SPFBI-0.4 ionomer was less compatible with the catalyst than the conventional ionomer
according to DLS analysis. Those results, however, still point out that the SPFBI-0.4 ionomer can
be utilized to prepare MEAs for not only SPFBI membranes but also Nafion membrane to obtain
acceptable cell performance. It must also state that hydrocarbon ionomers like SPFBI may behave
differently from Nafion ionomer, thus other factors (e.g., catalysts, gas flow rate or ionomer
loading) can be further optimized to be more suitable for SPFBI ionomer usage. Therefore, the cell
performance of SPFBI-0.4 ionomer MEAs can be improved with more suited MEAs designs,
which would be the target of our future works. To the extent of our knowledge, the application of
low-cost hydrocarbon polymers as ionomer binder in PEMFC has been rarely reported, as it mostly
resulted in inferior cell performances to Nafion [57] and the solvent for preparation of ionomer
solution was mostly DMSO which is aprotic and thus not sufficient for fuel cell manufacture
[58,59]. As this result demonstrate the application of SPFBI-0.4 ionomer binder for high PEMFC
performance, it encourages further developments of hydrocarbon polymers not only for PEM but
also for ionomer binder to completely replace the perfluorinated polymers.
28
Fig. 8. OCV decay over time for various MEAs fabricated with different membrane/ionomer
binders. (Test conditions: 90 oC, 30% RH, and gas inlet rate: 300 mL min-1 at both anode and
cathode).
Finally, the OCV in-situ stability tests were conducted to assess the effect of the SPFBI
membrane and ionomer on the long-term durability of the MEA. Under the harsh temperature and
humidity conditions, the OCV decay of MEAs was plotted over test time, as shown in Fig. 8. The
end-of-life point of MEAs was chosen as the time when OCV drops to 0 V. For MEAs using Nafion
membrane, the voltage could not sustain over 220 h, as it completely dropped after around 210 -
220 h test. On the contrary, the MEAs using SPFBI-0.2 membrane exhibited a much lower OCV
decay rate, resulting in the end-of-life point over 620 h, much higher than those of Nafion
membrane-used MEAs. This in-situ cell test illustrated surprisingly better durability of SPFBI-0.2
than Nafion, being different from the Fenton’s test results. Athough Nafion PEMs are well-known
for their excellent stability against chemical degradation [60,61], this mismatched correlation
between ex-situ Fenton’s and in-situ cell tests has been stated in many reports, especially when the
Nafion MEAs decay faster than the hydrocarbon MEAs in OCV test [14,62]. This difference is
due to the additional factors provided by in-situ cell test that cannot be obtained from ex-situ
Fenton’s test. For instance, the fuel (hydrogen and oxygen) crossover is one of the important
factors to be additionally considered in this in-situ test. Due to higher gas permeability of Nafion
than hydrocarbon membranes, the generation rate of OH radicals is much more higher in the
Nafion based MEA system than the hydrocarbon based one during cell operation. This provides
much more complex and preferential radical attacking situations for the chemical degradation of
membranes than the simple Fenton’s test conducted in the solution with the fixed OH radical
29
concentration [20,24]. Therefore, while the Fenton’s test provided good information about the
chemical degradation behavior of SPFBI membrane itself, the OCV test demonstrated much more
reliable durability of the SPFBI membrane in practical MEA operation.
The optical images of MEAs before and after the stability test were collected and shown in
Fig. S4. While the SPFBI-0.2 membrane-used MEAs have no observable defects even after over
620 h, some pinholes were found on the Nafion membrane-used MEAs after the test, indicating
severe damages caused by chemical degradation. This is in good accordance with the OCV decay
rate of the MEAs, demonstrating the excellent in-situ chemical stability of ether-free SPFBI-0.2
membrane. Besides, compared with Nafion ionomer, SPFBI-0.4 ionomer did not significantly
affect the OCV decay for both Nafion and SPFBI-0.2 membrane-based MEAs, since the MEAs
consisted of SPFBI-0.2 membrane and SPFBI-0.4 ionomer still illustrated an end-of-life point over
620 h. Overall, the in-situ OCV test results provide the application of SPFBI membrane and
ionomer for the long-term operation of PEMFC.
4. Conclusions.
To synthesize the ether-free polymer for the fabrication of high chemical stability proton
exchange membrane, we proposed a novel polymer synthesis via the superacid-catalyzed
polymerization of common and low-cost monomers. As a result, a series of ether-free sulfonated
poly(fluorene biphenyl indole) (SPFBI) were successfully synthesized with various sulfonation
degrees. Experimental results revealed that the excellent proton conductivity of SPFBI membranes
up to 0.1956 S cm-1 at 80 oC was observed under the low water uptake and swelling ratio compared
to other reported membranes. Owing to the free structure of SPFBI, its oxidative stability was
comparable to that of Pemion - the state-of-the-art ether-free polymer lectrolyte membrane and
30
superior to many common hydrocarbon membranes. Due to the excellent proton conductivity and
chemical stability, SPFBI-0.3 and SPFBI-0.4 membranes exhibited better cell performances than
the Nafion membrane, showing the sustainability of more than 620 h of the open-circuit voltage
test. More importantly, SPFBI-0.4 was possibly employed to prepare the ionomer binder due to
the solubility in the isopropanol and water mixture. Despite minor losses in the maximum power
density, the performance and stability of membrane electrode assemblies fabricated with SPFBI-
0.4 ionomer showed the potential promises for research on hydrocarbon ionomer binders. We
believe that the results in this study merit the further development of hydrocarbon-based ether-free
polymer lectrolyte membranes and ionomer binders for the fabrication of cost-effective and long-
term durable membrane electrode assembly for fuel cells.
Acknowledgments
This work was sponsored by the National Research Foundation of Korea Grant, funded by
the Korean Government (MEST) (NRF 2018M3D1A1058624).
31
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41
Table 1
Table 1. Summary of proton conductivity, IECex and swelling ratio of SPFBI-04 membrane and
some typical commercial and lab-synthesized PEMs.
a -1 IECex In-plane SRb

PEM σ (S cm ) Polymer type Ref.
(meq g-1) (%)
SPFBI-0.4 0.196 ± 0.005 3.25 ± 0.31 16.12 ± 0.16 Ether-free This work
Pemion
~ 0.265 3.28 ± 0.06 44.87c Ether-free [27]
(sPPN-H+)
Pemion
~ 0.170 3.19 ± 0.05 33.3c Ether-free [27]
(sPPB-H+)
SPPBP 40 0.162 2.45 10.8 Ether-free [48]
SIPiP 0.0975 2.50 11.5 Ether-free [49]
SPAES160 ~ 0.150 2.10 ± 0.24 19.57 Ether-containing [14]
SPEEK 0.170 1.654 51.3d Ether-containing [50]
SPFAE 0.1507 1.62 5.2 Ether-containing [51]
a
Measured at 80 oC, RH varies from 90 – 100%
b
Measured at 80 oC in water
c
Mathematically calculated from reported area swelling ratios, assuming that the sample shape
was square.
d
Measured at 60 oC and 100% RH
Table 2
Table 2. Residual weights of SPFBI samples after 1 h and 5 h Fenton’s test.
SPFBI-0.2 98.85 ± 1.25 43.33 ± 2.39

SPFBI-0.3 95.00 ± 0.52 29.07 ± 3.05
SPFBI-0.4 94.27 ± 0.40 18.27 ± 3.56
Table 3
Membrane Electrode Assembly (MEA)

Maximum power
density (mW cm-2)
Thickness
Membrane Ionomer binder
(µm)
Nafion 318 0.17373 0.39523

Nafion 90
SPFBI-0.4 294 0.18020 0.45080
Nafion 321 0.18121 0.43527
SPFBI-0.2 88
SPFBI-0.4 296 0.18682 0.48073
Nafion 346 0.13311 0.44089
SPFBI-0.3 87
SPFBI-0.4 - - -
Nafion 365 0.12421 0.43427
SPFBI-0.4 87
SPFBI-0.4 346 0.11330 0.47170
Fig. 1 Click here to access/download;Figure(s) - provided separately;Figure 1.tif
Fig. 3 Click here to access/download;Figure(s) - provided separately;Figure 3 revised.tif
Fig.6 Click here to access/download;Figure(s) - provided separately;Figure 6-revised2.tif
Fig. 7 Click here to access/download;Figure(s) - provided
separately;Figure 7-revised2.tif
Supplementary Materials
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Supplementary Materials
Supplementary information-revised(no marked
changes).docx
Credit Author Statement
FORM FOR AUTHOR STATEMENT

Manuscript ID number: POWER-D-22-04425
Manuscript Title: Ether-free sulfonated poly(fluorene biphenyl indole) membranes and ionomer
binders for proton exchange membrane fuel cells.
Details of authors to be added to the manuscript:
Name Email address Organization name City/Coun

try
First author Vu Dong Thuc dongthucv@gmail.com Chemical Engineering/ Republic
Sungkyunkwan University of Korea
Second author Vo Dinh Cong vodinhcongtinh@gmail. Chemical Engineering/ Republic
Tinh com Sungkyunkwan University of Korea
Corresponding Dukjoon Kim djkim@skku.edu Chemical Engineering/ Republic
author Sungkyunkwan University of Korea
CrediT author statement:

Vu Dong Thuc: Conceptualization, Investigation, Writing-Original draft preparation, Writing-
Review & Editing.
Vo Dinh Cong Tinh: Conceptualization, Investigation.
Dukjoon Kim: Supervision, Resources, Funding acquisition, Writing-Review & Editing.
Highlights
Highlights
 A series of ether-free SPFBI was synthesized by superacid-catalyzed polymerization.
 Both SPFBI proton exchange membrane and ionomer binder were studied.
 Chemically stable SPFBI membrane reached the proton conductivity of 0.1956 S cm-1.
 In-situ stability test demonstrated high durability of SPFBI membrane (> 620 h).
Declaration of Interest Statement
Declaration of interests
☒The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.
☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:
Revised Cleaned Manuscript (with no marked changes) Click here to view linked References
1
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Ether-free sulfonated poly(fluorene biphenyl indole) membranes and ionomer binders for
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8 proton exchange membrane fuel cells
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10 Vu Dong Thuca, Vo Dinh Cong Tinha, Dukjoon Kima*
11
12 a
13 School of Chemical Engineering, Sungkyunkwan University, 2066 Seobu-ro, Jangan-gu,
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15 Suwon, Gyeonggi 16419, Republic of Korea
16
17 *
18 Email: djkim@skku.edu
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20
21
22
23 Abstract
24
25 Because of the vulnerability of ether bonds to oxidative radicals, the ether-free polymer
26
27
electrolytes are synthesized to prepare chemically more stable proton exchange membranes for
28
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30 long time durable fuel cell application. Here, we present a series of ether-free sulfonated
31
32 poly(fluorene biphenyl indole)s (SPFBI) synthesized by a feasible and cost-effective process.
33
34
35 Owing to the ether-free structure, SPFBI membranes display great chemical stability comparable
36
37 to the commercial Pemion membranes from Fenton’s test. SPFBI membranes exhibit high proton
38
39
40 conductivity up to 0.1956 S cm-1 at 80 oC under the limited swelling ratio lower than 16.5%.
41
42 Consequently, while the SPFBI-0.4 membrane shows the excellent cell performance reaching the
43
44
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maximum power density of 365 mW cm-2, it also plays a decent role as an ionomer binder for both
46
47 SPFBI and Nafion membranes. In open circuit voltage stability test, the membrane electrode
48
49 assemblies using SPFBI-0.2 membrane can sustain more than 620 h without any severe defects at
50
51
52 90 oC under low relative humidity of 30%, outweighing the Nafion counterpart. This study
53
54 provides a remarkable approach for optimizing the ether-free hydrocarbon-based polymer
55
56
57 structure for the application of both polymer electrolyte membrane and ionomer binder with high
58
59 proton conductivity and chemical stability.
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62 1
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Keywords: Fuel cell; Proton exchange membrane; Ionomer binder; Chemical stability; Ether-free
7
8
9
10 1. Introduction.
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14
To satisfy the growing demand for the green energy with no harm to the environment,
15
16 proton-exchange membrane fuel cell (PEMFC) has been recognized as one of the promising
17
18 electrochemical energy sources due to its eco-friendliness and high energy density [1–4]. As a key
19
20
21 component of PEMFC, proton-exchange membrane (PEM) needs to fulfill various requirements,
22
23 such as high mechanical and chemical stability and low gas crossover in addition to high proton
24
25
26 conductivity [5,6]. While many attempts have been launched to fabricate high-quality PEMs with
27
28 enhanced properties so far, the perfluorosulfonic acid-based membranes including Nafion are the
29
30
31 most successful and popular PEMs for commercial applications. Nafion possesses good
32
33 mechanical and oxidative stability as well as a decent proton conductivity in humidified conditions
34
35
36
due to the formation of ion clusters by well-separated hydrophobic and hydrophilic phases [4,7,8].
37
38 Despite those advantages, Nafion has major drawbacks, including high gas permeability, poor
39
40 water retention, and high cost [6,9]. Because of the perfluorinated backbone structure, Nafion also
41
42
43 causes environmental concerns in its disposal process [10,11].
44
45 In order to replace the perfluorinated polymers with cost and disposal ineffectiveness,
46
47
48 hydrocarbon-based polymers with acidic functional groups have been developed. Those generally
49
50 consist of the hydrophobic aromatic backbones functionalized with the proton-conducting moieties
51
52
53
such as sulfonic acid or phosphonic acid groups statistically distributed. Depending on the polymer
54
55 designs, these acid groups can be either directly attached to the polymer backbone [12,13], or
56
57 located on the long alkyl chains grafted onto the polymer backbone [14,15]. Therefore, similar to
58
59
60 the perfluorinated polymer membranes, the phase-separated hydrophilic domains in hydrocarbon-
61
62 2
63
64
65
1
2
3
4
5
6
based PEMs allow the construction of interconnected water channels to facilitate the proton
7
8 transport. With many attempts to improve membrane properties, the hydrocarbon-based PEMs
9
10 currently not only exhibit high proton conductivity and cell performance [16–18], but also offer
11
12
13 cost reduction compared to perfluorinated PEMs.
14
15 Despite the aforementioned advantages, several limitations of hydrocarbon-based PEMs
16
17
18 hinder their commercialization. A major concern is about their chemical stability, since the
19
20 polymer structure typically contains more reactive functional groups and thus possesses less
21
22
23 oxidative resistance than Nafion composed of an inert Teflon-like backbone [19,20]. In such
24
25 polymer structures, the ether bond is the most commonly encountered heteroatom bond in the main
26
27
chain, usually resulting from the polymerization reaction to link monomer molecules together
28
29
30 [14,21]. Unfortunately, ether groups are very prone to attacking of ·OH radicals continuously
31
32 generated from the formation of reactive oxygen species and fuel crossover during the cell
33
34
35 operation [22,23]. The low oxidative stability of ether group is because the oxygen in ether
36
37 increases the electron density of neighboring aryl rings via the electron-donating effect and thus
38
39
40 weakens the resistance against oxidative species [1,24,25]. Since the ether groups do not have
41
42 crucial role in PEM properties, their elimination from the polymer structure can be considered an
43
44
45
attractive way to enhance the chemical stability of PEMs. Accordingly, many studies have been
46
47 conducted to synthesize ether-free PEMs. For instance, Miyake et al. reported a flexible
48
49 polyphenylene PEM (SPP-QP) with excellent flexibility and stability [26]. Pemion is also a
50
51
52 commercially available ether-free hydrocarbon-based PEM [27,28]. The synthetic process of
53
54 polymer electrolytes without ether linkages is usually quite complicated with the requirement of
55
56
57 costly metallic catalysts [27–29]. The superacid-catalyzed polymerization reaction was employed
58
59 as a good method, characterized by a short reaction time without the requirement of heating and
60
61
62 3
63
64
65
1
2
3
4
5
6
expensive catalysts [30,31]. This method has been widely used to synthesize ether-free polymers
7
8 for anion exchange membrane (AEM) [32,33], but just a few publications have been reported for
9
10 PEMs [34,35]. As the ether-free PEMs synthesized from the previous studies showed only
11
12
13 mediocre properties without profound investigation of chemical stability enhancement, it is
14
15 difficult to draw the potential of its methodological effectiveness.
16
17
18 In this work, the synthesis and characterization of sulfonated poly(fluorene biphenyl indole)
19
20 (SPFBI) are reported as a novel ether-free polymer electrolyte with improved PEM properties.
21
22
23 Compared to the previous ether-free polymers synthesized by superacid-catalyzed reaction, this
24
25 polymer structure was rationally designed from common monomers to establish the mechanically
26
27
robust rigid aromatic backbone grafted with long sulfonated alkyl chains to improve proton
28
29
30 conductivity. The synthetic procedure of SPFBI involves two main steps, starting from the
31
32 synthesis of poly(fluorene biphenyl indole) (PFBI) from isatin, biphenyl, and fluorene under
33
34
35 superacid conditions [31]. In the second step, the sulfonated alkyl groups were grafted to PFBI
36
37 backbone using 1,3-propane sultone and tetrabutylammonium bromide catalyst under basic
38
39
40 conditions [36,37]. By varying the monomer ratios, a series of SPFBI PEMs with different sulfonic
41
42 acid contents were prepared for an intensive investigation on proton conductivity, oxidative
43
44
45
stability, and PEMFC performance. Additionally, the solubility of SPFBI in isopropanol and water
46
47 mixture allowed its utilization as the ionomer binder for the preparation of catalyst ink in
48
49 membrane electrode assembly (MEA) process.
50
51
52
53
54 2. Experimental Section.
55
56
57 2.1. Materials.
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59 Fluorene, isatin, trifluoroacetic acid (TFA), trifluoromethanesulfonic acid (TFSA), 1,3
60
61
62 4
63
64
65
1
2
3
4
5
6
propane sultone (99.0%) and tetrabutylammonium bromide (TBAB) were purchased from Tokyo
7
8 Chemical Industry (TCI, Japan). Biphenyl, iron(II) sulfate heptahydrate (FeSO4.7H2O) and
9
10 hydrogen peroxide (H2O2) solution were obtained from Sigma-Aldrich (Milwaukee, WI, USA).
11
12
13 Nafion alcohol-based dispersion (5 wt%, EW1100) was supplied from Chemours (Wilmington,
14
15 DE, USA), as well as platinum (nominally 40% on carbon black) (Pt/C) was provided by Alfa
16
17
18 Aesar (Ward Hill, MA, USA) to prepare MEAs. Other common solvents (99.5% purity) were
19
20 obtained from Samchun Chemicals (Korea).
21
22
23
24
25 2.2. Synthesis of poly(fluorene biphenyl indole) (PFBI).
26
27
The synthetic process of PFBI is briefly represented in Scheme 1. In detail, isatin (150
28
29
30 mmol) was added to a three-neck round bottom flask, along with a total of 150 mmol of two other
31
32 monomers (biphenyl and fluorene). The ratio of biphenyl and fluorene was varied to control the
33
34
35 sulfonation degree of the final polymer product. Then, 15 mL of dichloromethane (CH2Cl2) was
36
37 poured into the flask to dissolve the monomers under magnetic stirring. Subsequently, TFA (10
38
39
40 mL) and TFSA (15 mL) were dropwise added, and the mixture was stirred and kept at 0-5 oC for
41
42 12 h. After the reaction was finished, the dark purple mixture was slowly poured into methanol to
43
44
45
obtain PFBI precipitation. The polymer was washed with methanol and water several times, and
46
47 then dried in a vacuum oven at 80 oC for 24 h. It is designated as PFBI-x, where x represents the
48
49 proportion of fluorene over the total amount of biphenyl + fluorene used for the synthesis. The
50
51
52 yield of the PFBI synthetic process was about 93-96%. 1H NMR (300 MHz, DMSO-d6): 10.78
53
54 ppm (Hi), 7.73 ppm (Hb), 7.55 ppm (Hc), 7.21 – 7.31 ppm (Hd,e,g), 6.93 – 7.19 ppm (Hf,h) and 3.74
55
56
57 ppm (Ha).
58
59
60
61
62 5
63
64
65
1
2
3
4
5
6
2.3. Synthesis of sulfonated poly(fluorene biphenyl indole) (SPFBI).
7
8 The second step in Scheme 1 illustrates the synthetic procedure of SPFBI. For each
9
10 synthesis, 3 g of PFBI and 0.116 g of TBAB were simultaneously dissolved in 70 mL of dimethyl
11
12
13 sulfoxide (DMSO) at 60 oC and then poured into a three-neck round bottom flask. Next, nitrogen
14
15 gas was continuously supplied into the flask to remove the oxygen, and 4 mL of 50 wt% KOH
16
17
18 was slowly added to the polymer solution by syringe, followed by adding an excess amount of 1,3-
19
20 propane sultone. The reaction mixture was stirred at 60 oC for 6 h, under a nitrogen atmosphere.
21
22
23 Afterward, the product was precipitated by dropwise adding into methanol, and then washed with
24
25 water and isopropyl alcohol (IPA) in sequence and dried. The obtained polymer is named SPFBI-
26
27
x, where x refers to the PFBI-x precursor. The yield of the sulfonation process is 85-88 %. 1H
28
29
30 NMR (300 MHz, DMSO-d6): 7.55 – 7.61 ppm (Hb,c), 7.21 – 7.40 ppm (Hd,e,g), 7.07 – 7.19 ppm
31
32 (Hf,h), 3.83 ppm (Hi), 2.34 – 2.46 ppm (Ha,l) and 1.89 ppm (Hk).
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62 6
63
64
65
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39 Scheme 1. Two-step synthetic process of SPFBI-x.
40
41
42
43
44 2.4. Preparation of membrane and catalyst ink.
45
46 To prepare the SPFBI membrane, 0.3 g of SPFBI was completely dissolved in DMSO at
47
48
49 60 oC, and then the polymer solution was poured into a petri dish and placed in a vacuum oven at
50
51 80 oC for 24 h. After that, the polymer membrane was peeled off to be immersed in 1 M H2SO4
52
53
54
solution for 24 h to convert the sulfonated groups to H+ form. Finally, the membrane was washed
55
56 with deionized water for 24 h. For membrane comparison, Nafion PEMs were prepared by casting
57
58 method. Nafion alcohol-based dispersion (5 wt%) was poured into a flat petri dish, then dried at
59
60
61
62 7
63
64
65
1
2
3
4
5
6
80 oC for 24 h. The formed film was peeled off from the dish to obtain a Nafion pristine membrane.
7
8 The thickness of all fabricated membranes in this work was controlled within a range of 80-90 µm.
9
10 For catalyst ink preparation, 5 wt% solution of SPFBI-0.4 was prepared in-house by
11
12
13 acidifying the polymer solid in 1 M H2SO4 solution. After rinsing it with water, it was dissolved
14
15 in a mixture of IPA and water (4:6 w/w). For comparison, the preparation of catalyst ink using
16
17
18 SPFBI-0.4 ionomer followed a similar procedure as that of Nafion ionomer. Pt/C catalyst was
19
20 mixed with deionized water, IPA, and 5 wt% polymer solution (Nafion or SPFBI-0.4) and
21
22
23 subsequently ultra-sonicated to obtain a colloidal catalyst slurry. In all catalyst ink solutions, the
24
25 ionomer binder:catalyst mass ratio was fixed at 1:4.
26
27
28
29
30 2.5. Characterizations.
31
32 Chemical structure. To confirm the synthesis of the polymers, the proton nuclear
33
34
35 magnetic resonance (1H NMR) spectra were obtained by a Varian Oxford 300 MHz NMR
36
37 spectrometer (CA, USA) using DMSO-d6 as a solvent to dissolve polymer samples. The standard
38
39
40 chemical shift of DMSO-d6 is determined at 2.50 ppm.
41
42 Intrinsic viscosity. The intrinsic viscosity ([η]) of SPFBI was determined by a method
43
44
45
using a Ubbelohde viscometer. The polymers were dissolved in DMSO to obtain solutions with
46
47 five different concentrations, and the efflux time of each solution was recorded at 20 oC. By
48
49 drawing a plot of reduced viscosity versus concentration, we obtained [η] at the y-intercept value.
50
51
52 Solubility testing. The solubility of polymers was measured in various common organic
53
54 solvents, water and a mixture of IPA and water (4:6 w/w). The tests were performed at room
55
56
57 temperature and 60 oC (only for solvents with a high boiling point). The polymer was considered
58
59 insoluble in a certain solvent if it cannot be dissolved in both room and elevated temperatures.
60
61
62 8
63
64
65
1
2
3
4
5
6
Membrane hydration properties and IEC. The water uptake (WU) and swelling ratio
7
8 (SR) of SPFBI membranes were measured using the weight and length change of membrane
9
10 samples in fully dry and wet states at different temperatures. The membrane was dried at 80 oC for
11
12
13 48 h, and then cut into a 1 x 3 cm rectangular piece to measure the mass (md) and length (ld) of the
14
15 dry sample. Next, the sample was immersed in deionized water for 48 h under stirring. After that,
16
17
18 the sample was removed, the excess water on the membrane surface was wiped off with tissue
19
20 papers to measure the mass and length of the membrane at wet state (mw and lw). The test was
21
22
23 repeated 3 times for each sample to obtain the average value of WU and SR according to the
24
25 following equations:
26
27
28
𝑊𝑈(%) = (𝑚𝑤 − 𝑚𝑑 )/𝑚𝑑 × 100 (1)
29
30 𝑆𝑅(%) = (𝑙𝑤 − 𝑙𝑑 )/𝑙𝑑 × 100 (2)
31
32 The experimental ion exchange capacity (IECex) was measured by acid-base titration
33
34
35 method. A dry membrane sample with the mass m (g) was submerged in standard NaOH solution
36
37 with the known concentration and volume (CNaOH, VNaOH) for 48 h. The base solution after
38
39
40 removing the membrane was titrated with standard HCl solution (CHCl, VHCl) to determine IECex
41
42 from equation (3):
43
44 𝐶𝑁𝑎𝑂𝐻 𝑉𝑁𝑎𝑂𝐻 − 𝐶𝐻𝐶𝑙 𝑉𝐻𝐶𝑙
45 𝐼𝐸𝐶𝑒𝑥 (meg g −1 ) = × 1000 (3)
𝑚
46
47
48 For comparison, the theoretical ion exchange capacity (IECtheo) was also calculated from
49
50 the chemical structure of SPFBI, based on the number of acid groups and the theoretical molecular
51
52
53
weight of the repeating unit of polymer.
54
55 Thermal and mechanical properties. The thermal stability of the membrane in proton
56
57 form was investigated by thermogravimetric analysis (TGA) using a Seiko Exstar 6000 instrument
58
59
60 (Seiko Instruments, Japan). The temperature range was set from 100 to 700 oC at the heating rate
61
62 9
63
64
65
1
2
3
4
5
6
of 10 oC min-1 under nitrogen atmosphere. In terms of mechanical property, both dry and hydrated
7
8 membranes were cut into a 1 x 5 cm rectangular piece to measure their tensile stress vs. strain
9
10 behavior using a universal tensile machine (UTM, Model 5565, Lloyd, Fareham, UK) with a 250
11
12
13 N load cell.
14
15 Proton conductivity. Proton conductivity (σ, S cm-1) was measured in in-plane dimension
16
17
18 by an electrochemical workstation (ZIVE SP2, Wonatech, Korea) connected with a four-probe
19
20 single cell (Bekktech LLC, Loveland, CO, USA). Each membrane was cut into a 1 x 3 cm shape
21
22
23 to place inside the cell, and the test was repeated three times at 95% relative humidity (RH). The
24
25 testing temperature varied from 30 to 80 oC and the oxygen gas rate was 500 mL min-1. The proton
26
27
conductivity of the membranes was calculated from equation (4):
28
29
30 𝜎 (𝑆 𝑐𝑚−1 ) = 𝑙/(𝑅 × 𝑡 × 𝑤) (4)
31
32 where l is the distance between electrodes (cm), R is sample resistance (Ω), t and w are sample
33
34
35 thickness (cm) and width (cm), respectively.
36
37 Oxidative stability. Fenton’s reagent (an aqueous solution containing 3 wt% H2O2 and 3
38
39
40 ppm Fe2+) was used to study the oxidative stability of SPFBI membranes. The membrane sample
41
42 was dried, weighed, and then immersed in the Fenton solution at 80 oC for 1 to 5 h. After the test,
43
44
45 the sample was gently washed with water and dried in a vacuum oven at 80 oC. The residual weight
46
47 (RW) of the sample was calculated from the before-test weight (mb) and after-test weight (ma) of
48
49
the sample, using equation (5):
50
51
52 𝑅𝑊 (%) = (𝑚𝑎 /𝑚𝑏 ) × 100 (5)
53
54 After the test, the proton conductivity of the treated membrane was measured following
55
56
57 the aforementioned procedure. Moreover, the chemical structure of the membrane sample was
58
59 analyzed using Fourier-transform infrared (FT-IR) spectroscopy (Nicolet iS20, Thermo Scientific,
60
61
62 10
63
64
65
1
2
3
4
5
6
Waltham, MA, USA).
7
8 Catalyst particle size. The catalyst ink was prepared as described in Section 2.4, and then
9
10 IPA was added to dilute the ink two-fold. Subsequently, the resultant solution was ultra-sonicated
11
12
13 for 30 min and the particle size of the catalyst was identified by employing a dynamic light
14
15 scattering (DLS) analyzer (ELS-Z2000, Photal Otsuka Electronics, Japan).
16
17
18 PEMFC tests. Membrane electrode assembly (MEA) was prepared by spraying catalyst
19
20 ink onto both sides of the PEM surface. A vacuum plate controller system (CNL Energy, Korea)
21
22
23 and a metal mask were used to maintain the flatness of the membrane, and the temperature was
24
25 kept at 60 oC to completely remove moisture and solvents during the spraying process. The Pt
26
27
loading was fixed at 0.4 mg cm-2 on an active area of 5 cm2 for each side of the membrane. Next,
28
29
30 the MEA was assembled with two gas diffusion layers (GDL, SGL GDL 39BB, CNL Energy,
31
32 Korea, thickness ~325 µm) and then sealed with two Teflon gaskets. The formed stack was inserted
33
34
35 between two graphite plates of the cell test unit in a PEMFC station (CNL Energy, Korea) for in-
36
37 situ fuel cell tests.
38
39
40 The PEMFC performance tests were conduct at 80 oC and 100% RH. Fully humidified
41
42 hydrogen and oxygen gases were supplied at anode and cathode, respectively, at the same flow
43
44
45
rate of 300 mL min-1. This flow rate corresponds to the stoichiometry values of hydrogen (λH2) and
46
47 oxygen (λO2) of 8.6 and 17.2, respectively, at 1000 mA cm-2. Electrochemical impedance
48
49 spectroscopy (EIS) measurements were carried out at cell conditions as the cell performance test
50
51
52 by connecting the fuel cell stack with ZIVE SP2 electrochemical workstation (Wonatech, Korea).
53
54 The EIS tests used the potentiostatic mode in the frequency range of 0.1 Hz – 100 kHz at the
55
56
57 potential amplitude of 6 mV. Nyquist plots were constructed and fitted by ZIVE Smart Manager
58
59 software.
60
61
62 11
63
64
65
1
2
3
4
5
6
In-situ open-circuit voltage (OCV) test of MEAs was carried out at 90 oC and 30% RH to
7
8 accelerate the degradation of MEA. The hydrogen and oxygen gas inlet rates were the same at 300
9
10 mL min-1. The MEA stability was demonstrated, as the OCV decays as a function of operation
11
12
13 time.
14
15
16
17
18 3. Results and discussion.
19
20 3.1. Polymer properties.
21
22
23 In the present study, we synthesized a series of ether-free SPFBI by a simple two-step
24
25 procedure: the polymerization under superacid-catalyzed condition to form PFBI without ether
26
27
groups, followed by the sulfonation reaction between PFBI and 1,3-propane sultone in an alkaline
28
29
30 solution. As described in section 2.2. and 2.3, the synthetic process of SFPBI has its remarkable
31
32 advantages: facile and short synthesis time and heating requirement of no more than 60 oC. Three
33
34
35 SPFBI samples, SPFBI-0.2, 0.3 and 0.4 with different sulfonation degrees, were synthesized by
36
37 simply adjusting the fluorene/biphenyl feed ratio to fabricate PEMs.
38
39
40 The chemical structures of PFBI and SPFBI were confirmed by 1H NMR spectra in Fig. 1.
41
42 The SPFBI consists of a hydrophobic poly(phenylene indole) backbone grafted with long alkyl
43
44
45
sulfonated side chains. In terms of the polymer backbone, fluorene was rationally employed as a
46
47 monomer along with biphenyl to increase and regulate the sulfonation degree of the final product.
48
49 Fluorene has a higher rotation energy barrier than biphenyl because the carbon C9 restricts the
50
51
52 movement of phenyl rings, and thus fluorene molecule is more planar than biphenyl, resulting in
53
54 higher reactivity towards the electrophilic substitution reaction [38]. Therefore, the use of fluorene
55
56
57 is also expected to improve the molecular weight and rigidity of polymer backbone, which is
58
59 beneficial for physicochemical properties of SPFBI PEMs. As a result, SPFBI-0.2, 0.3 and 0.4
60
61
62 12
63
64
65
1
2
3
4
5
6
showed different intrinsic viscosities ([η]). The [η] value of SPFBI-0.2 was 5.35 dL g-1, lower than
7
8 6.18 and 6.36 dL g-1 of SPFBI-0.3 and SPFBI-0.4, respectively. The difference of [η] implies the
9
10 increase of polymer molecular weight (MW) from SPFBI-0.2 to 0.4, based on the relationship
11
12
13 between [η] and MW in the Mark–Houwink–Sakurada relationship [39]. This result might
14
15 correspond to the increase of fluorene segment in polymer structure from 0.2 to 0.4 which
16
17
18 improves the polymerization reactivity.
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36 Fig. 1. 1H NMR spectra of (a) PFBI-0.4 and (b) SPFBI-0.4.
37
38
39
40
41 The solubility of polymers in common solvents is summarized in Table S1. When we
42
43
44
increased the fluorene content to 0.5, SPFBI-0.5 became so hydrophilic that it was dissolved in
45
46 water. Hence, the maximum fluorene ratio was fixed at 0.4, ensuring that the membrane can retain
47
48 and operate in fuel cell environments. Although the SPFBI with a lower sulfonation degree was
49
50
51 insoluble in individual water and IPA, it was surprising that it showed a decent solubility in a
52
53 mixture of IPA and water even at the ambient condition. The dissolution of SPFBI in IPA and water
54
55
56 mixture resulted in a light yellow and transparent solution (Fig. S1). When the solubility of this
57
58 polymer was further investigated in various IPA:H2O ratios (Table S2), the highest solubility was
59
60
61
62 13
63
64
65
1
2
3
4
5
6
exhibited at 4:6 w/w IPA:water mixture. The decent solubility in a mixture of those solvents
7
8 indicates that the polarity of the mixture is more suitable for SPFBI, and thus it allows the
9
10 utilization of the alcohol-based SPFBI solution as an ionomer binder. Because IPA and water are
11
12
13 easier to remove by heating after spraying catalyst onto a PEM, this alcohol-based polymer
14
15 solution is quite promising for the catalyst ink preparation compared to other attempts that
16
17
18 prepared the hydrocarbon ionomer solution in DMSO or dimethylacetamide [40,41]. In this study,
19
20 we used not only Nafion but also SPFBI as an ionomer binder to test the PEMFC performance for
21
22
23 comparison.
24
25
26
27
3.2. Physicochemical properties of membrane.
28
29
30 When the SPFBI membrane with H+ form was obtained after casting and ion-exchange in
31
32 acidic solution, it appeared as a yellow and transparent thin film. The thermal stability of the
33
34
35 membranes was studied by thermogravimetric analysis (TGA), as shown in Fig. 2a. All
36
37 membranes were thermally stable until the first significant degradation from 200 oC, and they
38
39
40 exhibited 28 – 30 % weight loss at 700 oC. The weight loss behavior of SPFBI membranes was
41
42 more clearly demonstrated by differential thermogravimetric (DTG) curves in Fig. 2b. In general,
43
44
45
the degradation behaviors of the membranes were similar to one another, illustrating two main
46
47 stages corresponding to two peaks in DTG - the thermal decomposition of sulfonic acid groups in
48
49 alkyl side chains (from 200 to around 425 oC) and the disintegration of the polymer main chain
50
51
52 (from 475 oC) [5,42]. The magnitude of DTG peaks was different among three membranes,
53
54 indicating more or less sulfonic acid group degradation compared to the backbone degradation.
55
56
57 This result was well consistent with the difference in sulfonation degree among the three polymers.
58
59 Overall, the high decomposition temperature of the membranes demonstrates that the thermal
60
61
62 14
63
64
65
1
2
3
4
5
6
stability of SPFBI PEMs satisfies the practical operation requirement of PEMFCs.
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22 Fig. 2. (a) TGA curves and (b) DTG curves of SPFBI membranes in nitrogen atmosphere.
23
24
25
26
27 Ion exchange capacity (IEC) is a key parameter to evaluate the hydration properties and
28
29 proton-conducting ability of PEMs. For SPFBI membranes, we determined IEC values from both
30
31
32
polymer structure based theoretical and the acid-base titration-based experimental methods. As
33
34 listed in Table S3, the experimental IEC values followed a consistent order with theoretical ones,
35
36 and as the higher sulfonic acid content increased IEC, the SPFBI-0.4 membrane exhibited the
37
38
39 highest value of 3.25.
40
41 The water uptake of SPFBI membranes was gravimetrically measured in the temperature
42
43
44 range of 30 – 80 oC as presented in Fig. 3a. In general, water uptake behavior of SPFBI membranes
45
46 followed two major trends. Firstly, the water uptake of all membranes increased with temperature,
47
48
49 because higher temperature increases polymer free volume and polymer - water interaction [43].
50
51 Secondly, the sulfonic acid groups enhanced the hydrophilicity of PEMs, allowing the membrane
52
53
to absorb more water. As a result, the SPFBI-0.4 membrane showed the highest water uptake of
54
55
56 46.03 % compared to 41.69 % of SPFBI-0.2 at 80 oC. It is worth mentioning that the increase of
57
58 water content from 30 to 80 oC was not significant (less than 10 %), due to the rigidity of SPFBI
59
60
61
62 15
63
64
65
1
2
3
4
5
6
backbone and high intrinsic viscosity as described [38]. Notably, SPFBI membranes synthesized
7
8 in this study exhibited relatively low water uptake compared to other PEMs, taking into account
9
10 very high IEC values that often lead to an excessive water content of PEM[27,44].
11
12
13 Fig. 3b shows the swelling ratio of SPFBI membranes. Similar to the water uptake behavior,
14
15 the membranes were more swollen at higher temperatures and higher sulfonation degrees. For
16
17
18 instance, while the swelling ratio of SPFBI-0.4 was 13.98 % at 30 oC, it was 16.12 % at 80 oC.
19
20 Moreover, taking the benefits from limited water uptake, the membranes were dimensionally quite
21
22
23 stable, showing the swelling ratio lower than 14 % at 30 oC. These relatively low water uptake and
24
25 swelling ratios of SPFBI membranes compared with the previously reported hydrocarbon
26
27
membranes [12,14,21], indicate a remarkable advantage of their dimensional stability for PEMFC
28
29
30 applications.
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Fig. 3. (a) Water uptake, (b) swelling ratio of SPFBI membranes at different temperatures, (c), (d)
61
62 16
63
64
65
1
2
3
4
5
6
stress-strain curves of the membranes at fully hydrated and dry forms, respectively.
7
8
9
10 Mechanical properties of SPFBI membranes were analyzed by UTM and the resulting
11
12
13 stress-strain behavior is depicted in Fig. 3c and 3d. With increasing sulfonation degree, the
14
15 membrane became more flexible in the hydrated state and thus the maximum tensile strength
16
17
18 decreased (from 35.4 MPa of SPFBI-0.2 to around 30 MPa of SPFBI-0.4 membrane), while the
19
20 elongation at break opposingly increased (from 24.2 % of SPFBI-0.2 to 29.6 % of SPFBI-0.4
21
22
23 membrane). Despite the highest intrinsic viscosity, the SPFBI-0.4 membrane was less rigid under
24
25 humidified conditions than other membranes because of the plasticizing effect of high water uptake.
26
27
To remove the effect of hydration, we also conducted the mechanical property test for dry
28
29
30 membranes. As expected, the tensile strength of membranes increased following the order 0.2 <
31
32 0.3 < 0.4, which is a different trend from the fully humidified test results. In the dry state, the
33
34
35 higher content of fluorene backbone contributes to the mechanical durability of the membranes,
36
37 even though it was outweighed by the effect of water uptake in the hydrated state. Due to the
38
39
40 highest tensile strength under humidified conditions, SPFBI-0.2 PEM was considered for use in
41
42 long-term stability test, as described later in this study.
43
44
45
46
47 3.3. Proton conductivity.
48
49 The proton conductivity of SPFBI membranes was measured in-plane at 95% RH and
50
51
52 temperatures between 30 and 80 oC, as depicted in Fig. 4a. We also measured the conductivity of
53
54 Nafion membrane for comparison. In general, as the hopping and/or vehicle movement of protons
55
56
57 is thermally activated in more hydrated state of the membranes, the proton conductivity of all
58
59 membranes gradually increased with temperature. Also, the membranes with higher IEC showed
60
61
62 17
63
64
65
1
2
3
4
5
6
higher proton conductivity; for instance, the SPFBI-0.4 membrane with the highest IEC exhibited
7
8 the highest proton conductivity of 0.121 S cm-1 at 30 oC and 0.1956 S cm-1 at 80 oC. This result
9
10 supports the positive effect of high sulfonic acid content on the proton conduction. Notably, the
11
12
13 SPFBI-0.3 and SPFBI-0.4 membranes outperformed the Nafion membrane in terms of proton
14
15 conductivity, and even the SPFBI-0.2 membrane reached a proton conductivity from 0.063 to
16
17
18 0.105 S cm-1, which is comparable to that of Nafion membrane.
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54 Fig. 4. (a) Proton conductivity of Nafion and SPFBI membranes at different temperatures, (b) the
55
56
57 corresponding Arrhenius plots of SPFBI membranes, (c) comparison of proton conductivity
58
59 correlating with IEC value and in-plane swelling ratio for various reported PEMs (details of test
60
61
62 18
63
64
65
1
2
3
4
5
6
conditions are summarized in Table 1).
7
8
9
10 To obtain more intensive information on the proton conduction behavior of SPFBI PEMs,
11
12
13 the activation energy (Ea) was calculated from the Arrhenius plots relating ln σ and T-1 (Fig. 4b).
14
15 As the gradual decrease in Ea was observed from 9.87 kJ mol-1 of SPFBI-0.2 to 8.67 kJ mol-1 of
16
17
18 SPFBI-0.4, it demonstrates that protons are more feasibly transported when the sulfonic acid
19
20 density increases. This activation energy behavior implies that the proton conduction behavior in
21
22
23 SPFBI membranes complies with the well-known Grotthuss and vehicular mechanisms [45].
24
25 Because the water uptake increased with the sulfonation degree as described, the expanded ionic
26
27
cluster dimension provided lower energy barriers for proton transport. Besides, the large amount
28
29
30 of sulfonic acids are beneficial for proton conduction via Grotthuss mechanism by shortening the
31
32 distance between acid groups for proton hopping [46,47]. In summary, as the increase of sulfonic
33
34
35 acid density reduces the energy barrier of proton-transfer pathways, the SPFBI-0.4 membrane
36
37 showed the highest conductivity. For comparison, we summarized the proton conductivity of the
38
39
40 0.4 membrane and various commercial and lab-synthesized hydrocarbon-based PEMs as a
41
42 function of swelling ratio and IEC as three-dimensionally illustrated in Fig. 4c. Table 1 provides
43
44
45
a more detailed comparison, including test results, test conditions, and polymer types. In general,
46
47 the SPFBI-0.4 membrane illustrated an excellent proton conductivity under relatively low swelling
48
49 when it was placed alongside the non-composite PEMs such as Nafion and Pemion.
50
51
52
53
54 Table 1. Summary of proton conductivity, IECex and swelling ratio of SPFBI-04 membrane and
55
56
57 some typical commercial and lab-synthesized PEMs.
58
59
60
61
62 19
63
64
65
1
2
3
4
5
6 IECex In-plane SRb
7 PEM σa (S cm-1) Polymer type Ref.
8 (meq g-1) (%)
9
10 SPFBI-0.4 0.196 ± 0.005 3.25 ± 0.31 16.12 ± 0.16 Ether-free This work
11
12
13
14 Pemion
~ 0.265 3.28 ± 0.06 44.87c Ether-free [27]
15 (sPPN-H+)
16
Pemion
17 ~ 0.170 3.19 ± 0.05 33.3c Ether-free [27]
18 (sPPB-H+)
19
20
SPPBP 40 0.162 2.45 10.8 Ether-free [48]
21
22 SIPiP 0.0975 2.50 11.5 Ether-free [49]
23
24 SPAES160 ~ 0.150 2.10 ± 0.24 19.57 Ether-containing [14]
25
26 SPEEK 0.170 1.654 51.3d Ether-containing [50]
27
28 SPFAE 0.1507 1.62 5.2 Ether-containing [51]
29 a
30 Measured at 80 oC, RH varies from 90 – 100%
b
31 Measured at 80 oC in water
c
32 Mathematically calculated from reported area swelling ratios, assuming that the sample shape
33
34
was square.
d
35 Measured at 60 oC and 100% RH
36
37
38
39 3.4. Oxidative stability.
40
41 The oxidative stability of SPFBI membranes was investigated by subjecting the membrane
42
43
44
samples to Fentons’s test where the chemical degradation of membrane was stimulated by •OH
45
46 radical generation. The membranes were treated with Fenton’s solution (3 wt% H2O2, 3 ppm Fe2+)
47
48 for 1 h and 5 h. During the test, membrane samples were gradually dissolved in the solution due
49
50
51 to polymer decomposition under ·OH radical bombardment. The residual weights of the samples
52
53 were determined and listed in Table 2, indicating how much the membrane retained after the test.
54
55
56 While the SPFBI-0.2 sample exhibited the highest residual weight of 98.95 % after 1 h and 43.33%
57
58 after 5 h, the SPFBI sample lost 5.73% and 81.73% of its original weight after 1 h and 5 h treatment,
59
60
61
62 20
63
64
65
1
2
3
4
5
6
respectively. For all samples, no significant mass loss and visual changes were observable after
7
8 the exposure for 1 h. As the oxidative stability of the membrane decreased with increasing
9
10 sulfonation degree, the ether-free phenylene backbone might be less prone to radical attack than
11
12
13 highly reactive -SO3H groups as reported in several studies [14,27,52]. To more precisely evaluate
14
15 the oxidative stability of SPFBI membranes, their Fenton’s test results were compared with those
16
17
18 of other hydrocarbon PEMs obtained under similar test conditions in Table S4 and S5. For 1 h test,
19
20 the stability of all SPFBI PEMs surpasses that of the common ether-containing hydrocarbon PEMs
21
22
23 even under harsher conditions. Even though Pemion illustrated better oxidative stability than
24
25 SPFBI PEMs for 1 h test, their residual weight difference was not significant. For 5 h test, although
26
27
the stability of PEMs varied with the sulfonation degree, SPFBI PEMs showed quite good
28
29
30 oxidative stability that could compete with Pemion, a state-of-the-art ether-free PEM. It is
31
32 necessary to mention that these 5 h Fenton’s test results under the similar experimental conditions
33
34
35 have been barely reported for other hydrocarbon PEMs because it often led to the entire
36
37 decomposition of membrane samples [46]. The improved chemical stability of this ether-free
38
39
40 SPFBI membrane compared to the ether-containing PEMs can be explained by the different bond
41
42 dissociation energy between aryl-aryl (C6H5-C6H5) segment (476 ± 6 kJ mol-1) and aryl-ether-aryl
43
44
45
(C6H5-O-C6H5) segments (355 ± 6 kJ mol-1)[53]. More importantly, the ether group creates
46
47 vulnerable sites on the neighboring aromatic rings due to the electron-donating effect [1,25,54], as
48
49 illustrated in Fig. S2. The attack of the oxidative radicals on those sites leads to the cleavage and
50
51
52 scission of the polymer backbone, resulting in poor chemical stability of the polymer membrane
53
54 in Fenton’s test.
55
56
57
58
59 Table 2. Residual weights of SPFBI samples after 1 h and 5 h Fenton’s test.
60
61
62 21
63
64
65
1
2
3
4
5
6
7
8
9 SPFBI-0.2 98.85 ± 1.25 43.33 ± 2.39
10
11 SPFBI-0.3 95.00 ± 0.52 29.07 ± 3.05
12
13 SPFBI-0.4 94.27 ± 0.40 18.27 ± 3.56
14
15
16
17 The proton conductivity test and FT-IR were employed to analyze the after-treatment
18
19
20 membrane samples. Because all membrane samples were almost intact after 1 h treatment, it was
21
22 available to measure the proton conductivity of SPFBI membranes with and without 1 h exposure
23
24
25 with Fenton’s solution for comparison (Fig. 5a). Despite slight conductivity losses due to the
26
27 chemical degradation, the membranes still exhibited a decent proton conductivity at various
28
29
30
temperatures, implying that most of the polymer structure and membrane morphology were not
31
32 significantly damaged. The recovered pieces of samples were also assessed by Fourier-transform
33
34 infrared (FT-IR) spectroscopy (Fig. 5b-d). For all samples, there were no serious changes in the
35
36
37 chemical structure after Fenton’s treatment. The IR bands originating from -SO3H groups in the
38
39 pristine membranes still can be clearly observed in the spectra of the membranes after treatment
40
41
42 for both 1 h and 5 h.
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62 22
63
64
65
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33 Fig. 5. (a) Proton conductivity of SPFBI membranes before and after 1 h Fenton’s test; FT-IR
34
35 spectra of (b) SPFBI-0.2, (c) SPFBI-0.3 and (d) SPFBI-0.4 membrane before and after 1 h and 5
36
37
38
h Fenton’s test.
39
40
41
42 3.5. PEMFC performance.
43
44
45 Compared with many other hydrocarbon polymers used to prepare PEMs, it was discovered
46
47 that SPFBIs have a decent solubility in a mixture of IPA and water, as previously presented. As
48
49
50 this behavior has been rarely reported from the hydrocarbon-based polymers for PEMs, this unique
51
52 solubility property of SPFBI was more detail exploited for its application as an ionomer binder as
53
54
55 well as PEM. As presented, SPFBI-0.4 showed the highest proton conductivity, compared to
56
57 SPFBI-0.2 and SPFBI-0.3 PEMs. When the size of particles agglomerated in catalyst ink was
58
59
60
analyzed using the dynamic light scattering (DLS) method, SPFBI-0.4 was more compatible with
61
62 23
63
64
65
1
2
3
4
5
6
Pt/C catalyst than the other two SPFBI samples (Fig. S3) [55]. Accordingly, taking into account
7
8 both membrane and ionomer properties, SPFBI-0.4 was chosen to prepare the ionomer solution,
9
10 along with the conventional Nafion ionomer as a reference. Using these ionomer binders, we
11
12
13 fabricated MEAs consisting of SPFBI and Nafion membranes for PEMFC operation.
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29 Fig. 6. (a) H2/O2 fuel cell performances of different MEAs using Nafion ionomer binder, (b)
30
31 corresponding Nyquist plots of MEAs using Nafion ionomer binder. (Test conditions: 80 oC, 100%
32
33
34 RH, and gas inlet rate of 300 mL min-1 at both anode and cathode).
35
36
37
38
39 First, we compared the cell performance of MEAs of SPFBI and Nafion PEMs fabricated
40
41 using the same ionomer binder. Fig. 6a shows the polarization curves of MEAs using the Nafion
42
43
44
binder at 80 oC under the fully humidified H2/O2 supply. As the thickness of membranes was
45
46 controlled by casting process, its difference among membranes was less than 3 µm as shown in
47
48 Table 3 to minimize its effect on cell performance. While the maximum power density of SPFBI-
49
50
51 0.2 MEA was quite similar to that of Nafion MEA, that of SPFBI-0.3 and SPFBI-0.4 MEAs
52
53 exhibited higher maximum power densities of 346 and 365 mW cm-2, respectively. This
54
55
56 performance improvement can be attributed to the superior proton conductivity of SPFBI
57
58 membranes. To further understand the effect of types of PEMs on PEMFC performance, the
59
60
61
62 24
63
64
65
1
2
3
4
5
6
electrochemical impedance spectroscopy (EIS) measurements were performed to obtain the
7
8 corresponding Nyquist plots for each MEA, as shown in Fig. 6b. All MEAs showed a semicircular
9
10 pattern of Nyquist plots, in which the high-frequency intercept (left intersection of the real axis)
11
12
13 provided the electrolyte resistance (Rel), and the semicircle diameter provided the charge-transfer
14
15 resistance (Rct) of MEA [56]. It can be seen that the differences in Rct among MEAs were small
16
17
18 because of the utilization of the same catalyst and ionomer binder for all MEAs. On the other hand,
19
20 the Rel values of MEAs varied quite a lot, following the order of SPFBI-0.4 < SPFBI-0.3 < Nafion
21
22
23 < SPFBI-0.2, which is in compliance with the cell performance results. These results demonstrate
24
25 the benefit of SPFBI PEMs that reduce the membrane resistance and thus lead to the enhancement
26
27
of cell performance.
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62 25
63
64
65
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46 Fig. 7. Comparison of H2/O2 cell performance of the MEAs fabricated with different PEMs and
47
48 ionomer: (a) Nafion membrane, (b) SPFBI-0.2 membrane, (c) SPFBI-0.4 membrane. The
49
50
51 corresponding Nyquist plots for (d) Nafion membrane, (e) SPFBI-0.2 membrane and (f) SPFBI-
52
53 0.4 membrane. (Test conditions: 80 oC, 100% RH, and gas inlet rates of 300 mL min-1 at both anode
54
55
56
and cathode).
57
58
59
60
61
62 26
63
64
65
1
2
3
4
5
6
7
8
9
10 Membrane Electrode Assembly (MEA)
11 Maximum power
12 density (mW cm-2)
13 Thickness
14 Membrane Ionomer binder
15 (µm)
16
17 Nafion 318 0.17373 0.39523
18 Nafion 90
19 SPFBI-0.4 294 0.18020 0.45080
20
21 Nafion 321 0.18121 0.43527
22 SPFBI-0.2 88
SPFBI-0.4 296 0.18682 0.48073
23
24 Nafion 346 0.13311 0.44089
25 SPFBI-0.3 87
26 SPFBI-0.4 - - -
27
28 Nafion 365 0.12421 0.43427
29 SPFBI-0.4 87
30 SPFBI-0.4 346 0.11330 0.47170
31
32
33
34 Next, PEMFC performance tests for Nafion, SPFBI-0.2 and SPFBI-0.4 MEAs using the
35
36 SPFBI-0.4 ionomer were also conducted. Their polarization curves were depicted along with those
37
38
39
of MEAs using the Nafion ionomer (Fig. 7a-c) and the corresponding EIS spectra (Fig. 7d-f) for
40
41 comparison. Additionally, some important experimental results including the maximum power
42
43 density, Rel and Rct, are summarized in Table 3. For all membranes, SPFBI-0.4 ionomer still
44
45
46 achieved decent cell performances, even though the Nafion ionomer showed better performances
47
48 with a 5 – 8% higher maximum power density. A similar conclusion can be drawn from the
49
50
51 comparison of Nyquist plots for MEAs fabricated with different ionomers. In each EIS curve,
52
53 although Rel was not significantly varied because the same types of PEMs were employed, Rct
54
55
56 increased when SPFBI-0.4 ionomer was used instead of Nafion. For instance, the MEA fabricated
57
58 using Nafion ionomer and Nafion PEM exhibited Rct of 0.39523 Ω cm2, which was lower than that
59
60
61
62 27
63
64
65
1
2
3
4
5
6
of the MEA using SPFBI-0.4 ionomer and Nafion PEM, 0.45080 Ω cm2. This difference probably
7
8 stems from the difference in proton transport in the catalyst layer affected by ionomer [8,55], as
9
10 the SPFBI-0.4 ionomer was less compatible with the catalyst than the conventional ionomer
11
12
13 according to DLS analysis. Those results, however, still point out that the SPFBI-0.4 ionomer can
14
15 be utilized to prepare MEAs for not only SPFBI membranes but also Nafion membrane to obtain
16
17
18 acceptable cell performance. It must also state that hydrocarbon ionomers like SPFBI may behave
19
20 differently from Nafion ionomer, thus other factors (e.g., catalysts, gas flow rate or ionomer
21
22
23 loading) can be further optimized to be more suitable for SPFBI ionomer usage. Therefore, the cell
24
25 performance of SPFBI-0.4 ionomer MEAs can be improved with more suited MEAs designs,
26
27
which would be the target of our future works. To the extent of our knowledge, the application of
28
29
30 low-cost hydrocarbon polymers as ionomer binder in PEMFC has been rarely reported, as it mostly
31
32 resulted in inferior cell performances to Nafion [57] and the solvent for preparation of ionomer
33
34
35 solution was mostly DMSO which is aprotic and thus not sufficient for fuel cell manufacture
36
37 [58,59]. As this result demonstrate the application of SPFBI-0.4 ionomer binder for high PEMFC
38
39
40 performance, it encourages further developments of hydrocarbon polymers not only for PEM but
41
42 also for ionomer binder to completely replace the perfluorinated polymers.
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62 28
63
64
65
1
2
3
4
5
6
Fig. 8. OCV decay over time for various MEAs fabricated with different membrane/ionomer
7
8 binders. (Test conditions: 90 oC, 30% RH, and gas inlet rate: 300 mL min-1 at both anode and
9
10 cathode).
11
12
13
14
15 Finally, the OCV in-situ stability tests were conducted to assess the effect of the SPFBI
16
17
18 membrane and ionomer on the long-term durability of the MEA. Under the harsh temperature and
19
20 humidity conditions, the OCV decay of MEAs was plotted over test time, as shown in Fig. 8. The
21
22
23 end-of-life point of MEAs was chosen as the time when OCV drops to 0 V. For MEAs using Nafion
24
25 membrane, the voltage could not sustain over 220 h, as it completely dropped after around 210 -
26
27
220 h test. On the contrary, the MEAs using SPFBI-0.2 membrane exhibited a much lower OCV
28
29
30 decay rate, resulting in the end-of-life point over 620 h, much higher than those of Nafion
31
32 membrane-used MEAs. This in-situ cell test illustrated surprisingly better durability of SPFBI-0.2
33
34
35 than Nafion, being different from the Fenton’s test results. Athough Nafion PEMs are well-known
36
37 for their excellent stability against chemical degradation [60,61], this mismatched correlation
38
39
40 between ex-situ Fenton’s and in-situ cell tests has been stated in many reports, especially when the
41
42 Nafion MEAs decay faster than the hydrocarbon MEAs in OCV test [14,62]. This difference is
43
44
45
due to the additional factors provided by in-situ cell test that cannot be obtained from ex-situ
46
47 Fenton’s test. For instance, the fuel (hydrogen and oxygen) crossover is one of the important
48
49 factors to be additionally considered in this in-situ test. Due to higher gas permeability of Nafion
50
51
52 than hydrocarbon membranes, the generation rate of OH radicals is much more higher in the
53
54 Nafion based MEA system than the hydrocarbon based one during cell operation. This provides
55
56
57 much more complex and preferential radical attacking situations for the chemical degradation of
58
59 membranes than the simple Fenton’s test conducted in the solution with the fixed OH radical
60
61
62 29
63
64
65
1
2
3
4
5
6
concentration [20,24]. Therefore, while the Fenton’s test provided good information about the
7
8 chemical degradation behavior of SPFBI membrane itself, the OCV test demonstrated much more
9
10 reliable durability of the SPFBI membrane in practical MEA operation.
11
12
13 The optical images of MEAs before and after the stability test were collected and shown in
14
15 Fig. S4. While the SPFBI-0.2 membrane-used MEAs have no observable defects even after over
16
17
18 620 h, some pinholes were found on the Nafion membrane-used MEAs after the test, indicating
19
20 severe damages caused by chemical degradation. This is in good accordance with the OCV decay
21
22
23 rate of the MEAs, demonstrating the excellent in-situ chemical stability of ether-free SPFBI-0.2
24
25 membrane. Besides, compared with Nafion ionomer, SPFBI-0.4 ionomer did not significantly
26
27
affect the OCV decay for both Nafion and SPFBI-0.2 membrane-based MEAs, since the MEAs
28
29
30 consisted of SPFBI-0.2 membrane and SPFBI-0.4 ionomer still illustrated an end-of-life point over
31
32 620 h. Overall, the in-situ OCV test results provide the application of SPFBI membrane and
33
34
35 ionomer for the long-term operation of PEMFC.
36
37
38
39
40 4. Conclusions.
41
42 To synthesize the ether-free polymer for the fabrication of high chemical stability proton
43
44
45
exchange membrane, we proposed a novel polymer synthesis via the superacid-catalyzed
46
47 polymerization of common and low-cost monomers. As a result, a series of ether-free sulfonated
48
49 poly(fluorene biphenyl indole) (SPFBI) were successfully synthesized with various sulfonation
50
51
52 degrees. Experimental results revealed that the excellent proton conductivity of SPFBI membranes
53
54 up to 0.1956 S cm-1 at 80 oC was observed under the low water uptake and swelling ratio compared
55
56
57 to other reported membranes. Owing to the free structure of SPFBI, its oxidative stability was
58
59 comparable to that of Pemion - the state-of-the-art ether-free polymer lectrolyte membrane and
60
61
62 30
63
64
65
1
2
3
4
5
6
superior to many common hydrocarbon membranes. Due to the excellent proton conductivity and
7
8 chemical stability, SPFBI-0.3 and SPFBI-0.4 membranes exhibited better cell performances than
9
10 the Nafion membrane, showing the sustainability of more than 620 h of the open-circuit voltage
11
12
13 test. More importantly, SPFBI-0.4 was possibly employed to prepare the ionomer binder due to
14
15 the solubility in the isopropanol and water mixture. Despite minor losses in the maximum power
16
17
18 density, the performance and stability of membrane electrode assemblies fabricated with SPFBI-
19
20 0.4 ionomer showed the potential promises for research on hydrocarbon ionomer binders. We
21
22
23 believe that the results in this study merit the further development of hydrocarbon-based ether-free
24
25 polymer lectrolyte membranes and ionomer binders for the fabrication of cost-effective and long-
26
27
term durable membrane electrode assembly for fuel cells.
28
29
30
31
32 Acknowledgments
33
34
35 This work was sponsored by the National Research Foundation of Korea Grant, funded by
36
37 the Korean Government (MEST) (NRF 2018M3D1A1058624).
38
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Journal of Power Sources

Ether-free sulfonated poly(fluorene biphenyl indole) membranes and ionomer binders

Manuscript Number: POWER-D-22-04425R2

Article Type: Research Paper

Corresponding Author: Dukjoon Kim, PhD

First Author: Thuc Vu Dong

Order of Authors: Thuc Vu Dong

Vo Dinh Cong Tinh

Suggested Reviewers: Simon Thiele

School of Chemical Engineering

Cong Tinh and Dukjoon Kim to Journal of Power Sources.

without the written consent of the Publisher.

Ph.D., Professor, SKKU Fellow

Executive Director of Korea Polymer Society

National Research Laboratory, School of Chemical Engineering, Sungkyunkwan University

Suwon, 16419, Republic of Korea

[Email] djkim@skku.edu; [Phone] +82-10-3017-7250

RESPONSE TO EDITOR’S COMMENT

Manuscript Number: POWER-D-22-04425R1

has changed to:

proton exchange membrane fuel cells

Vu Dong Thuca, Vo Dinh Cong Tinha, Dukjoon Kima*

Suwon, Gyeonggi 16419, Republic of Korea

poly(fluorene biphenyl indole)s (SPFBI) synthesized by a feasible and cost-effective process.

provides a remarkable approach for optimizing the ether-free hydrocarbon-based polymer

proton conductivity and chemical stability.

component of PEMFC, proton-exchange membrane (PEM) needs to fulfill various requirements,

causes environmental concerns in its disposal process [10,11].

the perfluorinated polymer membranes, the phase-separated hydrophilic domains in hydrocarbon-

cost reduction compared to perfluorinated PEMs.

Despite the aforementioned advantages, several limitations of hydrocarbon-based PEMs

commercially available ether-free hydrocarbon-based PEM [27,28]. The synthetic process of

mediocre properties without profound investigation of chemical stability enhancement, it is

difficult to draw the potential of its methodological effectiveness.

Compared to the previous ether-free polymers synthesized by superacid-catalyzed reaction, this

membrane electrode assembly (MEA) process.

Fluorene, isatin, trifluoroacetic acid (TFA), trifluoromethanesulfonic acid (TFSA), 1,3

obtained from Samchun Chemicals (Korea).

2.2. Synthesis of poly(fluorene biphenyl indole) (PFBI).

synthesis, 3 g of PFBI and 0.116 g of TBAB were simultaneously dissolved in 70 mL of dimethyl

2.4. Preparation of membrane and catalyst ink.

ionomer binder:catalyst mass ratio was fixed at 1:4.

chemical shift of DMSO-d6 is determined at 2.50 ppm.

𝑊𝑈(%) = (𝑚𝑤 − 𝑚𝑑 )/𝑚𝑑 × 100 (1)

𝑆𝑅(%) = (𝑙𝑤 − 𝑙𝑑 )/𝑙𝑑 × 100 (2)

from equation (3):

weight of the repeating unit of polymer.

by an electrochemical workstation (ZIVE SP2, Wonatech, Korea) connected with a four-probe

conductivity of the membranes was calculated from equation (4):

𝜎 (𝑆 𝑐𝑚−1 ) = 𝑙/(𝑅 × 𝑡 × 𝑤) (4)

thickness (cm) and width (cm), respectively.

the sample, using equation (5):

𝑅𝑊 (%) = (𝑚𝑎 /𝑚𝑏 ) × 100 (5)

scattering (DLS) analyzer (ELS-Z2000, Photal Otsuka Electronics, Japan).

situ fuel cell tests.

3. Results and discussion.

3.1. Polymer properties.

In the present study, we synthesized a series of ether-free SPFBI by a simple two-step

simply adjusting the fluorene/biphenyl feed ratio to fabricate PEMs.

improves the polymerization reactivity.

Fig. 1. 1H NMR spectra of (a) PFBI-0.4 and (b) SPFBI-0.4.

The solubility of polymers in common solvents is summarized in Table S1. When we