Chemical Engineering Journal 459 (2023) 141467

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Ether-free polymer based bipolar electrolyte membranes without an

interlayer catalyst for water electrolysis with durability at a high
current density
Yeeun Jeon, Vo Dinh Cong Tinh, Vu Dong Thuc, Dukjoon Kim *
School of Chemical Engineering, Sungkyunkwan University, Suwon, Gyeonggi 16419, Republic of Korea

A R T I C L E I N F O A B S T R A C T

Keywords: In this study, bipolar membranes (BPMs) were fabricated employing the sulfonated poly(fluorine biphenyl
Water electrolysis indole) based proton exchange membrane (PEM) and the poly(arylene piperidinium) based anion exchange
Ether-free polymer membrane (AEM) for the production of green hydrogen by water electrolysis. As those polymers comprise similar
Chemical durability
aromatic backbone structures without ether groups, excellent chemical durability of the constituent membranes
Bipolar membrane
was expected for the long-term energy efficient operation in a wide pH range. Three BPMs with different ionic
conductivity pairs between PEM and AEM were designed to explore its effect on water electrolysis performance.
At the fixed anionic conductivity of AEM of 0.0370–0.0923 S cm− 1 at 30–70 ◦ C, the proton conductivity of PEMs
was tuned as 0.0379–0.1196 S cm− 1, 0.0909–0.1598 S cm− 1, and 0.1104–0.1739 S cm− 1 at 30–70 ◦ C. BPMs were
steadily operated at low voltages below 1.5 V in the wide current density range of 0–1500 mA cm− 2. Among
them, the water electrolytic cell assembled with BPM 80/20 showed the best water electrolysis performance, as
the cell voltage of BPM 80/20, BPM 70/30, and BPM 60/40 was 0.75 V, 0.98 V, and 1.08 V, respectively, under
the current density of 700 mA cm− 2 at 70 ◦ C. It was much lower than that of AEM, 2.24 V and PEM 80/20, 1.81 V
even in the absence of interlayer catalyst. Also, the synthesized BPM 80/20 was not only thermally and me­
chanically stable up to 298 ◦ C and 19.15 MPa (tensile strength), but also chemically stable in the concentrated
acidic and basic environment, as its weight loss was less than 5.4 % and 4.62 % in 4 M H2SO4 and 4 M KOH
solutions for 4 weeks, respectively.

1. Introduction they can produce more pure hydrogen gas (>99.99 % H2) than AWE
(>99.5 % H2) in safe operation [5–7]. The proton exchange membrane
Hydrogen is one of the most promising renewable energy sources water electrolysis (PEMWE) can be functioned at high current densities
that can preserve the sustainable and prosperous world [1]. However, with high voltage efficiency and thus can be compactly designed, but it
the production of bulk hydrogen currently relies on fossil fuels which has high component cost and corrosion problems associated with the
generates 10 kg of CO2 per 1 kg of hydrogen [2]. To eliminate carbon operation in acidic environments [7,8]. As anion exchange membrane
emissions, the green hydrogen produced from water becomes more water electrolysis (AEMWE) takes advantage of AWE, it has low material
important [3]. In water electrolysis, hydrogen (H2) and oxygen (O2) expenses under alkaline media and low gas crossover [9]. However,
gases are formed at the cathode and anode, respectively, when water is AEM has a few critical drawbacks associated with poor mechanical and
dissociated into H+ and OH– through reverse bias [4]. chemical durability in alkaline environment and low ionic conductivity
In water electrolysis, alkaline water electrolysis (AWE) is the most compared to PEM [6]. To take pros from the two membranes, the bipolar
advanced technology, but it is not suitable for mass production because membrane combining PEM and AEM, has emerged as a promising option
of low operation pressure and limited current densities [5]. To improve recently for the application of electrochemical energy systems including
the production capacity per unit of electricity, the water electrolysis fuel cells [10], (photo)electrochemical CO2 reduction [2], flow batteries
based on polymer electrolyte membrane is currently emerging [6]. As [11], and water electrolysis [12].
the polymer electrolyte membranes have low gas crossover property, In bipolar membrane water electrolysis (BPMWE), acid media was

* Corresponding author.
E-mail address: [email protected] (D. Kim).

https://doi.org/10.1016/j.cej.2023.141467
Received 4 October 2022; Received in revised form 19 December 2022; Accepted 13 January 2023
Available online 16 January 2023
1385-8947/© 2023 Elsevier B.V. All rights reserved.
Y. Jeon et al. Chemical Engineering Journal 459 (2023) 141467

applied to the cathode for hydrogen evolution reaction (HER) and 2. Experimental section
alkaline media was applied to the anode for oxygen evolution reaction
(OER) depicted in equation (1a) and equation (1b) [13]. 2.1. Materials
+ -
Cathode: 4H + 4e → 2H2, 0 V (1a) Tetrabutylammonium-bromide (98 %, TBAB), trifluoromethane
Anode: 4OH- → O2 + 2H2O + 4e-, 0.40 V (1b) sulfonic acid (TFSA), trifluoroacetic acid (98 %, TFA), isatin (98 %),
biphenyl (99.5 %), and fluorene (95 %) were provided by Tokyo
Here, 0 V and 0.4 V are the standard reversible potentials which are Chemical Industry (TCI, Tokyo, Japan). Hydrochloric acid (10 % solu­
dependent on pH and pressure, and the corresponding Nernst equation is tion, HCl), dimethyl sulfoxide (DMSO), isopropanol (IPA), methyl
given in equation (S1). From the above electrochemical water splitting alcohol (99.5 %, MeOH) and potassium hydroxide (95 %, KOH) were
reactions, the theoretical standard thermodynamic potential of bipolar provided by Samchun Chemical (Bongeunsa-ro, Republic of Korea). N-
membrane (BPM) is thus 0.4 V per mole of water at 1 atm and at 25 ◦ C methyl-4-piperidone (97 %, MP), Sodium hydroxide (97 %, NaOH),
[14], while that of PEMWE and AEMWE is 1.23 V mol− 1, based on the dichloromethane (99.8 %, DCM), 1-bromobutane (99 %, C4H9Br) and
standard hydrogen electrode (SHE) [5]. Hence, BPMWE has advanta­ 1,3-propanesultone (98 %) were delivered by Sigma-Aldrich (Milwau­
geous features over PEMWE and AEMWE, such as 1) reduction of total kee, WI, USA). Platinum nominally 40 % on carbon black (Pt/C, Hi SPEC
potential required for water splitting 2) various selection of catalysts for 40, Alfa Aesar, Massachusetts, USA) and nickel foam (29–04275-02,
HER and OER under wide pH operation range. Nevertheless, the Invisible Inc Republic of Korea) were used as catalysts for HER and OER.
development of BPM is still in premature stage, because the actual water Gas diffusion layer (GDL, 39 BB, Sigracet, Texas, USA) was applied for
splitting voltage of BPM is still higher than 1 V [1,15]. As this high water the fabrication of membrane electrode assembly. Fumasep-FBM
splitting voltage seems to be caused by the over-potential at the BPM (5041614, Fumatech, Germany), Nafion 117 (NR211, Dupont, USA),
interface, many researches have been focused on the interfacial stability and Fumasep FAA 3–30 (5041719, Fumatech, Germany) were pur­
between PEM and AEM [16] – construction of a uniform interface chased as a reference BPM, PEM, and AEM for comparison, respectively.
structure [17–19], introduction of interface catalyst [20–22], and
theoretical calculation of the interface electric field [23–25]. Addition­ 2.2. Preparation of membranes
ally, the membrane thickness was adjusted to improve the water trans­
port rate for the high current density operation of BPM [26]. 2.2.1. Synthesis of sulfonated poly(fluorine biphenyl indole) (SPFBI)
To reduce the interface resistance between PEM and AEM layers, the Poly(fluorine biphenyl indole) (SPFBI) was synthesized via the
constituent polymer structures should be tuned to enhance the chemical superacid-polymerization reaction as depicted in Fig. S1. To control the
and physical compatibility. As the polymer structure effect on BPM sulfuric acid groups density, the molar ratio of biphenyl (1-x) to fluorene
performance has been scarcely investigated so far, we tried to synthesize (x) was varied at 0.8:0.2, 0.7:0.3, and 0.6:0.4. In particular, the synthetic
new polymer structures for BPM for long-time high performance water pathway of SPFBI (x = 0.2) follows: Firstly, 2 g (0.014 mol) of isatin,
electrolysis. The major requirements of BPM additionally include: 1) 2.515 g (0.016 mol) of biphenyl, and 0.678 g (0.004 mol) of fluorene
sufficient water transport capacity of polymer electrolyte membranes to were completely dissolved at room temperature with 15 mL of DCM in a
prevent interface dehydration, 2) enhancement of water dissociation 50 mL three-neck round bottom flask. Subsequently, the temperature of
rate, 3) high chemical stability to avoid chemical degradation in strong the mixture was set up from 0 to 5 ◦ C using an ice bath. Next, 15 mL of
acids and strong bases. In this contribution, we synthesized sulfonated TFSA and 10 mL of TFA were poured into the flask under nitrogen at­
poly(fluorene biphenyl indole) (SPFBI) as a PEM and poly(arylene mosphere for 6 h while changing the color of the mixture from orange to
piperidinium) (PAP) as an AEM for the application of BPMWE. To dark purple. After that, the viscous reaction solution was slowly
enhance the chemical and mechanical stability as well the compatibility, precipitated into 1 L of methanol to obtain poly (fluorene biphenyl
both polymers have similar aromatic backbone structures without ether indole) (PFBI). To remove impurities, the polymer was repeatedly
group, as C–C bonds is much more chemically invulnerable than cleaned by IPA and deionized (DI) water, following which it was dried
C–O–C bonds [27,28]. Although the polymer structure-related chem­ for 1 day in an 80 ◦ C vacuum oven. The yield was 93–96 %. For sulfo­
ical stability of AEM is still being under analysis [29,30], it has been nation, 3 g of PFBI and 0.116 g (0.36 × 10-3 mol) of TBAB were spon­
noticed that high nucleophilicity of OH-1 makes it easy to attack the taneously dissolved and stirred in 80 mL of DMSO at 60 ◦ C in a vial. The
electron-deficient sites in AEM, leading to degradation of polymer polymer solution in a 50 mL three-neck round bottom flask was stirred,
[9,31]. To enhance alkaline stability, thus in this study, 1-butyl-1- while the nitrogen gas was continuously supplied to eliminate oxygen
methyl-piperidinium containing quaternary ammonium with steric gas. Afterward, 4 mL of KOH (50 wt%) was slowly injected into the
hindrance, was applied as the anion conducting functional groups in the reaction solution by syringe, along with the addition of excess amount of
synthesis of AEM. For the synthesis of PEM, the long chain pendant 1,3-propane sultone. The pale yellow color of the polymer solution was
sulfonic acid groups were grafted to the polymer backbone for good converted to a deep orange color. After stirring at 60 ◦ C for 12 h under
proton conducting performance with minimization of nucleophilic nitrogen atmosphere, the color of solution turned into dark green at the
substitution reaction to ensure high chemical durability [32]. end of sulfonation. To purify the product, the reaction solution was
Because the movement of hydroxide ions is slower than protons, carefully dropped into methanol and stirred for 12 h, during which its
AEM has generally lower conductivity than PEM [33]. In commercial color was converted to yellow. Next, the precipitation was rinsed three
BPMs, thus, the ionic conductivity difference inevitably exists between times using deionized (DI) water and IPA, and lastly completely dried for
the two monopolar membrane layers. Although this conductivity dis- 1 day in a 80 ◦ C vacuum oven to collect the sulfonated poly(fluorene
match resulted in poor performance of BPM membranes, there has biphenyl indole) (SPFBI) (yield: 85–88 %).
been little researches upon this issue. To further understand the in­
fluences of conductivity correlation between two membranes on 2.2.2. Synthesis of poly(arylene piperidinium) (PAP)
BPMWE performance, the PEMs with three different ionic conductivities Poly(arylene piperidinium) (PAP) was synthesized via the superacid-
were synthesized and combined with an AEM to fabricate BPM in this polymerization reaction between piperidones and aromatic hydrocar­
study. After the synthesis and morphology of membranes were investi­ bons, as depicted in Fig. S2. First, a 50 mL three-necked round bottom
gated using 1H NMR, FTIR, and FE-SEM, their thermal, mechanical, flask equipped with a 50 mL dropping funnel and condenser was used to
chemical stability, ionic conductivity, and water electrolysis perfor­ dissolve 3.02 g (0.02 mol) of biphenyl in 15 mL of DCM. The solution
mance were deeply analyzed. was mechanically stirred at room temperature to form a homogeneous
solution. Next, the temperature was set up to 0 ◦ C and the nitrogen gas

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Y. Jeon et al. Chemical Engineering Journal 459 (2023) 141467

was injected into the reaction solution. Subsequently, stirred for 30 min An Ubbelohde viscometer (WITEG, Germany) measured the intrinsic
followed by the addition of MP 2.11 g (0.0205 mol) to the reaction so­ viscosity of the polymer, η at 25 ◦ C and 1 atm using DMSO. The polymer
lution. Thereafter, the dropping funnel was used to gradually add 15 mL solutions with three different concentrations (c) were prepared. In a plot
of TFSA and 2 mL of TFA to the flask, respectively. After that, the yellow of reduced viscosity (ηred ) versus c the y-intercept was obtained by
solution turned dark blue and the viscosity of the reaction solution extrapolation to calculate the intrinsic viscosity (η). The flow time for
increased with reaction time. The high viscosity mixture was slowly each solution was recorded 3 times, and the average result was used for
dropped into 1 L of KOH (1 M) solution and then stirred for 1 day. After determination of intrinsic viscosity:
several times washing with deionized (DI) water, the 4.9 g of white ( )/
t
precipitate (yield: 98 %) was collected and dried in an 80 ◦ C oven for 1 ηred = 1 − 1 c (4)
t0
day.
Here, t0 denotes the efflux time for DMSO solvent, t1 denotes the
2.2.3. Fabrication of bipolar membrane (BPM) efflux time of the polymer solution and c denotes the concentration of
Bipolar membranes were prepared with the SPFBI based PEM and the polymer solution.
PAP based AEM using a hot-press. Firstly, 0.3 g of SPFBI was dissolved in
7 mL of DMSO in a vial under stirring for 24 h. This mixture was cast into 2.3.2. Ionic conductivity
a glass petri dish and put in an 80 ◦ C oven for 1 day to dry. After that, the The proton and anionic conductivity of polymer electrolyte mem­
membrane was slowly taken from the petri dish and immersed in 70 mL brane was analyzed in the frequency range from 1 MHz to 1 Hz using
of 2 M HCl solution for ion exchange from K+ to H+. Finally, the Zahner IM6e alternating current (AC) impedance-spectroscopy (Ger­
membrane was soaked in 70 mL of deionized (DI) water. many). The bulk resistance was determined by Impedance spectroscopy
For PAP membranes, 0.2 g of polymer and 50 μ L of 1-bromobutane with a four-probe cell of in-plane type (BEKKTECH, USA). The mem­
were dissolved in 10 mL of DMSO with stirring for 1 day at 40 ◦ C. brane sample in the dimension of 1 × 3 cm was soaked in 2 M HCl and 2
Subsequently, the mixture was cast into a glass petri dish and dried in an M KOH, for 1 day, respectively, and washed with deionized (DI) water,
80 ◦ C oven for 20 h before being heated to 100 ◦ C for 4 h to obtain previous to analysis. While the membrane was fully hydrated, the con­
completely dried membranes. To convert Br- form to OH– form, the ductivity of the membrane was measured at temperatures from 30 ◦ C to
membrane was submerged in 70 mL of 2 M KOH solution for 1 day and 70 ◦ C. The ionic conductivity (σ, S cm− 1 ) of the polymer electrolyte
finally repeatedly rinsed using deionized (DI) water. membrane was determined by the equation given below:
The hot press approach is preferred by most researchers because it
L
shortens processing time and is easy to use safely [34]. A specific hot σ(S cm− 1 ) = (5)
press setting of 100 ◦ C and 10 MPa for 3 min, was chosen for providing R×T ×W
suitable binding power between PEM and AEM without deformation. Where, L denotes the length between the two electrodes (cm), R
PEM and AEM were carefully superimposed before hot pressing. Once denotes the in-plane resistance (Ω), T denotes the thickness (cm) and W
the membranes were combined, it was difficult to physically revert denotes the width (cm) of the membrane.
because of the strong adhesion force between two membranes. The
fabricated BPM was kept in deionized (DI) water. 2.3.3. Water uptake and swelling percentage
The weight difference before and after absorbed deionized (DI) water
2.3. Characterization determined water uptake of the polymer electrolyte membrane. The
membranes with a 1 × 3 cm area were throughly dried in a 80 ◦ C oven
2.3.1. Chemical structure identification and morphology for 1 day to attain equilibrium. After recording the dry membrane
1
H-nuclear magnetic resonance (1H NMR) spectra were obtained by weight (mdry ) and length (Ldry ), the samples were submerged in deion­
an NMR 500 MHz spectroscopy (Unity Inova, Varian Technology, USA). ized (DI) water at a given temperature until equilibrium. Once the
The 1H NMR spectra with DMSO‑d6 solvent were applied to figure out weight of the membrane was invariant over time, the free water on its
the chemical structure of the synthesized SPFBI and PAP. The cross- surface was eliminated with filter paper. The water uptake can be
sectional morphology of the BPM was identified with the field emis­ determined using the equation depicted below:
sion scanning electron microscope (FE-SEM, JEOL, JSM-IT800, Japan). mwet − mdry
The cross-sectional area of the membrane was recorded using the Oxford water uptake(%) = × 100% (6)
mdry
INCA system energy-dispersive X-ray spectroscopy (EDS, UK). Before
FE-SEM and EDS investigations, the membranes were coated with The swelling percentage of the membranes was estimated by the wet
iridium. (Lwet ) and dry membrane (Ldry ) lengths, as shown in equation:
The ion exchange capacity (IEC) of membranes was conducted three Lwet − Ldry
times using titration measurements. After drying the protonated PEM in swelling percentage(%) = × 100% (7)
Ldry
an oven until equilibration, it was submerged in 100 mL of NaOH so­
lution (0.1 N). Subsequently, a Waltham Orion 420 + pH meter (MA,
2.3.4. Thermal and mechanical properties
USA) was conducted to back-titrate the solution with HCl solution (0.1
A thermos-gravimetric analyzer (TGA, SEICO INST TG/DTA7300,
N). the proton exchange capacity (IECPEM ) was computed using the
Japan) examined the thermal stability of the membranes. After drying
following equation:
for 1 day 10 mg of the membrane in a 100 ◦ C vacuum oven to evaporate
VNaOH × MNaOH − VHCl × MHCl the water, it was placed in a sample pan. The TGA curves were observed
IECPEM = (2)
at a fixed heating rate of 10 C min− 1 from 100 ◦ C to 800 ◦ C under ni­
◦
mdry
trogen gas. Additionally, the mechanical properties of the membranes
The same approach was applied to evaluate the anion exchange ca­
were measured with a Lloyd universal tensile machine (UTM, 5565-
pacity (IECAEM ). The AEM was thoroughly dried in an oven for 1 day and
model, Fareham, UK). Membranes were thoroughly hydrated and
treated in HCl (0.1 N). Subsequently, it was titrated using NaOH solution
sliced into 1 × 5 cm sheets. Then, the stress and strain of the membrane
(0.1 N). The anion exchange capacity (IECAEM ) was computed, as shown
were identified under a load of 250 N at a 10 mm min− 1 pulling rate at
in equation:
room temperature.
VHCl × MHCl − VNaOH × MNaOH
IECAEM = (3)
mdry

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Y. Jeon et al. Chemical Engineering Journal 459 (2023) 141467

Fig. 1. TIF 1H NMR spectra of (a) SPFBI and (b) PAP, (c) cross-sectional image of BPM along with the elemental mapping for O and S.

2.3.5. Chemical stability electrodes, membranes, and bipolar plates, while PEM was placed onto
While membranes were immersed at room temperature in 4 M H2SO4 facing the cathode and AEM facing the anode. To keep the whole cell
and 4 M KOH solutions for 4 weeks, their acidic and alkaline chemical warmed up, the cartridge heater and thermocouple were utilized. Inside
stability was assessed. Before being weighed, membranes in 1 × 3 cm the cell, 1 M H2SO4 and 2 M KOH were injected from cathode and anode
were dried for 1 day in a 80 ◦ C vacumnoven to reach an equilibrium chambers, respectively. The solution was continuously circulated be­
state. Samples were taken out of the solution weekly and cleaned three tween the chamber and MEA at a flow rate of 60 mL min− 1 by a Longer
times using deionized (DI) water to eliminate residual ions. Subse­ pump (BT100-2 J, CNL, Republic of Korea). The electrochemical anal­
quently, the samples were dried until equilibrium was reached in a 60 ◦ C ysis was carried out using the power supply equipment (Zive SP2,
oven. The weight loss of the membrane was estimated via recording the WonATech, Republic of Korea). The I-V curves were obtained by
changes of both the samples before and after immersion, as indicated by applying a 10 mA s− 1 scan current rate at elevated temperatures under
the equation below: the galvanostatic mode (GStat IV curve) with current ranging from 0 to 2
A. EIS analysis was conducted in the galvanostatic EIS mode with
Wf − Wi
weight loss(%) = (8) various amplitudes, under the frequencies from 100 kHz to 100 MHz.
WI
The chronopotentiometry test was collected at 500 mA cm− 2 and at
Here,Wf denotes the final weight of the membrane after treatment in 60 ◦ C in the galvanostatic mode.
acidic or alkaline solution and Wi denotes the initial weight of the
membrane. 3. Results and discussion

2.3.6. MEA fabrication, water electrolysis performance, and Nyquist plots 3.1. Chemical structure and morphology
For the cathode, 2.5 × 2.5 cm2 pieces of carbon paper (Sigract 39BB)
were used as the gas diffusion layer. To prepare the cathode catalyst, 0.1 As described in Fig. 1(a) and Fig. 1(b), 1H NMR (500 MHz,
g of Pt/C, 0.67 g of Nafion, 8.17 g of isopropyl alcohol and 1 mL of DMSO‑d6) was used to identify the chemical structure of the synthesized
deionized (DI) water were ultrasonicated for 1 h to ensure good SPFBI and PAP. The protons in benzene rings of SPFBI backbone
dispersion. Next, a carbon paper surface had 2.5 × 2.5 cm2 active area revealed NMR signals at 7.46 ppm, 7.43 ppm, 7.35 ppm, and 7.34 ppm,
was coated with catalyst ink. The spray coating was stopped when the as shown in Fig. 1(a). The proton signals in pendant functional groups
loading reached 0.4 mg Pt cm− 2 at 80 ◦ C utilizing a vacumn manage­ are shown at 3.83, 2.97, and 2.00 ppm (peak 7, 8, 9). Furthermore, the
ment device (CNL, Republic of Korea). Furthermore, the nickel foams in protons in fluorene groups with -SO3H are identified at 3.83, 1.87, and
2.5 × 2.5 cm2 area and 1.6 mm thickness were used for the anode. The 1.61 ppm (peak 7, 5, 6). On the other hand, the NMR signals at 7.38 and
electrochemical cell configuration for the polarization curve was 7.29 ppm corresponded to the protons in benzene rings in the main
modeled and constructed in our laboratory. The MEA consists of chain of PAP in Fig. 1(b). The proton signal of the cyclohexane ring in

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Y. Jeon et al. Chemical Engineering Journal 459 (2023) 141467

Fig. 2. TIF (a) Anionic conductivity of AEM and proton conductivity of PEM at different temperature, (b) the temperature dependence of water uptake, and (c)
swelling percentage of the membranes.

piperidinium is observed at 2.11, 3.29 ppm (peak 3, 4). The protons in drop. To confirm the ionic conductivity difference effect between PEM
ion conductive functional groups were identified at 3.30, 3.24, 1.73, and AEM on the BPM performance, PEMs with three different proton
1.31, and 0.90 ppm (peak 5, 6, 7, 8, 9). Additionally, Fig. S3 shows the conductivities and an AEM with fixed anionic conductivity were syn­
1
H NMR spectra of PFBI and poly(arylene methyl piperidine). In Fig. S3 thesized to measure their ionic conductivity. As shown in Fig. S1, SPFBI
(a), the proton signal at 7.77 ppm corresponding to –NH group of PFBI consists of two ether-free backbones with different sulfone densities. The
disappeared after sulfonation. Similar to this, the signal at 2.22 ppm molar backbone percentage of low sulfone density to that of high sulfone
from the methyl group attached to the nitrogen in piperidine dis­ density was expressed as A/B after PEM such as PEM 80/20, followed by
appeared after the quaternization reaction in Fig. S3(b). PEM 70/30 and PEM 60/40. Also, the bipolar membrane prepared from
Fig. 1(c) depicts the cross-sectional morphology of BPM as observed PEM 80/20 and AEM is termed as BPM 80/20, while BPM 70/30 and
by FE-SEM. Both polymer electrolyte membranes were uniformly com­ BPM 60/40 were manufactured from PEM 70/30 and PEM 60/40,
bined without vacancies in the interface. As the interfacial structure of respectively. As depicted in Fig. 2(a), all fabricated membranes showed
BPM affects the electric field required for water dissociation, a uniform increment of ionic conductivity with increasing temperature, as it en­
and well adhered interface without dielectric gaps is essential for BPM. hances polymeric chain mobility and enlarges ion cluster dimension in
[34] The elements of interest such as oxygen (O) and sulfur (S) were membranes [30]. While the proton conductivity of PEM 80/20, PEM 70/
conducted by EDS mapping for both PEM and AEM in the cross-section 30, and PEM 60/40 was 0.1196 S cm− 1, 0.1598 S cm− 1, and 0.1739 S
area of BPM. As the functional group of PEM is composed of S (sulfur), N cm− 1, correspondingly, at 70 ◦ C, the anion conductivity of AEM was
(nitrogen), O (oxygen), C (carbon) and H (hydrogen) elements, while 0.0923 S cm− 1 at the same temperature. These values were higher than
that of AEM is of N, H, and C, the elemental mapping of O and S made it that of Nafion 117, 0.102 S cm− 1 and Fumasep FAA 3–30, 0.013 S cm− 1
possible to clearly distinguish between two membranes. As shown in at 70 ◦ C. It was intentionally designed to synthesize three PEMs among
Fig. 1(c), PEM and AEM were distinguishably aligned in the upper and which one has similar conductivity to AEM. Actually, the PEM with
bottom layers. lower conductivity than AEM was not easy in spite of many trials.
The water uptake and swelling percentage of polymer electrolyte
membranes are exhibited in Fig. 2(b) and Fig. 2(c), respectively. Water
3.2. Ionic conductivity, water uptake, and swelling percentage
uptake and swelling percentage influence not only water electrolysis
performance but also durability of membranes [26]. The proper water
In Fig. 2(a), the ionic conductivity of PEM and AEM was compared,
uptake and swelling minimize the dehydration of the interface operable
as it directly affects water electrolysis performance. The faster H+ and
at high current densities. It also continuously supplies water to the
OH– ions moving to the cathode and anode, respectively, the higher the
interface, allowing the water dissociation reaction (WDR) to occur.
efficiency of hydrogen production.[13] Also, the high conductivity of
However, the excessive water uptake and swelling induce the problems
membranes enables the use of a high current density with a low voltage

Fig. 3. TIF (a) Schematic of the zero-gap configuration of BPMWE, (b) protonation-deprotonation reaction of PEM, and (c) protonation-deprotonation reaction of
AEM in this work.

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Y. Jeon et al. Chemical Engineering Journal 459 (2023) 141467

Fig. 4. TIF Water electrolysis performance of BPM at (a) 30 ◦ C, (b) 50 ◦ C, and (c) 70 ◦ C. Nyquist plots of BPM with DC current at 70 ◦ C, (d) BPM 80/20 at 100 mA
cm− 2, and (e) BPM 80/20, BPM 70/30, and BPM 60/40 at 1000 mA cm− 2. (f) Stability comparison between Fumasep FBM and BPM 80/20 at 500 mA cm− 2 at 60 ◦ C.

associated with co-ion leakage, the inflated interface separating two

AH + H2 O⇄A− + H3 O+ (9a)
mono-polar membrane layers and limiting the mechanical strength of
the membrane [35]. The temperature raise resulted in increased water
A− + H2 O⇌AH + OH− (9b)
uptake and swelling of the membranes. As such, the water uptake of
PEM 80/20, BPM 80/20, and AEM were 87.91 %, 75.57 %, and 36.65 %, * AH is a neutral acid
respectively at 70 ◦ C. Meanwhile, the swelling percentage of PEM 80/
B + H2 O⇌BH+ + OH− (10a)
20, BPM 80/20, and AEM were 30.13 %, 15.36 %, and 10.52 %,
respectively. PEM showed higher water uptake and swelling percentage
BH+ + H2 O⇌B + H3 O+ (10b)
than AEM. In Fig. 2(b), the water uptake of BPM was predominantly
influenced by PEM, because the sulfone group of PEM is more hydro­ * B is a neutral base.
phobic than the piperidinium group of AEM. On the contrary to this, the The weak-acid and weak-base in the polymers’ functional head
swelling percentage of BPM was more governed by AEM, as both PEM group act as a catalyst for the WDR, and the electric field across the
and AEM share the single dimension in BPM by interface construction, as interface of the BPM contributes to the acceleration of the water splitting
shown in Fig. 2(c). Even if PEM swelled more, BPM followed the rela­ rate-limiting step [42]. The rate of the second reaction, i.e. equation (9b)
tively small swelling of AEM because of the interfacial resistance. and equation (10b) depends on the electric field whereas the rate of the
Table S1 shows the theoretical and titrated IEC values and intrinsic first reaction, i.e. equation (9a) and equation (10a) does not depend on
viscosity of the membranes. the electric field [16].
Fig. 4(a), (b), and (c) depict the water electrolysis performance at
3.3. EIS (Electrochemical impedance spectroscopy) analysis of the bipolar 30 ◦ C, 50 ◦ C and 70 ◦ C of the three fabricated BPM. All measurements
membrane were conducted at 1 M H2SO4||BPM||2M KOH, using Pt/C for the
cathode and nickel foam for the anode. The difference in ionic con­
Fig. 3 shows the BPMWE system operated in this study. As shown in ductivity of BPM was in order of BPM 80/20 < BPM 70/30 < BPM 60/
Fig. 3(a), the zero gap configuration of BPM device was designed to 40. BPMs synthesized in this work were stably operated up to high
minimize cell over-potential by establishing close contact between current density of 1500 mA cm− 2 and the cell voltage was below 1.5 V
electrodes and membrane. The cathode facing PEM used Pt/C coated for BPMs at various temperatures. The cell performance was enhanced
carbon paper, while the anode facing AEM employed nickel foam. To by raising the temperature because it increased the ionic conductivity of
keep the pH gradient of 14 between the catholyte and anolyte, 1 M the membrane [43]. As the water electrolysis performance followed the
H2SO4 and 2 M KOH were pumped to either side, respectively. order of BPM 80/20 > BPM 70/30 > BPM 60/40, which is different from
Fundamentally, BPMWE has a unique mechanism for dissociating ionic conductivity, the cell performance was improved when the ionic
water at the interface, whereas water splitting in mono-polar mem­ conductivity difference between PEM and AEM was reduced. In more
branes i.e. PEM, AEM occurs at the electrode [24]. Despite recent detail, the applied cell voltage was 0.61 V, 0.71 V, and 0.87 V for BPM
research developments, the reaction variables and mechanism of WDR 80/20, BPM 70/30, and BPM 60/40, respectively, under 200 mA cm− 2,
at BPM interface remain unresolved. The second-Wien effect [36] and at 70 ◦ C. At the same temperature and current density of 700 mA cm− 2,
protonation-deprotonation [37–39] theories are considered to be their voltage was recorded at 0.75 V, 0.98 V, and 1.08 V. The ideal BPM
acceptable. The second-Wien effect (SWE) referred to that the weak polarization curve could be generally separated into two areas, the first,
electrolytes in free solutions improve the dissociation rate under strong an activation loss region that starts WDR and the second, an ohmic loss
electric fields [40]. However, as it is not enough to clearly explain the region [3]. In Fig. 4(c), the polarization curve of BPM 80/20 at 70 ◦ C
complicated WDR of BPM under steady-state and reverse bias [40], the illustrated a transition voltage in the range of 98–116 mA cm− 2 while
WDR of BPM has been generally explained in the form of a combination those of BPM 70/30 and BPM 60/40 showed the two transition voltages
of SWE and protonation-deprotonation reaction [15,41]. The at 155–160 mA cm− 2 and 164–177 mA cm− 2, respectively. As indicated
protonation-deprotonation is a reaction that occurs between a water in Fig. 4(d) and (e), the overall and rate-determining resistance in water
molecule and the functional head group of polymers (Fig. 3(a) and (b)), electrolysis could be analyzed by Nyquist plots. Two semicircles were
following the reaction equations described below: sequentially obtained at 100 mA cm− 2 in the transition voltage range of

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Y. Jeon et al. Chemical Engineering Journal 459 (2023) 141467

Fig. 5. TIF Illustration of the electric field in BPM interface at thermal equilibrium state.

BPM 80/20, as depicted in Fig. 4(d). The first and second semicircles membranes and cell performance can be explained using the following
correspond to the resistance to WDR and HER, respectively [44]. On the electric field formation mechanism. As the space charge region (SCR) is
other side, it was difficult to obtain perfect semicircles for BPM 70/30 formed by diffusion of carrier ions, i.e. H+, OH– in the absence of a
and BPM 60/40 since they required higher current densities than 100 reverse bias, an electric field is generated as a result of charge imbalance
mA cm− 2 for WDR. As illustrated in Fig. 4(e), the Nyquist plot corre­ between PEM and AEM at the interface [45], as illustrated in Fig. 5. In
sponding to each ohmic region was clearly observed when 1000 mA SCR, the potential barrier (built-in potential, Vbi ) preventing the electron
cm− 2 was applied to each BPM instead. It also verifies that the ohmic movement, is established because of the different ionic conductivity
resistance of BPM increases with the elevation of ionic conductivity between PEM and AEM. To support this phenomenon, the built-in po­
difference between PEM and AEM. This means that as the ohmic resis­ tential, Vbi , was calculated for the synthesized membranes with the
tance dominated at high current density, the WDR at the BPM interface following equation provided by Grew, et al [25]:
is the most governing factor in overall water electrolysis performance.
RT [OH − ]AEM • [H + ]PEM
The chronopotentiometry test was conducted at 60 ◦ C for 50 h under ΔVbi = × ln (11)
F KW (T)
500 mA cm− 2 to compare the durability and stability of BPM 80/20 with
the commercial Fumasep FBM, depicted in Fig. 4(f). When operated for a
where, F denotes the faraday constant (96485C mol− 1), KW (T) denotes
long time, the Fumasep FBM ran steadily up to 36 h at around 2.2–2.6 V,
the thermal water auto-ionization constant (1.0 × 10-14 mol L-1 at
but after this, voltage fluctuated due to the physical or chemical dete­
25 ◦ C), T denotes the absolute temperature (K) and R denotes the ideal
rioration of the membrane. On the other hand, BPM 80/20 was stably
gas constant (8.314 J mol− 1 K− 1) and brackets represent molar con­
operated up to 50 h in the low voltage range of 0.6–0.8 V. Additionally,
centration. As the Vbi values for BPM 80/20, BPM 70/30, and BPM 60/
when the photo-images of BPM 80/20 membranes before and after
40 were 0.8823 V, 0.8858 V, and 0.8888 V, respectively, for the pure
measurement were compared as shown in Fig. S4, there was no physical
water at 25 ◦ C, the BPM 80/20 with the smallest ionic conductivity
delamination and noticeable degradation at the interface, presumably
difference resulted in the lowest Vbi . Because the over-potential for WDR
because of the similar ether-free polymer backbone structure of AEM
at the interface is governed by this Vbi , it is crucial to minimize the ionic
and PEM with high interfacial compatibility.
conductivity between AEM and PEM to reduce the overall water elec­
The relationship between the ionic conductivity difference between
trolysis over-potential. As a supplement, the built-in potential formation

Table 1
Comparison of cell performance between the BPM fabricated in this study and others recently reported.
Type of BPM materials Catalyst materials Condition performance Ref
PEM AEM Cathode Anode Interface Current density limit Voltage limit
(mA • cm− 2 ) (V)

Nafion NR-211 PBI Pt Pt X RT, ~20 ~1.2 [47]

0.5 M H2SO4, 1 M KOH
Fumasep FBM CoP NiFe X RT, ~35 ~2.0 [48]
LDH 0.5 M H2SO4, 1 M KOH
Fumasep FBM CO-Ni-P CO-Ni-P X RT, ~100 ~1.8 [45]
0.5 M H2SO4, 1 M NaOH
Nafion NR-211 Perfluorinated Pt Pt graphite oxide (GOx) RT, ~500 ~4 • [49]
AEM 1 M H2SO4,
1 M NaOH
Nafion NR-211 Neosepta Pt Pt graphite oxide RT, ~120 ~1 [22]
AHA (GO) 1 M HClO4,
1 M NaOH
Nafion® Sustainion® AEL Pt black IrO2 IrO2|NiO RT, ~800 ~2.2 [21]
1 M H2SO4,
1 M KOH
PAEK-SDPA PAEK- Pt/C Pt/C X RT, ~160 ~2.31 [33]
APEI 1 M H2SO4,
2 M KOH
BPM 80/20 Pt/C Nickel foam X 30 ◦ C, ~1500 ~1.32 This work
1 M H2SO4,
2 M KOH

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Y. Jeon et al. Chemical Engineering Journal 459 (2023) 141467

Fig. 6. TIF (a) Thermal degradation behavior and (b) mechanical property of the AEM, BPM 80/20, and PEM 80/20. Weight loss of the electrolyte membrane after
immersion in 4 M H2SO4 and 4 M KOH solution for 4 weeks for (c) PEM 80/20, PEM 70/30, PEM 60/40, and AEM and for (d) BPM 80/20.

at the BPM interface is additionally explained in SI with Fig. S5 and S6.

Fig. S7 shows the water electrolysis performance of BPM 80/20, Table 2
Thickness, elongation at breakage, and tensile strength of the electrolyte
PEM 80/20, and AEM. In comparison, BPM 80/20 shows the best per­
membranes in a hydrated state.
formance. Basically, in all electrochemical reactions, the slowest step
determines the overall reaction rate [46]. In the case of AEM, the slowest Membrane Thickness Tensile elongation Tensile strength
(μm) at breakage (MPa)
reaction is HER, which occurs in a nickel foam cathode under alkaline
(%)
media. On the other hand, the slowest reaction of PEM occurs at Pt/C
AEM ~60 11.65 20.00
anode under acid media. So, the BPM recorded the highest performance
BPM 80/20 ~120 16.25 19.15
among the three membranes, due to OER in alkaline media and HER in PEM 80/20 ~60 20.04 17.10
acid media. According to Fig. S7(a), AEM and PEM showed almost
similar performance at 30 ◦ C from 200 mA cm− 2 to 450 mA cm− 2. The
cell performance of BPM 80/20 and Fumasep FBM compares in Fig. S8. 298 ◦ C.
At 30 ◦ C while the Fumasep FBM recorded 1.93 V under 300 mA cm− 2, Fig. 6(b) presents the stress vs strain curves of membranes in the
BPM 80/20 was 0.83 V. In addition, Table 1 presents a comparison of hydrated state. As the absorbed water plasticizes the membranes, it
this BPM performance with that of other bipolar membranes recently generally reduces the tensile strength but increases strain [51]. In
published. The water electrolytic voltage of BPM 80/20 was quite low in consideration of water uptake difference, the tensile strength of AEM,
a wide range of current density up to 1500 mA cm− 2 without interlayer BPM 80/20, and PEM 80/20 was recorded at 20.00 Mpa, 19.15 Mpa, and
catalyst between membranes, compared with that of other membranes 17.10 Mpa, respectively, while the elongation at breakage was 11.65 %,
including commercial ones. 16.25 %, and 20.04 %, respectively. The thickness of PEM and AEM of
this work was maintained at 60μ m to eliminate the effect of the thick­
ness difference, and thus, that of BPM was 120μ m, as shown in Table 2.
3.4. Thermal, mechanical properties and chemical stability The chemical durability was assessed by measuring the weight loss in
4 M H2SO4 and 4 M KOH at room temperature, as depicted in Fig. 6(c)
The poor thermal and mechanical properties lead to unrecoverable and (d). In terms of the monopolar membrane, the total weight loss of
damage and shorten the cell life under long-term operation [50]. Fig. 6 PEM 80/20, PEM 70/30, and PEM 60/40 immersed was 4.09 %, 4.88 %,
(a) showed the TGA spectra of AEM, BPM 80/20, and PEM 80/20 and 5.14 %, respectively, in 4 M H2SO4 and the weight loss of AEM
measured under nitrogen atmosphere. There were two noticeable steps immersed in 4 M KOH was 2.84 %. Additionally, Fig. S9 demonstrates
of weight loss until 800 ◦ C. AEM and PEM show the first decomposition the photo images of the membranes taken every week. It confirms that
at 300–350 ◦ C, attributed to the de-bonding of 1-butyl-1-methyl-piperi­ all membranes were stable for 4 weeks without any pinhole or cracking.
dinium and pendant sulfuric acid groups. BPM started to decompose at Fig. S10 shows the 1H NMR spectra of the membranes before and after
298 ◦ C because of the same reason. Subsequently, the second decom­ immersion in solvent for 4 weeks. Overall, the polymeric membranes
position of AEM, PEM 80/20, and BPM 80/20 was recorded at 490 ◦ C, were stable with no degradation in the backbone from proton signals in
463 ◦ C, and 460 ◦ C, respectively, corresponding to the breakage of C–C the range of 7.46 ppm to 7.29 ppm. As depicted in Fig. 6(d), BPM 80/20
bond in the backbone of the polymer. According to the TGA measure­ recorded a weight loss of 5.4 % and 4.62 % in 4 M H2SO4 and 4 M KOH
ment, the BPM synthesized in this study was thermally stable until for 4 weeks, respectively, while Fumasep FBM recorded a total weight

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Y. Jeon et al. Chemical Engineering Journal 459 (2023) 141467

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