i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 8 7 e1 0 2

Available online at www.sciencedirect.com

ScienceDirect

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

Evaluating the performance of hybrid proton

exchange membrane for PEM water electrolysis

Ali Abdel-Motagali a,b, Serge Al Bacha a,b, Waleed M. A. El Rouby b,

Janick Bigarre c, Pierre Millet a,b,*
a
ICMMO-CNRS UMR 8182, Universite Paris-Saclay, 17 Avenue des Sciences, 91400 Orsay, France
b
Elogen, 8 Avenue du Parana, 91940 Les Ulis, France
c
CEA, DAM, Le Ripault, F-37260 Monts, France

highlights

Hybrid nanocomposite membrane was assessed in small and large scale PEMWE.

Multiple layers of hybrid nanocomposite membrane-based CCM enhance the performance.

Clamping the hybrid membrane between two Nafion membranes improves its lifetime.

article info abstract

Article history:
Received 28 January 2023
Received in revised form
27 June 2023
Accepted 28 June 2023
Available online 07 August 2023
Keywords:
Hybrid nanocomposite membrane
Catalyst-coated membrane
Membrane degradation mechanism
PEM water electrolysis
Hydrogen production
Partially fluorinated membrane
Owing to their attractive properties (e.g. reduced gas permeation, comparable proton
conductivity, enhanced thermal stability, lower cost), hybrid nanocomposite membranes
(HNC) are more attractive for proton exchange membrane water electrolysis (PEMWE).
Compared to perfluoro sulfonic acid polymers, this study evaluated the interest in using an
HNC membrane for PEMWE. Despite the bulk membrane exhibiting high chemical and
mechanical instability (decreasing the cell performance), a multi-layer approach was
adopted to increase its lifespan in PEMWE operation. Thus, different strategies for pre-
paring Catalyst-Coated Membrane (CCM) with more than one PEM were investigated. The
longevity of the HNC membrane is enhanced from a few hours to a few hundred hours by
clamping it between two half-coated Nafion 212 membranes. The degradation mechanisms
are discussed based on the physicochemical analysis of the membrane and its degradation
products after electrolysis.
© 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

this issue, and this is exactly what is intended when processes

Introduction
A crucial step in the growth of the hydrogen-energy sector is
the creation of efficient, environmentally friendly methods for
mass producing hydrogen. Water electrolysis can alleviate
are electrified, especially in the energy sector. Proton Ex-
change Membrane (PEM) water electrolysis is one of the po-
tential methods for producing high-purity hydrogen at low
temperatures, such as less than 100 C, when paired with

* Corresponding author. ICMMO-CNRS UMR 8182, Universite  Paris-Saclay, 17 Avenue des Sciences, 91400 Orsay, France.
E-mail address: pierre.millet@universite-paris-saclay.fr (P. Millet).
https://doi.org/10.1016/j.ijhydene.2023.06.330
0360-3199/© 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
88 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 8 7 e1 0 2
intermittent or renewable power sources [1e6] The produc-
tion of hydrogen by water electrolysis using the so-called
proton exchange membrane or polymer electrolyte mem-
brane technology was developed in the 1970s, following the
discovery and marketing of proton-conducting perfluoro sul-
fonic acid ionomers (PFSA) by the US company Dupont de
Nemours under the trade name of Nafion®. PFSAs are the
commonly used polymeric membranes for PEM water elec-
trolysis (PEMWE) because of their high proton conductivity
and strong mechanical and chemical robustness [7]. However,
the continued quest for alternate membrane materials is
fueled by the expensive cost and environmental concerns (e.g.
the Registration, Evaluation, Authorization and Restriction of
Chemicals European regulation) connected with PFSAs' fluo-
rine chemistry, as well as their significant gas (particularly H2)
permeability and poor mechanical stability at high tempera-
tures (T > 80  C) [8].
Although various PFSA are commercially available and
shows good properties for operation in PEMWE (Nafion [9] and
Aquivion [10]), there is still a need for developing membranes
with minimal environmental impact and with new polymeric
structure capable of proton conduction for PEM electrolysis at
high temperatures (e.g. 120 C). The high cost of PFSA mem-
branes, as mentioned earlier, is mainly due to the expensive
fluorination step. Thus, substantial efforts are made towards
the development of alternative PEM materials. Promising ones
are partially fluorinated ionomer containing acidic function
groups (e.g. sulfonic, phosphonic) in the main polymer chain,
or in the side chain [11e14]. Additionally, recent studies
showed that the crosslinking of the proton conductive poly-
mers improves the thermal stability of the membrane (e.g.
100 C [15] and 160 C [16]). In this regard, Labalme et al.
developed covalently crosslinked phosphonated poly-
electrolytes (proton conducting phase) with partially fluori-
nated polymer (e.g. poly(vinylidene fluoride co-
chlorotrifluoroethylene) abbreviated as poly(VDF-co-CTFE)
[17,18]. The presence of fluorine atoms in poly(VDF-co-CTFE)
permitted the fabrication of membranes with improved
structural integrity, mechanical strength and resistance to
oxidation in the presence of radicals. Under fully hydrated
conditions, the best result reveals a 40 mS/cm proton con-
ductivity at a temperature of 80 C [17].
Hybrid nanocomposite membranes, consisting of func-
tionalized inorganic nanoparticles dispersed into a macro-
scopic organic matrix [19], offer a particularly attractive
alternative to conventional membrane in different fields of
application such as microbial fuel cells [20], borohydride fuel
cells [21] and PEM fuel cells [22e26]. This class of membranes
is interesting for proton conduction application (PEM fuel cells
and PEM electrolysis) due to their morphology, which results
in a significantly lower gas crossover, similar conductivity to
the state-of-the art PFSA membranes (namely when fully
hydrated), better thermal stability, lower production cost. The
fact that they are the primary step toward fluorine-free
membrane should make them ideally suited for PEM water
electrolysis. Several attempts to prepare a high proton con-
ductivity nanocomposite membrane have been made by Seck
et al. [27,28]. The authors directly synthesized Poly(vinylidene
fluoride-co-hexafluoropropylene) (PVDF-HFP)/silica-SH nano-
composites in a single extrusion step [27]. The authors
demonstrated that it is possible to generate a high concen-
tration of inorganic silica in a PVDF-HFP polymer via sole gel
chemistry during extrusion without any degradation issues.
Then, the interface between the matrix and the inorganic-rich
phase was tailored to increase ionic conductivity by incorpo-
rating interfacial agents [28]. The nanocomposite membrane
reached a 54 mS/cm conductivity comparable to that of Nafion
N112 (52 mS/cm) at 100% RH and a temperature of 25 C [28].
The CEA (Commissariat a  l’Energie Atomique et aux En-
ergies Alternatives) has developed a new family of hybrid
nanocomposite (HNC) membranes, less fluorinated than
PFSAs, for PEM fuel cell and water electrolysis applications
[29,30]. This HNC membrane consists of a polystyrene sulfonic
acid (PSSA) chain grafted onto silica nanoparticles which are
then dispersed into activated PVDF/HFP matrix. The HNC
membrane was crosslinked with 2,2,4-trimethyl-1,6-
hexanediamine (THDA) to anchor the functional acid groups
to the hydrophobic organic phase (PVDF/HFP) and post-
annealed at 180 C for 2 hours (h) [30]. The membrane is a
hybrid nanocomposite membrane since silica nanoparticles
(inorganic) are functionalized with polystyrene sulfonic
groups (organic) required for proton-conductivity [29,30].
In the frame of the French ADEME (Agence de la Transition
Energetique) project entitled Me thycentre [31], a Power-to-Gas
demonstration project led by Storengy to support the energy
transition to meet clean mobility needs and partially replace
fossil methane in Engie's gas networks, we evaluated the
performance and durability of a new hybrid nanocomposite
membrane (HNC) as a possible alternative to the commercially
available PFSA membranes for PEMWE. The HNC membrane
and commercial catalysts have been used to manufacture the
catalyst-coated membrane (CCM). The electrochemical
behavior of the prepared CCMs has been studied, evaluated,
and compared to the performance of reference CCMs.
Materials and methods
Materials
Nafion ionomer 5 wt.% (Nafion™ 1100 W) and Pt/C (40 wt.%)
was purchased from Sigma Aldrich. IrO2 from SurePure
Chemetals Inc. Isopropanol was provided by Carlo-Erba Re-
agents. Cyclohexanol 99% was supplied from Alfa Aesar.
Nafion membrane 212 was kindly provided by Chemours
Company FC, LLC and the 80 mm thick Hybrid NanoComposite
membrane (HNC) was developed and manufactured by CEA,
Le Ripault.
Catalyst ink preparation
Cathode: The hydrogen evolution reaction (HER) catalyst inks
were prepared by dispersing commercial Pt/C catalyst in iso-
propanol in an ultrasonic bath. A dispersion of Nafion ion-
omer was added as dispersing agent and source of proton
conductivity in the catalyst layer. The composition of the
cathode ink was adjusted as follows: 94 wt.% isopropanol,
4 wt.% of Pt/C and 2 wt.% of Nafion ionomer.
Anode: The oxygen evolution reaction (OER) catalyst ink
was prepared by dispersing IrO2 in isopropanol following the
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 8 7 e1 0 2
procedure mentioned above. The composition of the anode
ink was adjusted as follows: 95 wt.% isopropanol, 4 wt.% IrO2
and 1 wt.% of Nafion ionomer. The prepared inks were soni-
cated prior to the deposition.
For the CCM preparation using HNC membranes, iso-
propanol was replaced by cyclohexanol to reduce the swelling
of the membrane.
CCM preparation
Lab-scale CCM using nafion 212 membrane
The CCM was prepared by hand spray coating of HER & OER
inks over PTFE substrates followed by their transfer to the
virgin membrane by the so-called DECAL process. In a typical
experiment, the cathode ink (Pt/C) was sprayed over the HER-
PTFE substrate (surface area of 4 cm2). For the anode catalyst
layer, IrO2 ink was sprayed over the OER-PTFE substrate
(surface area of 4 cm2). In both cases, the catalyst layer was
dried by placing the PTFE sheets on a hot plate at 60 C,
allowing solvent evaporation. The loadings of Pt/C and IrO2
were adjusted to 0.7 mg cm2 and 1.4 mg cm2 respectively.
The HER and OER catalyst layers formed on the PTFE sub-
strates were then transferred to the Nafion membrane,
sandwiched between the two substrates, by thermal pressing
at 135 C for 5 minutes (min) under 5 tons. The Nafion mem-
brane was used as received without any specific treatment.
Lab-scale CCM using the HNC membrane
The HNC membrane was always used ‘as-received’, without any
pre-treatment or cleaning, due to its suspected high sensitivity
to hydrolysis. For the manufacturing of HNC-based CCM, the
catalyst inks were sprayed onto the membrane to avoid the
common thermal pressing step since The HNC membrane has a
very low the glass transition temperature of the PVDF is lower
than that of the Nafion (i.e. 35 C vs. 135 C). In a typical exper-
iment, Pt/C cyclohexanol-based ink was directly sprayed over
the membrane forming a coated area of 4 cm2. The hot plate
temperature was set to 60 C to prevent absorption of the solvent
by the membrane. Similarly, IrO2 cyclohexanol-based ink was
directly sprayed over the second surface of the membrane of
4 cm2 area. The hot plate temperature was set at 60 C to evap-
orate the dispersion solvent. The adhesion of the catalyst to the
membrane was achieved by sandwiching the coated membrane
between two PTFE and pressing at room temperature under five
tones for 5 min. Ambient temperature was chosen because of
the low glass transition temperature of the PVDF polymer used
in the HNC membrane.
Upscaling and testing in short stack configuration (250 cm2
active area CCM) used for testing the hybrid nanocomposite
membranes for pre-industrial qualification were prepared
following the same approach as described earlier. However, a
SONO-TEK ExactaCoat ink printer equipped with ultrasonic
nozzle was used to spray the catalyst ink on the PTFE sub-
strate (for the transfer on the Nafion membrane with the
DECAL method) to reach better homogeneity of the deposited
catalyst layer. A mask with a circular hole of 17.8 cm in
diameter and adhered to the PTFE substrate was used to
delimit the coating area. The anode ink contains 95 wt.%
isopropanol, 4 wt.% IrO2 and 1 wt.% of PFSA ionomer. The
cathode ink contains 94 wt.% isopropanol, 4 wt.% of Pt/C and
89
2 wt.% of PFSA ionomer. The IrO2 and Pt/C loading of each
CCM was determined by weighing the substrate before and
after catalyst transfer. Different loadings of the catalysts were
prepared and described in section Upscaling and testing in
short stack configuration using 250 cm2 CCM. The water up-
take and the swelling ratio were determined following equa-
tions (1) and (2) respectively [32]:
ðmW  md Þ
Water uptake ð%Þ ¼ 1
md
ðXW  Xd Þ
Swelling ratio ð%Þ ¼ 2
Xd
where mW and md are the weight of the membrane in wet and
dry conditions respectively while XW and Xd are the length of
the membrane in wet and dry conditions respectively.
The tensile strength test was performed using an exten-
someter device RT-201 A Computer Servo Universal Testing
Machine from Dongguan Right Instrument Co.,Ltd.
Electrochemical characterization
A compact water electrolysis cell (4 cm2 active area) equipped
with an adjustable clamping pressure controller from
Fraunhofer ISE, Freiburg was used. The cell clamping pressure
was set to 3.5 MPa unless stated otherwise. Conventional
electrochemical measurements were performed to charac-
terize and evaluate the performance levels of CCMs using a
Voltalab potentiostat PGZ 301: (i) polarization curves (so-called
iV curves), (ii) Accelerated Stability Tests (ASTs) (mainly chro-
nopotentiometry by applying current cycles), (iii) cyclic vol-
tammetry to measure the electrochemical surface area (ECSA)
and (iv) electrochemical impedance spectroscopy (EIS). An
external power supply connected with a digital multimeter was
used to measure the iV curve of the cell at high current den-
sities. For large surface area HNC-based CCMs testing, PEMWE
test benches available at ElogenH2 site in Les Ulis, France were
used. EIS and Cyclic Voltammetry were performed using Met-
rohm Autolab PGSTAT302 N equipped with a 20 A booster.
Results and discussion
Electrochemical characterization at the lab-scale
Reference Nafion-115 membrane
Nafion is the reference material commonly used as polymer
electrolyte in PEM water electrolysis cells. It is known for its
great chemical stability which allows in the industry to
accumulate tens of thousands of hours of operation. A refer-
ence CCM made of Nafion 115 was used to set the baseline
against which the performance levels of HNC membranes
were evaluated. This reference CCM was prepared as
described in the experimental section, using a commercially
available Nafion 115 membrane (Chemours Co.), and clamped
in the test cell at a clamping pressure of 3.5 MPa. An AST was
then applied by cycling current density between 25 and
250 mA.cm2 (Fig. 1a). The test lasted about 85 h, enough time
to get a good idea of the quality of the CCM manufactured and
thus validate the loadings of catalysts and the manufacturing
90 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 8 7 e1 0 2
protocol used. During the test, the cell voltage increased
slightly but remained sufficiently stable to set a convincing
baseline.
Fig. 1 b shows EIS spectra recorded at different time intervals
during AST. The high frequency side of the EIS diagrams, espe-
cially the High Frequency Resistances (HFR) measured on the
real axis at 25 mA.cm2 (numerical values are compiled in Table
1) remained stable during the test (i.e., the cell impedance
remained constant). On the contrary, the low frequency value of
the cell impedance increased slightly. This is due to a slight in-
crease in the diameter of the semi-circle which, to a first
approximation can be attributed to the oxygen evolution reac-
tion, and corresponds to an activation phase during which the
catalytic layers are structured under the effect of gas evolution.
These different results show that the protocol used for
manufacturing CCM is correctly controlled and allows endur-
ance tests of a few tens of hours to be carried out.
CCM with a single HNC membrane
The performance level of HNC membranes (i.e. their me-
chanical resistance, proton conductivity and stability over
time) in PEM water electrolysis was first evaluated using a
CCM containing a single HNC membrane (this CCM is denoted
as Cathode/HNC/Anode). Considering the small thickness (ca
80 mm) and the tensile value (43 MPa when dry vs. 14 MPa
when wet) of the HNC membrane, a reduced clamping pres-
sure of 1.5 MPa was applied to prevent the occurrence of po-
tential electrical short-circuits. The electrochemical behavior
of this CCM was then evaluated by applying the same AST
(current density cycles between 25 and 250 mA.cm2) as for
the Nafion-115-based CCM. Details of the AST (current density
cycles and and chronopotentiometric cell response) are
shown in Fig. 2 a. EIS spectra recorded during the AST at
different time intervals are plotted in Fig. 2 b and the corre-
sponding HFR values are compiled in Table 2.
Despite the reduced clamping pressure used, the AST las-
ted only 9.5 h (h) before a short circuit occurred.
Variation of HFR values during the AST: The data in Table
2 shows that the HFR of the cell decreases during the AST,
Fig. 1 e a) AST between 25 and 250 cm2 performed on the CCM with Nafion 115 membrane and b) Nyquist plot at
25 mA.cm¡2 and 60  C.
Table 1 e HFR measured on the CCM with a Nafion-115
membrane during the AST.
Time HFR (mU.cm2)
BoT 452
10 h 396
20 h 392
30 h 387
40 h 389
50 h 393
60 h 392
70 h 395
80 h 396
from 626 mU cm2 (BoT value) down to 519 mU cm2 (last
measurement before EoT). It is well established in the liter-
ature that in PEM water electrolysis, the surface resistance of
the membrane is inversely proportional to its thickness
[33,34]. It is therefore logical to speculate that if the surface
resistance decreases, it is because the thickness of the
membrane decreases. A possible mechanism would be that
the absorption of water by the membrane, which occurs
during electrolysis (by direct contact of the membrane with
liquid water and due to the electro-osmotic flow of water
associated to the transport of protons across the membrane),
induces a decrease in the tensile strength of the membrane.
The amount of water absorbed (a swelling ratio of 23.3% and
a water uptake of 65 wt.% have been measured on the HNC
membrane) and its softening effect directly impact the me-
chanical properties of the membrane (the tensile strength
goes from 43 MPa for a dry membrane to 14 MPa for a wet
membrane). Even if the clamping pressure used is reduced
compared to the previous experiment made with the Nafion-
CCM, since the membrane gradually softens during the AST
due to water absorption, the clamping force exerted on the
membrane gradually reduces its thickness until an electrical
short circuit occurs.
Variation of EIS spectra during the AST: During the AST,
the EIS spectra remain almost stable (only the HFR decreases
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 8 7 e1 0 2
Fig. 2 e a) AST between 25 and 250 mA/cm2 performed on the CCM with HNC membrane and b) Nyquist plot at 25 mA.cm¡2 and
60  C.
Table 2 e HFR measured on the CCM with a single HNC
membrane during the AST.
Time HFR (mU.cm2)
BoT 626
2h 649
4h 561
6h 528
8h 519
as discussed in the previous paragraph). However, the diam-
eter of the semicircle tends to increase, indicating that the
charge transfer resistance of the oxygen evolution reaction is
increasing.
In conclusion, the results show that during the first hours
of AST, the mechanical properties of the HNC membrane
dictate the electrochemical behavior of the CCM. The loss of
tensile strength resulting from water absorption leads to the
formation of electrical short-circuits.
CCM with two HNC membranes
In an attempt to solve the short-circuit issue and to extend the
duration of the AST, another CCM with two HNC membranes
placed side-by-side was prepared. The anode catalyst ink was
deposited on the first HNC membrane while the cathode
catalyst ink was deposited on the secondone. As the thickness
of the membrane has been doubled (total thickness z 160 mm),
a larger clamping pressure of 3.5 MPa was applied to reduce as
much as possible the internal cell resistance while avoiding
any immediate risk of electrical short-circuit. The thickness of
the CCM thus obtained is close to the one made with the
Nafion-115 (z140 mm), allowing direct performance compari-
son. This two half-coated membranes is denoted as
HNCcathode | HNCanode. Details of the AST (current density cy-
cles and and chronopotentiometric cell response) are shown
in Fig. 3 a. EIS spectra recorded during the AST at different
time intervals are plotted in Fig. 3 b and the corresponding
91
HFR values are compiled in Table 3. Under such conditions,
the AST lasted 25.5 h before a short circuit occurred.
Comparison of CCM with one and two HNC membranes at
BoT: A comparison of the data of Fig. 2b and Fig. 3b shows that
the HFR is approximately the same at BoT despite the fact that
the number of membrane (and the polymer thickness) is
doubled. This is attributed to the fact that the clamping pres-
sure is different (1.5 MPa for the CCM with one HNC membrane
and 3.5 MPa for the CCM with two HNC membranes).
Comparison of CCM with one and two HNC membranes
during the AST: in both cases, the cell impedance tends to
decrease during the first few hours of the AST before
increasing. As discussed before, the decrease of HFR is
attributed to water sorption which leads to membrane soft-
ening (i.e., decrease of tensile strength) and thickness reduc-
tion. However, after z12 h of AST, the resistivity of the
membrane increases with time. Bulk membrane degradation
can be suspected and a more detailed analysis of the situation
is discussed in section Degradation of the HNC membranes.
Comparison of CCM with two HNC membranes and
Nafion-115 during the AST: A direct comparison of HFR values
measured at the BoT on the CCM with Nafion 115 (Table 1) and
the CCM with two HNC membranes (Table 2) is possible
because in both cases, the total polymer thickness is close in
both cases (135 mm for Nafion 115 and 160 mm for the two HNC
membranes). The HFR measured on Nafion-115
is z450 mU cm2 and the HFR measured on the two-HNC
membrane is z 570 mU cm2. The ratio of the thicknesses is
close to the ratio of the HFRs. Therefore, the HNC membrane
has a specific conductivity close to that of Nafion at BoT.
In conclusion, the beneficial effect resulting from the in-
crease of the HNC membrane thickness is not sufficient to
solve the short-circuit problems. It was therefore decided to
mechanically reinforce the CCM by introducing a poly-
phenylene sulphide (PPS) mesh between the two HNC mem-
branes, in order to prevent as much as possible electrical short
circuits. Results are discussed in the next paragraph.
92 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 8 7 e1 0 2
Fig. 3 e a) AST between 25 and 250 mA/cm2 performed on the CCM with two HNC membranes and b) Nyquist plot at
25 mA.cm¡2 and 60  C.
Table 3 e HFR of the two HNC membrane e based cell
evolution during the ASTs.
Time HFR (mU.cm2)
BoT 572
6h 690
12 h 694
18 h 719
24 h 787
CCM with two HNC membranes reinforced with PPS
In an attempt to mechanically reinforce the HNC membrane,
as this is commonly done with PFSA materials [35], a PPS mesh
(thickness of ca. 60 mm and porosity of ca. 48%) was pressed
between two half-coated HNC membranes and clamped
directly inside the cell with a pressure of 5.5 MPa to ensure
contact between the two membranes for the proton conduc-
tion from the anode catalyst layer to the cathode catalyst
layer. The half-coated HNC membrane was prepared
following the same procedure as for HNCcathode | HNCanode.
The life service during the AST was significantly improved to
up to 55 h without short-circuit (Fig. 4a), giving more time to
analyze, through EIS, the evolution of the HNC membrane
during the AST.
The EIS spectra (Fig. 4b) show two semicircles. The new
highefrequency small semicircle was ascribed to the HNC
membrane-membrane interface presumptively due to the
relatively thick insulating PPS mesh sandwiched between the
two HNC membranes. The high-frequency cell resistance and
the diameter of the high-frequency semicircle both increased
during the AST implying a loss of the ionic conductivity of the
membrane (higher HFR, Cf. Table 4) since the mechanical
strength of the CCM is ensured by the reinforcement The
second and larger semicircle observed at middle to lower
frequencies is attributed to the OER half-cell reaction [36]. This
semicircle was almost constant during the test, thus showing
the stability of the anode catalyst layer.
The reason for the HFR stepwise change between 20 and
30 h of AST is not clear (1311e2413 mU cm2). We speculate that
it may be induced by significant hydrolysis of the crosslinking
imine bond, and rapid loss of the sulphonic function group.
Asymmetric two membranes CCM
In an attempt to further improve the chemical stability of the
membrane, the half-coated HNC membrane at the anode was
replaced by half-coated Nafion 212 membrane to prevent the
oxidative degradation of the hydrocarbon membrane (e.g.
polystyrene sulfonate) induced by the radicals formed during
the OER [37]. In fact, Nafion is a fluorocarbon polymer more
resistant to oxidative degradation [38]. Therefore, half-coated
HNC membrane (with Pt/C) was clamped with half-coated
Nafion 212 (with IrO2) inside the PEMWE cell under 3.5 MPa
(denoted as HNCcathode |N212anode).
Even though the Nafion membrane improved the me-
chanical strength of the CCM (i.e. no short-circuits occurred),
the asymmetric CCM electrochemical performances
decreased gradually during the AST (Fig. 5a). Note that the
higher current density of the AST was diminished from 250 to
125 mA.cm2 after 11.5 h of the beginning of test to prevent
the high increase of the cell voltage above 2.1 V.
On the other hand, the HFR increased during the AST (Fig. 5
b and Table 5) from 778 mU cm2 (beginning of test) to
4607 mU cm2 (end of test). These results show that the
degradation of the HNC membrane is not solely driven by the
oxidative degradation at the anode. Therefore, bare HNC
membrane was clamped between two half-coated Nafion 212
membranes.
HNC membrane clamped between two nafion membranes
In a last attempt to significantly increase the life service of the
HNC membrane for PEMWE, the membrane was sandwiched
between two half-coated Nafion 212 membranes to limit the
release of functionalized silica nanoparticles leading to the
degradation of the membrane. The three membranes were
then clamped inside the cell at a pressure of 3.5 MPa (denoted
N212cathode | HNC |N212anode).
The confinement of the HNC membrane between two N212
membranes prolonged the life service of the hybrid
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 8 7 e1 0 2 93

Fig. 4 e a) AST between 25 and 250 mA/cm2 performed on the CCM with two HNC membrane reinforced with a PPS mesh
and b) Nyquist plot at 25 mA.cm¡2 and 60 C.

proton diffusion at the interfaces between the membranes)

Table 4 e HFR of the two HNC membrane reinforced with
increased with time, but the HFR did not change significantly.
a PPS mesh e based cell evolution during the ASTs.
The diameter of the low-frequency semicircle (the second
Time HFR (mU.cm2) semicircle, which most probably represents the charge
BoT 732 transfer resistance of the OER catalytic reaction) remained
10 h 1007 relatively constant during the AST. This suggests that its
20 h 1311
origin comes from membrane-membrane interfaces. In this
30 h 2413
sandwich structure with three membranes pressed against
40 h 2903
55 h 3243 each other, the silica nanoparticles and sulfonic compounds,
which are larger in diameter than the water nanochannel of
the Nafion membrane [39] are expected to be confined at the
membrane to more than 150 h (Fig. 6a). However, a significant interfaces between the HNC and Nafion membranes. Howev-
reduction of the cell efficiency was observed during the test. er, during the AST itself (Fig. 6a), the cell voltage continuously
To avoid cell voltage going higher than 2 V, which may oxidize increased, as was already the cases previously described with
the titanium PTL at the anode and increase the cell's internal 1 or 2 HNC membranes CCM.
resistance, the current density was periodically reduced from To better characterize the 3-membrane CCM, the cell was
250 to 200, 150 and 125 mA.cm2. dismantled after completion of the AST and the nano-
EIS spectra (Fig. 6b) show two main semi-circles. The composite membrane was removed from the sandwich
diameter of the high-frequency semicircle (the contribution of structure. Then the two Nafion membranes were clamped

Fig. 5 e a) AST between 25 and 250 mA/cm2 performed on the asymmetric CCM with HNC membrane on the cathode side
and Nafion 212 membrane on the anode side and b) Nyquist plot at 25 mA.cm¡2 and 60  C.
94 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 8 7 e1 0 2

again to form a new CCM with 2 membranes only (denoted as membrane-membrane interface is removed. Therefore, it can be
N212cathode |N212anode). The AST continued with the new CCM concluded that once the nanocomposite membrane is extracted
from 155 h to 235 h (Fig. 7a). from the cell, the electrochemical performances are stable.
As can be seen from Fig. 7 b, the HFR remained constant once
the nanocomposite membrane was removed. The diameter of the Upscaling and testing in short stack configuration using
HF semicircle becomes smaller after the removal of the nano- 250 cm2 CCM
composite membrane: this is consistent with the fact that one
In defiance of the stability problems encountered during the lab-
scale qualifications, three large areas HNC membrane-based
Table 5 e HFR of the asymmetric CCM with HNC CCMs (250 cm2) and a lab-made reference CCM (two Nafion
membrane on the cathode side and Nafion 212 N212 membranes) were prepared with different catalyst
membrane on the anode side cell evolution during the loading. The HNC membrane-based CCM consists of bare
ASTs. membrane clamped between two half-coated Nafion 212 (N212)
Time HFR (mU.cm2) membranes. For the pre-industrial qualification of the CCMs, a
BoT 778 so-called “rainbow stack” was built i.e. a stack with different
10 h 1258 types of CCM inside for direct in-situ comparison. The electro-
20 h 2309 chemical performance of the three prepared HNC membrane-
30 h 3326 based CCMs were compared to a Lab-made reference and to a
40 h 4607
Commercial reference CCMs. The CCMs are named as follows.

Fig. 6 e a) AST between 25 and 250 mA/cm2 performed on the CCM with HNC membrane clamped between two Nafion 212
membranes and b) Nyquist plot at 25 mA.cm¡2 and 60 C.

Fig. 7 e a) AST between 25 and 250 mA/cm2 performed on the CCM two Nafion 212 after removing the HNC membrane and b)
Nyquist plot at 25 mA.cm¡2 and 60 C.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 8 7 e1 0 2 95

CCM Cathode Electrolyte Anode

Low HNC: Pt/C (0.6 mgPt/C.cm2) N212 | HNC |N212 IrO2 (1.0 mgIrO2.cm2)
High HNC: Pt/C (0.8 mgPt/C.cm2) N212 | HNC |N212 IrO2 (1.8 mgIrO2.cm2)
Moderate HNC: Pt/C (0.7 mgPt/C.cm2) N212 | HNC |N212 IrO2 (1.4 mgIrO2.cm2)
Lab-made reference: Pt/C (0.7 mgPt/C.cm2) N212 |N212 IrO2 (1.3 mgIrO2.cm2)
Commercial reference: Pt/C N115 IrO2

Performances are measured at the beginning of the test
(BoT) and then periodically. The chronopotentiometry was
stopped periodically to re-assess the performance levels of
the CCMs. The full chronopotentiometry test is shown in
Fig. 8. The voltage of Moderate HNC was not stable and
increased gradually. However, the loss of the electro-
chemical performance of Moderate HNC is slower than the
High HNC and Low HNC respectively. In contrast, the elec-
trochemical performances of the reference CCMs (Lab-made
and Commercial) were more stable with insignificant voltage
increase, as expected.
After 11 h, the Low HNC voltage reached the End-of-Life
voltage (i.e. 2.3 V). Consequently, HNC membranes were
removed for Low HNC and High HNC for the analysis of the
degradation mechanism while the best performing HNC CCM
(Moderate HNC) was kept in the stack. Note that when the
stack was opened, the presence of droplets of a yellow liquid
was observed and collected on the bipolar plate for the anal-
ysis of the degradation products (emphasized in Section
Degradation of the HNC membranes). In agreement with the
chronopotentiometry, iV measurements (Fig. 9) showed that
both reference CCMs (lab-made and Commercial reference)
are relatively stable compared to all HNC containing CCMs.
The specific areal capacitances (the sum of the electric
double-layer capacitor (EDLC) and the pseudo-capacitance) of
the catalyst layer in the CCMs were estimated from the cyclic
voltammograms (CV) using Eq. (1) [40]:

Z 

Cs ¼ Idv 2ðv:DVÞ 3
where Cs is the specific areal capacitance (mF.cm2), I is the
current density (mA.cm2), v is the scan rate (mV/s.) and DV is
the voltage scan window (1.4 V).
Specific capacitance values deduced from the CVs shown
in Fig. 10 are compiled in Table 6. The CVs (Fig. 10) show an
increase of the specific areal capacitance (Cs) for the 4 lab-
made CCMs, namely the Lab-made reference CCM with the
highest Cs of 36.9 mF/cm2, very close to the Commercial
reference CCM (38 mF cm2).
At the end of the AST, Cs values range from 19.1 to
25.7 mF.cm2. A comparable Cs values were previously re-
ported for CCM having equivalent catalyst loadings [41,42].
The value range is lower than the reference CCMs
(36.9e38.2 mF.cm2) in similar test conditions. To some
extent, this is an indication that less catalyst is in contact with
the polymer electrolyte.
At the end of the electrochemical characterization, the
stack was opened, and the last HNC membrane was removed.
Similarly to Low HNC and High HNC, a yellow liquid was
observed and collected for physico-chemical analysis.

Fig. 8 e Cell voltage evolution during chronopotentiometry test at 25 mA.cm¡2 and 60 C.
96 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 8 7 e1 0 2

Fig. 9 e Polarization curves of a) Low HNC, b) High HNC, c) Moderate HNC, d) Lab-made reference and e) Commercial
reference CCMs measured at 60  C.

Degradation of the HNC membranes
The as-received HNC membrane has the following charac-
teristics: areal density of 1105 mg/100 cm2 and an Ion Ex-
change Capacity (IEC) of 1.8 meq/g. On the one hand, the HNC
membrane extracted from Low HNC had an areal density of
820 mg/100 cm2 (25.8% less than the initial weight) and an IEC
of 1 meq/g (45% less than the initial value). On the other hand,
the membrane extracted from High HNC had a density of 840
mg/100 cm2 (24% weight less than the initial value), and an IEC
of 0.91 meq/g (50% less than the initial value). Finally, the HNC
membrane of Moderate HNC had a very low IEC of less than 0.1
meq/g, 95% less than the initial IEC. Furthermore, this mem-
brane's areal density was reduced by 44% (618 mg/100 cm2).
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 8 7 e1 0 2 97

Fig. 10 e Cyclic voltammograms of a) Low HNC, b) High HNC, c) Moderate HNC, d) Lab-made reference and e) Commercial
reference CCMs measured at a scan rate of 10 mV/s.

These results confirm the major loss of conductive sulfonic
groups in the Moderate HNC membrane during the 225 h of
electrolysis.
On the other hand, the collected resin liquid had a pH of ca.
2 (acidic) and an ionic conductivity of 1204 mS/cm, which is
4000 times higher than initial water before electrolysis (0.3 mS/
cm). The excess water was removed from the collected yellow
liquid using the rotary evaporator, and a polymeric resin film
was deposited on the wall of the glass flask. After scratching
the polymeric films, an amount of 400 mg was obtained.
The chemical modifications of the HNC membrane
induced by electrolysis were determined by comparing the
98 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 8 7 e1 0 2

Table 6 e Specific areal capacitance values of the CCMs Table 8 e EDS elemental analysis of the HNC membrane
measured at a scan rate of 10 mV/s during the AST. before and after electrolysis and the collected resin.
Cell Specific areal capacitance (mF.cm2) Element Before After Collected
electrolysis electrolysis resin
BoT 70 h 225 h
O (at.%) 25.9 5.5 72.3
Low HNC 9.5 15.5 19.1
F (at.%) 66.9 93.7 0.3
High HNC 9.7 20.9 25.7
Si (at.%) 0.8 0.4 0.3
Moderate HNC 9.5 14.4 18.6
S (at.%) 6.4 0.4 21.1
Lab-made reference 11.0 32.3 36.9
Na (at.%) N/A N/A 1.8
Commercial reference 49.6 40.6 38.2
K (at.%) N/A N/A 4.2

Fig. 11 e FT-IR spectra of Moderate HNC membrane before (black) and after (red) electrolysis and the collected resin (blue).
The pink lines mark the characteristic peaks of PVDF-HFP and the green lines mark the distinct peaks of PSSA.

Table 7 e Characteristic FT-IR features of PVDF-HFP [43e45] and PSSA [46e48].

Wavenumber (cm1) Attribution
PVDF-HFP 762/794/974/1210 crystalline a-phase of PVDF-HFP
871 crystalline b-phase PVDF-HFP
1068 eCeCe bending
1180/1278 eCF2e bending
1383 eCH2e bond wagging
PSSA 664 bending of CeH in 1,4-substituted benzene ring (out-of-plane)
775 CeH wagging
830 CeH bending
1004/1031 deformation in aromatic ring (in-plane)
1123/1210 O]S]O stretching

FT-IR spectra of the HNC membrane before and after elec-
trolysis and the collected resin (Fig. 11).
The FT-IR spectra of the HNC membrane of Moderate HNC
reveals a complete absence of the characteristic PSSA peaks;
only the pure PVDF-HFP peaks are observed. This result is in
agreement with the IEC titration measurements, which also
show that an insignificant amount of sulfonic groups remains
present in the HNC membrane at the end of the test. In fact, the
“as-received” HNC membrane contains two phases: PVDF-HFP
(host matrix) and the SiO2-grafted PSSA (ionic conducting
phase). The crystalline a-phase was identified in the FT-IR
spectrum of PVDFeHFP by the vibrational bands observed at
760, 790, 973, and 1210 cm1. Furthermore, the crystalline b-
phase of PVDF-HFP was assigned at 870 cm1. The CH2 bond
wagging was detected at 1380 cm1, corresponding to the
vinylidene group of the host polymer [43e45]. The FT-IR
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 8 7 e1 0 2 99

Fig. 12 e Mechanism of imine bond hydrolysis in an aqueous acidic medium [50].

Fig. 13 e The principal of oxidative degradation reactions occurring in polystyrene sulfonate polymer [51].

spectrum of PSSA is characterized by the presence of the ben-
zene ring. The out-of-plane bending of CeH in a 1,4-substituted
benzene ring was assigned at 664 cm1. Meanwhile, the CeH
wagging and bending were observed at 775 and 830 cm1,
respectively. The in-plane deformation of the benzene ring was
detected at 1004 and 1031 cm1. The presence of O]S]O vi-
bration stretching at 1125 and 1210 cm1 is specific to the sul-
fonic groups of the PSSA [46e48]. An overlap between the O]
S]O stretching of the PSSA and the vibrational band of crys-
talline a-phase PVDF-HFP can be observed at 1210 cm1. The
FT-IR peaks of PVDF-HFP and PSSA are summarized in Table 7.
Elementary analysis of bare HNC membrane, the one
recovered from Moderate HNC CCM after electrolysis and the
dried collected resin were performed with energy-dispersive
X-ray spectroscopy (EDS). Before electrolysis, HNC mem-
brane has an initial sulfur-to-fluorine ratio of 1:10.5 (Table 8).
The Sulfur-to-fluorine ratio decreased by 22 times (1:234.5, a
reduction of 95.5%) as well as the Oxygen and the Silicon
content after the electrolysis as a result of the loss of proton
conductive sulfonic groups. These observations are consistent
with the decrease of the IEC and the areal density of the HNC
membrane during the AST.
100 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 8 7 e1 0 2
These results led us to the conclusion that the nano-
composite membrane is not chemically stable during elec-
trolysis. It loses matter and, most importantly, its functional
property (i.e. proton conductivity).
The HNC membrane was initially developed for fuel cell
applications [29], where the quantities of water present are
less than in water electrolysis (i.e. humidified gases vs water
circulation). The large electro-osmotic water flow which takes
place during electrolysis accelerates the degradation of the
membrane. The silica nanoparticles functionalized with poly
(styrene sulfonic acid) dispersed in the PVDF matrix of the
HNC may be extracted from the polymer matrix by electro-
phoresis or by simple elution.
Mechanism of the HNC membrane degradation
PEM water electrolysis technology requires excess hot water
(e.g. 60  C) to improve the kinetics of the electrocatalytic water
splitting [1]. The HNC suffers from two major deficiencies: the
imine and enamine functional group instability and the
oxidative degradation of the polystyrene sulfonic polymer.
In the case of the HNC membrane, the imine and enamine
functional groups are susceptible to acidic hydrolysis mean-
ing that they are susceptible to be thermally decomposed to
amine and carbonyl groups in water and an acidic medium
(Fig. 12) [49]. The stability of these functional groups is affected
by numerous issues.
(i) the imine bond of the HNC polymer is not stable by
reason of the acidic sulfonic groups which ensure the
proton conductivity and the acidity of the membrane,
(ii) the protons' migration inside the membrane (when a DC
electric voltage is applied) will increase the chance of
attacking the imine bond by protons and accelerate the
degradation of the imine bonds,
(iii) the enamine bonds are nucleophilic owing to their sig-
nificant resonance form with a negative charge on the
alpha carbon (susceptible to hydrolysis in concentrated
acidic media),
(iv) the imine and enamine undergo tautomerization:
enamine can transform into imine and vice versa.
Additionally, the polystyrene sulfonic polymer is also not
stable and prone to oxidative degradation, as shown in Fig. 13.
Under the harsh operating conditions of water electrol-
ysis for the HNC membrane, local decomposition of the
polystyrene backbone can occur due to a chemical attack by
free radicals e.g. hydroxyl radicals (OHC) formed during OER
at the anode catalyst layer/electrolyte interface. This can
result in the disruption of the structure's regularity thus
accelerating the membrane's degradation. The OHC can
rapidly react with the ortho carbon of aromatic rings, form-
ing isomeric hydroxy-cyclohexadienyl radicals (Fig. 13, Re-
action A). The resultant OH-adduct may generate other
highly reactive radicals. Furthermore, OHC can react with an
aliphatic linear polymer chain via abstraction of the labile
tertiary protons and forming benzyl radicals (Fig. 13, Reac-
tion B), followed by chain scission and polymer degradation.
The oxidative radical attached to the tertiary carbon of the
benzyl groups can then cause polymer chain scission (Fig. 13,
Reaction C) [52].
Conclusion
In the present study, we evaluated the interest of replacing the
existing PFSA polymers by a new type of hybrid nano-
composite (HNC) material. An innovative multi-layer
approach was developed throughout this work aiming to
extend the lifespan of the HNC membrane in PEMWE opera-
tion. It consists of sandwiching more than one proton ex-
change membrane (HNC and/or Nafion) to form the Catalyst
Coated Membrane (CCM). The electrochemical testing of
different configuration of HNC membrane based CCM, at the
laboratory scale (4 cm2) and at large scale (250 cm2) high-
lighted that the bulk HNC membrane itself is not stable under
the conditions of PEM water electrolysis. The membrane ex-
hibits high chemical instability in the presence of liquid water
(mainly the hydrolysis of both imine and enamine bonds and
the degradation of PSSA polymer), even at rest conditions.
During electrolysis, this leads to a rapid increase in the cell
voltage, due in particular to the loss of proton conduction.
By analyzing the degradation processes in more detail, we
were able to emphasize that the core of the membrane are
mechanically and chemically weak leading to a loss of acid
functions and accelerated degradation in PEMWE operation
(rapid increase in the cell voltage). From a mechanical point of
view, the HNC membrane brought into contact with liquid water
is subject to softening and strong dimensional changes. This
weakens its mechanical strength, which can promote electrical
short circuits during electrolysis. On the chemical side, the hy-
drolysis of the acid functions occurs as soon as the membrane is
exposed to liquid water. Furthermore, styrene sulfonic groups
exposed to the positive voltage of the anode are also suspected to
be unstable and to undergo electrochemical oxidation. These
various weaknesses contribute to reduce operating times, which
are incompatible with the target applications.
Eventhough we succeeded in increasing the longevity of
the HNC membrane from a few hours to a few hundred hours
by our multi-layer approach (clamping the HNC membrane
between two half-coated Nafion 212 membranes), it did not
prevent its degradation. One can thus conclude that
these types of hybrid nanocomposite membranes require
improvement in their chemical structure by a completely new
chemistry that resist to hydrolysis and increased crosslinking
degree to improve the stability of this electrolytic material.
Declaration of competing interest
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.
Acknowledgement
This work was financially supported by Storengy. Dr. Nelly
Rameau and Dr. Benoit Blondel from CEA are acknowledged
for the synthesis of the HNC membrane. The authors also
thank ElogenH2, in particular Dr. Raphael Faure, Dr. Angel
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 8 7 e1 0 2
Eduardo Villagra, and Mr. Olivier Debellemaniere for their
support in the testing of the HNC membrane in short-stack
configuration.
references
[1] Chatenet M, Pollet BG, Dekel DR, Dionigi F, Deseure J, Millet P,
et al. Water electrolysis: from textbook knowledge to the
latest scientific strategies and industrial developments.
Chem Soc Rev 2022;51:4583e762. https://doi.org/10.1039/
D0CS01079K.
[2] Millet P, Dragoe D, Grigoriev S, Fateev V, Etievant C.
GenHyPEM: a research program on PEM water electrolysis
supported by the European Commission. Int J Hydrogen
Energy 2009;34:4974e82. https://doi.org/10.1016/
j.ijhydene.2008.11.114.
[3] Millet P, Ngameni R, Grigoriev SA, Fateev VN. Scientific and
engineering issues related to PEM technology: water
electrolysers, fuel cells and unitized regenerative systems.
Int J Hydrogen Energy 2011;36:4156e63. https://doi.org/
10.1016/j.ijhydene.2010.06.106.
[4] Millet P, Mbemba N, Grigoriev SA, Fateev VN, Aukauloo A,
Etievant C. Electrochemical performances of PEM water
electrolysis cells and perspectives. Int J Hydrogen Energy
2011;36:4134e42. https://doi.org/10.1016/
j.ijhydene.2010.06.105.
[5] Millet P, Ngameni R, Grigoriev SA, Mbemba N, Brisset F,
Ranjbari A, et al. PEM water electrolyzers: from
electrocatalysis to stack development. Int J Hydrogen Energy
2010;35:5043e52. https://doi.org/10.1016/
j.ijhydene.2009.09.015.
[6] Millet P, Ngameni R, Grigoriev SA, Fateev VN. Scientific and
engineering issues related to PEM technology: water
electrolysers, fuel cells and unitized regenerative systems.
Int J Hydrogen Energy 2011;36:4156e63. https://doi.org/
10.1016/j.ijhydene.2010.06.106.
[7] Coms FD. The chemistry of fuel cell membrane chemical
degradation. ECS Trans 2008;16:235e55. https://doi.org/
10.1149/1.2981859.
[8] Feng M, Qu R, Wei Z, Wang L, Sun P, Wang Z.
Characterization of the thermolysis products of Nafion
membrane: a potential source of perfluorinated compounds
in the environment. Sci Rep 2015;5:9859. https://doi.org/
10.1038/srep09859.
[9] Ito H, Maeda T, Nakano A, Takenaka H. Properties of Nafion
membranes under PEM water electrolysis conditions. Int J
Hydrogen Energy 2011;36:10527e40. https://doi.org/10.1016/
j.ijhydene.2011.05.127.
[10] Siracusano S, Baglio V, Stassi A, Merlo L, Moukheiber E,
Arico AS. Performance analysis of short-side-chain
Aquivion® perfluorosulfonic acid polymer for proton
exchange membrane water electrolysis. J Membr Sci
2014;466:1e7. https://doi.org/10.1016/j.memsci.2014.04.030.
[11] Yin Y, Liu S, Yang Y, Gong D, Liu M, Liu G, et al.
Polyethyleneimine-polyvinylchloride-based crosslinked
membranes for use in PEM water electrolysis operating
above 100  C. Int J Hydrogen Energy 2023;48:24e34. https://
doi.org/10.1016/j.ijhydene.2022.09.221.
[12] Siracusano S, Baglio V, Nicotera I, Mazzapioda L, Arico  AS,
Panero S, et al. Sulfated titania as additive in Nafion
membranes for water electrolysis applications. Int J
Hydrogen Energy 2017;42:27851e8. https://doi.org/10.1016/
j.ijhydene.2017.05.136.
[13] Sharma PP, Gupta H, Kulshrestha V. Phosphorylated hybrid
silica-sulfonated polyethersulfone composite proton-
101
exchange membranes: magnetic resonance investigation for
enhanced proton-exchange dynamics. Int J Hydrogen Energy
2020;45:16955e64. https://doi.org/10.1016/
j.ijhydene.2019.09.106.
[14] Kerres J, Atanasov V. Cross-linked PBI-based high-
temperature membranes: stability, conductivity and fuel cell
performance. Int J Hydrogen Energy 2015;40:14723e35.
https://doi.org/10.1016/j.ijhydene.2015.08.054.
[15] Yin Y, Liu S, Yang Y, Gong D, Liu M, Liu G, et al.
Polyethyleneimine-polyvinylchloride-based crosslinked
membranes for use in PEM water electrolysis operating
above 100  C. Int J Hydrogen Energy 2023;48:24e34. https://
doi.org/10.1016/j.ijhydene.2022.09.221.
[16] Wei W, Dai Y, Xu S, Wang J, Liu X, He R. Crosslinked poly
(isatin biphenyl spirofluorene) membranes for proton
conduction over a wide temperature range from 40 to 160

C. Int J Hydrogen Energy 2023. https://doi.org/10.1016/
j.ijhydene.2023.03.429.
[17] Labalme E, David G, Buvat P, Bigarre J. A simple strategy
based on a highly fluorinated polymer blended with a
fluorinated polymer containing phosphonic acid to improve
the properties of PEMFCs. New J Chem 2019;43:11141e7.
https://doi.org/10.1039/C9NJ03037A.
[18] Labalme E, David G, Souquet J, Buvat P, Bigarre J. Use of a new
crosslinking method to obtain semi-IPN membranes with
phosphonic acid groups for a PEMFC application. J Mater
Chem 2014;2:9792e802. https://doi.org/10.1039/C4TA01472C.
[19] Palanisamy P, Chavali M, Kumar EM, Etika KC. Hybrid
nanocomposites and their potential applications in the field
of nanosensors/gas and biosensors. Nanofabrication for
Smart Nanosensor Applications 2020:253e80. https://doi.org/
10.1016/B978-0-12-820702-4.00011-8. Elsevier.
[20] Ali AKM, Ali MEA, Younes AA, Abo El fadl MM, Farag AB.
Proton exchange membrane based on graphene oxide/
polysulfone hybrid nano-composite for simultaneous
generation of electricity and wastewater treatment. J Hazard
Mater 2021;419:126420. https://doi.org/10.1016/
j.jhazmat.2021.126420.
[21] Gouda MH, Elessawy NA, Santos DMF. Synthesis and
characterization of novel green hybrid nanocomposites for
application as proton exchange membranes in direct
borohydride fuel cells. Energies 2020;13:1180. https://doi.org/
10.3390/en13051180.
[22] Salarizadeh P, Javanbakht M, Askari MB, Hooshyari K,
Moradi M, Beydaghi H, et al. Novel proton conducting
coreeshell PAMPS-PVBS@Fe2TiO5 nanoparticles as a
reinforcement for SPEEK based membranes. Sci Rep
2021;11:4926. https://doi.org/10.1038/s41598-021-84321-7.
[23] Zhang W, Li MKS, Yue P-L, Gao P. Exfoliated Pt-Clay/Nafion
nanocomposite membrane for self-humidifying polymer
electrolyte fuel cells. Langmuir 2008;24:2663e70. https://
doi.org/10.1021/la702153v.
[24] Gandhimathi S, Krishnan H, Paradesi D. Development of
proton-exchange polymer nanocomposite membranes for
fuel cell applications. Polym Polym Compos 2020;28:492e501.
https://doi.org/10.1177/0967391119888319.
[25] Soleimani B, Asl AH, Khoshandam B, Hooshyari K. Enhanced
performance of nanocomposite membrane developed on
sulfonated poly (1, 4-phenylene ether-ether-sulfone) with
zeolite imidazole frameworks for fuel cell application. Sci
Rep 2023;13:8238. https://doi.org/10.1038/s41598-023-34953-8.
[26] Nauman Javed RM, Al-Othman A, Nancarrow P, Tawalbeh M.
Zirconium silicate-ionic liquid membranes for high-
temperature hydrogen PEM fuel cells. Int J Hydrogen Energy
2022. https://doi.org/10.1016/j.ijhydene.2022.05.009.
[27] Seck S, Magana S, Pre  be
 A, Niepceron F, Bounor-Legare
 V,
Bigarre  J, et al. PVDF-HFP/silica-SH nanocomposite synthesis
for PEMFC membranes through simultaneous one-step
102 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 8 7 e1 0 2
solegel reaction and reactive extrusion. Mater Chem Phys
2015;163:54e62. https://doi.org/10.1016/
j.matchemphys.2015.07.014.
[28] Seck S, Magana S, Pre  be
 A, Buvat P, Bigarre  J, Chauveau J,
et al. New fluorinated polymer- based nanocomposites via
combination of sol-gel chemistry and reactive extrusion for
polymer electrolyte membranes fuel cells (PEMFCs). Mater
Chem Phys 2020;252:123004. https://doi.org/10.1016/
j.matchemphys.2020.123004.
[29] Bredel T. Elaboration and characterization of crosslinked
hybrid nanocomposite membranes for PEMFC and PEMEC
application. Normandie Universite ; 2019.
[30] Niepceron F, Lafitte B, Galiano H, Bigarre  J, Nicol E, Tassin J-F.
Composite fuel cell membranes based on an inert polymer
matrix and proton-conducting hybrid silica particles. J
Membr Sci 2009;338:100e10. https://doi.org/10.1016/
j.memsci.2009.04.022.
[31] Me thycentre. https://methycentre.eu/projet/. [Accessed 26
January 2023].
[32] Kumar V, Kumar P, Nandy A, Kundu PP. A nanocomposite
membrane composed of incorporated nano-alumina within
sulfonated PVDF-co-HFP/Nafion blend as separating barrier
in a single chambered microbial fuel cell. RSC Adv
2016;6:23571e80. https://doi.org/10.1039/C6RA03598A.
[33] Millet P, Grigoriev S. Water electrolysis technologies.
Renewable Hydrogen Technologies, Elsevier; 2013. p. 19e41.
https://doi.org/10.1016/B978-0-444-56352-1.00002-7.
[34] Ito H, Maeda T, Nakano A, Takenaka H. Properties of Nafion
membranes under PEM water electrolysis conditions. Int J
Hydrogen Energy 2011;36:10527e40. https://doi.org/10.1016/
j.ijhydene.2011.05.127.
[35] Siracusano S, Panto  F, Tonella S, Oldani C, Arico  AS.
Reinforced short-side-chain Aquivion® membrane for
proton exchange membrane water electrolysis. Int J
Hydrogen Energy 2022;47:15557e70. https://doi.org/10.1016/
j.ijhydene.2022.03.061.
[36] Barsoukov E, Macdonald JR. Impedance spectroscopy :
theory, experiment, and applications. 3rd ed. Hoboken, NJ,
USA: John Wiley & Sons, Inc.; 2018. https://doi.org/10.1002/
9781119381860.
[37] Klose C, Saatkamp T, Münchinger A, Bohn L, Titvinidze G,
Breitwieser M, et al. All-hydrocarbon MEA for PEM water
electrolysis combining low hydrogen crossover and high
efficiency. Adv Energy Mater 2020;10:1903995. https://doi.org/
10.1002/aenm.201903995.
[38] Yandrasits M, Hamrock S. Poly(Perfluorosulfonic acid)
membranes. Polymer Science: A Comprehensive Reference
2012:601e19. https://doi.org/10.1016/B978-0-444-53349-
4.00283-1. Elsevier.
[39] Duan Q, Wang H, Benziger J. Transport of liquid water
through Nafion membranes. J Membr Sci
2012;392e393:88e94. https://doi.org/10.1016/
j.memsci.2011.12.004.
[40] Zhao S, Yu H, Maric R, Danilovic N, Capuano CB, Ayers KE,
et al. Calculating the electrochemically active surface area of
iridium oxide in operating proton exchange membrane
electrolyzers. J Electrochem Soc 2015;162:F1292e8. https://
doi.org/10.1149/2.0211512jes.
[41] Mandal M, Valls A, Gangnus N, Secanell M. Analysis of inkjet
printed catalyst coated membranes for polymer electrolyte
electrolyzers. J Electrochem Soc 2018;165:F543e52. https://
doi.org/10.1149/2.1101807jes.
[42] Rasten E, Hagen G, Tunold R. Electrocatalysis in water
electrolysis with solid polymer electrolyte. Electrochim Acta
2003;48:3945e52. https://doi.org/10.1016/j.electacta.2003.04.001.
[43] Parangusan H, Ponnamma D, Al-Maadeed MAA. Stretchable
electrospun PVDF-HFP/Co-ZnO nanofibers as piezoelectric
nanogenerators. Sci Rep 2018;8:754. https://doi.org/10.1038/
s41598-017-19082-3.
[44] Feng Y, Li WL, Hou YF, Yu Y, Cao WP, Zhang TD, et al.
Enhanced dielectric properties of PVDF-HFP/BaTiO3
-nanowire composites induced by interfacial polarization
and wire-shape. J Mater Chem C Mater 2015;3:1250e60.
https://doi.org/10.1039/C4TC02183E.
[45] Dwivedi J. Optical properties and ionic conductivity studies
of an 8 MeV electron beam irradiated poly(vinylidene
fluoride- co -hexafluoropropylene)/LiClO4 electrolyte film for
opto-electronic applications. RSC Adv 2018;8:15297e309.
https://doi.org/10.1039/C8RA00970H.
[46] Fathy M, Abdel Moghny Th, Alblehy A. Cation exchange resin
nanocomposites based on multi-walled carbon nanotubes.
Appl Nanosci 2014;4:103e12. https://doi.org/10.1007/s13204-
012-0178-5.
[47] Lei Y, Luo Y, Chen F, Mei L. Sulfonation process and
desalination effect of polystyrene/PVDF semi-
interpenetrating polymer network cation exchange
membrane. Polymers 2014;6:1914e28. https://doi.org/
10.3390/polym6071914.
[48] Braglia M, Ferrari IV, Djenizian T, Kaciulis S, Soltani P, di
Vona ML, et al. Bottom-up electrochemical deposition of
poly(styrene sulfonate) on nanoarchitectured electrodes.
ACS Appl Mater Interfaces 2017;9:22902e10. https://doi.org/
10.1021/acsami.7b04335.
[49] Abdel-Magid AF. 8.02 reduction of CN to CHeNH by metal
hydrides. Comprehensive Organic Synthesis II 2014:85e150.
https://doi.org/10.1016/B978-0-08-097742-3.00802-8. Elsevier.
[50] Innocenti R, Lenci E, Trabocchi A. Recent advances in
copper-catalyzed imine-based multicomponent reactions.
Tetrahedron Lett 2020;61:152083. https://doi.org/10.1016/
j.tetlet.2020.152083.
[51] Walkowiak-Kulikowska J, Wolska J, Koroniak H. Polymers
application in proton exchange membranes for fuel cells
(PEMFCs). Physical Sciences Reviews 2017;2. https://doi.org/
10.1515/psr-2017-0018.
[52] Albert A, Lochner T, Schmidt TJ, Gubler L. Stability and
degradation mechanisms of radiation-grafted polymer
electrolyte membranes for water electrolysis. ACS Appl
Mater Interfaces 2016;8:15297e306. https://doi.org/10.1021/
acsami.6b03050.