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

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

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

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

* 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- demonstrated that it is possible to generate a high concen-
tion of hydrogen by water electrolysis using the so-called tration of inorganic silica in a PVDF-HFP polymer via sole gel
proton exchange membrane or polymer electrolyte mem- chemistry during extrusion without any degradation issues.
brane technology was developed in the 1970s, following the Then, the interface between the matrix and the inorganic-rich
discovery and marketing of proton-conducting perfluoro sul- phase was tailored to increase ionic conductivity by incorpo-
fonic acid ionomers (PFSA) by the US company Dupont de rating interfacial agents [28]. The nanocomposite membrane
Nemours under the trade name of Nafion®. PFSAs are the reached a 54 mS/cm conductivity comparable to that of Nafion
commonly used polymeric membranes for PEM water elec- N112 (52 mS/cm) at 100% RH and a temperature of 25 C [28].
trolysis (PEMWE) because of their high proton conductivity The CEA (Commissariat a  l’Energie Atomique et aux En-
and strong mechanical and chemical robustness [7]. However, ergies Alternatives) has developed a new family of hybrid
the continued quest for alternate membrane materials is nanocomposite (HNC) membranes, less fluorinated than
fueled by the expensive cost and environmental concerns (e.g. PFSAs, for PEM fuel cell and water electrolysis applications
the Registration, Evaluation, Authorization and Restriction of [29,30]. This HNC membrane consists of a polystyrene sulfonic
Chemicals European regulation) connected with PFSAs' fluo- acid (PSSA) chain grafted onto silica nanoparticles which are
rine chemistry, as well as their significant gas (particularly H2) then dispersed into activated PVDF/HFP matrix. The HNC
permeability and poor mechanical stability at high tempera- membrane was crosslinked with 2,2,4-trimethyl-1,6-
tures (T > 80  C) [8]. hexanediamine (THDA) to anchor the functional acid groups
Although various PFSA are commercially available and to the hydrophobic organic phase (PVDF/HFP) and post-
shows good properties for operation in PEMWE (Nafion [9] and annealed at 180 C for 2 hours (h) [30]. The membrane is a
Aquivion [10]), there is still a need for developing membranes hybrid nanocomposite membrane since silica nanoparticles
with minimal environmental impact and with new polymeric (inorganic) are functionalized with polystyrene sulfonic
structure capable of proton conduction for PEM electrolysis at groups (organic) required for proton-conductivity [29,30].
high temperatures (e.g. 120 C). The high cost of PFSA mem- In the frame of the French ADEME (Agence de la Transition
branes, as mentioned earlier, is mainly due to the expensive Energetique) project entitled Me thycentre [31], a Power-to-Gas
fluorination step. Thus, substantial efforts are made towards demonstration project led by Storengy to support the energy
the development of alternative PEM materials. Promising ones transition to meet clean mobility needs and partially replace
are partially fluorinated ionomer containing acidic function fossil methane in Engie's gas networks, we evaluated the
groups (e.g. sulfonic, phosphonic) in the main polymer chain, performance and durability of a new hybrid nanocomposite
or in the side chain [11e14]. Additionally, recent studies membrane (HNC) as a possible alternative to the commercially
showed that the crosslinking of the proton conductive poly- available PFSA membranes for PEMWE. The HNC membrane
mers improves the thermal stability of the membrane (e.g. and commercial catalysts have been used to manufacture the
100 C [15] and 160 C [16]). In this regard, Labalme et al. catalyst-coated membrane (CCM). The electrochemical
developed covalently crosslinked phosphonated poly- behavior of the prepared CCMs has been studied, evaluated,
electrolytes (proton conducting phase) with partially fluori- and compared to the performance of reference CCMs.
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) Materials and methods
permitted the fabrication of membranes with improved
structural integrity, mechanical strength and resistance to Materials
oxidation in the presence of radicals. Under fully hydrated
conditions, the best result reveals a 40 mS/cm proton con- Nafion ionomer 5 wt.% (Nafion™ 1100 W) and Pt/C (40 wt.%)
ductivity at a temperature of 80 C [17]. was purchased from Sigma Aldrich. IrO2 from SurePure
Hybrid nanocomposite membranes, consisting of func- Chemetals Inc. Isopropanol was provided by Carlo-Erba Re-
tionalized inorganic nanoparticles dispersed into a macro- agents. Cyclohexanol 99% was supplied from Alfa Aesar.
scopic organic matrix [19], offer a particularly attractive Nafion membrane 212 was kindly provided by Chemours
alternative to conventional membrane in different fields of Company FC, LLC and the 80 mm thick Hybrid NanoComposite
application such as microbial fuel cells [20], borohydride fuel membrane (HNC) was developed and manufactured by CEA,
cells [21] and PEM fuel cells [22e26]. This class of membranes Le Ripault.
is interesting for proton conduction application (PEM fuel cells
and PEM electrolysis) due to their morphology, which results Catalyst ink preparation
in a significantly lower gas crossover, similar conductivity to
the state-of-the art PFSA membranes (namely when fully Cathode: The hydrogen evolution reaction (HER) catalyst inks
hydrated), better thermal stability, lower production cost. The were prepared by dispersing commercial Pt/C catalyst in iso-
fact that they are the primary step toward fluorine-free propanol in an ultrasonic bath. A dispersion of Nafion ion-
membrane should make them ideally suited for PEM water omer was added as dispersing agent and source of proton
electrolysis. Several attempts to prepare a high proton con- conductivity in the catalyst layer. The composition of the
ductivity nanocomposite membrane have been made by Seck cathode ink was adjusted as follows: 94 wt.% isopropanol,
et al. [27,28]. The authors directly synthesized Poly(vinylidene 4 wt.% of Pt/C and 2 wt.% of Nafion ionomer.
fluoride-co-hexafluoropropylene) (PVDF-HFP)/silica-SH nano- Anode: The oxygen evolution reaction (OER) catalyst ink
composites in a single extrusion step [27]. The authors 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 89

procedure mentioned above. The composition of the anode 2 wt.% of PFSA ionomer. The IrO2 and Pt/C loading of each
ink was adjusted as follows: 95 wt.% isopropanol, 4 wt.% IrO2 CCM was determined by weighing the substrate before and
and 1 wt.% of Nafion ionomer. The prepared inks were soni- after catalyst transfer. Different loadings of the catalysts were
cated prior to the deposition. prepared and described in section Upscaling and testing in
For the CCM preparation using HNC membranes, iso- short stack configuration using 250 cm2 CCM. The water up-
propanol was replaced by cyclohexanol to reduce the swelling take and the swelling ratio were determined following equa-
of the membrane. tions (1) and (2) respectively [32]:

CCM preparation ðmW  md Þ

Water uptake ð%Þ ¼ 1
md
Lab-scale CCM using nafion 212 membrane
ðXW  Xd Þ
The CCM was prepared by hand spray coating of HER & OER Swelling ratio ð%Þ ¼ 2
Xd
inks over PTFE substrates followed by their transfer to the
virgin membrane by the so-called DECAL process. In a typical where mW and md are the weight of the membrane in wet and
experiment, the cathode ink (Pt/C) was sprayed over the HER- dry conditions respectively while XW and Xd are the length of
PTFE substrate (surface area of 4 cm2). For the anode catalyst the membrane in wet and dry conditions respectively.
layer, IrO2 ink was sprayed over the OER-PTFE substrate The tensile strength test was performed using an exten-
(surface area of 4 cm2). In both cases, the catalyst layer was someter device RT-201 A Computer Servo Universal Testing
dried by placing the PTFE sheets on a hot plate at 60 C, Machine from Dongguan Right Instrument Co.,Ltd.
allowing solvent evaporation. The loadings of Pt/C and IrO2
were adjusted to 0.7 mg cm2 and 1.4 mg cm2 respectively. Electrochemical characterization
The HER and OER catalyst layers formed on the PTFE sub-
strates were then transferred to the Nafion membrane, A compact water electrolysis cell (4 cm2 active area) equipped
sandwiched between the two substrates, by thermal pressing with an adjustable clamping pressure controller from
at 135 C for 5 minutes (min) under 5 tons. The Nafion mem- Fraunhofer ISE, Freiburg was used. The cell clamping pressure
brane was used as received without any specific treatment. was set to 3.5 MPa unless stated otherwise. Conventional
electrochemical measurements were performed to charac-
Lab-scale CCM using the HNC membrane terize and evaluate the performance levels of CCMs using a
The HNC membrane was always used ‘as-received’, without any Voltalab potentiostat PGZ 301: (i) polarization curves (so-called
pre-treatment or cleaning, due to its suspected high sensitivity iV curves), (ii) Accelerated Stability Tests (ASTs) (mainly chro-
to hydrolysis. For the manufacturing of HNC-based CCM, the nopotentiometry by applying current cycles), (iii) cyclic vol-
catalyst inks were sprayed onto the membrane to avoid the tammetry to measure the electrochemical surface area (ECSA)
common thermal pressing step since The HNC membrane has a and (iv) electrochemical impedance spectroscopy (EIS). An
very low the glass transition temperature of the PVDF is lower external power supply connected with a digital multimeter was
than that of the Nafion (i.e. 35 C vs. 135 C). In a typical exper- used to measure the iV curve of the cell at high current den-
iment, Pt/C cyclohexanol-based ink was directly sprayed over sities. For large surface area HNC-based CCMs testing, PEMWE
the membrane forming a coated area of 4 cm2. The hot plate test benches available at ElogenH2 site in Les Ulis, France were
temperature was set to 60 C to prevent absorption of the solvent used. EIS and Cyclic Voltammetry were performed using Met-
by the membrane. Similarly, IrO2 cyclohexanol-based ink was rohm Autolab PGSTAT302 N equipped with a 20 A booster.
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 Results and discussion
membrane was achieved by sandwiching the coated membrane
between two PTFE and pressing at room temperature under five Electrochemical characterization at the lab-scale
tones for 5 min. Ambient temperature was chosen because of
the low glass transition temperature of the PVDF polymer used Reference Nafion-115 membrane
in the HNC membrane. Nafion is the reference material commonly used as polymer
Upscaling and testing in short stack configuration (250 cm2 electrolyte in PEM water electrolysis cells. It is known for its
active area CCM) used for testing the hybrid nanocomposite great chemical stability which allows in the industry to
membranes for pre-industrial qualification were prepared accumulate tens of thousands of hours of operation. A refer-
following the same approach as described earlier. However, a ence CCM made of Nafion 115 was used to set the baseline
SONO-TEK ExactaCoat ink printer equipped with ultrasonic against which the performance levels of HNC membranes
nozzle was used to spray the catalyst ink on the PTFE sub- were evaluated. This reference CCM was prepared as
strate (for the transfer on the Nafion membrane with the described in the experimental section, using a commercially
DECAL method) to reach better homogeneity of the deposited available Nafion 115 membrane (Chemours Co.), and clamped
catalyst layer. A mask with a circular hole of 17.8 cm in in the test cell at a clamping pressure of 3.5 MPa. An AST was
diameter and adhered to the PTFE substrate was used to then applied by cycling current density between 25 and
delimit the coating area. The anode ink contains 95 wt.% 250 mA.cm2 (Fig. 1a). The test lasted about 85 h, enough time
isopropanol, 4 wt.% IrO2 and 1 wt.% of PFSA ionomer. The to get a good idea of the quality of the CCM manufactured and
cathode ink contains 94 wt.% isopropanol, 4 wt.% of Pt/C 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

Table 1 e HFR measured on the CCM with a Nafion-115
slightly but remained sufficiently stable to set a convincing
membrane during the AST.
baseline.
Time HFR (mU.cm2)
Fig. 1 b shows EIS spectra recorded at different time intervals
during AST. The high frequency side of the EIS diagrams, espe- BoT 452
cially the High Frequency Resistances (HFR) measured on the 10 h 396
20 h 392
real axis at 25 mA.cm2 (numerical values are compiled in Table
30 h 387
1) remained stable during the test (i.e., the cell impedance 40 h 389
remained constant). On the contrary, the low frequency value of 50 h 393
the cell impedance increased slightly. This is due to a slight in- 60 h 392
crease in the diameter of the semi-circle which, to a first 70 h 395
approximation can be attributed to the oxygen evolution reac- 80 h 396
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 from 626 mU cm2 (BoT value) down to 519 mU cm2 (last
manufacturing CCM is correctly controlled and allows endur- measurement before EoT). It is well established in the liter-
ance tests of a few tens of hours to be carried out. ature that in PEM water electrolysis, the surface resistance of
the membrane is inversely proportional to its thickness
CCM with a single HNC membrane [33,34]. It is therefore logical to speculate that if the surface
The performance level of HNC membranes (i.e. their me- resistance decreases, it is because the thickness of the
chanical resistance, proton conductivity and stability over membrane decreases. A possible mechanism would be that
time) in PEM water electrolysis was first evaluated using a the absorption of water by the membrane, which occurs
CCM containing a single HNC membrane (this CCM is denoted during electrolysis (by direct contact of the membrane with
as Cathode/HNC/Anode). Considering the small thickness (ca liquid water and due to the electro-osmotic flow of water
80 mm) and the tensile value (43 MPa when dry vs. 14 MPa associated to the transport of protons across the membrane),
when wet) of the HNC membrane, a reduced clamping pres- induces a decrease in the tensile strength of the membrane.
sure of 1.5 MPa was applied to prevent the occurrence of po- The amount of water absorbed (a swelling ratio of 23.3% and
tential electrical short-circuits. The electrochemical behavior a water uptake of 65 wt.% have been measured on the HNC
of this CCM was then evaluated by applying the same AST membrane) and its softening effect directly impact the me-
(current density cycles between 25 and 250 mA.cm2) as for chanical properties of the membrane (the tensile strength
the Nafion-115-based CCM. Details of the AST (current density goes from 43 MPa for a dry membrane to 14 MPa for a wet
cycles and and chronopotentiometric cell response) are membrane). Even if the clamping pressure used is reduced
shown in Fig. 2 a. EIS spectra recorded during the AST at compared to the previous experiment made with the Nafion-
different time intervals are plotted in Fig. 2 b and the corre- CCM, since the membrane gradually softens during the AST
sponding HFR values are compiled in Table 2. due to water absorption, the clamping force exerted on the
Despite the reduced clamping pressure used, the AST las- membrane gradually reduces its thickness until an electrical
ted only 9.5 h (h) before a short circuit occurred. short circuit occurs.
Variation of HFR values during the AST: The data in Table Variation of EIS spectra during the AST: During the AST,
2 shows that the HFR of the cell decreases during the AST, the EIS spectra remain almost stable (only the HFR decreases

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.
 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 91

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.

HFR values are compiled in Table 3. Under such conditions,

the AST lasted 25.5 h before a short circuit occurred.
Table 2 e HFR measured on the CCM with a single HNC Comparison of CCM with one and two HNC membranes at
membrane during the AST.
BoT: A comparison of the data of Fig. 2b and Fig. 3b shows that
Time HFR (mU.cm2) the HFR is approximately the same at BoT despite the fact that
BoT 626 the number of membrane (and the polymer thickness) is
2h 649 doubled. This is attributed to the fact that the clamping pres-
4h 561 sure is different (1.5 MPa for the CCM with one HNC membrane
6h 528 and 3.5 MPa for the CCM with two HNC membranes).
8h 519
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
as discussed in the previous paragraph). However, the diam- increasing. As discussed before, the decrease of HFR is
eter of the semicircle tends to increase, indicating that the attributed to water sorption which leads to membrane soft-
charge transfer resistance of the oxygen evolution reaction is ening (i.e., decrease of tensile strength) and thickness reduc-
increasing. tion. However, after z12 h of AST, the resistivity of the
In conclusion, the results show that during the first hours membrane increases with time. Bulk membrane degradation
of AST, the mechanical properties of the HNC membrane can be suspected and a more detailed analysis of the situation
dictate the electrochemical behavior of the CCM. The loss of is discussed in section Degradation of the HNC membranes.
tensile strength resulting from water absorption leads to the Comparison of CCM with two HNC membranes and
formation of electrical short-circuits. Nafion-115 during the AST: A direct comparison of HFR values
measured at the BoT on the CCM with Nafion 115 (Table 1) and
CCM with two HNC membranes the CCM with two HNC membranes (Table 2) is possible
In an attempt to solve the short-circuit issue and to extend the because in both cases, the total polymer thickness is close in
duration of the AST, another CCM with two HNC membranes both cases (135 mm for Nafion 115 and 160 mm for the two HNC
placed side-by-side was prepared. The anode catalyst ink was membranes). The HFR measured on Nafion-115
deposited on the first HNC membrane while the cathode is z450 mU cm2 and the HFR measured on the two-HNC
catalyst ink was deposited on the secondone. As the thickness membrane is z 570 mU cm2. The ratio of the thicknesses is
of the membrane has been doubled (total thickness z 160 mm), close to the ratio of the HFRs. Therefore, the HNC membrane
a larger clamping pressure of 3.5 MPa was applied to reduce as has a specific conductivity close to that of Nafion at BoT.
much as possible the internal cell resistance while avoiding In conclusion, the beneficial effect resulting from the in-
any immediate risk of electrical short-circuit. The thickness of crease of the HNC membrane thickness is not sufficient to
the CCM thus obtained is close to the one made with the solve the short-circuit problems. It was therefore decided to
Nafion-115 (z140 mm), allowing direct performance compari- mechanically reinforce the CCM by introducing a poly-
son. This two half-coated membranes is denoted as phenylene sulphide (PPS) mesh between the two HNC mem-
HNCcathode | HNCanode. Details of the AST (current density cy- branes, in order to prevent as much as possible electrical short
cles and and chronopotentiometric cell response) are shown circuits. Results are discussed in the next paragraph.
in Fig. 3 a. EIS spectra recorded during the AST at different
time intervals are plotted in Fig. 3 b and the corresponding
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.

it may be induced by significant hydrolysis of the crosslinking

Table 3 e HFR of the two HNC membrane e based cell
evolution during the ASTs. imine bond, and rapid loss of the sulphonic function group.

Time HFR (mU.cm2)

Asymmetric two membranes CCM
BoT 572 In an attempt to further improve the chemical stability of the
6h 690
membrane, the half-coated HNC membrane at the anode was
12 h 694
18 h 719
replaced by half-coated Nafion 212 membrane to prevent the
24 h 787 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
CCM with two HNC membranes reinforced with PPS resistant to oxidative degradation [38]. Therefore, half-coated
In an attempt to mechanically reinforce the HNC membrane, HNC membrane (with Pt/C) was clamped with half-coated
as this is commonly done with PFSA materials [35], a PPS mesh Nafion 212 (with IrO2) inside the PEMWE cell under 3.5 MPa
(thickness of ca. 60 mm and porosity of ca. 48%) was pressed (denoted as HNCcathode |N212anode).
between two half-coated HNC membranes and clamped Even though the Nafion membrane improved the me-
directly inside the cell with a pressure of 5.5 MPa to ensure chanical strength of the CCM (i.e. no short-circuits occurred),
contact between the two membranes for the proton conduc- the asymmetric CCM electrochemical performances
tion from the anode catalyst layer to the cathode catalyst decreased gradually during the AST (Fig. 5a). Note that the
layer. The half-coated HNC membrane was prepared higher current density of the AST was diminished from 250 to
following the same procedure as for HNCcathode | HNCanode. 125 mA.cm2 after 11.5 h of the beginning of test to prevent
The life service during the AST was significantly improved to the high increase of the cell voltage above 2.1 V.
up to 55 h without short-circuit (Fig. 4a), giving more time to On the other hand, the HFR increased during the AST (Fig. 5
analyze, through EIS, the evolution of the HNC membrane b and Table 5) from 778 mU cm2 (beginning of test) to
during the AST. 4607 mU cm2 (end of test). These results show that the
The EIS spectra (Fig. 4b) show two semicircles. The new degradation of the HNC membrane is not solely driven by the
highefrequency small semicircle was ascribed to the HNC oxidative degradation at the anode. Therefore, bare HNC
membrane-membrane interface presumptively due to the membrane was clamped between two half-coated Nafion 212
relatively thick insulating PPS mesh sandwiched between the membranes.
two HNC membranes. The high-frequency cell resistance and
the diameter of the high-frequency semicircle both increased HNC membrane clamped between two nafion membranes
during the AST implying a loss of the ionic conductivity of the In a last attempt to significantly increase the life service of the
membrane (higher HFR, Cf. Table 4) since the mechanical HNC membrane for PEMWE, the membrane was sandwiched
strength of the CCM is ensured by the reinforcement The between two half-coated Nafion 212 membranes to limit the
second and larger semicircle observed at middle to lower release of functionalized silica nanoparticles leading to the
frequencies is attributed to the OER half-cell reaction [36]. This degradation of the membrane. The three membranes were
semicircle was almost constant during the test, thus showing then clamped inside the cell at a pressure of 3.5 MPa (denoted
the stability of the anode catalyst layer. N212cathode | HNC |N212anode).
The reason for the HFR stepwise change between 20 and The confinement of the HNC membrane between two N212
30 h of AST is not clear (1311e2413 mU cm2). We speculate that 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 the catalyst layer in the CCMs were estimated from the cyclic
(BoT) and then periodically. The chronopotentiometry was voltammograms (CV) using Eq. (1) [40]:
stopped periodically to re-assess the performance levels of
Z 

the CCMs. The full chronopotentiometry test is shown in Cs ¼ Idv 2ðv:DVÞ 3
Fig. 8. The voltage of Moderate HNC was not stable and
increased gradually. However, the loss of the electro- where Cs is the specific areal capacitance (mF.cm2), I is the
chemical performance of Moderate HNC is slower than the current density (mA.cm2), v is the scan rate (mV/s.) and DV is
High HNC and Low HNC respectively. In contrast, the elec- the voltage scan window (1.4 V).
trochemical performances of the reference CCMs (Lab-made Specific capacitance values deduced from the CVs shown
and Commercial) were more stable with insignificant voltage in Fig. 10 are compiled in Table 6. The CVs (Fig. 10) show an
increase, as expected. increase of the specific areal capacitance (Cs) for the 4 lab-
After 11 h, the Low HNC voltage reached the End-of-Life made CCMs, namely the Lab-made reference CCM with the
voltage (i.e. 2.3 V). Consequently, HNC membranes were highest Cs of 36.9 mF/cm2, very close to the Commercial
removed for Low HNC and High HNC for the analysis of the reference CCM (38 mF cm2).
degradation mechanism while the best performing HNC CCM At the end of the AST, Cs values range from 19.1 to
(Moderate HNC) was kept in the stack. Note that when the 25.7 mF.cm2. A comparable Cs values were previously re-
stack was opened, the presence of droplets of a yellow liquid ported for CCM having equivalent catalyst loadings [41,42].
was observed and collected on the bipolar plate for the anal- The value range is lower than the reference CCMs
ysis of the degradation products (emphasized in Section (36.9e38.2 mF.cm2) in similar test conditions. To some
Degradation of the HNC membranes). In agreement with the extent, this is an indication that less catalyst is in contact with
chronopotentiometry, iV measurements (Fig. 9) showed that the polymer electrolyte.
both reference CCMs (lab-made and Commercial reference) At the end of the electrochemical characterization, the
are relatively stable compared to all HNC containing CCMs. stack was opened, and the last HNC membrane was removed.
The specific areal capacitances (the sum of the electric Similarly to Low HNC and High HNC, a yellow liquid was
double-layer capacitor (EDLC) and the pseudo-capacitance) of 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 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
The as-received HNC membrane has the following charac- mg/100 cm2 (24% weight less than the initial value), and an IEC
teristics: areal density of 1105 mg/100 cm2 and an Ion Ex- of 0.91 meq/g (50% less than the initial value). Finally, the HNC
change Capacity (IEC) of 1.8 meq/g. On the one hand, the HNC membrane of Moderate HNC had a very low IEC of less than 0.1
membrane extracted from Low HNC had an areal density of meq/g, 95% less than the initial IEC. Furthermore, this mem-
820 mg/100 cm2 (25.8% less than the initial weight) and an IEC 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 cm). The excess water was removed from the collected yellow
groups in the Moderate HNC membrane during the 225 h of liquid using the rotary evaporator, and a polymeric resin film
electrolysis. was deposited on the wall of the glass flask. After scratching
On the other hand, the collected resin liquid had a pH of ca. the polymeric films, an amount of 400 mg was obtained.
2 (acidic) and an ionic conductivity of 1204 mS/cm, which is The chemical modifications of the HNC membrane
4000 times higher than initial water before electrolysis (0.3 mS/ 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- “as-received” HNC membrane contains two phases: PVDF-HFP
trolysis and the collected resin (Fig. 11). (host matrix) and the SiO2-grafted PSSA (ionic conducting
The FT-IR spectra of the HNC membrane of Moderate HNC phase). The crystalline a-phase was identified in the FT-IR
reveals a complete absence of the characteristic PSSA peaks; spectrum of PVDFeHFP by the vibrational bands observed at
only the pure PVDF-HFP peaks are observed. This result is in 760, 790, 973, and 1210 cm1. Furthermore, the crystalline b-
agreement with the IEC titration measurements, which also phase of PVDF-HFP was assigned at 870 cm1. The CH2 bond
show that an insignificant amount of sulfonic groups remains wagging was detected at 1380 cm1, corresponding to the
present in the HNC membrane at the end of the test. In fact, 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- Elementary analysis of bare HNC membrane, the one
zene ring. The out-of-plane bending of CeH in a 1,4-substituted recovered from Moderate HNC CCM after electrolysis and the
benzene ring was assigned at 664 cm1. Meanwhile, the CeH dried collected resin were performed with energy-dispersive
wagging and bending were observed at 775 and 830 cm1, X-ray spectroscopy (EDS). Before electrolysis, HNC mem-
respectively. The in-plane deformation of the benzene ring was brane has an initial sulfur-to-fluorine ratio of 1:10.5 (Table 8).
detected at 1004 and 1031 cm1. The presence of O]S]O vi- The Sulfur-to-fluorine ratio decreased by 22 times (1:234.5, a
bration stretching at 1125 and 1210 cm1 is specific to the sul- reduction of 95.5%) as well as the Oxygen and the Silicon
fonic groups of the PSSA [46e48]. An overlap between the O] content after the electrolysis as a result of the loss of proton
S]O stretching of the PSSA and the vibrational band of crys- conductive sulfonic groups. These observations are consistent
talline a-phase PVDF-HFP can be observed at 1210 cm1. The with the decrease of the IEC and the areal density of the HNC
FT-IR peaks of PVDF-HFP and PSSA are summarized in Table 7. 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- Conclusion
trolysis. It loses matter and, most importantly, its functional
property (i.e. proton conductivity). In the present study, we evaluated the interest of replacing the
The HNC membrane was initially developed for fuel cell existing PFSA polymers by a new type of hybrid nano-
applications [29], where the quantities of water present are composite (HNC) material. An innovative multi-layer
less than in water electrolysis (i.e. humidified gases vs water approach was developed throughout this work aiming to
circulation). The large electro-osmotic water flow which takes extend the lifespan of the HNC membrane in PEMWE opera-
place during electrolysis accelerates the degradation of the tion. It consists of sandwiching more than one proton ex-
membrane. The silica nanoparticles functionalized with poly change membrane (HNC and/or Nafion) to form the Catalyst
(styrene sulfonic acid) dispersed in the PVDF matrix of the Coated Membrane (CCM). The electrochemical testing of
HNC may be extracted from the polymer matrix by electro- different configuration of HNC membrane based CCM, at the
phoresis or by simple elution. laboratory scale (4 cm2) and at large scale (250 cm2) high-
lighted that the bulk HNC membrane itself is not stable under
Mechanism of the HNC membrane degradation the conditions of PEM water electrolysis. The membrane ex-
PEM water electrolysis technology requires excess hot water hibits high chemical instability in the presence of liquid water
(e.g. 60  C) to improve the kinetics of the electrocatalytic water (mainly the hydrolysis of both imine and enamine bonds and
splitting [1]. The HNC suffers from two major deficiencies: the the degradation of PSSA polymer), even at rest conditions.
imine and enamine functional group instability and the During electrolysis, this leads to a rapid increase in the cell
oxidative degradation of the polystyrene sulfonic polymer. voltage, due in particular to the loss of proton conduction.
In the case of the HNC membrane, the imine and enamine By analyzing the degradation processes in more detail, we
functional groups are susceptible to acidic hydrolysis mean- were able to emphasize that the core of the membrane are
ing that they are susceptible to be thermally decomposed to mechanically and chemically weak leading to a loss of acid
amine and carbonyl groups in water and an acidic medium functions and accelerated degradation in PEMWE operation
(Fig. 12) [49]. The stability of these functional groups is affected (rapid increase in the cell voltage). From a mechanical point of
by numerous issues. view, the HNC membrane brought into contact with liquid water
is subject to softening and strong dimensional changes. This
(i) the imine bond of the HNC polymer is not stable by weakens its mechanical strength, which can promote electrical
reason of the acidic sulfonic groups which ensure the short circuits during electrolysis. On the chemical side, the hy-
proton conductivity and the acidity of the membrane, drolysis of the acid functions occurs as soon as the membrane is
(ii) the protons' migration inside the membrane (when a DC exposed to liquid water. Furthermore, styrene sulfonic groups
electric voltage is applied) will increase the chance of exposed to the positive voltage of the anode are also suspected to
attacking the imine bond by protons and accelerate the be unstable and to undergo electrochemical oxidation. These
degradation of the imine bonds, various weaknesses contribute to reduce operating times, which
(iii) the enamine bonds are nucleophilic owing to their sig- are incompatible with the target applications.
nificant resonance form with a negative charge on the Eventhough we succeeded in increasing the longevity of
alpha carbon (susceptible to hydrolysis in concentrated the HNC membrane from a few hours to a few hundred hours
acidic media), by our multi-layer approach (clamping the HNC membrane
(iv) the imine and enamine undergo tautomerization: between two half-coated Nafion 212 membranes), it did not
enamine can transform into imine and vice versa. prevent its degradation. One can thus conclude that
these types of hybrid nanocomposite membranes require
Additionally, the polystyrene sulfonic polymer is also not improvement in their chemical structure by a completely new
stable and prone to oxidative degradation, as shown in Fig. 13. chemistry that resist to hydrolysis and increased crosslinking
Under the harsh operating conditions of water electrol- degree to improve the stability of this electrolytic material.
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
Declaration of competing interest
at the anode catalyst layer/electrolyte interface. This can
result in the disruption of the structure's regularity thus
The authors declare that they have no known competing
accelerating the membrane's degradation. The OHC can
financial interests or personal relationships that could have
rapidly react with the ortho carbon of aromatic rings, form-
appeared to influence the work reported in this paper.
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 Acknowledgement
tertiary protons and forming benzyl radicals (Fig. 13, Reac-
tion B), followed by chain scission and polymer degradation. This work was financially supported by Storengy. Dr. Nelly
The oxidative radical attached to the tertiary carbon of the Rameau and Dr. Benoit Blondel from CEA are acknowledged
benzyl groups can then cause polymer chain scission (Fig. 13, for the synthesis of the HNC membrane. The authors also
Reaction C) [52]. 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 2 101

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