Journal of Power Sources 274 (2015) 636e644

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Journal of Power Sources

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Assemblies of protective anion exchange membrane on air electrode

for its efcient operation in aqueous alkaline electrolyte

dric Vancaeyzeele, Se

verine Alfonsi, Odile Fichet*
Bruno Bertolotti, Linda Chikh, Ce
Laboratoire de Physicochimie des Polym
eres et des Interfaces (LPPI e EA 2528) e I-Mat e Universit

e de Cergy-Pontoise e 5, mail Gay-Lussac, 95031 CergyPontoise, France

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

Air electrode stability is increased

from 50 to 650 h in alkaline
electrolyte.

Network and IPN protecting membranes are synthesized over the air
electrode.

The additional polarization due to the
membrane/electrode interface is
negligible.

The membrane/air electrode assembly can be regenerated.

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 27 August 2014
Received in revised form
4 October 2014
Accepted 13 October 2014
Available online 20 October 2014

Aqueous alkaline metal-air batteries represent promising energy storage devices when supplied with
atmospheric air. However, under this condition, the air electrode shows a very short life time (i.e. 50 h of
operation in 5 M LiOH at 10 mA cm2), mainly due to the precipitation of carbonates inside the
electrode porosity. The air electrode can then be protected by an anion exchange membrane on the
electrolyte side. In this paper, we demonstrate that the efciency of this protective membrane depends
on the assembly method on the electrode. When a modied poly(epichlorohydrin) (PECH) network is
synthesized directly on the electrode, the polymer seeps inside the electrode porosity, and a suitable
interface inducing negligible additional polarization in comparison with classical pressure-assembled
membranes is obtained. This protected electrode shows improved stability of up to 160 h of operation
in 5 M LiOH. This performance is improved to 350 h by adjusting the conductivity and the ionic exchange
capacity. Finally, the interest of interpenetrating polymer network (IPN) architecture compared to a
single network is conrmed. Indeed, an electrode protected with a PECH/poly(2-hydroxyethyl methacrylate) (PHEMA) IPN is stable for 650 h in 5 M LiOH. In addition, degradation process becomes reversible
since the assembly can be regenerated, which is not possible for the bare electrode.
2014 Elsevier B.V. All rights reserved.

Keywords:
Membrane/electrode assembly
Anion exchange membrane
Interpenetrating polymer networks
Non-treated air
Metal-air battery

1. Introduction
Air electrodes are widely used as positive electrodes in energy
conversion and storage systems such as fuel cells and metal/air

* Corresponding author. Tel.: 33 134 257 050; fax: 33 134 257 071.
E-mail address: odile.chet@u-cergy.fr (O. Fichet).
http://dx.doi.org/10.1016/j.jpowsour.2014.10.079
0378-7753/ 2014 Elsevier B.V. All rights reserved.

batteries [1]. The electrode has usually a three-layer structure

composed of a current collector, a hydrophobic gas diffusion layer
and a porous active layer [2]. The special feature of these electrodes
is that the active component, i.e. oxygen, for discharge process
(Equation 1) is not stored in the electrode material but comes from
atmospheric air. The capacity of the air electrode is therefore
considered as unlimited.

B. Bertolotti et al. / Journal of Power Sources 274 (2015) 636e644

O2 2H2 O 4e /4OH

(1)

Use of the air electrode in presence of alkaline electrolyte leads

to an increase of the reaction kinetic, and allows the use of cheaper
catalysts based on non-noble metals in the active layer [3,4].
However, if the air electrode is supplied with atmospheric air
instead of pure oxygen, carbon dioxide contained in air reacts with
liquid alkaline electrolyte (LiOH, KOH, etc.) leading to carbonate
formation [5,6]. When insoluble carbonates precipitate inside air
electrode porosity, the electrode structure is damaged leading to a
decrease in the electrochemical activity [7]. This side reaction has
been identied as the main cause of ageing of air electrodes
working in alkaline electrolyte [8]. The most common ways to avoid
the deleterious inuence of carbon dioxide are to remove it by
using CO2 scrubbers or to supply the electrode with pure oxygen.
However, these strategies reduce substantially the interest of air
electrode (unlimited capacity).
Under atmospheric air and in alkaline environment, one solution to preserve the electrochemical performance of the air electrode is to protect it with a polymer membrane positioned on the
electrolyte side. This membrane must ensure the hydroxide conduction required for electrochemical reactions occurring at the
electrode. It must also prevent transport of cationic species (K, Li,
Zn2, etc.) from the electrolyte towards the reaction zone to limit
carbonate formation inside the air electrode structure (Fig. 1). To
our knowledge, very few publications report experimental results
on the assembly method of an air electrode with a polymer
membrane in a conguration comparable to that of an aqueous
metal-air battery. However, the assembly method is important
because the presence of the protective membrane induces an
additional polarization that reduces the battery performance.
The contact between the catalyst layer and the membrane must
be as good as possible in order to reduce the contact resistance
which strongly depends on the membrane-electrode assembly
(MEA) process. In a common manufacture process, the electrolyte
membrane is hot pressed over an air electrode. Some publications
have studied the effect of clamping pressure on the performance of
fuel cells [9,10]. As the air electrode is a porous medium, it is highly
sensitive to the clamping pressure: the thickness, the porosity and
permeability of the MEA change with the applied pressure, thus
modifying the electrochemical performance. For instance, Okur et al.
[11] optimized recently the parameters of assembly for a fuel cell by
taking account of the manufacturing cost and difculties in operating conditions. The maximum power density was obtained when
assembly is carried out at 97  C for 3.6 min and at 66 kg cm2
pressure. In the case of an aqueous zinc-air cell, the air cathode was
protected with a pressure assembled poly(methylsulfonio-1,4phenylenethio-1,4-phenylene triuoromethanesulfonate) membrane sandwiched between the anode and air cathode electrode
[12,13]. The efciency of this conductive membrane was compared
with that of the commercial Celgard membrane. The polysulfonium
based membrane is effective in preventing cation permeation and

Fig. 1. Schematic representation of anion exchange membrane protected air electrode.

637

the cell capacity was increased (0.6 V, 124.8 h, 86.4 mAh g1)
compared to the use of Celgard as separator (1.32 V, 70.5 h,
14.5 mAh g1). More recently, an air electrode was protected by a
hydrogenated anion exchange membrane containing quaternary
ammonium groups (1.4 meq. g1, thickness: 27 mm) supplied by
Tokuyama Corp. This membrane was associated to a homemade air
electrode by hot-pressing [14]. The modied electrode was tested in
half-cell, in a equivalent conguration to that used in rechargeable
metaleair batteries, with 4 M KOH(aq). It showed a decrease of about
0.16 V in the oxygen reduction reaction at 10 mA cm2, accompanied by a resistance increase from 13 to 27 U cm2. No other information of the capacity of the battery is detailed.
Finally, interpenetrating polymer networks (IPN) were also
developed as solid anion-exchange membranes to protect an
electrode working in concentrated LiOH environment [15]. Those
IPN membranes associate an anionic conducting network: poly(epichlorohydrin) (PECH) modied with 1,4-diazabicyclo-[2,2,2]octane (DABCO), with cross-linked poly(2-hydroxyethyl methacrylate) (PHEMA) in different mass proportions. These membranes
were assembled over the air electrode by slightly pressing at room
temperature. The modied air electrode exhibits discharge stability
ten times higher than the bare air electrode under the same conditions (10 h at rest/10 h at 10 mA cm2 cycling).
The polymer membranes are thus generally synthesized beforehand and then applied by pressing on the air electrode [16].
However, the quality of the interface between this membrane and
the air electrode is primordial. Indeed, the electrochemical reaction
takes place at the three phase boundary formed by the electrolyte,
solid catalyst and gas. Thus, a high degree of intimacy between the
catalyst particles and the membrane is required to allow for oxygen
diffusion during electrode operation [17]. This is why the rst
purpose of this paper is to study the effect of the interface between
the air electrode and polymer membrane on the stability of the
assembly working in alkaline electrolyte. In a second time, the effects of conductivity and selectivity of the polymer membrane on
the electrode stability will be particularly studied. Indeed, the
membrane conductivity and selectivity have to be as high as
possible in order to get simultaneously a reduced additional
induced polarization and a reduced carbonate formation. PECH
crosslinked with DABCO (PECH network) has been chosen as
polymer membrane because its conductivity and selectivity is
easily modied by adjusting the DABCO crosslinker proportion.
Ammonium groups created during the cross-linking reaction acting
as cationic functions also. Stability tests were systematically performed to conrm efciency on the electrode protection. To
conclude, the optimized process has been transferred to a PECH/
PHEMA 68/32 wt.% IPN membrane previously developed.
2. Experimental
2.1. Materials
Poly(epichlorohydrin) (PECH) modied with 0.10 eq.
1,4-diazabicyclo-[2,2,2]-octane (DABCO) was purchased as
solution (18 wt.% PECH) in dimethylformamide (DMF)
from ERAS Labo (France). 2-hydroxyethyl methacrylate (HEMA SigmaeAldrich), ethylene glycol dimethacrylate (EGDMA
cross-linker e SigmaeAldrich), potassium hydroxide (KOH > 90% e
SigmaeAldrich), DABCO (Acros Organics), DMF (Acros Organics)
and lithium hydroxide (LiOH 98% e Acros Organics) were used
without further purication. Free-radical initiator 2-20 -azobisisobutyronitrile (AIBN) from SigmaeAldrich was recrystallized in
methanol before use.
All the electrolyte solutions (KOH and LiOH solutions) were
prepared with deionized water.

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B. Bertolotti et al. / Journal of Power Sources 274 (2015) 636e644

The air electrode (E5), purchased from Electric Fuel, is

composed of a porous polytetrauorethylene (PTFE) lm combined
with a cobalt based catalyzed carbon supported on a nickel grid.

neutralized HCl solutions were titrated with a 0.1 M KOH solution.

IEC was calculated from the ratio of the difference between HCl
molar before (mmolHCl,O) and after immersion (mmolHCl,E), and the
dried material weight (Wd).

2.2. Membrane synthesis

mmolHCl;O mmolHCl;E
IEC mmol g1
Wd

2.3. Characterization
After synthesis, the membranes were dried under vacuum at
70  C for 3 days. Soluble fractions (non-crosslinked fraction in the
material) of PECH networks and PECH15/PHEMA IPN were quantied by extraction of a known weight of dry material (W0) in a
Soxhlet apparatus with DMF for 72 h. After extraction, materials
were dried under vacuum at 70  C for 3 days and weighted (WE).
The soluble fraction (SF) was calculated as a weight ratio:

SFwt:%

W0  WE
100
W0

(2)

The soluble fractions were analyzed by NMR spectroscopy. The

H and 13C NMR spectra were recorded with a Bruker Avance DPX250 spectrometer (1H NMR 250 MHz and 13C NMR 62.9 MHz) in
deuterated DMSO (SigmaeAldrich) with tetramethylsilane (TMS e
Acros Organics) as internal standard.
For the characterization of the membranes and their assembly in
their OH form, all PECH networks, IPN and membrane-electrode
assemblies were immersed just after synthesis in 1 M KOH for 3
days to remove DMF and to exchange Cl with OH ions. Finally, the
membranes were rinsed with pure water until neutral pH, and the
assemblies were analyzed without further treatment.
Water uptake was determined by measuring the weight difference of water swollen and dried materials. The water swollen
materials were wiped rapidly and weighted (Ww). They were then
dried at 70  C until constant weight (Wd). The water uptake (WU) is
calculated as follows:

(4)

Intrinsic ionic conductivity was measured on water swollen

samples by electrochemical impedance spectroscopy using a BioLogic Science Instruments VSP potentiostat. Samples were put between two platinized blocking electrodes. Nyquist plots were
recorded with a Frequency Response Analysis (FRA) over frequency
range of 1000 kHz e 10 Hz with oscillation amplitude of 10 mV.
Electrical resistance (R) was measured from the intercept of the
Nyquist plot at high frequency with the real impedance axis. The
ionic conductivity is then calculated as:



s S cm1

l
RS

(5)

where l and S denote the thickness and the surface of the material,
respectively.
Membrane transport numbers (t) were determined according
to a static method (AFNOR NFX45 e 200e1995) derived from
Henderson's equation [18]. The membrane separates the cell in two
compartments each containing KOH solutions with concentrations
of 0.1 and 1.0 mol L1. The voltage measured between two Hg/HgO
electrodes immersed in each compartment is the sum of Nernst
potential (ENernst) and membrane potential (EM). The anionic
transport number is calculated as:


t 1 2 1
=

The single PECH network was synthesized by pouring the PECH

solution into a closed mold made from two glass plates clamped
together and sealed with a 500 mm Teon gasket. It was heated at
100  C for 4 h. A homogeneous and transparent PECH membrane
swollen with DMF is obtained. When the DABCO proportion is
increased in the PECH network, the appropriated DABCO quantity
was dissolved in PECH solution so that molar DABCO concentration
is increased to targeted proportion of 0.15 and 0.20 eq. and the
same protocol was applied. Single PECH networks are designated as
PECHx, where the subscript X refers to DABCO proportion in mol %
per PECH repeat unit.
PECH15/PHEMA 68/32 IPN contains 68 and 32 wt.% in the dry
nal material of PECH and PHEMA, respectively. It is synthesized by
adding the PHEMA network precursors to the PECH solution.
Accordingly, 10 g PECH solution were mixed with 0.097 g DABCO
(0.867 mmol) and stirred until complete dissolution. 0.089 g
EGDMA and 0.804 g HEMA were added. The mixture was stirred
under argon for 10 min and then 0.036 g AIBN was added (4 wt.%
methacrylate monomers). The solution was stirred under argon for
10 min. The solution was then injected in the mold previously
described, which was then heated at 70  C for 2 h and at 100  C for
4 h.

F
EM
RT lnaKOH;1M /aKOH;0:1M


(6)

where F is Faraday constant, R gas constant, T temperature, and a

activities of different KOH solutions (aKOH,1M 0.756 and
aKOH,0.1M 0.0798 [19]).
Scanning Electron Microscopy (SEM) images of dried modied
electrodes were recorded with an S430i LEICA microscope without
further treatment because they are electron conductive. EDX
measurements were performed simultaneously with a detector
SYNERGIE 4 Quantax from Bruker.

WUwt:%

Ww  Wd
100
Wd

(3)

Ionic Exchange Capacity (IEC) of the membranes was determined

by titration. The membranes in hydroxide form were immersed for
24 h in 10 mL of a 0.1 M HCl solution. After this period, partially

2.4. Membrane/electrode assemblies and electrochemical

characterization
Two types of membrane/electrode assembly (MEA) were prepared. For the ex-situ assembly, the polymer membrane was synthesized beforehand (Section 2.2). The water swollen membrane
was then placed on the air electrode, placed between two Teon
plates and pressed at 3 bar and 60  C for 30 min. To ensure ionic
contact between the PECH membrane and the air electrode, a
concentrated PECH solution was used as membrane solution. For
the in-situ assembly, the polymer membrane was directly synthesized on the air electrode. The reaction solution was poured over
the catalyst side of the air electrode, and placed between two glass
plates sealed with a 500 mm Teon gasket.
Electrochemical characterizations were performed in a conventional three-electrode homemade half-cell. The modied air
electrode with active surface of 0.78 cm2 was used as working
electrode. Hg/HgO/1 M KOH electrode was used as reference, and
large area platinized titanium grid as counter electrode. 5 M LiOH
aqueous solution was used as alkaline electrolyte. All measurements were carried out at ambient temperature and under

B. Bertolotti et al. / Journal of Power Sources 274 (2015) 636e644

atmospheric pressure with untreated air. The air-electrodes were

equilibrated with electrolyte for at least 1 h before starting
measurements.
Potential vs. current density (polarization) curves were recorded
by applying different current densities, in step-wise increases
from 1 to 30 mA cm2. Each current density was maintained
until a stable potential was reached and then measured.
Electrode potential vs. time (stability) curves were recorded by
cycling air electrode for 10 h at open circuit voltage followed by a
10 h at 10 mA cm2 current density. This cycling was chosen to
reproduce the operation of the air electrode in the bi-electrode
conguration during full cell cycling [20]. This conguration consists of an air electrode in combination with another electrode on
which the charge occurs [21] in order to prevent the air electrode
degradation. For readability, only potential at the end of each
discharge step was reported vs. time on the stability curves. The
stability time of the assembly is determined when the air electrode
potential reaches 400 mV/(Hg/HgO).
3. Results and discussion
An air electrode supplied with atmospheric air, containing carbon dioxide, in presence of alkaline electrolyte, is rapidly damaged
by carbonate formation in its porous structure. To slow this
degradation, a polymer membrane can be placed on the active layer
of the air electrode. This polymer membrane allows hydroxide
conduction from the catalytic layer to the electrolyte while preventing the transport of cations from the electrolyte to the catalytic
layer. It should also diminish permeation or leakage of alkaline
electrolyte into the gas-diffusion layer. However, the presence of
the membrane must not cause an excessive increase of the polarization of the modied electrode in order to maintain its performance. Therefore, we have studied the effect of the membrane
properties and of the assembly process of the membrane on the air
electrode on the electrochemical performance and lifetime of an
air electrode, under atmospheric air and concentrated alkaline
electrolyte.
3.1. Membrane/electrode assembly (MEA) optimization
Poly(epichlorohydrin) (PECH) can be cross-linked by 1,4diazabicyclo[2.2.2]octane (DABCO), according to a nucleophilic
substitution reaction (SN2) between one tertiary amine and a secondary carbon a-to a chloride atom of PECH (Fig. 2). This reaction
simultaneously allows the crosslinking of the polymer and the
introduction of cationic sites on the backbone. In addition, these
cationic sites have been reported as particularly stable towards the

639

Table 1
Characteristics of dried and non-dried PECH10 membranes before anion exchange.
PECH10 network membranes

Conductivity (mS cm1)

Water uptake (wt.%)

Dried
Non-dried

1.8
0.4

200
1200

Hofmann degradation reaction [22] generally observed on polymers bearing quaternary ammonium groups in alkaline electrolyte.
Some characteristics of dried or not dried PECH10 membranes
before anion exchange were reported in Table 1. The dried membrane has a higher conductivity (1.8 mS cm1) and a greatly
reduced water swelling (200 wt.%) compared to the non-dried one
(conductivity 0.4 mS cm1 and water uptake 1200 wt.%). This difference can be due to a post-crosslinking of the membrane during
drying, leading to higher crosslinking, and thus a higher number of
ionic sites.
First, we investigated the effect of assembly process of the
PECH10 network membrane on the interface resistance, by
recording the polarization curves (Fig. 3).
The bare air electrode potential is about 30 mV/(Hg/HgO)
at 1 mA cm2 current density, and attains a value of 130 mV
at 10 mA cm2. The ex-situ assembly is prepared with a PECH10
network membrane synthesized beforehand, dried and OH
exchanged that is pressed on the electrolyte side of air electrode.
The membrane adheres slightly to the air electrode and the assembly potential is higher than 1 V (results not shown). This high
polarization indicates an important resistance due to an insufcient
ionic contact between the electrode and the membrane. Thus, to
improve this ionic contact, a concentrated PECH solution in DMF
(~18 wt.%) is used as adhesive membrane solution [23]. In this
conguration, the membrane/electrode assembly shows a polarization of 500 mV at 10 mA cm2. Thus the PECH membrane
induces an additional polarization of 370 mV compared with the
bare electrode at this current density. These rst results show that
while the ionic conductivity of the dried PECH membrane seems
most appropriate, the complete drying of the membrane leads to
the excessive increase of the polarization of the modied air electrode. In order to decrease this additional polarization induced by
the membrane, it was not dried before anion exchange. Only slight
pressure is applied for assembly because the PECH network is
fragile due to its high water uptake (1200 wt.%). When the nondried PECH10 network is assembled over the electrode without
membrane solution, the polarization of the modied electrode is
equal to 700 mV at 10 mA cm2. In addition, when this membrane is assembled with the membrane solution, the potential
decreases from 700 to 400 mV at 10 mA cm2 corresponding
to a reduced additional polarization of 270 mV compared with bare

Fig. 2. Nucleophilic substitution between DABCO and PECH leading to the crosslinking of polymer.

640

B. Bertolotti et al. / Journal of Power Sources 274 (2015) 636e644

Fig. 3. Polarization curves recorded on bare air-electrode (C), air electrode modied
with dried PECH10 network associated with membrane solution (, e Photo A) and
with non-dried PECH10 network without () and with (B e Photo B) membrane solution. Inserted photos are taken after test in half-cell.

air electrode. After the polarization tests in half cell, the assemblies
are removed from the half-cell. The PECH10 membranes are broken
and detached from the electrode (photos inserted in Fig. 3). The
interface between the electrode and the membrane is not preserved, and once the PECH10 network is damaged, the air electrode
is exposed to the electrolyte.
Consequently, high polarization of these assemblies along with
the physical damage of the membrane make this assembly method
inadequate for the application, and a new approach is studied to
assemble the polymer membrane on the electrode.
3.2. In-situ membrane/electrode assembly
To obtain a better interface between electrode and polymer
membrane, this later is synthesized directly over the air electrode.
Synthesis solution is thus expected to impregnate the air electrode
and effectively cover the catalyzed carbon black particles. This insitu assembly was made by pouring the PECH10 reaction solution
directly over the catalyst side of the air electrode, placed between
two glass plates (Fig. 4A). Membrane thickness was xed by the
Teon gasket, which acts also as hermetic seal during reaction.
The mold was heated at 100  C for 4 h. Previously, we checked that
the air electrode was not damaged by this synthesis process: its
potential-current density and potentialetime curves were not
altered by temperature and solvent presence. After synthesis, the
in-situ assembly is easily unmolded (Fig. 4B).
To compare the impregnation of the polymer solution into the
catalyst layer according the assembly process, a transversal cut of
ex-situ and in-situ PECH10 network/air electrode assemblies have
been observed by scanning electron microscopy (Fig. 5). EDX analyses were simultaneously recorded on both assemblies and
different elements (i.e. Cl, C, Ni, and Si) have been identied.
However, only the distribution of chloride in the assemblies is
interesting because it is only present in the polymer membrane. In

the in-situ assembly, chloride atoms are found inside the catalyst
layer conrming that the PECH polymer has diffused in the catalyst
layer (Fig. 5D), covering a higher surface of carbon black particles. In
the same analysis of an ex-situ assembly carried out with a
concentrated PECH solution as adhesive membrane solution
(Fig. 5B), the chloride signal is not observed inside the air electrode.
Thus the polyelectrolyte does not diffuse inside the catalyst layer
which can explain the poorer interface between the electrode and
the membrane.
The polarization of the in-situ assembly is then measured and
compared with those of the bare electrode and the ex-situ assembly
(Fig. 6).
The potential of air electrode modied according to the in-situ
assembly was 200 mV at 10 mA cm2, i.e. only 70 mV polarization higher than that of bare electrode. This additional polarization is about four times smaller than that of the corresponding exsitu assembly. This reduction is due to a better interface between
polymer membrane and electrode. The in-situ assembly resistance
calculated from the slope of linear part of polarization curve is only
12 U cm2, i.e. only an additional resistance of 3 U cm2 (the resistance of bare electrode is 9 U cm2).
Fig. 7 shows the evolution of the potential as function of time
of air electrode modied with a PECH10 network according to the
in-situ assembly, by cycling 10 h at rest and 10 h at 10 mA cm2 in
5M LiOH. The same measurement carried out with non-modied
electrode is reported for comparison.
At the beginning of the rst discharge, the potential of in-situ
assembly is 200 mV/(Hg/HgO), and corresponds to the value
measured during the polarization test (Fig. 6). The potential of assembly decreases slowly during stability test, and it has
reached 400 mV after 160 h. The assembly stability is about 3
times higher than that of a bare electrode (50 h). These results
conrm that an air electrode functioning in 5 M LiOH aqueous
solution, with ambient air, is protected from the lithium carbonate
formation by applying an anion conducting membrane on the
electrolyte side. When the assembly polarization is higher
than 400 mV/(Hg/HgO), the PECH10 network modied electrode
shows no apparent damage (Photo inserted in Fig. 7) contrarily to
what has been observed with the ex-situ assembly.
A better method of assembly of anion-exchange membranes on
air electrode having been determined, the effects of the conductivity and selectivity of PECH membrane on the polarization and
stability of the assembly have been then studied.

3.3. Modication of the PECH network properties

DABCO contained in PECH network is responsible of antagonist
features. Indeed cationic sites formed in the PECH - DABCO reaction
are grafted on the polymer backbone and are responsible for ionic
conduction: the higher the DABCO concentration is, the higher
ionic conduction is and the higher water uptake is. However,
DABCO is also the crosslinker of PECH polymer: the higher the
crosslink density is, the lower the water uptake is. DABCO content

Fig. 4. (A) Schema of the mold for membrane synthesis over an air electrode and (B) Photo of 500 mm thick PECH10 network/air electrode assembly carried out by in-situ process.

B. Bertolotti et al. / Journal of Power Sources 274 (2015) 636e644

641

Fig. 5. SEM images of an (A) ex-situ and (C) in-situ PECH10/air electrode assemblies. 1: PECH10 network. 2: Current collector (Ni). 3: Catalyst layer. 4: PTFE lm separating electrode
from air. (B) and (D): Corresponding EDX analyses: carbon (red), chloride (blue), nickel (orange) and silica (green). (For interpretation of the references to colour in this gure legend,
the reader is referred to the web version of this article.)

can therefore signicantly affect the resulting properties of the

material, and has to be experimentally assessed.
Thus, PECH networks were synthesized with 15 and 20 mol %
DABCO with respect to chloromethyl function instead of 10 mol %
for the previous PECH networks. To conrm the PECH crosslink by
the additional DABCO, soluble fractions contained in these networks were determined by Soxhlet extraction for 72 h with DMF.
The soluble fraction decreases from 9 to 3 wt.% when the DABCO
content increases from 10 to 20 mol %. The increase in crosslinker
concentration reduces the probability of having free linear PECH in
the material, thus decreasing the soluble fraction. 1H and 13C NMR
analyses of soluble fractions allowed identifying non-crosslinked
PECH but did not reveal the presence of unreacted DABCO. These
results conrm that additional DABCO reacts with PECH.
Ionic exchange capacity (IEC) allows quantifying the number of
cationic sites per gram material and the hydrophilic behavior of the

Fig. 6. Polarization curves recorded on bare air electrode (C), and air electrode
modied with non-dried PECH10 network according to () in-situ and (B) ex-situ (with
membrane solution) processes.

network can be assessed by water uptake measurement. These

different values are reported in Fig. 8A. IEC of PECH network increases from 0.8 to 2.0 meq. g1 when the DABCO molar proportion
is increased from 10 to 15 mol %. However, when DABCO content is
increased from 15 to 20 mol %, the IEC value was not signicantly
modied. An incomplete exchange of Cl counterions could lead to
the underestimation of the IEC value, as it has been already reported [20]. However, another reason for this underestimation
could be due to Manning counterion condensation onto the polyelectrolyte [24]: for many polyelectrolytes, an increase in the ionic
sites number is masked by the partial neutralization of ionic sites.
On the opposite, water uptake of the PECH networks increases
with increasing DABCO content from 1200 to 2400 wt.% for PECH10
and PECH20 networks, respectively. Thereby, the water uptake of
PECH network is doubled by only 5 mol % DABCO increase. The

Fig. 7. Stability curves of bare electrode (C) and a PECH10 modied electrode according to the (B) in-situ assembly method. Cycle: OCV for 10 h and 10 mA cm2 for
10 h e Inserted photo corresponds to in-situ PECH10/air electrode assembly after 150 h
of stability test.

642

B. Bertolotti et al. / Journal of Power Sources 274 (2015) 636e644

(Fig. 9A). The potential of assembly with PECH15 network is 30 mV

higher than that of the bare electrode at 10 mA cm2, while it is of
70 mV higher at the same current density with PECH10 network.
The total assembly resistances are calculated from these polarization curves. When DABCO molar proportion in the network is equal
to 15 mol %, the additional resistance becomes negligible; the assembly has the same resistance as bare air electrode (9 U cm2). As
expected, the increase of the membrane conductivity leads to a
reduction in polarization of the corresponding in-situ assembly.
This result is in agreement with the conductivity values of PECH10
and PECH15 networks, which are respectively equal to 0.4 and 0.9
mS cm1.
Bare electrode and assembly with PECH10 network are stable for
50 and 160 h, respectively, whereas air electrodes modied with
PECH15 network has a greatly improved stability of 360 h (Fig. 9B).
Thus, the optimization of the physicochemical characteristics of
the polymer membrane improves also the lifetime of the air electrode used in aqueous alkaline medium. Nevertheless, the membranes show excessive water swelling and are still fragile. To
improve these features, the combination of a PECH network with a
neutral polymer network through an interpenetrating polymer
network (IPN) architecture is studied.
3.5. PECH15/PHEMA 68/32 IPN/air electrode assembly

Fig. 8. (A) Ion exchange capacity (IEC) (C) and water uptake (B) and (B) ionic conductivity (-) and transport number t ( ) of PECH networks with different DABCO
contents.

We previously reported the synthesis of IPN membranes associating an anionic conducting PECH network and a poly(hydroxyethylmethacrylate) (PHEMA) network. The presence of the
neutral PHEMA network reinforces the mechanical properties
(G0 IPN 3.62 kPa and G0 PECH 1.62 kPa) of the protecting membrane and limits its water uptake. The air electrode modied with a
PECH10/PHEMA (68/32) IPN membrane according to an ex-situ
process assembly has a stability of 280 h in 5 M LiOH, compared to
50 h for the bare electrode [15]. These promising performances

concentration of cationic sites makes PECH network more hydrophilic despite the increasing crosslinking density.
As expected, all PECH networks are ion conducting (Fig. 8B):
they have a conductivity increasing from 0.4 mS cm1 for PECH10
network to 0.9 mS cm1 for PECH15 network. When the DABCO
proportion is increased up to 20 mol %, the ionic conduction of the
material is not improved, which is in agreement with the IEC
measurements.
Finally, selectivity towards cations of the different PECH networks has been checked by measuring transport numbers. All PECH
networks have similar transport number t of about 0.78, which is
intermediate between the values reported by Agel et al. [18] for
alkaline membranes: 0.95 for membranes dried after synthesis and
0.60 for alkaline gels. Thus, an increase in the DABCO content has no
inuence on t value while IEC value increases. It can be due to
dilution effect since the water uptake increases simultaneously to
reach a maximum value for PECH20.
From these characterizations, the PECH15 network with 15 % mol
DABCO per PECH repeat unit has been chosen for the next assemblies on the air electrode. Indeed, its ionic conductivity is sufcient
(about 1 mS cm1), and it is selective (t 0.78). This assumption is
conrmed by measurements of polarization and stability of in-situ
assemblies.
3.4. Polarization and stability of PECH15 network/electrode in-situ
assembly
Regardless the current density, the polarization of the in-situ
assemblies decreases as DABCO content increases in PECH network

Fig. 9. (A) Polarization curves and (B) potential at discharge vs. time curves for the
bare electrode (C), PECH10 () and PECH15 ( ) network modied electrodes according
to the in-situ process.

B. Bertolotti et al. / Journal of Power Sources 274 (2015) 636e644

should still be outperformed by the different improvements of the

assemblies, that is to say with the increase of DABCO content from
10 to 15 mol % for the PECH network and the in-situ assembly of the
membrane over the air electrode.
First, a PECH/PHEMA 68/32 IPN with 15 mol % DABCO was
synthesized. Its characteristics are compared to those of the single
PECH15 network (Table 2). PECH15 single network and PECH15/
PHEMA 68/32 IPN present a water uptake of 2200 and 1000 wt.%,
respectively. Thus, introduction of only 32 wt.% PHEMA in PECH15
network reduces the water uptake of the material by 2. IEC value
was equal to 1.3 meq. g1, as expected for an IPN containing 68 wt.%
PECH15 with an IEC value of 2.0 meq. g1. The ionic conductivity of
the PECH15/PHEMA IPN is 2 mS cm1, twice the conductivity of the
PECH15 network. This conductivity increase, while IEC is lower, can
be explained by the limited swelling. The charges are thus twice as
concentrated. No loss in selectivity is observed for the IPN
compared to the single PECH network. Finally, the IPN architecture
has been checked by recording tan detemperature curves by dynamic mechanical analysis (Q800 model, TA Instruments, 1 Hz
frequency, 3  C min1 heating rate). PECH15/PHEMA(68/32) IPN
show a unique mechanical relaxation at 110  C; i.e. a temperature
intermediate to those of the PECH15 network (Ta 80  C) and
PHEMA one (Ta 120  C). It demonstrates a satisfactory interpenetration degree in the IPNs.
This PECH15/PHEMA 68/32 IPN has been then directly synthesized over the catalyst side of the air electrode and the polarization
curves of in-situ assembly has been recorded (Fig. 10A). As for
PECH15 network membrane, the polarization of in-situ PECH15/
PHEMA 68/32 IPN MEA is low, 160 mV at 10 mA cm2 that is
closer to the value of bare electrode. These results conrm the
choice of the in-situ assembly method. In addition, the stability of
air electrode is increased to 650 h when it is modied with a
PECH15/PHEMA 68/32 IPN membrane (Fig. 10B). This stability is
twice that of the electrode modied with a single PECH15 network
(360 h). This improvement in the assembly stability can be
explained by the presence of the PHEMA neutral network which
limits the swelling by the alkaline electrolyte, increases the assembly conductivity without decreasing its selectivity. It demonstrated the efciency of the IPN architecture as protective
membrane to limit the carbonation inside the electrode. After the
stability test, no visible damage or delamination of the membrane
is observed conrming also the quality of the interface between the
polymer membrane and the electrode (Photo inserted in Fig. 10B).
To conrm the role of carbonate precipitation in the loss of
stability of air electrode, any possible precipitate has been removed
from 650 h tested air electrodes. For that, in-situ PECH15/PHEMA
68/32 IPN based assembly is rinsed by immersion in a large excess
of deionized water and water is changed daily during two weeks.
The same procedure is applied for a non-modied aged electrode as
a reference. No visible change is observed after rinsing. The
different air electrodes were then assembled in half-cell and their
stability was tested again (Fig. 11).
The low polarization of non-modied electrode is not recovered
after this rinsing, suggesting an irreversible damage. This can be
due to the modication or deformation of the catalytic layer of the
electrode by carbonate precipitate, as observed by Rolla et al. [8].

643

Fig. 10. (A) Polarization curves and (B) potential at discharge vs. time curves recorded
on the bare electrode (C), in-situ PECH15/PHEMA 68/32 IPN (:), and PECH15 ( )
modied electrodes. e Inserted photo corresponds to IPN/air electrode assembly after
650 h of stability test.

Inversely, the IPN modied electrode recovers its initial polarization and it is stable for more than 600 additional hours, despite a
higher polarization at the end of the rst stability test. These results
suggest that the IPN membrane protects the catalytic sites of
electrode from irreversible damage by the precipitate and delay
this carbonation reaction. They conrm also that the precipitation
of lithium carbonate causes the loss of stability of the air electrode.

4. Conclusion
When an air electrode is supplied with untreated air, it shows a
signicant increase in polarization after 50 h operation in 5 M

Table 2
PECH15 network and PECH15/PHEMA 68/32 IPN characteristics.
Membrane

Conductivity
(mS cm1)

Water uptake IEC

Transport
(wt.%)
(meq. g1) number t

PECH15
PECH15/PHEMA
68/32 IPN

0.9
2

2200
1000

2
1.3

0.79
0.74

Fig. 11. Initial stability curves for the non-modied electrode (C) and in-situ PECH15/
PHEMA 68/32 IPN assembly (:) and stability curves after the rinsing for the nonmodied electrode (B) and IPN assembly (D).

644

B. Bertolotti et al. / Journal of Power Sources 274 (2015) 636e644

LiOH. This lifetime is increased by protecting it with a PECH

membrane crosslinked with ammonium group membrane. We
achieved a very good interface between the electrode and the
polymer membrane by synthesizing directly the PECH network on
the air electrode (in-situ process), and obtained an initial polarization close to that of bare air electrode. Stability of the air electrode was increased from 160 to 350 h by increasing the DABCO
content in the PECH network from 10 to 15 mol %. This increase
corresponds to an increase in conductivity from 0.4 to
0.9 mS cm1 and the IEC from 0.8 to 2.0 meq. g1, for the PECH10
and PECH15 networks, respectively. The best performance obtained
with the PECH15 network is in agreement with its physicochemical
characteristics. These results conrm that the air electrode is
efciently protected from carbonation by a polymer membrane
placed on the electrolyte side. Finally, the interest of polymer
materials with interpenetrating polymer network architecture
compared to single polymer networks was clearly shown. Indeed,
the original combination of PECH and PHEMA networks inside IPN
decreases signicantly the PECH polyelectrolyte swelling while
preserving good hydroxide conductivity. Finally, the air electrode
stability is increased up to 650 h when modied with PECH15/
PHEMA 68/32 IPN according to the in-situ process. In addition, the
degradation process of the air electrode becomes reversible and
the assembly can be regenerated, which is not possible on the bare
electrode.
Acknowledgments
This work is sponsored by the Agence Nationale de la Recherche
(ANR) of France (ANR-10-Stock-E-LIO2). The authors would like to
thank Dr. Philippe Stevens and Dr. Gwenaelle Toussaint from EDF
France for many fruitful discussions.

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