Journal of Power Sources 274 (2015) 488e495

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Journal of Power Sources

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

Stability in alkaline aqueous electrolyte of air electrode protected with

uorinated interpenetrating polymer network membrane
dric Vancaeyzeele, Se
verine Alfonsi,
Bruno Bertolotti, Houssam Messaoudi, Linda Chikh, Ce
*
Odile Fichet
Laboratoire de Physicochimie des Polym
eres et des Interfaces (LPPI e EA 2528), I-Mat, Universit
e de Cergy-Pontoise, 5, mail Gay-Lussac,
95031 Cergy-Pontoise, 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

IPNs combining a polyelectrolyte

network with a uorinated one has
been developed.

IPNs show good conductivity and
cation selectivity, and limited water
swelling.

IPNs have been used to modify an air
electrode on its electrolyte side.

The modied air electrode works in
LiOH electrolyte with air for more
than 1000 h.

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 29 August 2014
Received in revised form
27 September 2014
Accepted 9 October 2014
Available online 17 October 2014

We developed original anion exchange membranes to protect air electrodes operating in aqueous
lithium-air battery conguration, i.e. supplied with atmospheric air and in concentrated aqueous lithium
hydroxide. These protective membranes have an interpenetrating polymer network (IPN) architecture
combining a hydrogenated cationic polyelectrolyte network based on poly(epichlorohydrin) (PECH) and
a uorinated neutral network based on peruoropolyether (Fluorolink MD700). Two phases, each one
rich in one of the polymer, are co-continuous in the materials. This morphology allows combining their
properties according to the weight proportions of each polymer. Thus, PECH/Fluorolink IPNs show ionic
conductivity varying from 1 to 2 mS cm1, water uptake from 30 to 90 wt.% and anionic transport
number from 0.65 to 0.80 when the PECH proportion varies from 40 to 90 wt.%. These membranes have
been systematically assembled on air electrodes. Air electrode protected with PECH/Fluorolink 70/30 IPN
shows outstanding stability higher than 1000 h, i.e. a 20-fold increase in the lifetime of the non-modied
electrode. This efcient membrane/air electrode assembly is promising for development of alkaline
electrolyte based storage or production energy systems, such as metal air batteries or alkaline fuel cells.
2014 Elsevier B.V. All rights reserved.

Keywords:
Interpenetrating polymer networks
Anion exchange membrane
Air electrode
Fluorinated polymer
Atmospheric air

1. Introduction
Standard air electrodes are composed of a mixture of carbon
black, catalyst and poly(tetrauoroethylene) (PTFE) binder, supported on a porous hydrophobic lm. Under operating conditions,

* 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.2014.10.059
0378-7753/ 2014 Elsevier B.V. All rights reserved.

the catalyst particles form porous and electronically conducting

agglomerates lled with electrolyte. The PTFE binder, which holds
together the catalyst layer, creates hydrophobic channels for gas
diffusion [1,2]. Thus, air electrodes are typically gas diffusion electrodes used in proton or direct methanol fuel cell, alkaline fuel cell
and in metal air batteries. However, technical barriers delay the
development of aqueous metal-air batteries supplied with ambient
air and operating with aqueous alkaline electrolyte. In these batteries, air electrode works as oxygen reduction electrode only.

B. Bertolotti et al. / Journal of Power Sources 274 (2015) 488e495

However, under those conditions, air electrodes show limited stability, mainly due to the reaction between carbon dioxide from
atmospheric air and the alkaline electrolyte, leading to carbonate
formation (Equation (1)). The precipitation of carbonate inside the
air electrode porosity blocks oxygen and hydroxide diffusion. As a
result, the resistance of the system increases, and a high increase of
the electrode polarization is observed after a few hours of operation, time being dependent on the solubility of the carbonate in the
electrolyte.
Under atmospheric air, a solution to achieve a better electrochemical stability of the electrode in alkaline environment is to
protect it with a polymer membrane placed on the electrolyte side.
This polyelectrolyte membrane must ensure the hydroxide conduction from the air electrode to the electrolyte for the electrochemical reactions (Equation (2)) and prevent the transport of
cationic species from the electrolyte towards the electrode to avoid
the carbonate formation (Equation (1)).

2M 2OH CO2 /M2 CO3 H2 O

(1)

O2 2H2 O 4e /4OH

(2)

Very few publications, to our knowledge, report experimental results of air cathodes protected with polyelectrolyte membranes for
aqueous metal-air batteries supplied with ambient air. Tsuchida
et al. [3,4] conceived an assembly of an aqueous zinc-air cell, in
which electrolyte is 1 M KOH and the air cathode was protected
with a poly(methylsulfonio-1,4-phenylenethio-1,4-phenylene triuoromethanesulfonate) membrane. The cell lifetime was thus
increased to 124.8 h instead of 70.5 h when a polypropylene
separator swollen with electrolyte was used as protecting membrane. More recently an air electrode has been modied with a
anion exchange polymer membrane containing quaternary
ammonium groups (1.4 meq g1, Tokuyama Corp.) and tested in
half-cell, under atmospheric air in the presence of aqueous 4 M
KOH [5]. The resistance of the modied electrode does not increase
when it is supplied with pure CO2 for 2 h while this is not the case of
the non-modied electrode. The cation selective membrane limits
the diffusion of cations in the electrode, and thus the precipitation
of carbonate in the pores of the air electrode.
Solid anion-exchange membranes based on interpenetrating
polymer networks (IPN) can be used as protecting membrane. IPNs
were dened by Sperling [6] as the combination of two or more
polymer networks synthesized in juxtaposition. The entanglement
of two cross-linked polymers into the IPN leads to forced miscibility
of usually incompatible polymer blends, and the resulting materials
exhibit a good dimensional stability. The purpose of this type of
polymer associations is generally to combine each partner's properties inside a homogenous material, due to a co-continuous
morphology of both polymer phases. Specic applications of
these materials have been developed due to their improved mechanical properties and solvent resistance. Thus, IPN membranes
have been developed to protect an air electrode working in lithiumair aqueous battery conditions [7]. These IPNs associate an anionic
conducting poly(epichlorohydrin) (PECH) network entangled
within a cross-linked poly(2-hydroxyethyl methacrylate) (PHEMA)
in different mass proportions. The IPN modied electrode exhibits a
stable potential for 300 h cycling (10 h rest e 10 h discharge), i.e. six
times higher than the bare electrode under the same conditions [8].
The air electrode stability has been then increased to more than
600 h by optimizing the interface between the polymer membrane
and the air electrode and the intrinsic properties of the membrane
(ionic conductivity and selectivity) [9].
Most of current research on new polyelectrolytes focuses on
hydrogenated linear or crosslinked polymers. No hydroxide

489

conductive hydrogenated/uorinated IPN, to our best knowledge,

are reported in the literature for anion exchange membrane
application certainly because the association of a uorinated
compound with a polyelectrolyte retaining the ionic conductivity of
the latter is a challenge [10,11]. However, the introduction of a
uorinated network inside the PECH ones should improve the
membrane physicochemical characteristics. Indeed, these membranes would be more chemically stable because uorinated
compounds exhibit exceptionally high chemical and thermal stability [12e14]. Furthermore, a reduced swelling of the membrane in
aqueous electrolyte due to the hydrophobicity of the uorinated
polymer should increase anion selectivity and chemical stability, as
observed in PEMFCs [15]. In ne, these membranes should increase
the stability in discharge of the IPN-modied air electrode.
Fluorolink MD700, a bifunctional urethane methacrylate peruoropolyether (PFPE) developed by Solvay Specialty Polymers
[16e18] was identied as polymer network precursor, and in a rst
time, syntheses of Fluorolink single network and PECH/Fluorolink
IPNs were achieved. In a second time, physicochemical characterization of these IPNs and the electrochemical behavior of IPNs
membrane/electrode assemblies supplied with atmospheric air
were evaluated in the presence of 5 M LiOH electrolyte.
2. Experimental
Poly(epichlorohydrin) (PECH) modied with 0.10 eq. 4diazabicyclo-[2,2,2]-octane (DABCO) by PECH repeat unit was
purchased as 10 wt.% solution in dimethylformamide (DMF) from
ERAS Labo (France). Free-radical initiator 2-20 azobisisobutyronitrile
(AIBN) from SigmaeAldrich was recrystallized in methanol before
use. Bifunctional urethane methacrylate peruoropolyether oligomer, Fluorolink MD700 (PFPE backbone Mw 1800 g mol1)
was graciously supplied by Solvay Specialty Polymers. DABCO,
lithium hydroxide (LiOH) and DMF from ACROS Organics were used
without further purication. Deionized water was used for electrolyte solution preparation and ionic exchange process.
Air electrode (E-5), purchased from Electric Fuel, is composed
of a porous PTFE lm combined with a cobalt based catalyzed
carbon supported on a metal mesh.
2.1. Membrane synthesis
Single Fluorolink MD700 network was synthesized as follows:
20 wt.% Fluorolink MD700 oligomer was mixed in DMF and
0.15 wt.% AIBN (with respect to oligomer) was dissolved in the
solution. It was degassed under argon for 10 min and poured into a
mold made of two glass plates clamped together and sealed with a
500 mm thick Teon gasket. The mold was heated at 70  C for 2 h.
A homogeneous and transparent material swollen with DMF was
obtained after unmolding.
To synthesize the single PECH network, the commercial PECH
solution functionalized with DABCO was concentrated at 18 wt.%.
Then DABCO was added to the solution to increase the molar
DABCO concentration to 0.15 eq. The PECH solution was poured into
the mold previously described, then was heated at 70  C for 2 h and
at 100  C for 4 h. A homogeneous and transparent PECH membrane
swollen with DMF was obtained.
The PECH/Fluorolink IPNs were prepared by a one-pot process.
For example, for a PECH/Fluorolink 70/30 IPN, 10 g PECH solution at
18 wt.% in DMF (1.73 mmol DABCO already grafted) were mixed
with 0.097 g DABCO (0.867 mmol) and stirred until complete
dissolution. 0.813 g (0.45 mmol) Fluorolink MD700 oligomer were
added and the mixture was stirred under argon before addition of
1.2 mg AIBN (0.15 wt.% with respect to Fluorolink MD700 oligomer). The mixture was poured into the mold previously described.

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It was heated at 70  C for 2 h and at 100  C for 4 h. The PECH/

Fluorolink 70/30 IPN swollen in DMF was unmolded at room
temperature.
IPNs with different PECH network contents ranging from 40 to
90 wt.% were synthesized. They are noted PECH/Fluorolink y/z IPN,
where y and z are the weight proportions of PECH and Fluorolink,
respectively, in the dry nal material.
Semi-IPNs (IPN in which one of the polymers is linear) were
synthesized according to the same synthesis pathway and thermal
program as for IPNs. In this case, PECH non functionalized with
DABCO (SigmaeAldrich) was used and DABCO was not added to
obtain semi-IPNs in which PECH is linear and only Fluorolink is
crosslinked.
2.2. Characterization
The samples were dried to constant weight under vacuum
(5 mmHg) at 70  C for 3 days before characterization. Soluble
fraction (i.e. the non-crosslinked fraction of the material) was
quantied by solideliquid extraction of a known weight of dried
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). Soluble fraction was calculated as:

SFwt:%

Wo  WE
 100
W0

(3)

Scanning Electron Microscopy (SEM) images were recorded

with S430i LEICA microscope with an accelerating voltage of 5 kV.
Modied and unmodied electrodes were analyzed without
further treatment because they are electron conductive. Energy
dispersive X-ray spectroscopy (EDX) was performed simultaneously with a detector SYNERGIE 4 Quantax from Bruker.
Thermal gravimetric analysis (TGA) measurements were made
in a Q50 apparatus (TA instruments) under synthetic air operating
from room temperature to 700  C with a 20  C min1 heating rate.
The degradation temperatures were measured at 5 % weight loss.
For the following characterizations, the chloride counter-ion has
been previously exchanged into OH. Thus, the dried materials
were immersed for 24 h in an excess of 1 M KOH solution and
nally rinsed in water until neutral pH.
Confocal laser scanning microscopy images were recorded on a
ZEISS microscope (LSM 710). Dried samples were immersed for
24 h in 0.05 wt.% aqueous rhodamine B (Acros) solution for staining
and then rinsed thoroughly. Rhodamine B was exited at 561 nm and
uorescence collected from 570 to 640 nm. The excitation light was
focused to a diffraction-limited spot in the sample using a planapochromatic 63/1.4 oil-immersion objective.
Water uptake was determined by measuring the weight difference between 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) was calculated as:

WUwt:%

Ww  Wd
 100
Wd

(4)

For the following characterizations, the materials were not dried

after synthesis. PECH networks, IPNs and polymer membrane/
electrode assemblies were immersed after synthesis in an excess of
1 M KOH for at least 3 days, to remove DMF and to exchange Cl
with OH. They were nally rinsed with water until neutral pH.
The ionic exchange capacity (IEC e the mole number of functional ionic sites per gram of dried material) was determined by
titration. The membranes were immersed for 24 h in 10 mL of 0.1 M
HCl. After this period, the HCl solution was titrated with a pH

electrode with 0.1 M KOH. The IEC was calculated from the difference between the mol HCl before (mmolHCl,O) and after immersion
(mmolHCl,E), and the dried material weight (Wd).

 mmol
HCl;O  mmolHCl;E
IEC mmol g1
Wd

(5)

Ionic conductivity was measured by electrochemical impedance

spectroscopy using a BioLogic Science Instruments VSP potentiostat. Rectangular samples were placed between two platinized
blocking electrodes. Nyquist plots were recorded with a Frequency
Response Analysis (FRA) over frequency range of 1000 kHze10 Hz
with oscillation amplitude of 10 mV. The electrical resistance (R)
was measured from the intercept of the Nyquist plot at high frequency with the real impedance axis. The ionic conductivity was
then calculated using the relation:


s S cm1

l
RS

(6)

where l denotes the thickness and S (width  length) is the surface

of the sample placed between the two electrodes.
Membrane transport numbers (t) were determined according
to NF X 45-200 procedure of the French Normalization Association
(AFNOR). The membrane separates a cell in two compartments
each containing KOH solutions with concentrations of 0.1 and
1.0 M. The voltage measured between two Hg/HgO electrodes
immersed in each compartment is the sum of the Nernst potential
(ENernst) and the membrane potential (EM). The anionic transport
number was calculated as:

#
F
EM



t 1=2 1 
RT ln aKOH;1M aKOH;0:1M
"

(7)

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].
Chemical stability of the PECH/Fluorolink (70/30) IPN was
investigated by immersing in 5 M LiOH at 50  C. Each 24 h, a piece
of IPN was removed from the solution, rinsed until neutral pH and
its conductivity was measured.
The membrane/air electrode assemblies (MEA) were prepared
by directly synthesizing the membrane over the air electrode as
described elsewhere [9]. They were characterized by electrochemical experiments performed in a homemade conventional
three-electrode half-cell. The unmodied or 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. Aqueous 5 M LiOH
solution was used as alkaline electrolyte. All measurements were
made at ambient temperature and under atmospheric pressure
with untreated air. The air electrodes were equilibrated with the
electrolyte for at least 1 h before starting the measurements.
Potential vs. current (polarization) curves were recorded by
applying different current densities, in step-wise increasing
from 1 to 30 mA cm2. Each current density was maintained
until a stable potential was reached and measured.
Potential vs. time (stability) curves were recorded by cycling the
air electrode for 10 h at open circuit voltage (OCV) followed by a
10 h polarization step (10 mA cm2 current density). This cycling
was chosen to reproduce the operation of the air electrode in the bielectrode conguration during full cell cycling [8]. For readability,
only the air electrode potential at the end of each discharge is reported as function of time in the stability curves. The stability time

B. Bertolotti et al. / Journal of Power Sources 274 (2015) 488e495

of air electrode was determined at the moment when the air

electrode potential reaches 400 mV /(Hg/HgO).
3. Results and discussion
New interpenetrating polymer networks (IPNs) have been
synthesized as solid anion-exchange membranes to protect the
commercial air electrodes from carbonation. These new materials
are based on an anionic conducting PECH network entangled
within a uorinated network. After their ex-situ characterization,
the IPNs were synthesized on the catalytic side of air electrodes,
and polarization of these assemblies supplied with atmospheric air
were characterized in the presence of aqueous 5 M LiOH electrolyte.

491

extraction for 72 h with DMF. All materials show soluble fraction

amounts lower than 5 wt.%, which identied by 13C NMR (Bruker
Avance DPX-250, 13C NMR 62.9 MHz in d6-DMSO) as linear PECH.
Polymers can thus be considered as correctly crosslinked in the
IPNs. Simultaneously, to verify that no grafting reaction occurs
between both networks during the IPN synthesis, attributable to a
radical transfer from the Fluorolink growing network to the chlorine atom of PECH, a PECH/Fluorolink 50/50 semi-IPN in which
linear PECH is entrapped in a Fluorolink network was synthesized.
If no grafting reaction occurs, the linear polymer can be quantitatively extracted from the semi-IPN. As expected, all unmodied
PECH can be extracted of the semi-IPN; i.e. the soluble fraction is
equal to 50 wt.%. This result shows that no grafting reaction
occurred between the two polymers.

3.1. Polymer membrane synthesis

3.2. Morphology of PECH/Fluorolink IPNs
Polyepichlorhydrin (PECH) modied with 1,4-diazabicyclo[2,2,2]-octane (DABCO) was chosen as polyelectrolyte [20,21]. The
second amine of DABCO can react at 100  C by nucleophilic substitution with hanging CH2eCl groups of poly(ethylene oxide)
skeleton leading to the formation of cationic cross-linking nodes. In
order to limit its swelling in aqueous electrolyte solution, this
polyelectrolyte network has been associated with a peruoropolyether (PFPE) polymer through interpenetrating polymer
networks (IPN) (Fig. 1). Fluorolink MD700 (called Fluorolink afterwards) is a bifunctional urethane methacrylate PFPE exhibiting
high chemical and thermal stabilities. Fluorolink is also miscible
with the PECH solvent (DMF), this allows for the synthesis of the
IPN by one-pot method.
PECH/Fluorolink IPNs with PECH contents ranging from 40 to
90 wt.% were synthesized (for PECH proportions lower than
40 wt.%, a macroscopic phase separation is observed and the materials are not homogeneous). Fluorolink is rst crosslinked by free
radical polymerization initiated by AIBN at 70  C for 2 h, and then
the PECH polyelectrolyte is cross-linked by nucleophilic substitution with 15 mol % DABCO (0.15 eq.) at 100  C for 4 h. All the IPN
materials are macroscopically homogeneous.
To conrm correct crosslinking of polymers, soluble fractions
contained in the different IPNs were determined by Soxhlet

Polymer co-continuity in the IPN is preferred for preservation of

each partner respective characteristic, such as the limited swelling
from Fluorolink and the ionic conductivity from PECH.
First, morphology of PECH/Fluorolink 50/50, 70/30 and 90/10
IPNs was studied by laser scanning confocal microscopy by red
staining the hydrophilic phase with water soluble dye, rhodamine B
(Fig. 2). This staining is observed in PECH single network but not in
Fluorolink single network (data not shown) which appears black. In
PECH/Fluorolink IPNs, the hydrophilic PECH rich phase is stained
red whereas the hydrophobic phase, composed of Fluorolink
network, is free of uorophore and appears in black. Continuous
non-uorescent (uorinated) and red (hydrogenated) domains of
micrometer size are observed in the different PECH/Fluorolink IPNs.
The phase separation between both polymers is limited; this is in
agreement with the homogeneous aspect of the samples (Photo
Fig. 1). Such a limited phase separation is in agreement with that
observed on amphiphilic networks based on Fluorolink and
poly(ethylene oxide) (PEO) dimethacrylate [22]. Indeed, these
amphiphilic networks, whichever their initial oligomer proportion,
show bulk morphologies with separated phases between 1 and
100 mm length with 550 and 750 g mol1 PEO, respectively. Thus,
the confocal microscopy images of PECH/Fluorolink IPNs suggest a

Fig. 1. Scheme of PECH/Fluorolink IPN synthesis.

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B. Bertolotti et al. / Journal of Power Sources 274 (2015) 488e495

Fig. 2. Laser scanning confocal microscopy images of PECH/Fluorolink 50/50 (A), 70/30 (B) and 90/10 (C) IPNs. Scale bar: 10 mm e The PECH phase is stained with Rhodamine B (red),
the uorinated phase appears black. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)

co-continuous phase morphology in the IPN containing from 50 to

90 wt.% PECH network.
Second, the continuity of the various phases is conrmed by
measuring the water uptake ratio of the IPNs. Indeed, PECH is the
only phase that swells in water, and if PECH is the only continuous,
the uptake will be high. Whereas the uptake will be low if the
uorinated phase is the only continuous. An intermediate and
continuous evolution of the water uptake with the composition
proves the phase co-continuity. The water uptake values of the IPNs
materials are reported in Fig. 3.
Single PECH and Fluorolink networks have a water uptake of 100
and 0 wt.% respectively. The water uptake increases linearly from
around 30 to 90 wt.% with the increase in the PECH proportion from
40 to 90 wt.%. This intermediate and continuous evolution of the
water uptake with the composition conrms the PECH and Fluorolink phase co-continuity. The continuity of the Fluorolink
network, whereas it is not the major component, is possible
because the Fluorolink network is synthesized before the PECH
network. Indeed, the rst formed network forms generally a
continuous phase in the IPNs [23,24].
Thus, confocal microscopy and water uptake measurements
have shown that the PECH and Fluorinated rich phases are
continuous in the whole materials with a large composition range.
It is then important to conrm that the properties of each
partner, such as ionic conductivity, have been conferred to IPNs.
Indeed, this property is required in the IPN to ensure the hydroxide
transport from the electrode to the electrolyte. For that, PECH
crosslink nodes, which are also the ionic sites assuming ionic

conduction, have to be still accessible to efciently participate to

the ionic conductivity in the presence of uorinated network inside
the IPN. So, the ion exchange capacity (IEC) of the single PECH
network and of the different PECH/Fluorolink IPNs has been
measured vs. PECH proportion (Fig. 4A).
The measured IEC of the single PECH network of 2.1 meq. g1 is
below the theoretic value (2.7 meq. g1) calculated assuming all
nitrogen atoms have reacted. An underestimation in the IEC measurement has already been observed on such material and has been
explained as an incomplete exchange of the Cl ions in the network
[25]. Thus, the main part of the PECH ionic sites is accessible. As
expected, IEC values measured on the PECH/Fluorolink IPNs increase linearly with the PECH content. For instance, the PECH/
Fluorolink 50/50 IPN, composed of half less PECH compared to the

Fig. 3. Water uptake of single PECH and Fluorolink networks and different PECH/
Fluorolink IPNs vs. PECH weight proportion.

Fig. 4. (A) Ionic exchange capacity and (B) ionic conductivity of single PECH network
and of different IPNs vs. PECH weight proportion.

B. Bertolotti et al. / Journal of Power Sources 274 (2015) 488e495

Fig. 5. Anionic transport number of PECH/Fluorolink IPNs vs. PECH network weight
proportion.

single PECH, has an IEC twice lower than single PECH network.
Thus, the main part of ionic groups of the polyelectrolyte network is
accessible for aqueous solution, as well in the uorinated IPN as in
the single PECH network. The access to ionic sites is not obscured by
the Fluorolink network. This result is again in accordance with a
morphology in which the PECH rich phase is continuous
throughout the material.
The IEC values directly should inuence ionic conductivity of
IPNs with various PECH weight proportions. These values,
measured at room temperature, are shown in Fig. 4B. The ionic
conductivity of the single PECH network in the fully hydrated state
(100 wt.% uptake) is 1 mS cm1. A maximum conductivity of
approximately 2 mS cm1 is obtained for the PECH/Fluorolink 70/
30 IPN. Curiously, no signicant increase of anionic conductivity is
found when the PECH proportion in the IPN increases. However,
ionic conductivity of solid polyelectrolyte can reach a plateau value
when IEC values increase whatever the polyelectrolyte nature as
shown for proton conductivity [16]. Apparently, in the PECH/Fluorolink IPNs, the effect of the increase of IEC with PECH proportion
on the ionic conductivity is counter balanced by the local charge
carrier dilution generated by the water uptake increase. Consequently, the uorinated network does not induce a reduction of the
conductivity of the IPN.
The anionic transport number (Fig. 5) assesses the selectivity of
a polymer membrane towards cationic species: the higher the
anionic transport number is, the higher the material selective

493

towards cation is. Transport numbers (t) of PECH/Fluorolink IPNs

varies from 0.65 to 0.80. The highest t, and thus the highest selective IPN, is obtained with the IPN containing 70 wt.% PECH. This
maximum can correspond to the optimal conditions of IEC and
water uptake values.
Finally, IPN stability was studied under different conditions. On
the one hand, in the dry state, PECH/Fluorolink IPNs are thermally
stable until 250  C, where a main weight loss is detected. On the
other hand, chemical stability of a PECH/Fluorolink 70/30 IPN was
studied in 5 M LiOH at 50  C. Under those corrosive alkaline conditions, quaternary ammonium of PECH network, the most sensitive group to hydroxide ions [20,26] may degrade according to
Hofmann mechanism, which would lead to loss of the ionic groups,
and thus, a decrease in ionic conductivity [27,28]. However, no
alteration of the conductivity was observed in 13 days of this
particularly harsh test. The especially high stability of uorinated
IPN networks has been established in the electrolyte.
From the ex-situ characterizations, these new PECH/Fluorolink
IPNs swell moderately in water, are ionic conductors, are selective
toward cations and are stable at high temperature and in 5 M LiOH
electrolyte. Successively, they were assembled on air electrode and
the assemblies were tested in half-cell in aqueous 5 M LiOH as
electrolyte.
3.3. Interface between air electrode and PECH/Fluorolink IPNs
As the IPN membranes are placed on the electrolyte side of air
electrode, the interface between the membrane and the electrode
must be preserved during the electrochemical tests to limit a polarization increase. PECH/Fluorolink IPNs with different compositions were thus synthesized directly over the catalyst side of the air
electrode, as previously detailed [9]. The IPN thickness was xed by
a 500 mm thick Teon gasket.
First, the interface quality between the air electrode and a PECH/
Fluorolink 70/30 membrane was veried by SEM-EDX. The cross
section of the PECH/Fluorolink IPNs MEA and the corresponding
EDX analysis are reported in Fig. 6A and B respectively. Fluorine
being present in the laminated PTFE layer and in the uorinated
binder of the air electrode, it cannot be used to characterize the IPN
presence in the air electrode porosity. However, the IPN presence
can be revealed by the Cl signal because this element is only present in the PECH polymer. Cl element is highly concentrated in the
IPN membrane mainly located on the air electrode surface and is
also detected through the carbon black porosity. During the
membrane synthesis, black carbon particles are thus impregnated
with the polymer solution and cross-linking reactions of both

Fig. 6. (A) SEM image of the cross-section of PECH/Fluorolink 70/30 IPN MEA and (B) the corresponding EDX analysis: chloride (pink) and uorine (green). (For interpretation of the
references to color in this gure legend, the reader is referred to the web version of this article.)

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B. Bertolotti et al. / Journal of Power Sources 274 (2015) 488e495

polymers occur in the thickness of the air electrode. We can

conclude from these observations that an especially correct interface between the air electrode and the uorinated IPN membrane is
obtained.

3.4. Electrochemical properties

The additional polarization induced by presence of the membrane over the air electrode is studied by recording the polarization
curves of the air electrode modied with the PECH/Fluorolink IPNs
(Fig. 7).
Compared to the bare electrode, the presence of PECH/Fluorolink IPN on air-electrodes does not induce a signicant increase in
polarization (except for PECH/Fluorolink 40/60 IPN for which the
polarization is higher at current densities above 10 mA cm2). No
signicant polarization difference is found when the IPN contains
PECH proportions varying from 50 to 90 wt.% (polarization curves
with PECH/Fluorolink 60/40 IPN not shown). As the non-modied
electrode, the air electrodes modied with the IPNs have a polarization of 140 mV at 10 mA cm2 current density. The ionic
contact between the membrane and the electrode is thus ensured,
i.e. the interface is correct. The resistance of the IPN membrane
swollen with electrolyte is thus almost negligible despite the
presence of the hydrophobic Fluorolink network.
Afterward, stability of the potential of different assemblies
supplied with ambient air and under atmospheric pressure was
assessed in cycling, at rest for 10 h and then at 10 mA cm2 for
10 h in 5 M LiOH electrolyte at room temperature (Fig. 8). This
cycling program is chosen to reproduce only the discharge of the air
electrode in combination with a secondary oxygen evolution electrode during full cell cycling [29].
Whatever the IPN composition, polarizations of assemblies
during the rst discharges are of the order of 140 mV, and are
relatively stable. The potential of the bare electrode increases
abruptly after about 50 h cycling. The air electrode protected
with a PECH single network has a stable potential up to 300 h.
The stability of the air electrode strongly depends on the
composition of protecting IPN membrane: for the assemblies
based on PECH/Fluorolink 40/60, 50/50 and 90/10 IPNs, the potential remains stable for times equivalent or lower to that of the
PECH single network (between 250 and 300 h). However, the
potential of air electrodes modied with PECH/Fluorolink 60/40,

0.00

E (V) / Hg/HgO

-0.10
-0.20
-0.30
-0.40
-0.50
-0.60
-35

-30

-25

-20
-15
j (mA cm-2)

-10

-5

Fig. 7. Potentialecurrent density curves recorded on bare electrode (C), and air
electrodes modied with PECH network (-), PECH/Fluorolink 40/60 (B), 50/50 ( ),
70/30 (A) 80/20 () and 90/10 ( ) IPNs. Electrolyte: 5 M LiOH. Room temperature,
atmospheric pressure. Reference electrode: Hg/HgO.

Fig. 8. Polarization curves for bare air electrode (C) and air electrodes modied with
PECH network (-) and PECH/Fluorolink 40/60 (B), 50/50 (:), 60/40 (D), 70/30 (A),
80/20 () and 90/10 ( ) IPNs. Cycle: rest for 10 h and 10 mA cm2 for 10 h. Electrolyte: 5 M LiOH. Room temperature, ambient air and atmospheric pressure. Reference electrode: Hg/HgO.

70/30 and 80/20 IPNs are stable beyond 500 h. Particularly, the
potential of assembly with the PECH/Fluorolink 70/30 IPN is
stable more than 1000 h under the same cycling conditions. In all
these cases, the IPN membrane effectively protects the commercial air electrode.
This stability is higher than any previous result found in the
literature for an aqueous metal-air battery. Indeed, Tsuchida et al.
[4] reported a stability of 124.8 h (0.6 V, 86.4 mAh g1) for an
aqueous zinc-air cell with KOH 1 M, in which the air electrode was
protected with a poly(methylsulfonio-1,4-phenylenethio-1,4phenylene triuoromethanesulfonate) membrane and of 70.5 h
(1.32 V, 14.5 mAh g1) with a Celgard one. As reported in Introduction, hydrogenated IPNs based on poly(hydroxymethyl methacylate) and poly(epichlorohydrin) increases the air electrode
stability from 50 to 300 h under the same test conditions used in
this article (10 h at rest/10 h at 10 mA cm2) [8]. Stability of the air
electrode covered with a PECH/Fluorolink membrane has been thus
increased 20 times, and these results conrm the interest of a
protecting membrane over the electrode to improve its stability
when it is fed with ambient air.
The degradation of the electrode performance always results in
a sudden increase of the polarization, which appears for all assemblies after a period at rest. When the duration of stabilities are
higher than 700e800 h, a white solid is observed on the PTFE layer
(air side) of the electrode. Due to the experimental conditions used,
this precipitate may be LiOH becoming from the electrolyte or
lithium carbonate due to the reaction between the carbon dioxide
from atmospheric air and lithium hydroxide from the electrolyte
(Equation (1)). This solid was thus analyzed by ATR FT-IR (PerkineElmer Spectrum One) and identied as Li2CO3 as revealed by
the strong absorption bands at 1415 and 860 cm1 [30]. This conrms that the diffusion of lithium cations and precipitation of
Li2CO3 cause the increase of the air electrode polarization witnessing of its degradation.
The diffusion of Li cations through the air electrode can be
greatly slowed by the presence of the membrane. This assumption
can be related to the transport number t of the membrane as
shown in Fig. 9 where the stabilities of the air electrodes modied
with PECH/Fluorolink IPNs are reported according to the transport
number of the IPN membrane. The highest stability, exceeding
1000 h, is obtained with a PECH/Fluorolink 70/30 IPN, which shows
one of the highest conductivities (2 mS cm1) and the highest anion

B. Bertolotti et al. / Journal of Power Sources 274 (2015) 488e495

495

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. Our gratitude also goes to
Solvay Specialty Polymers for supplying the uorinated monomer
used in this research and for its valuable scientic advice. Finally,
we would like to thank the Region Ile-de-France for its sponsoring in
the acquisition of the confocal laser scanning microscope (Sesame
e COMICER project) used in this work.
References

Fig. 9. Stability of the air electrodes modied with PECH/Fluorolink IPNs vs. anionic
transport number. Cycle: rest for 10 h and 10 mA cm2 for 10 h. Electrolyte: 5 M LiOH.
Room temperature, ambient air and atmospheric pressure. Reference electrode: Hg/
HgO.

transport number (t 0.80). The peruoropolyether based anion

exchange membrane selectivity seems thus to be the most important parameter inuencing the IPN modied air electrode stability.
Thus, a selective membrane prevents passage of cation from the
electrolyte to air electrode. Carbonates formation in the porosity is
delayed; and air electrode keeps a polarization lower
than 400 mV. As a result, the stability of air electrode modied
with PECH/Fluorolink 70/30 IPN was increased from 50 to an
average of 1000 h, more than 20 times than for non-modied
electrode.
4. Conclusions
The interest of the original combination of PECH and Fluorolink
networks in an interpenetrating polymer networks has been
demonstrated. This association reduces swelling of the polyelectrolyte while preserving hydroxide conductivity and anion
selectivity. This is possible because of the co-continuous
morphology of PECH/Fluorolink IPNs in the microscopic range.
PECH/Fluorolink 70/30 IPN shows the more interesting physicochemical properties for the protecting air electrode application: an
ionic conductivity of 2 mS cm1, and a transport number of 0.80.
Subsequently, this PECH/Fluorolink IPN was synthesized directly
over the catalyst side of the air electrode. This modication process
allows, as observed by EDX, obtaining highly concentrated membrane on the surface and diffuse distribution through the electrode
porosity, leading to the absence of additional polarization induced
by the presence of the IPN membranes. Furthermore, the lifetime of
the modied air electrode is increased to an average of 1000 h, i.e.
20 times the stability of the non-modied electrode. Further
research is being made to improve the selectivity of this particular
IPN, which seems of great interest.

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