materials

Article
Electrochemical Impedance Spectroscopy as a
Diagnostic Tool in Polymer Electrolyte
Membrane Electrolysis
Stefania Siracusano, Stefano Trocino, Nicola Briguglio, Vincenzo Baglio ID
and
Antonino S. Aricò * ID
CNR-ITAE, Via Salita S. Lucia sopra Contesse 5, 98126 Messina, Italy; siracusano@itae.cnr.it (S.S.);
trocino@itae.cnr.it (S.T.); nicola.briguglio@itae.cnr.it (N.B.); baglio@itae.cnr.it (V.B.)
* Correspondence: arico@itae.cnr.it; Tel.: +39-090-624237




Received: 29 June 2018; Accepted: 3 August 2018; Published: 7 August 2018


Abstract: Membrane–electrode assemblies (MEAs) designed for a polymer electrolyte membrane

(PEM) water electrolyser based on a short-side chain (SSC) perfluorosulfonic acid (PFSA) membrane,
Aquivion® , and an advanced Ir-Ru oxide anode electro-catalyst, with various cathode and
anode noble metal loadings, were investigated. Electrochemical impedance spectroscopy (EIS),
in combination with performance and durability tests, provided useful information to identify
rate-determining steps and to quantify the impact of the different phenomena on the electrolysis
efficiency and stability characteristics as a function of the MEA properties. This technique appears
to be a useful diagnostic tool to individuate different phenomena and to quantify their effect on
the performance and degradation of PEM electrolysis cells.

Keywords: water electrolysis; hydrogen generation; impedance spectroscopy; polymer electrolyte

membrane; membrane-electrode assembly; oxygen evolution; iridium catalysts; platinum catalysts

1. Introduction
Water electrolysis appears to be as one the foremost technologies for a sustainable production
of hydrogen from renewable energy to feed next generation fuel cell vehicles. This technology is
characterized by the ability to rapidly follow the intermittent production of renewable energy and,
thus, can provide efficient energy storage and grid-balancing service in power-to-gas processes [1–8].
These characteristics will become very important in the next future because of the increasing impact of
renewable sources on the grid and the differences in supply and demand for energy generation and
consumption [1–4].
Accordingly, it is important to get a better understanding of the reaction process and
performance limiting phenomena in membrane-electrode assemblies which are the core part of a PEM
electrolysis system [8–16]. In this regard, electrochemical impedance spectroscopy appears an excellent
diagnostic tool for electrochemical processes and devices especially when there is no possibility
of using an internal reference electrode to help in deconvoluting different phenomena [17–20].
Ac-impedance analysis is frequently used to separate the contribution of the different mechanisms
influencing the polarisation characteristics [8,20]. Electrochemical impedance spectroscopy (EIS) allows
to discern between the various phenomena on the basis of the different relaxation times of the single
processes and the variation of relevant components of the equivalent circuits upon a change in the
operating parameters such as potential, current density, temperature and MEA characteristics, e.g.,
catalyst loading [17,20]. In most cases, a first qualitative analysis of electrochemical impedance spectra
allows to clearly distinguish between ohmic and polarization resistance providing a first insight if the

Materials 2018, 11, 1368; doi:10.3390/ma11081368 www.mdpi.com/journal/materials

Materials 2018, 11, 1368 2 of 15

system needs to be improved in terms of electrolyte or electrodes, if there are relevant interface issues
or there is an occurrence of diffusion-related phenomena [17]. However, the relevant information
provided by the ac-impedance spectra would require an in-depth investigation using equivalent circuit
analysis [20]. This can be carried out in combination with a systematic variation of the main variables
influencing the electrochemical process such as potential, temperature, current density and the specific
MEA characteristics having a major or specific impact on a single process [20].
Several groups have already used electrochemical impedance spectroscopy to interpret more
in detail the observed electrochemical phenomena and to derive information useful in improving
performance and durability [8,13–16,20–30]. However, the response of a PEM electrolysis system
varies significantly with regard to the type and thickness of membrane used, the different anode
electrocatalyst, the type of current collector and diffusion media etc. [4–9]. Thus, the results are often
specific of the system under consideration and some phenomena are linked to the MEA configuration
and materials used.
Recently, we have shown that high electrolysis current density (3 A cm−2 ) corresponding to
reduced capital costs can be achieved with a low or moderate platinum group metals (PGM) catalyst
loading (0.5–1.5 mg cm−2 MEA ) while maintaining a very high conversion efficiency (>80%) and good
stability [8,25,28]. This is obtained in the presence of a nanostructured Ir-Ru electro-catalyst for oxygen
evolution (the rate determining step in the electrolysis process) in combination with a short-side chain
perfluorosulfonic acid membrane [8,25,28]. The stability of this system is essentially governed by the
reaction turn-over frequency, i.e., the combination of the effects of the operating current density and
catalyst loading [8].
To further advance in this field, it is important to get proper insights about the rate determining
steps and the contribution of each process and component of the membrane-electrode assembly to the
overall polarisation behaviour and the related efficiency characteristics. Thus, it is necessary to extract
all relevant information from the available electrochemical characterisation to help in understanding
relevant aspects such as the effect of the catalyst loading, membrane and electro-catalysts contributions
to the cell polarisation, possible occurrence of mass transport limitations and degradation issues.
It is considered that, beside the conventional steady-state characterization, time-resolved techniques,
such as ac-impedance spectroscopy, can provide further insights on the relevant phenomena and help
to differentiate between the characteristics of the different PEM electrolysis systems to identify properly
limiting steps thus allowing to develop effective solutions. The aim of this work is to get a deeper
understanding of the behaviour of these PEM electrolysis MEAs by carrying out an electrochemical
impedance spectroscopy study in combination with equivalent circuit analysis.
Electrochemical Impedance Spectroscopy is a powerful diagnostic tool for several electrochemical
processes. However, in this method, data validation is very important to avoid interferences by
non-steady state or non-linear behaviour [17,18]. In particular, an analysis of the residuals is always
necessary to understand the appropriateness of the model and the resulting equivalent circuit should
lead to a realistic physical interpretation [17,18]. Equivalent circuits are in general useful in analysing
impedance spectra arising from reaction mechanisms and their use appears very appropriate in this
context [20]. They provide a useful model to validate the data whereas the circuit elements can be used
to screen the relevant mechanisms.
In this work, we have addressed all these aspects and specific attention was devoted to minimise
the deviation between the experimental results and the fitting; this is shown in both Nyquist and Bode
plots. We have used a very small perturbation signal to avoid non-linearities under all conditions while
trying to avoid relevant data scattering [17,18]. The approach used in this work for the ac-impedance
analysis was to carry sequential measurements of impedance by Fourier analysis. The electrolysis
cell under investigation can be considered like a stationary system being the cell voltage very stable
during galvanostatic operation. The sequence of frequencies (f) and the frequency intervals, ∆f/f,
were properly selected to minimise the time associated to each measurement while providing a highly
resolved profile.
Materials 2018, 11, 1368 3 of 15

In this method, the measurements at each frequency are independent of each other. Their consistency
with the Kramers–Kronig relations [17,18] is an important step of the validation procedure.
Moreover, to corroborate the interpretation of the results and the corresponding equivalent circuits,
specific parameters such as catalyst loading or temperature have been systematically varied to verify if
their effect on the impedance response was in agreement with the suggested model.

2. Materials and Methods

2.1. Materials and Cells

Unsupported IrRuOx catalyst (70% at. Ir: 30% at. Ru), prepared by using a modified Adams
process, was used as anode electrocatalyst [31]. A 40% Pt/Vulcan XC-72 was synthesized according to
the sulphite complex process [31,32] and utilised at the cathode.
A chemically stabilised Aquivion® short-side chain extruded film (E98–09S), with a thickness
of 90 µm and an equivalent weight (EW) of 980 g/eq developed by Solvay Specialty Polymers,
specifically for water electrolysis applications, was used as membrane separator. An ionomer
dispersion (830 g/eq equivalent weight-based Aquivion® ionomer—D83–06A) was used as ionic
conductor in both the composite catalytic inks [28,32].
Membrane-electrode assemblies (MEAs) were manufactured by using a catalyst-coated membrane
(CCM) preparation procedure [8]. Separate catalyst slurries of IrRuOx and Pt/C with the Aquivion®
ionomer dispersion (D83–06A) were sprayed in sequence onto the different faces of the Aquivion®
membrane. The ionomer content in the catalytic layers was 15 wt. % at the anode and 28 wt. %
at the cathode. The properties of the catalytic inks were examined by using a combination of
transmission electron microscopy and X-ray diffraction (XRD). Structural analysis was carried out by
a Panalytical X-Pert diffractometer using a CuKa as radiation source operating at 40 kV and 20 mA.
The diffraction patterns were interpreted using the Joint Committee on Powder Diffraction Standards
(JCPDS). The morphology of the catalytic layers was investigated by transmission electron microscopy
(TEM) using a FEI CM12 instrument.
CCMs were hot-pressed at 190 ◦ C to favour hot bonding of the catalytic layers to the membrane at
a temperature higher than the glass transition temperature of the Aquivion® polymer. The MEA was
installed in an electrolysis cell housing consisting of Ti plates. A carbon based gas diffusion layer (GDL
ELAT) was used as backing layer at the cathode whereas a titanium fibre mesh (Bekaert Toko Metal
Fiber Co., NV Bekaert SA Bluepoint, Brussels, Belgium) was used as diffusion layer for the anode.
The PGM loading was varied as reported in the results section. The total geometrical area of each
electrode (anode and cathode) was 5 cm2 . This was assumed as the active electrode area; this value
(5 cm2 ) was used to normalise the current to the specific electrode area (current density).

2.2. Electrochemical Studies

The performance of the PEM electrolysis cells was studied at different temperatures and at
ambient pressure. Milli-Q Integral, Millipore deionized water, with a resistivity of 18 MΩ·cm,
was supplied to the anode with a flow rate of 1 mL·min−1 cm−2 and recirculated at the same
temperature of the cell. The electrochemical investigation included galvanostatic polarization curves,
electrochemical impedance spectroscopy (EIS), and chronopotentiometric studies under galvanostatic
conditions. These studies were carried out using an electrochemical set-up made of an Autolab PGSTAT
302 Potentiostat/Galvanostat, a 20 A booster (Metrohm, Herisau, Switzerland) and FRA (frequency
response analyser).
The working and sense wires of the Autolab were both connected to the anode (positive electrode)
current collector whereas the counter and reference wires were connected to the cathode (negative
electrode) current collector. Thus, the cell potential (sense vs. reference) was sampled directly on the
cell terminals/current collectors while current was passing through the working and counter wires of
the Autolab machine.
Materials 2018, 11, x FOR PEER REVIEW 4 of 15

Materials
directly the11,
on2018, 1368
cell terminals/current collectors while current was passing through the working and 4 of 15

counter wires of the Autolab machine.

Polarization curves (cell potential versus cell current) were carried out in the galvanostatic mode
Polarization curves (cell potential versus cell current) were carried out in the galvanostatic mode
by recording the cell voltage vs. the imposed current density. A stepwise logarithm increase of
by recording the cell voltage vs. the imposed current density. A stepwise logarithm increase of current
current was used for the galvanostatic polarization curves using a cut-off voltage of 2 V. Variation of
was used for the galvanostatic polarization curves using a cut-off voltage of 2 V. Variation of the
the current density was carried out in steps and the duration of each step was 1 min (pseudo steady
current density was carried out in steps and the duration of each step was 1 min (pseudo steady
state-condition). The change in the cell voltage for 1 min, generated by variation of current was
state-condition). The change in the cell voltage for 1 min, generated by variation of current was
registered. The average potential was reported at each current density.
registered. The average potential was reported at each current density.
Electrochemical impedance spectroscopy analysis was performed at 1.5 V and 1.8 V under
Electrochemical impedance spectroscopy analysis was performed at 1.5 V and 1.8 V under
different conditions by varying the frequency from 100 kHz to 100 mHz in single sine mode and
different conditions by varying the frequency from 100 kHz to 100 mHz in single sine mode and using
using a sinusoidal excitation signal of 10 mV pk-pk.
a sinusoidal excitation signal of 10 mV pk-pk.
3. Results and
3. Results Discussion
and Discussion

3.1.3.1.
Structure andand
Structure Morphology of the
Morphology Electro-Catalytic
of the Inks
Electro-Catalytic Inks
The TheXRDXRD analysis
analysis of of
thethecatalyst
catalyst inks shows
inks shows forfor
thethe
mixed
mixed IrRuOx-ionomer
IrRuOx-ionomer inkink
thethetetragonal
tetragonal
rutile crystallographic
rutile crystallographic structure
structure of of
IrO 2 with
IrO 2 withRuO 2 forming
RuO 2 forming a solid
a solidsolution
solution as as
suggested
suggested byby thethe
shift
shift
of the diffraction
of the diffractionpeaks
peaks towards
towards higher
higher Bragg
Braggangles
angles [31]. There
[31]. Thereis aisminimal
a minimal evidence
evidence of the
of theionomer
ionomer
peak
peakat 16° ◦ 2-theta
at 162-theta (Figure
(Figure 1a).1a).
From
From thethe
broadening
broadening of of
thethe
XRDXRD peaks
peaks a mean
a mean crystallite
crystallitesize of of
size 8 nm
8 nm
is determined.
is determined. The amount
The amount of of
Aquivion ® ®
Aquivionionomer ionomer in the anode
in the anode inkink is minimized
is minimized to to
avoid
avoid hindering
hindering
electronic
electronic percolation
percolation in in
thethe
oxide
oxideanode
anode [20]. OnOn
[20]. thetheother hand,
other hand, thethe ionomer
ionomer peakpeakis well
is wellevident
evidentin in
thethe
catalytic ink of the cathode due to the larger ionomer content used in
catalytic ink of the cathode due to the larger ionomer content used in the presence of the carbon the presence of the carbon
supported
supported Pt Pt
catalyst
catalyst (Figure
(Figure 1).1).
This
This shows
shows the conventional
the conventionalface-cantered
face-canteredcubic cubicstructure
structureofofPt Ptwith
with a
a crystallite
crystallitesize
sizeofof33nmnmas asdetermined
determinedfrom fromthetheX-ray
X-raypeaks
peaksbroadening.
broadening.
Ionomer
Ionomer dispersion
dispersion around
around thethe catalyst
catalystagglomerates
agglomerates is observed
is observed in in
thethe
TEM TEM pictures
pictures of of
thethe
catalytic
catalytic inks (Figure
inks (Figure 1b,c). TheThe
1b,c). ionomer
ionomer forms
formsa film
a filmaround
around thethe catalyst
catalystagglomerates
agglomerates without
without
affecting
affecting significantly
significantly electronic
electronic percolation
percolation while providing
while providing network
network forforionic conduction
ionic conduction inside thethe
inside
catalytic
catalytic ink. This
ink. Thisisisaaprerequisite
prerequisite to obtainobtainaaproper
properextension
extension of of
thethe catalyst-electrolyte
catalyst-electrolyte interface
interface inside
inside the catalytic
the catalytic layer.layer. Gas evolution
Gas evolution thus occurs
thus occurs at the triple-phase
at the triple-phase boundary boundary
betweenbetween catalyst-
catalyst-electrolyte
electrolyte and gasThe
and gas phase. phase. The Pt particles
Pt particles appear in
appear uniform uniform in size the
size whereas whereas
IrRuOx theisIrRuOx
composed is composed
of both fine
of and
bothlarge
fine and large particles.
particles. The latterThe latter are
however however are not
not larger thanlarger
20 nm. than 20 nm.

Figure 1. X-ray diffraction of IrRuOx +15% ionomer and 40% Pt/C + 28% ion (a); TEM image of 40%
Figure 1. X-ray diffraction of IrRuOx +15% ionomer and 40% Pt/C + 28% ion (a); TEM image of 40%
Pt/C + 28%
Pt/C ion ion
+ 28% (b); (b);
TEM image
TEM of IrRuOx
image +15%
of IrRuOx ion ion
+15% (c). (c).
Materials 2018, 11, 1368 5 of 15

Materials 2018,
3.2. Operating 11, x FOR
Regime of PEER
a PEMREVIEW
Electrolyser 5 of 15

Polarisation
3.2. Operatingstudies
Regime are
of a carried out at 80 ◦ C in a current density range where the voltage efficiency
PEM Electrolyser
is appropriate for practical applications (>70% vs. H2 high heating value). Depending on the operating
Polarisation studies are carried out at 80 °C in a current density range where the voltage
temperature this range varies up to 2 or 3 A cm−2 . Ac-impedance spectra are collected at two
efficiency is appropriate for practical applications (>70% vs. H2 high heating value). Depending on
operating cell voltages, 1.5 V and 1.8 V, which correspond to the system operation under activation
the operating temperature this range varies up to 2 or 3 A cm−2. Ac-impedance spectra are collected
or ohmic-diffusion control, respectively. The first part
at two operating cell voltages, 1.5 V and 1.8 V, which correspond of this study deals with
to the cell operation
system operationatunder
1.5 V
to get a more in
activation or depth understanding
ohmic-diffusion control,of the catalytic processes.
respectively. The first part Theofsecond part isdeals
this study related
withtocell
the
operation
operation at 1.5 V to get a more in depth understanding of the catalytic processes. The second partthe
at high potentials where ohmic and diffusion constraints affect the normal operation of is
PEMrelated
electrolysis
to thesystem
operation at the nominal
at high current
potentials density.
where ohmic and diffusion constraints affect the normal
Generally,ofthe
operation thenominal operating
PEM electrolysis current
system density
at the of acurrent
nominal PEM electrolysis
density. system is deriving from
a compromise between hydrogen production rate, durability and
Generally, the nominal operating current density of a PEM electrolysis system efficiency [8,32].is The hydrogen
deriving from
production is linked
a compromise to the operating
between current density
hydrogen production according and
rate, durability to the Faraday’s
efficiency law.The
[8,32]. Operation
hydrogen at
production
higher currentsisreduces
linked to the operating
capital currentthe
costs because density
sameaccording to the Faraday’s
stack hardware is used law. Operation
to produce at
more
higher per
hydrogen currents
unit of reduces capital costs
time [8,32]. because
However, the sameatstack
operation veryhardware
high currentis used to produce
density reducesmore
the
hydrogen per unit of time [8,32]. However, operation at very high current density
voltage efficiency and increases the degradation rate [8]. These characteristics influence the operating reduces the voltage
efficiency operation
expenditures; and increases the degradation
at higher reaction rate rate [8]. These
but lower characteristics
efficiency can be lessinfluence
useful whenthe the
operating
cost of
expenditures;
electricity is high. operation at higherinfluence
All these aspects reaction rate but lower
the final cost ofefficiency can behydrogen.
the produced less useful when the cost
of
A electricity
practical is high. All
system these aspects
operates influence
at conditions the final
where cost costs
capital of the and
produced hydrogen.
operating expenditures are
A practical system operates at conditions where capital costs
acceptable in the specific context where the electrolyser is installed [32]. The ac-impedance and operating expenditures are
analysis
acceptable in the specific context where the electrolyser is installed [32]. The ac-impedance analysis
at low current density is of practical interest because of the possibility of partial load operation in
at low current density is of practical interest because of the possibility of partial load operation in
grid-balancing service and the fact that the observed phenomena mainly reflect the electrocatalyst
grid-balancing service and the fact that the observed phenomena mainly reflect the electrocatalyst
behaviour. These are of relevant interest since there is always the need to minimize the PGM loading
behaviour. These are of relevant interest since there is always the need to minimize the PGM loading
without affecting considerably performance and stability.
without affecting considerably performance and stability.
Instead ac-impedance analysis at high current densities is very useful to get information on the
Instead ac-impedance analysis at high current densities is very useful to get information on the
limiting steps
limiting during
steps duringoperation
operation at at
nominal
nominalcurrent
currentdensity.
density. Besides,
Besides, thetheoperating
operatingtemperature
temperature of of
a
a PEM electrolyser can vary depending on the stack and system design
PEM electrolyser can vary depending on the stack and system design as well as a function of theas well as a function of the
active materials
active involved.
materials involved.Accordingly,
Accordingly, ananimpedance
impedancestudy studyshould
shouldcover
cover these
these variables. Moreover,
variables. Moreover,
the operating
the operatingpressure alsoalso
pressure plays an important
plays an important rolerole
since a practical
since a practical electrolyser
electrolyser usually
usuallyoperates
operatesinina
pressurized modemode
a pressurized [1]; however, this effect
[1]; however, is not
this effect is studied in this
not studied work.
in this work.

3.3. Effect of Different

3.3. Effect Cathode
of Different Loadings
Cathode Loadings
Polarisation curves
Polarisation andand
curves ac-impedance
ac-impedancewere both
were used
both to assess
used thethe
to assess electrochemical behaviour
electrochemical behaviour of
electrolysis MEAs (Figures
of electrolysis 2 and 3).
MEAs (Figures For what
2 and concerns
3). For the polarization
what concerns curves (Figure
the polarization curves 2), an increase
(Figure 2), an
of cell potential
increase at apotential
of cell fixed current density
at a fixed means
current a decrease
density means aofdecrease
voltage of
efficiency since more
voltage efficiency energy
since moreis
usedenergy is used
to produce thetosame
produce the same
amount amount of hydrogen.
of hydrogen.

1.9
80 °C
1.8
1.7
Potential / V

1.6
1.5 1.5 (anode) + 0.5 (cathode) mg·cm-2
1.4
1.5 (anode) + 0.1 (cathode) mg·cm-2
1.3
1.2
0 0.3 0.6 0.9 1.2 1.5 1.8 2.1 2.4 2.7 3

Current Density / A·cm-2

Figure
Figure 2. Comparison
2. Comparison of the
of the water
water electrolysispolarization
electrolysis polarizationcurves
curvesfor
for different
different cathode
cathode catalyst
catalyst
loading-based MEAs at◦80
loading-based MEAs at 80 C. °C.
Materials 2018, 11, 1368 6 of 15

Materials 2018, 11, x FOR PEER REVIEW 6 of 15

A first qualitative analysis of Nyquist spectra (Figure 3a,d) allows to distinguish between series
A first qualitative analysis of Nyquist spectra (Figure 3a,d) allows to distinguish between series
or ohmic resistance and polarization resistance. The high frequency intercept of the semicircles on
or ohmic resistance and polarization resistance. The high frequency intercept of the semicircles on
the x-axis in the Nyquist plots is associated to the ohmic resistance (more precisely reported as series
the x-axis in the Nyquist plots is associated to the ohmic resistance (more precisely reported as series
resistance, Rs ). The difference between the low frequency intercept in the Nyquist plot and Rs is
resistance, Rs). The difference between the low frequency intercept in the Nyquist plot and Rs is
assumed as the polarisation resistance (Rp ). The total resistance corresponding to the low frequency
assumed as the polarisation resistance (Rp). The total resistance corresponding to the low frequency
intercept on the abscissa in the Nyquist plot (Rs + Rp ) is corresponding to the differential resistance of
intercept on the abscissa in the Nyquist plot (Rs + Rp) is corresponding to the differential resistance of
the polarization curves.
the polarization curves.
Polarisation
Polarisationcurvescurves of of MEAs
MEAs containing
containing constant anode loading
constant anode loadingbut butcathode
cathodecatalyst
catalystloading
loading
varying five-times (0.1 and 0.5 mg cm −2 ) are shown in Figure 2. It is interesting to note that the
varying five-times (0.1 and 0.5 mg cm ) are shown in Figure 2. It is interesting to note that the curves
−2
curves are overlapping
are overlapping at all current
at all current densities
densities indicating
indicating no influence
no influence of the of
Ptthe Pt C loading.
C loading. However,
However, the
the shape of the Nyquist and Bode plots obtained from the electrochemical
shape of the Nyquist and Bode plots obtained from the electrochemical ac-impedance analysis of the ac-impedance analysis
oftwo
the cells
two at cells
1.5atV1.5
cellVvoltage,
cell voltage,
i.e., ini.e., in a region
a region wherewhere the catalytic
the catalytic effectseffects
should should be relevant,
be relevant, are
are significantly different (Figure 3a–e). Figure 3 shows both the experimental
significantly different (Figure 3a–e). Figure 3 shows both the experimental ac-impedance data and ac-impedance data
and related
related curve curve fitting
fitting in Nyquist
in Nyquist (a,d)Bode
(a,d) and andmode
Bode(b,e).
mode (b,e).3c,f
Figure Figure
show3c,f show the equivalent
the equivalent electrical
electrical
circuits used to fit the ac-impedance data obtained for the high and low-cathode loaded MEA.loaded
circuits used to fit the ac-impedance data obtained for the high and low-cathode The
MEA. The equivalent
equivalent electrical
electrical circuits circuits
include an include an ohmic(series
ohmic resistance resistance (seriesconnected
resistance) resistance) inconnected
series within
series with two components
two components each consisting
each consisting of a parallel of between
a parallelabetween
resistance a resistance and aphase
and a constant constant phase
element
element (CPE) [18,26]. The series resistance reflects the ohmic phenomena
(CPE) [18,26]. The series resistance reflects the ohmic phenomena whereas the RQ components are whereas the RQ components
are associated
associated to the
to the electrode-electrolyte
electrode-electrolyte interfacial
interfacial properties
properties andand related
related faradaic
faradaic processes
processes [18,26].
[18,26]. In
Inparticular,
particular,the theconstant
constantphase
phaseelement,
element,here hererepresented
representedwithwiththetheQQsymbol,
symbol,reflects
reflectsthe
thefractal nature
fractal nature
andthe
and theroughness
roughnessofofthe theinterface
interfacebetween
between the the electrocatalyst
electrocatalyst and
and thethe ionomer
ionomerelectrolyte
electrolyte[17–20].
[17–20].

0.075 0.25 16
1.5 V |Z| R = 0.031 Ωcm2 R = 0.061 Ωcm2
anode: 1.5 + cathode: 0.5 mg cm-2 1.5 V 14
● 1.5 (anode) + 0.5 (cathode) mg·cm-2 80°C Fitting
0.2
▬ fitting -Phase 12
- Phase/ degrees

Fitting
0.05 80°C R = 0.087 Ωcm2
Fitting
|Z| / ohm·cm2
-Z" / ohm·cm2

0.15 10
8
0.025 0.1 6
4
0.05
a b 2 c
Y0 = 0.264 Scm-2 s^n Y0 = 1.97 Scm-2 s^n
0 n = 0.901 n = 0.42
0.05 0.1 0.15 0.2 0 0
Z' / ohm·cm2
1 10 100 1000 10000
0.075 Frequency / Hz
0.25 12
1.5 (anode)
anode: 1.5 + 0.1 (cathode)
cathode: 0.1 mg·cm-2
mg cm-2 1.5 V |Z| R = 0.032 Ωcm2 R = 0.051 Ωcm2
Fitting Fitting 10
1.5 V 0.2 80°C
-Z" / ohm·cm2

-Phase
- Phase/ degrees

0.05 Fitting R = 0.089 Ωcm2

8
|Z| / ohm·cm2

80°C 0.15
6
0.025 0.1
4
0.05
d e
2 Y0 = 0.170 Scm-2 s^n Y0 = 0.582 Scm-2 s^n
0 f n = 0.772 n = 0.921
0.05 0.1 0.15 0.2 0 0
1 10 100 1000 10000
Z' / ohm·cm2 Frequency / Hz

Figure3.3. EIS
Figure EIS at
at 1.5
1.5VVand °C◦for
and8080 high
C for (a–c),
high 0.5 mg
(a–c), 0.5 cm
mg , cm
−2 and−2medium (d–f), 0.1(d–f),
, and medium mg cm0.1 ,mg cm−2 ,
−2 cathode

cathode catalyst loading MEAs. Nyquist plots are reported in (a) and (d). Bode plots are reported and
catalyst loading MEAs. Nyquist plots are reported in (a) and (d). Bode plots are reported in (b) in (b)
(e),(e),
and equivalent circuits
equivalent are are
circuits reported in (c)
reported inand (f). (f).
(c) and

In both cases, there are two overlapping semicircles in the Nyquist plots (Figure 3a,d)
In both cases, there are two overlapping semicircles in the Nyquist plots (Figure 3a,d)
corresponding to two different relaxation times in the Bode plots in Figure 3b,e. These are represented
corresponding to two different relaxation times in the Bode plots in Figure 3b,e. These are represented
by two overlapping peaks in the curves related to the phase shift. A small semicircle is occurring at
byhigh
two frequencies
overlappingin peaks
bothincases.
the curves
This related to the phase
is characterized byshift.
smallAresistance
small semicircle is occurring
especially when the at high
Pt
frequencies
loading in the cathode is relatively large. The resistance associated to this semicircle increasesin
in both cases. This is characterized by small resistance especially when the Pt loading
the cathode is relatively
considerably when the large. The resistance
Pt loading associated
at the cathode to thisfrom
is reduced semicircle
0.5 to increases
0.1 mg cmconsiderably when
−2. This evidence

the Pt loading at the cathode is reduced from 0.5 to 0.1 mg cm −2 . This evidence clearly indicates that
clearly indicates that the cathode process is responsible for the high frequency arc. The arc occurring
the
at cathode process
low frequency is responsible
and characterized forbythe highpolarization
higher frequency arc. The arceven
resistance, occurring
when at
thelow frequency
cathode and
catalyst
characterized by higher polarization
loading is substantially reduced, isresistance,
attributedeven when
to the the cathode
anode catalyst
(the oxygen loadingisis the
evolution substantially
slowest
reduced, is attributed to the anode (the oxygen evolution is the slowest mechanism
mechanism in the electrolysis process). The presence of a high Pt content at the cathode thus reduces in the electrolysis
process). The presence
significantly the high of a high Ptsemicircle
frequency content atinthethecathode
Nyquistthusplotreduces
(Figuresignificantly the highrelaxation
3a) and its related frequency
time peak (Figure 3b) is not well evident in the Bode plot. In the literature, the high frequency arc in
Materials 2018, 11, 1368 7 of 15

Materials 2018, 11, x FOR PEER REVIEW 7 of 15

semicircle in the Nyquist plot (Figure 3a) and its related relaxation time peak (Figure 3b) is not well
evident in theplot
the Nyquist Bode
of aplot.
PEM In the literature,
electrolysis MEA the high frequency
is attributed either toarctheinhydrogen
the Nyquist plot of
evolution a PEMor
process
electrolysis
to a chargeMEA is attributed
transfer either to thedouble
process combining hydrogen layerevolution
effects ofprocess or to a and
the ionomer charge transfer
oxides process
in the active
combining double layer effects of the ionomer and oxides in the active anode layer
anode layer [33]. However, because of the very low cathode catalyst loading, in the present case, the [33]. However,
because
hydrogen of the very low
evolution cathode
process catalyst
seems loading,
to have in theeffect
a relevant present
on case,
the highthe hydrogen
frequencyevolution
semicircle. process
seemsInterestingly,
to have a relevant effectvariation
the main on the high
thatfrequency
is observed semicircle.
in the Nyquist plot is essentially related to the
Interestingly, the main variation that is observed
capacitive effects at high frequency but there is essentially in thenoNyquist
change plotin theis overall
essentially related(low
resistance to
the capacitive
frequency effects on
intercept at high frequency
the x-axis). Thus,but
thethere is essentially
polarization curvesnoare change in the overall
overlapping resistance
in this region. It is
(low frequency intercept on the x-axis). Thus, the polarization curves are overlapping
evident that the anode contribution is dominating, in both cases, the overall polarization behaviour. in this region.
ItThe
is evident
anode that the anodeiscontribution
contribution is dominating,
almost comparable in both cases,of
to the contribution the overall
the seriespolarization
resistance inbehaviour.
this range
The anode contribution is almost comparable to the contribution of the
of current densities (Figure 3c,f). In general, ac-impedance spectra reveal features thatseries resistance in this range
the
ofpolarization
current densities (Figure 3c,f). In general,
curves do not make evident. ac-impedance spectra reveal features that the polarization
curves do not make evident.
3.4. Electrochemical Characterization of an Electrolysis MEA at Different Temperatures
3.4. Electrochemical Characterization of an Electrolysis MEA at Different Temperatures
Focusing on the MEA having a low Pt content, a set of polarization curves at increasing
Focusing on the MEA having a low Pt content, a set of polarization curves at increasing
temperatures is shown in Figure 4. Two relevant features can be observed: (i) the increase of cell
temperatures is shown in Figure 4. Two relevant features can be observed: (i) the increase of cell
potential at low current density (activation control) is more relevant as the temperature decreases, (ii)
potential at low current density (activation control) is more relevant as the temperature decreases,
the slope of the polarization curves increase as the temperature decreases. Both effects are related to
(ii) the slope of the polarization curves increase as the temperature decreases. Both effects are related
a variation of efficiency. The first aspect is essentially related to the activation process and it is
to a variation of efficiency. The first aspect is essentially related to the activation process and it is
associated to the catalytic system and the reactions involved; the second aspect is related to the proton
associated to the catalytic system and the reactions involved; the second aspect is related to the proton
conductivity of the membrane that it is also a temperature-activated process [34,35].
conductivity of the membrane that it is also a temperature-activated process [34,35].

1.9
1.5 (anode) + 0.1 (cathode) mg·cm-2
1.8

1.7
Potential / V

1.6 30 °C
1.5 40 °C
60 °C
1.4 80 °C
90 °C
1.3
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2
Current Density / A·cm-2
Figure4.4. Polarization
Figure Polarization curves
curves atatdifferent
differenttemperatures
temperaturesfor
forthe
themedium
mediumcatalyst
catalystloading
loading(1.6
(1.6mg
mg
cm−−2MEA)-based MEA.
2
cm MEA )-based MEA.

To understand the effect of temperature on the catalytic processes at low current density, ac-
To understand the effect of temperature on the catalytic processes at low current density,
impedance spectra collected at 1.5 V and different temperatures are shown in Figure 5 with reference
ac-impedance spectra collected at 1.5 V and different temperatures are shown in Figure 5 with reference
to the low cathode loading MEA. For this MEA with low Pt loading, the Nyquist plots clearly show
to the low cathode loading MEA. For this MEA with low Pt loading, the Nyquist plots clearly show that
that the high frequency arc is not much affected by the temperature differently from the series
the high frequency arc is not much affected by the temperature differently from the series resistance
resistance and the low frequency arc. Quantification of the resistance associated to the high frequency
and the low frequency arc. Quantification of the resistance associated to the high frequency arc
arc according to the curve fitting procedure and related equivalent circuit analysis indicates a
according to the curve fitting procedure 2and related equivalent circuit analysis indicates a moderate
moderate decrease from 0.053 Ohm cm at 30 °C to 0.032 Ohm cm2 at 80 °C (Figure 6a). On the other
decrease from 0.053 Ohm cm2 at 30 ◦ C to 0.032 Ohm cm2 at 80 ◦ C (Figure 6a). On the other hand,
hand, the resistance associated to the low frequency arc associated to the anode reaction decreases
the resistance associated to the low frequency arc associated to the anode reaction decreases from 1.2 to
from 1.2 to 0.035 Ohm cm2 (almost one order of magnitude) in the same temperature range (Figure
0.035 Ohm cm2 (almost one order of magnitude) in the same temperature range (Figure 6a). The series
6a). The series resistance, associated mainly to the membrane, decreases by one half, i.e., from 0.163
resistance,2 associated mainly to the 2membrane, decreases by one half, i.e., from 0.163 Ohm cm2 at
Ohm cm at 30 °C to 0.081 Ohm cm at 80 °C. According, to this analysis, the anode reaction benefits
30 ◦ C to 0.081 Ohm cm2 at 80 ◦ C. According, to this analysis, the anode reaction benefits much more
much more than the other two processes from the increase of temperature (Figure 6a). Figure 6b
clearly shows that the increase of cell current density at 1.5 V with temperature is inversely
proportional to the decrease of the anode polarization resistance. Moreover, at 90 °C, the sum of the
Materials 2018, 11, 1368 8 of 15

than the2018,
Materials other11,two processes
x FOR PEER REVIEWfrom the increase of temperature (Figure 6a). Figure 6b clearly shows8 that of 15
the increase of cell current density at 1.5 V with temperature is inversely proportional to the decrease
contributions
of of the electrodes
the anode polarization to the
resistance. Moreover, at 90 ◦ C, the
overall resistance is slightly lower
sum of the than the contribution
contributions from
of the electrodes
thethe
to electrolyte (Figure 6a).
overall resistance is slightly lower than the contribution from the electrolyte (Figure 6a).
Another interesting
interestingaspect
aspectisisthat
thatthethe
relaxation
relaxation frequencies for the
frequencies foranode and the
the anode andcathode, which
the cathode,
are well separated at 30 °C, become◦ similar at 90 °C (Figure ◦5b,p). This
which are well separated at 30 C, become similar at 90 C (Figure 5b,p). This evidence and evidence and the values of the
the
polarization
values of the resistances
polarization recorded at 90recorded
resistances °C indicate ◦
at 90that C the oxygen
indicate evolution
that process
the oxygen is characterized
evolution process is
by a reaction rate similar to that of the hydrogen evolution process at 90 °C.
characterized by a reaction rate similar to that of the hydrogen evolution process at 90 C. Accordingly, ◦
Accordingly, an
important
an important strategy
strategyto to
increase
increasethetheperformance
performanceofofthe thePEMPEMelectrolyser
electrolyserwould
wouldbebe to increase the
to increase the
operating temperature
operating temperature provided
provided thatthat the
the stability
stabilityisisnot
notaffected.
affected.

2 40
0.8 1.5 V |Z| 30 °C R = 0.53 Ω
R=0.053 cm22
Ωcm R = 1.2 Ωcm2
1.5 V 1.8 35
0.7 30 °C
1.6 Fitting
-Z" / ohm·cm2

Fitting 30

- Phase/ degrees
0.6 1.4 -Phase 30 °C
R = 0.163 Ωcm2
25
|Z| / ohm·cm2

0.5 1.2 Fitting

0.4 1 20
0.3 0.8 15
0.6
0.2
a 0.4
b
10
0.1
0
0.2 5 c Y0 = 0.094 Scm-2 s^n Y0 = 0.498 Scm-2 s^n
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 0 0 n = 0.764 n = 0.868
0.1 1 10 100 1000 10000
Z' / ohm·cm2
Frequency / Hz
0.4 1.8 35
40 °C 1.5 V |Z| 40 °C R = 0.034 Ωcm2 R = 0.508 Ωcm2
1.6 1.5 V
Fitting 30
0.3 Fitting 1.4 -Phase 40 °C

- Phase/ degrees
25
-Z" / ohm·cm2

1.2 Fitting R = 0.134 Ωcm2

|Z| / ohm·cm2

0.2 1 20
0.8 15
0.1 0.6
d 0.4
10

0
0 0.2 0.4 0.6 0.8
0.2 e 5
f Y0 = 0.09 Scm-2 s^n Y0 = 0.504 Scm-2 s^n
0 0 n = 0.799 n = 0.874
Z' / ohm·cm2 0.1 1 10 100 1000 10000
0.15 Frequency / Hz
0.4 18
60 °C 1.5 V 1.5 V |Z| 60 °C R = 0.033 Ωcm2 R = 0.131 Ωcm2
0.35 Fitting 16
Fitting -Phase 60 °C 14
0.3
- Phase/ degrees
-Z" / ohm·cm2

0.1 Fitting R = 0.106 Ωcm2

12
0.25
|Z| / ohm·cm2

10
0.2
8
0.05 0.15
g 0.1
6
4

0
0.05 h 2 i Y0 = 0.194 Scm-2 s^n Y0 = 0.536 Scm-2 s^n
0 0.1 0.2 0.3 0 0 n = 0.743 n = 0.91
Z' / ohm·cm2 0.1 1 10 100 1000 10000
Frequency / Hz
0.2 R = 0.032 Ωcm2 R = 0.051 Ωcm2
0.1 1.5 V |Z| 80 °C 14
80 °C 1.5 V Fitting 12
0.15
- Phase/ degrees

0.075 Fitting -Phase 80 °C R = 0.089 Ωcm2

10
-Z" / ohm·cm2

Fitting
|Z| / ohm·cm2

0.05 0.1 8
6
0.025
l 0.05 m 4

0
0
2
0
n Y0 = 0.170 Scm-2 s^n Y0 = 0.582 Scm-2 s^n
n = 0.772 n = 0.921
0 0.05 0.1 0.15 0.2
0.1 1 10 100 1000 10000
Z' / ohm·cm2
Frequency / Hz
0.1
1.5 V 0.2 10 R = 0.032 Ωcm2 R = 0.035 Ωcm2
90 °C 1.5 V
|Z| 90 °C
0.175 Fitting
0.075 Fitting -Phase 90 °C
- Phase/ degrees

0.15 7.5
-Z" / ohm·cm2

Fitting R = 0.081 Ωcm2

|Z| / ohm·cm2

0.05 0.125
0.1 5
0.025
o 0.075
0.05 2.5
0 0.025 p q Y0 = 0.173 Scm-2 s^n Y0 = 0.720 Scm-2 s^n
0 0.05 0.1 0.15 0.2 n = 0.782 n = 0.933
0 0
Z' / ohm·cm2
0.1 1 10 100 1000 10000
Frequency / Hz

Figure 5. EIS
Figure 5. EIS analysis
analysis at
at 1.5
1.5 V
V and
and increasing
increasing temperatures
temperatures forfor the
the medium
medium catalyst
catalyst loading
loading (1.6
(1.6 mg
mg
cm − 2 )-based MEA. Nyquist plots are reported in (a,d,g,l,o); Bode plots are reported in (b,e,h,m,p);
cm MEA)-based MEA. Nyquist plots are reported in (a,d,g,l,o); Bode plots are reported in (b,e,h,m,p);
−2 MEA
equivalent
equivalent circuits
circuits are
are reported
reported in
in(c,f,i,n,q).
(c,f,i,n,q).
Materials 2018, 11, 1368 9 of 15

Figure 6. Variation of relevant electrochemical parameters at 1.5 V as a function of temperature for the
medium catalyst loading (1.6 mg cm−2 MEA )-based MEA. (a) Rs refers to the series resistance; R1 and R2
refer to the high and low frequency relaxation processes, respectively. (b) Variation of current density
with temperature at 1.5 V.

3.5. Analysis of an Electrolysis MEA with Reduced Anode and Cathode Catalyst Loadings
When the anode loading is decreased by about three times, from 1.5 to 0.4 mg cm−2 , the activation
losses at low current density increase by 30–40 mV and this is reflected in the overall range of current
density (Figure 7). The slopes of the polarization curves at high current density are essentially
determined by the membrane but their onset potential is affected by the content of the anode
electrocatalyst in the investigated range (Figure 7). Electrochemical impedance spectroscopy data
(Figure 8a–f) show that a decrease of the anode loading causes an increase in the corresponding
polarization resistance that overlaps to the cathode process. In comparison, the polarization resistance
of the cathode almost disappears (Figure 8a,d). The same effect is observed for the relaxation
frequencies in the Bode plot (Figure 8b,e). The overall resistance increases in this case (Figure 8)
and this is reflected in the relevant change of the slope in the polarization curves at low current
densities for the low anode loading MEA (Figure 7).
 Materials
Materials 2018,
11,11, x FOR PEER REVIEW 1010
ofof
1515
Materials 2018,
2018, 11, x1368
FOR PEER REVIEW 10 of 15

1.9
1.9
1.8
1.8 8080
°C°C
Potential / V 1.7
1.7
Potential / V

1.6
1.6
1.5
1.5 (1.5anode
(1.5 anode+ +0.1
0.1cathode)
cathode)mg·cm
mg·cm
-2
-2
1.4
1.4
1.3 (0.4anode
(0.4 anode+ +0.1
0.1cathode)
cathode)mg·cm
mg·cm
-2
-2
1.3
1.2
1.2
0 0 0.3
0.30.6
0.60.9
0.91.2 1.21.5
1.51.8 1.82.12.12.4
2.42.7
2.7 3 3

CurrentDensity
Density/ A·cm
/ A·cm -2
Current -2

Figure7.7.Comparison
Comparison ofthe
thewater
waterelectrolysis
electrolysispolarization
polarizationcurves
curvesfor
fordifferent
differentanode
anodecatalyst
catalystloading
loading
Figure
Figure 7. Comparison ofofthe water electrolysis polarization curves for different anode catalyst loading
-based
-based MEAs
MEAs atat ◦
8080 °C.
C.
-based MEAs at 80 °C.
0.075
0.075 0.25 12
anode: 1.5 ++cathode:
1.5 (anode) 0.1 mg
0.1 (cathode) mg·cmcm-2
-2 0.25 1.5 V |Z| 12 R = 0.032 Ωcm2 R = 0.051 Ωcm2
anode: 1.5 ++cathode:
1.5 (anode) 0.1 mg
0.1 (cathode) cm-2
mg·cm -2 1.5 V
|Z| Fitting R = 0.032 Ωcm2 R = 0.051 Ωcm2
Fitting 0.2 80°C 10
1.5 V Fitting
-Z" / ohm·cm2

-Phase 10

- Phase/ degrees
Fitting 0.2 80°C
0.05 1.5 V
-Z" / ohm·cm2

-Phase
Fitting
- Phase/ degrees
0.05 8 R = 0.089 Ωcm2
|Z| / ohm·cm2

80°C 0.15 Fitting 8 R = 0.089 Ωcm2

|Z| / ohm·cm2

80°C 0.15 6
0.1 6
0.025
0.025 0.1 4
4
0.05
a 0.05 b
2 Y0 = 0.170 Scm-2 s^n Y0 = 0.582 Scm-2 s^n
0 a c
2
b Y0 = 0.170nScm -2 s^n -2 s^n
= 0.772 Y0 = 0.582nScm
= 0.921
0 0.05 0.1 0.15 0.2 0 0 0 c n = 0.772 n = 0.921
0.05 0.1 0.15 0.2 1 10 100 1000 0
10000
Z' / ohm·cm2 1 10 100 1000 10000
Frequency / Hz
Z' / ohm·cm2 Frequency / Hz
0.15 0.3 20
0.3 1.5 V 20 18
0.15
0.4 (anode) + 0.1 (cathode) mg·cm-2 1.5 V 0.25 e 1.5 V 18
0.125 anode: 0.4 + cathode: 0.1 mg cm-2
0.4 (anode) + 0.1 (cathode) mg·cm-2 1.5 V 0.25 e 16
- Phase/ degrees

0.125 anode:Fitting
0.4 + cathode: 0.1 mg cm-2
80°C 16 14
- Phase/ degrees

Fitting 80°C 0.2 80°C 14

|Z| / ohm·cm2

0.1
80°C 0.2 12
-Z" / ohm·cm2

|Z| / ohm·cm2

0.1
12 10
-Z" / ohm·cm2

0.15
0.075
0.15 10 8
0.075
0.1 |Z| 8 6
0.05 0.1 |Z| Fitting 6 4
0.05
0.05 Fitting
-Phase 4 2 f
0.025
d 0.05 -Phase
Fitting f
0.025
0
d 0
0 Fitting 2 0
0
1 10 100 1000 10000
0 0 0.05 0.1 0.15 0.2 0.25 0.3
1 10 100 1000 10000
0 0.05 0.1 0.15
Z' / ohm·cm0.2
2 0.25 0.3 Frequency / Hz
Z' / ohm·cm2 Frequency / Hz

Figure 8. EIS at 1.5 V and 80 °C for high (a–c), 1.5 mg cm −2, and medium (d–f), 0.4 mg cm−2, anode
Figure
Figure8.8.EIS
EISat at
1.51.5
VVand
and °C ◦for
80 80 high
C for (a–c),
high 1.5 mg
(a–c), 1.5 cm −2 ,medium
, and
mg−2cm (d–f), (d–f),
and medium 0.4 mg0.4
cmmg cm−2 ,
−2, anode
catalyst loading MEAs.
catalyst loadingloading
anode catalyst MEAs. MEAs.

3.6. Effect of the Operating Potential Windows

3.6.
3.6.Effect
Effectofofthe
theOperating
OperatingPotential
PotentialWindows
Windows
Figure 9 shows the ac-impedance spectra collected at 1.8 V for the MEA characterized by low
Figure
Figure99shows
showsthe theac-impedance
ac-impedancespectraspectracollected
collectedatat1.8 1.8VVfor
forthe
theMEA
MEAcharacterized
characterizedby bylow
low
catalyst loadings. The series resistance associated to the membrane contribution is dominating the
catalyst
catalystloadings.
loadings.The Theseries
seriesresistance
resistanceassociated
associatedto tothe
themembrane
membranecontribution
contributionisisdominating
dominatingthe the
overall polarization behaviour at the different temperatures. The role of the membrane is significant
overall polarization behaviour at the different temperatures. The role of the
overall polarization behaviour at the different temperatures. The role of the membrane is significant membrane is significant
(>80% contribution) at higher current density and high temperatures (Figures 9 and 10). The overall
(>80%
(>80%contribution)
contribution)atathigher
highercurrent
currentdensity
densityand andhigh
hightemperatures
temperatures(Figures
(Figures99and
and10).
10).TheTheoverall
overall
polarization resistance (difference between high and low frequency intercept) decreases more than
polarization resistance (difference between
polarization resistance (difference between high high and low frequency intercept) decreases more than than
and low frequency intercept) decreases more three
three times, from 0.06 to 0.015 Ohm cm 2, passing from 25 ◦°C to 90 °C whereas series resistance is
three times, from 0.06 to 0.015 Ohm 2
times, from 0.06 to 0.015 Ohm cm , passing from cm 2, passing from
25 ◦ C to 2590°C Ctowhereas
90 °C whereas
series series resistance
resistance is reduced is
reduced to one half from 0.16 to 0.08 2Ohm cm 2 (Figures 9 and 10). Thus, the polarization resistance is
reduced
to one halfto one
fromhalf
0.16from 0.16 Ohm
to 0.08 to 0.08cm Ohm cm (Figures
(Figures
2
9 and 10).9 and 10). Thus,
Thus, the polarization
the polarization resistance
resistance is moreis
more affected by the increase of temperature in terms of relative variation, whereas the membrane
more affected by the increase of temperature in terms of relative variation, whereas
affected by the increase of temperature in terms of relative variation, whereas the membrane resistance, the membrane
resistance, being dominant, is more influenced by the temperature in terms of absolute values. The
resistance,
being dominant,being is
dominant, is moreby
more influenced influenced by the temperature
the temperature in terms
in terms of absolute of absolute
values. The curvevalues. Theis
fitting
curve fitting is still sufficiently valid using two semicircles in series with the ohmic (membrane)
curve fitting is still
still sufficiently validsufficiently valid usingintwo
using two semicircles seriessemicircles
with the ohmicin series with the resistance.
(membrane) ohmic (membrane)
However,
resistance. However, being the hydrogen process characterized by a very low resistance at high
resistance.
being the hydrogen process characterized by a very low resistance at high current density, aatprecise
However, being the hydrogen process characterized by a very low resistance high
current density, a precise estimation of its contribution is not easy (Figure 9). The same for the
current density, a precise estimation of its contribution is not easy (Figure
estimation of its contribution is not easy (Figure 9). The same for the relaxation times in the Bode 9). The same for the
relaxation times in the Bode plots (Figure 9). A relaxation frequency at high frequency is envisaged
relaxation times in the Bode plots (Figure 9). A relaxation frequency at high frequency is envisaged
from the experimental data (Figure 9); however, the curve fitting slightly deviates from the
from the experimental data (Figure 9); however, the curve fitting slightly deviates from the
Materials 2018, 11, 1368 11 of 15

plotsMaterials
(Figure 9). 11,
2018, A xrelaxation frequency at high frequency is envisaged from the experimental data
FOR PEER REVIEW 11 of 15
(Figure 9); however, the curve fitting slightly deviates from the experimental data in that range failing
to determine
experimentalthe exact
data hydrogen relaxation
in that range frequency
failing to determine(this
theisexact
shifted to very relaxation
hydrogen high frequencies where
frequency (this is
membrane
shiftedeffects
to veryare dominating
high the where
frequencies process).
membrane 90 ◦ C are
Finally, ateffects anddominating
1.8 V (Figurethe
9),process).
some deviation
Finally,ofat 90
the curve
°C and fitting
1.8 from the experimental
V (Figure data at low
9), some deviation of frequency
the curve may suggest
fitting from the
theonset of a mass data
experimental transfer
at low
controlled
frequencyprocess.
may Unfortunately,
suggest the onset measurements at very
of a mass transfer low frequency
controlled process.are significantly affected
Unfortunately, by
measurements
noiseatinvery
the low
presence of a large
frequency gas evolution.
are significantly affected by noise in the presence of a large gas evolution.

Figure 9. EIS at9.1.8

Figure EISVat
for1.8
low catalyst
V for low catalyst at 25 ◦ C at
loading loading (a–c), ◦ C (d–f), 60 ◦ C (g–i), 80 ◦ C (l–n), 90 ◦ C (o–q).
40 (a–c),
25 °C 40 °C (d–f), 60 °C (g–i), 80 °C (l–n), 90 °C
(o–q).
Materials 2018, 11, 1368 12 of 15
Materials
Materials2018,
2018,11,
11,xxFOR
FORPEER
PEERREVIEW
REVIEW 12
12of
of15
15

Figure 10.
Figure10.
Figure 10.Variation
Variationof
Variation of relevant
ofrelevant electrochemical
electrochemicalparameters
relevantelectrochemical parametersat
parameters at1.8
at 1.8V
1.8 VVas aafunction
asa
as function
functionof
of temperature
temperaturefor
oftemperature for
for
the
thelow
low catalyst
catalyst loading-based
loading-based MEA.
MEA. Rs
Rsrefers
refersto
tothe
theseries
seriesresistance;
resistance;R1
R1 and
andR2
R2 refer
referto
tothe
the
the low catalyst loading-based MEA. Rs refers to the series resistance; R1 and R2 refer to the high and high
highand
and
low
lowfrequency
low relaxation
frequencyrelaxation
frequency processes,
relaxationprocesses, respectively.
processes,respectively.
respectively.

3.7.
3.7.Analysis
3.7. Analysisof
Analysis ofMEA
of MEADegradation
MEA Degradation
Degradation
Electrochemical
Electrochemical impedance
Electrochemicalimpedance spectroscopy
spectroscopyisisisalso
impedancespectroscopy also
alsoa apowerful
apowerful
powerful tooltoto
tool
tool to understand
understand
understand thethe
the degradation
degradation
degradation of
of
of an
an MEA
MEA in
in aa durability
durability experiment
experiment (Figure
(Figure 11).
11). AA time-study
time-study at
at 33 AA
− cm
cm
2
an MEA in a durability experiment (Figure 11). A time-study at 3 A cm was thus carried out for the
−2
−2 was
was thus
thus carried
carried out
out for
for
the
theMEA
MEA MEA characterised
characterised
characterised by bybythe
the lowlow
the low catalyst
catalyst
catalyst loading
loading
loading at at
atboth
bothboth electrodes
electrodes
electrodes (total
(total
(total PGM
PGMPGM loading
loading0.5
loading 0.5 mg
0.5mg
mgcmcm
cm 2)))
−−2−2
showing
showingaaadegradation
showing degradation
degradation rate
rate
rate of
of about
of aboutabout 20
20 µV/h
20 µV/h µV/h in
in aa 1000-h
in a 1000-h 1000-h durability
durability
durability test
test according
test according according to
to a best fit aa best
best fit
toprocedure fit
procedure
procedure (Figure
(Figure 11
11 inset).
inset). The
The polarization
polarization curves
curves before
before and
and after
after the
the
(Figure 11 inset). The polarization curves before and after the durability test show an increase of celldurability
durability test
test show
show an
an
increase
increase of
potential of cell
cell potential
slightly potential slightly
smaller thanslightly smaller
20 mVsmaller
at lowthan
than 20
20 mV
current mV at
at low
densities current
lowafter the densities
current densities after
time-study. after the
the time-study.
However, time-study.
this loss
However,
However, this
this loss
lossis
isin
in part
part recovered
recovered
is in part recovered at high current densities. at
athigh
high current
current densities.
densities.

1.9
1.9
00 hh 80
80°C
°C
1.8
1.8
1000
1000 hh
V
Potential // V

1.7
1.7
Potential

2.2
2.2
1.6
1.6 2.1
2.1
22 33A·cm
A·cm-2-2
80
80°C
°C
Cell Potential / V
Cell Potential / V

1.9
1.9
1.5
1.5 1.8
1.8
1.7
1.7
1.6
1.6
1.4
1.4 1.5
1.5
1.4
1.4
Anode:
Anode:0.4
0.4mg·cm
mg·cm-2-2 1.3
1.3
1.3
1.3 Cathode:
Cathode:0.1
0.1mg·cm
mg·cm-2-2
1.2
1.2
00 200
200 400
400 600
600 800
800 1000
1000
Time
Time/ h
/h
1.2
1.2
00 0.5
0.5 11 1.5
1.5 22 2.5
2.5 33
Current
CurrentDensity
Density//A·cm
A·cm -2
-2

Figure
Figure11.
Figure 11.Polarization
11. Polarizationcurves
Polarization curvesat
curves at80
at 80°C
80 C before
◦°C beforeand
before andafter
and afteraaa1000
after 1000hhhdurability
1000 durabilitytest
durability testfor
test foraaalow-loading
for low-loadingMEA
low-loading MEA
MEA
(both low anode 0.4 mg cm
(both low anode 0.4 mg cm and cathode 0.1 mg cm loadings). The inset shows the durability tests
and cathode 0.1 mg cm
(both low anode 0.4 mg cm
−−2
−2
2 and cathode 0.1 mg cm −−22loadings).
−2
loadings).The
The inset
inset shows
shows the
thedurability
durability tests
tests
at
at 3 A∙cm
at33A
A∙cm −2
·cm ..
− .
−2
2

Figure
Figure12 12shows
shows that
thatafter
after1000
1000 hh ofof operation
operationat at33 A Acmcm−2−2,, there
there isisaa substantial
substantialincrease
increase of
of the
the
Figure 12 shows that after 1000 h of operation at 3 A cm−2 , there is a 2substantial increase of the
anode
anode polarization
polarization resistance
resistance atat low
low frequency
frequency (from(from 0.10.1 to
to 0.17
0.17 OhmOhm cm cm2).).2 A
A moderate
moderate increase
increase ofof
anode polarization resistance at low frequency (from 0.1 to 0.17 Ohm cm ). A moderate increase
the high frequency arc (from 0.03 to 0.04 Ohm cm 22) is also observed whereas the series (ohmic)
the high frequency arc (from 0.03 to 0.04 Ohm cm ) is also observed whereas the series (ohmic)
of the high frequency arc (from 0.03 to 0.04 Ohm cm2 ) is also observed whereas the series (ohmic)
resistance
resistance(high
(highfrequency
frequencyintercept
intercepton onthe
theabscissa
abscissaininthe
theNyquist
Nyquistplot) plot)shows
showsaavery verysmall
smalldecrease.
decrease.
resistance (high frequency intercept on the abscissa in the Nyquist plot) shows a very small decrease.
This
Thisdecrease
decrease(from (from0.09
0.09toto0.08
0.08Ohm
Ohmcm cm222))is,
is,however,
however,in inpart
partsufficient
sufficientto toallow
allowrecovering
recoveringat athigh
high
This decrease (from 0.09 to 0.08 Ohm cm ) is, however, in part sufficient to allow recovering at high
current
currentdensity
densitysome someof ofthe
theperformance
performanceloss losscaused
causedby bythetheanode
anodedeactivation.
deactivation.As Asdiscussed
discussedabove,
above,
current density some of the performance loss caused by the anode deactivation. As discussed above,
the
the membrane
membrane plays plays aa dominant
dominant role role at
at high
high operating
operating currents.
currents. This This decrease
decrease of of the
the membrane
membrane
the membrane plays a dominant role at high operating currents. This decrease of the membrane
resistance
resistance maymay be be associated
associated with
with some
some restructuring
restructuring of of the
the membrane
membrane during during operation
operation atat high
high
resistance may be associated with some restructuring of the membrane during operation at high
currents.
currents.The Theimpedance
impedancespectroscopy
spectroscopyshows showsthat thatthere
thereisisaadegradation
degradationfor forbothbothanode
anodeandandcathode
cathode
currents. The impedance spectroscopy shows that there is a degradation for both anode and cathode
but
but the
the first
firstisis more
more pronounced.
pronounced. This Thisisis somewhat
somewhat expected
expected because
because the theanode
anode operates
operates ininaa much
much
but the first is more pronounced. This is somewhat expected because the anode operates in a much
higher potential window.
higher potential window.
higher potential window.
Materials 2018, 11, 1368 13 of 15
Materials 2018, 11, x FOR PEER REVIEW 13 of 15

Figure 12. EIS at

12. EIS at 1.5
1.5 V
V and
and 80 ◦ C, before and after a 1000 h durability test at 3 A cm−2 , for a low-loading
80 °C,
Figure before and after a 1000 h durability test at 3 A cm−2, for a low-loading
MEA (both low anode 0.4 mg cm −2 and cathode 0.1 mg cm−2 loadings). Nyquist plots are reported in
MEA (both low anode 0.4 mg cm−2 and cathode 0.1 mg cm−2 loadings). Nyquist plots are reported in
(a,d); Bode plots are reported in (b,e); equivalent circuits
(a,d); Bode plots are reported in (b,e); equivalent circuits are
are reported
reported in
in (c,f).
(c,f).

4. Conclusions
4. Conclusions
This work
This work shows
shows that
that electrochemical
electrochemical impedance
impedance spectroscopy
spectroscopy can can provide
provide relevant
relevant information
information
to identify and quantify the contribution of the electrode processes to the polarization behaviour ofof
to identify and quantify the contribution of the electrode processes to the polarization behaviour a
a PEM
PEM electrolysis
electrolysis cell.
cell. ThisThis is especially
is especially useful
useful when when the single
the single cella or
cell or a stack
stack cannot cannot be equipped
be equipped with
with
an an internal
internal reference
reference electrode,
electrode, eithereither
for theforspecific
the specific
design design
usedused
or forortheforoperating
the operating conditions
conditions e.g.,
e.g., high pressure. Ac-impedance spectra are collected under the specific
high pressure. Ac-impedance spectra are collected under the specific operating conditions of operating conditions of the
the
electrolysis cell
electrolysis cell and,
and, thus,
thus, this
this technique
technique is is not
not invasive.
invasive. It It supplies
supplies important
important information
information on on the
the
limiting phenomena and it can provide useful insights to drive the research
limiting phenomena and it can provide useful insights to drive the research efforts towards a specific efforts towards a specific
cell component
cell component in in the
the case
case ofof post-operation
post-operation degradation
degradation studies.
studies.
The present
The present study
study has
has shown
shown that that membrane
membrane resistance
resistance plays
plays aa dominant
dominant role role at
at high
high current
current
density, which is usually the nominal operating condition under stationary
density, which is usually the nominal operating condition under stationary mode, whereas the anode mode, whereas the anode
process is
process is relevant
relevant under
under partial
partial loadload operation.
operation. The The latter
latter condition
condition is is frequently occurring under
frequently occurring under
grid-balancing service. An increase of temperature strongly activates all these
grid-balancing service. An increase of temperature strongly activates all these processes, especially processes, especially the
anode reaction. At 90 ◦ C, the anode contribution to the polarisation resistance is not significantly
the anode reaction. At 90 °C, the anode contribution to the polarisation resistance is not significantly
higher than
higher than that
that associated
associated to to the
the cathode,
cathode, whereas
whereas at at low
low temperature
temperature and and low
low potentials
potentials thethe anode
anode
process is the rate determining
process is the rate determining step. step.
The registration
The registration of of ac-impedance
ac-impedance spectra spectra during
during thethe course
course or or at
at the
the end
end ofof durability
durability studies
studies
provides aa non-invasive
provides non-invasive tool tool to to identify
identify which
which component
component is is more
more affected
affected by by degradation.
degradation. In In the
the
present study, the anode was identified to contribute to the degradation
present study, the anode was identified to contribute to the degradation behaviour in a more behaviour in a more
pronounced extent
pronounced extent than
than the
the cathode,
cathode, whereas
whereas the the decrease
decrease of of the
the series
series resistance
resistance would
would suggest
suggest
some restructuring of the polymer during operation but, in some
some restructuring of the polymer during operation but, in some cases, it may be associated to cases, it may be associated to aa
membrane thinning effect. Thus, an analysis of the evolution of the EIS
membrane thinning effect. Thus, an analysis of the evolution of the EIS spectra during cell or stack spectra during cell or stack
operation may
operation mayprovide
provideuseful
useful insights
insights intointo
the the
statestate
of theofelectrolysis systemsystem
the electrolysis servingserving
as a non-invasive
as a non-
diagnostic tool.
invasive diagnostic tool.
Author Contributions: S.S. prepared the electrocatalysts and the MEAs and carried out the electrochemical
Author Contributions: S.S. prepared the electrocatalysts and the MEAs and carried out the electrochemical
experiments and data analysis; S.T. carried out the impedance data fitting; N.B. designed the electrolysis
experiments and
cell hardware; data
V.B. analysis;
assisted S.T. carried out
at experimental the impedance
researches and datadata fitting;A.S.A.
analysis; N.B. designed
conceivedthe electrolysis
and designed cell
the
hardware; V.B.
experiments, andassisted at manuscript.
wrote the experimental researches and data analysis; A.S.A. conceived and designed the
experiments, and wrote the manuscript.
Funding: This research was funded by the FCH JU through the HPEM2GAS project. This project has received
funding from
Funding: This the Fuel Cells
research and Hydrogen
was funded 2 Joint
by the FCH JU Undertaking under grant project.
through the HPEM2GAS agreement
ThisNo 700008.
project hasThis Joint
received
funding from the Fuel Cells and Hydrogen 2 Joint Undertaking under grant agreement No 700008. This Joint
Materials 2018, 11, 1368 14 of 15

Undertaking receives support from the European Union’s Horizon 2020 research and innovation programme and
Hydrogen Europe and Hydrogen Europe Research.
Acknowledgments: The authors thank G. Monforte (CNR-ITAE) for assistance with electrolysis test station.
Conflicts of Interest: The authors declare no conflict of interest.

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